Search results for: selective%20catalytic%20reduction
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 801

Search results for: selective%20catalytic%20reduction

51 Hexahydropyrimidine-2,4-Diones: Synthesis and Cytotoxic Activity

Authors: M. Koksal, T. Ozyazici, E. Gurdal, M. Yarım, E. Demirpolat, M. B. Y. Aycan

Abstract:

The discovery of new drugs in cancer chemotherapy is still a major topic because of severe side effects, selectivity problems and resistance development potential of existing drugs. In recent years, combined anticancer therapies or multi-acting drugs are clinically preferred over traditional cytotoxic treatment, with the aim of avoiding resistance and toxic side effects. Arrangement of multi-acting targets can be carried out either by combination of several drugs with different mechanisms or by usage of a single chemical compound capable of regulating several targets of a disease with multiple factors. In literature, several pyrimidine and piperazine derivatives have been involved in the structure of many compounds which have been used as chemotherapeutic agents along with wide clinical applications. The aim of this study is to combine pyrimidine and piperazine core structures to research and develop novel piperazinylpyrimidine derivatives with selective cytotoxicity over cancer cells. In this study, a group of novel 6-fluorophenyl-3-[2-(substitutedpiperazinyl)ethyl] hexahydropyrimidine-2,4-dione derivatives designed to observe the desired anticancer activity due to pyrimidine and piperazine based scaffolds. Target compounds were obtained by the reaction of appropriate piperazine derivatives and 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-dione. The synthetic pathway of 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-dione was started with Rodionov reaction using aldehyde, malonic acid and ammonium acetate in ethanol. Isolated β-fluorophenyl-β-amino acids were treated with 2-chloroethylisocyanate in the presence of an aqueous sodium hydroxide solution at room temperature to yield the sodium salts of the corresponding ureido acids. By addition of a mineral acid, ureido acids were precipitated. Later, these ureido acids were refluxed in thionyl chloride to give the 6-(2/4-fluorophenyl)-3-(2-chloroethyl)hexahydropyrimidine-2,4-di-one which were furthermore treated with secondary amines. Structures of purified compounds were characterized with IR, 1H-NMR, 13C-NMR, mass spectroscopies and elemental analysis. All of the compounds gave satisfactory analytical and spectroscopic data, which were in full accordance with their depicted structures. In IR spectra of the compounds, N-H group was seen at 3230-3213 cm⁻¹. C-H was seen at 3100-2820 cm⁻¹ and C=O vibrational peaks were observed approximately at 1725 and 1665 cm⁻¹ in accordance with literature. In the NMR spectra of target compounds, the methylene protons of piperazine give two separate multiplet peaks around 3.5 and 4.5 ppm representing the successful N-alkylation of the structure. The cytotoxic activity of the synthesized compounds was investigated on human bronchial epithelial (BEAS 2B), lung (A549), colon adenocarcinoma (COLO205) and breast (MCF7) cell lines, by means of sulphorhodamine B (SRB) assays in triplicate. IC₅₀ values of the screened derivatives were found in range of 11.8-78 µM. This project was supported by The Scientific and Technological Research Council of Turkey (TUBITAK, Project no: 215S157).

Keywords: cytotoxicity, hexahydropyrimidine, piperazine, sulphorhodamine B assay

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50 Concentration and Stability of Fatty Acids and Ammonium in the Samples from Mesophilic Anaerobic Digestion

Authors: Mari Jaakkola, Jasmiina Haverinen, Tiina Tolonen, Vesa Virtanen

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These process monitoring of biogas plant gives valuable information of the function of the process and help to maintain a stable process. The costs of basic monitoring are often much lower than the costs associated with re-establishing a biologically destabilised plant. Reactor acidification through reactor overload is one of the most common reasons for process deterioration in anaerobic digesters. This occurs because of a build-up of volatile fatty acids (VFAs) produced by acidogenic and acetogenic bacteria. VFAs cause pH values to decrease, and result in toxic conditions in the reactor. Ammonia ensures an adequate supply of nitrogen as a nutrient substance for anaerobic biomass and increases system's buffer capacity, counteracting acidification lead by VFA production. However, elevated ammonia concentration is detrimental to the process due to its toxic effect. VFAs are considered the most reliable analytes for process monitoring. To obtain accurate results, sample storage and transportation need to be carefully controlled. This may be a challenge for off-line laboratory analyses especially when the plant is located far away from the laboratory. The aim of this study was to investigate the correlation between fatty acids, ammonium, and bacteria in the anaerobic digestion samples obtained from an industrial biogas factory. The stability of the analytes was studied comparing the results of the on-site analyses performed in the factory site to the results of the samples stored at room temperature and -18°C (up to 30 days) after sampling. Samples were collected in the biogas plant consisting of three separate mesofilic AD reactors (4000 m³ each) where the main feedstock was swine slurry together with a complex mixture of agricultural plant and animal wastes. Individual VFAs, ammonium, and nutrients (K, Ca, Mg) were studied by capillary electrophoresis (CE). Longer chain fatty acids (oleic, hexadecanoic, and stearic acids) and bacterial profiles were studied by GC-MSD (Gas Chromatography-Mass Selective Detector) and 16S rDNA, respectively. On-site monitoring of the analytes was performed by CE. The main VFA in all samples was acetic acid. However, in one reactor sample elevated levels of several individual VFAs and long chain fatty acids were detected. Also bacterial profile of this sample differed from the profiles of other samples. Acetic acid decomposed fast when the sample was stored in a room temperature. All analytes were stable when stored in a freezer. Ammonium was stable even at a room temperature for the whole testing period. One reactor sample had higher concentration of VFAs and long chain fatty acids than other samples. CE was utilized successfully in the on-site analysis of separate VFAs and NH₄ in the biogas production site. Samples should be analysed in the sampling day if stored in RT or freezed for longer storage time. Fermentation reject can be stored (and transported) at ambient temperature at least for one month without loss of NH₄. This gives flexibility to the logistic solutions when reject is used as a fertilizer.

Keywords: anaerobic digestion, capillary electrophoresis, ammonium, bacteria

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49 Improvement of Greenhouse Gases Bio-Fixation by Microalgae Using a “Plasmon-Enhanced Photobioreactor”

Authors: Francisco Pereira, António Augusto Vicente, Filipe Vaz, Joel Borges, Pedro Geada

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Light is a growth-limiting factor in microalgae cultivation, where factors like spectral components, intensity, and duration, often characterized by its wavelength, are well-reported to have a substantial impact on cell growth rates and, consequently, photosynthetic performance and mitigation of CO2, one of the most significant greenhouse gases (GHGs). Photobioreactors (PBRs) are commonly used to grow microalgae under controlled conditions, but they often fail to provide an even light distribution to the cultures. For this reason, there is a pressing need for innovations aiming at enhancing the efficient utilization of light. So, one potential approach to address this issue is by implementing plasmonic films, such as the localized surface plasmon resonance (LSPR). LSPR is an optical phenomenon connected to the interaction of light with metallic nanostructures. LSPR excitation is characterized by the oscillation of unbound conduction electrons of the nanoparticles coupled with the electromagnetic field from incident light. As a result of this excitation, highly energetic electrons and a strong electromagnetic field are generated. These effects lead to an amplification of light scattering, absorption, and extinction of specific wavelengths, contingent on the nature of the employed nanoparticle. Thus, microalgae might benefit from this biotechnology as it enables the selective filtration of inhibitory wavelengths and harnesses the electromagnetic fields produced, which could lead to enhancements in both biomass and metabolite productivity. This study aimed at implementing and evaluating a “plasmon-enhanced PBR”. The goal was to utilize LSPR thin films to enhance the growth and CO2 bio-fixation rate of Chlorella vulgaris. The internal/external walls of the PBRs were coated with a TiO2 matrix containing different nanoparticles (Au, Ag, and Au-Ag) in order to evaluate the impact of this approach on microalgae’s performance. Plasmonic films with distinct compositions resulted in different Chlorella vulgaris growth, ranging from 4.85 to 6.13 g.L-1. The highest cell concentrations were obtained with the metallic Ag films, demonstrating a 14% increase compared to the control condition. Moreover, it appeared to be no differences in growth between PBRs with inner and outer wall coatings. In terms of CO2 bio-fixation, distinct rates were obtained depending on the coating applied, ranging from 0.42 to 0.53 gCO2L-1d-1. Ag coating was demonstrated to be the most effective condition for carbon fixation by C. vulgaris. The impact of LSPR films on the biochemical characteristics of biomass (e.g., proteins, lipids, pigments) was analysed as well. Interestingly, Au coating yielded the most significant enhancements in protein content and total pigments, with increments of 15 % and 173 %, respectively, when compared to the PBR without any coating (control condition). Overall, the incorporation of plasmonic films in PBRs seems to have the potential to improve the performance and efficiency of microalgae cultivation, thereby representing an interesting approach to increase both biomass production and GHGs bio-mitigation.

Keywords: CO₂ bio-fixation, plasmonic effect, photobioreactor, photosynthetic microalgae

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48 The Role of Uterine Artery Embolization in the Management of Postpartum Hemorrhage

Authors: Chee Wai Ku, Pui See Chin

Abstract:

As an emerging alternative to hysterectomy, uterine artery embolization (UAE) has been widely used in the management of fibroids and in controlling postpartum hemorrhage (PPH) unresponsive to other therapies. Research has shown UAE to be a safe, minimally invasive procedure with few complications and minimal effects on future fertility. We present two cases highlighting the use of UAE in preventing PPH in a patient with a large fibroid at the time of cesarean section and in the treatment of secondary PPH refractory to other therapies in another patient. We present a 36-year primiparous woman who booked at 18+6 weeks gestation with a 13.7 cm subserosal fibroid at the lower anterior wall of the uterus near the cervix and a 10.8 cm subserosal fibroid in the left wall. Prophylactic internal iliac artery occlusion balloons were placed prior to the planned classical midline cesarean section. The balloons were inflated once the baby was delivered. Bilateral uterine arteries were embolized subsequently. The estimated blood loss (EBL) was 400 mls and hemoglobin (Hb) remained stable at 10 g/DL. Ultrasound scan 2 years postnatally showed stable uterine fibroids 10.4 and 7.1 cm, which was significantly smaller than before. We present the second case of a 40-year-old G2P1 with a previous cesarean section for failure to progress. There were no antenatal problems, and the placenta was not previa. She presented with term labour and underwent an emergency cesarean section for failed vaginal birth after cesarean. Intraoperatively extensive adhesions were noted with bladder drawn high, and EBL was 300 mls. Postpartum recovery was uneventful. She presented with secondary PPH 3 weeks later complicated by hypovolemic shock. She underwent an emergency examination under anesthesia and evacuation of the uterus, with EBL 2500mls. Histology showed decidua with chronic inflammation. She was discharged well with no further PPH. She subsequently returned one week later for secondary PPH. Bedside ultrasound showed that the endometrium was thin with no evidence of retained products of conception. Uterotonics were administered, and examination under anesthesia was performed, with uterine Bakri balloon and vaginal pack insertion after. EBL was 1000 mls. There was no definite cause of PPH with no uterine atony or products of conception. To evaluate a potential cause, pelvic angiogram and super selective left uterine arteriogram was performed which showed profuse contrast extravasation and acute bleeding from the left uterine artery. Superselective embolization of the left uterine artery was performed. No gross contrast extravasation from the right uterine artery was seen. These two cases demonstrated the superior efficacy of UAE. Firstly, the prophylactic use of intra-arterial balloon catheters in pregnant patients with large fibroids, and secondly, in the diagnosis and management of secondary PPH refractory to uterotonics and uterine tamponade. In both cases, the need for laparotomy hysterectomy was avoided, resulting in the preservation of future fertility. UAE should be a consideration for hemodynamically stable patients in centres with access to interventional radiology.

Keywords: fertility preservation, secondary postpartum hemorrhage, uterine embolization, uterine fibroids

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47 Energizing Value Added Farming in Agriculture Economic Aspects towards Sustaining Crop Yield, Quality and Food Safety of Small-Scale Cocoa Farmer in Indonesia

Authors: Burmansyah Muhammad, Supriyoto Supriyoto

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Crop yield, quality and food safety are three important components that all estate and food crops must put into consideration to lifting the economic value. These measurements should be evaluated because marketplace demand is simultaneously changing and farmers must adapt quickly to remain competitive. The increase in economic value could be done by producing high quality product that aligns with harvest collector preferences. The purpose of this study is to examine the causal effects of value added farming in agriculture economic aspects towards crop yield, quality and food security. This research is using descriptive survey research by employing data from small-scale cocoa farmers listed to off-taker company, located on Sulawesi area of Indonesia. The questionnaire was obtained from 650 cocoa farmers, selected randomly. Major findings of the study indicate that 78% of respondents agree that agriculture inputs have positive effect on crop yield, quality and food safety. The study recommended that cocoa stakeholders should ensure access to agriculture inputs in first priority and then followed by ensuring access to cocoa supply chain trader and micro-financing. Value Added Farming refers to lifting the economic value of a commodity through particular intervention. Regarding access to agriculture inputs, one of significant intervention is fertilization and plant nutrition management, both organic and inorganic fertilizer. Small-scale cocoa farmers can get access to fertilizer intervention through establishment of demo farm. Ordinary demo farm needs large area, selective requirements, lots of field resources and centralization impact. On the contrary, satellite demo farm is developing to wide-spread the impact of agriculture economic aspects and also the involvement in number of farmers. In Sulawesi Project, we develop leveling strata of small-scale demo farm with group of farmers and local cooperative. With this methodology, all of listed small-scale farmers can get access to agriculture input, micro-financing and how to deliver quality output. PT Pupuk Kaltim is member firm of holding company PT Pupuk Indonesia, private company belongs to the government of Indonesia. The company listed as Indonesia's largest producer of urea fertilizers, besides ammonia, Compound Fertilizer (NPK) and biological fertilizers. To achieve strategic objectives, the company has distinguished award such as SNI Platinum, SGS Award IFA Protect and Sustain Stewardship and Gold Rank of Environment Friendly Company. This achievement has become the strategic foundation for our company to energize value added farming in sustaining food security program. Moreover, to ensure cocoa sustainability farming the company has developed partnership with international companies and Non-Government Organization (NGO).

Keywords: fertilizer and plant nutrition management, good agriculture practices, agriculture economic aspects, value-added farming

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46 Low-Cost, Portable Optical Sensor with Regression Algorithm Models for Accurate Monitoring of Nitrites in Environments

Authors: David X. Dong, Qingming Zhang, Meng Lu

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Nitrites enter waterways as runoff from croplands and are discharged from many industrial sites. Excessive nitrite inputs to water bodies lead to eutrophication. On-site rapid detection of nitrite is of increasing interest for managing fertilizer application and monitoring water source quality. Existing methods for detecting nitrites use spectrophotometry, ion chromatography, electrochemical sensors, ion-selective electrodes, chemiluminescence, and colorimetric methods. However, these methods either suffer from high cost or provide low measurement accuracy due to their poor selectivity to nitrites. Therefore, it is desired to develop an accurate and economical method to monitor nitrites in environments. We report a low-cost optical sensor, in conjunction with a machine learning (ML) approach to enable high-accuracy detection of nitrites in water sources. The sensor works under the principle of measuring molecular absorptions of nitrites at three narrowband wavelengths (295 nm, 310 nm, and 357 nm) in the ultraviolet (UV) region. These wavelengths are chosen because they have relatively high sensitivity to nitrites; low-cost light-emitting devices (LEDs) and photodetectors are also available at these wavelengths. A regression model is built, trained, and utilized to minimize cross-sensitivities of these wavelengths to the same analyte, thus achieving precise and reliable measurements with various interference ions. The measured absorbance data is input to the trained model that can provide nitrite concentration prediction for the sample. The sensor is built with i) a miniature quartz cuvette as the test cell that contains a liquid sample under test, ii) three low-cost UV LEDs placed on one side of the cell as light sources, with each LED providing a narrowband light, and iii) a photodetector with a built-in amplifier and an analog-to-digital converter placed on the other side of the test cell to measure the power of transmitted light. This simple optical design allows measuring the absorbance data of the sample at the three wavelengths. To train the regression model, absorbances of nitrite ions and their combination with various interference ions are first obtained at the three UV wavelengths using a conventional spectrophotometer. Then, the spectrophotometric data are inputs to different regression algorithm models for training and evaluating high-accuracy nitrite concentration prediction. Our experimental results show that the proposed approach enables instantaneous nitrite detection within several seconds. The sensor hardware costs about one hundred dollars, which is much cheaper than a commercial spectrophotometer. The ML algorithm helps to reduce the average relative errors to below 3.5% over a concentration range from 0.1 ppm to 100 ppm of nitrites. The sensor has been validated to measure nitrites at three sites in Ames, Iowa, USA. This work demonstrates an economical and effective approach to the rapid, reagent-free determination of nitrites with high accuracy. The integration of the low-cost optical sensor and ML data processing can find a wide range of applications in environmental monitoring and management.

Keywords: optical sensor, regression model, nitrites, water quality

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45 Prevalence and Molecular Characterization of Extended-Spectrum–β Lactamase and Carbapenemase-Producing Enterobacterales from Tunisian Seafood

Authors: Mehdi Soula, Yosra Mani, Estelle Saras, Antoine Drapeau, Raoudha Grami, Mahjoub Aouni, Jean-Yves Madec, Marisa Haenni, Wejdene Mansour

Abstract:

Multi-resistance to antibiotics in gram-negative bacilli and particularly in enterobacteriaceae, has become frequent in hospitals in Tunisia. However, data on antibiotic resistant bacteria in aquatic products are scarce. The aims of this study are to estimate the proportion of ESBL- and carbapenemase-producing Enterobacterales in seafood (clams and fish) in Tunisia and to molecularly characterize the collected isolates. Two types of seafood were sampled in unrelated markets in four different regions in Tunisia (641 pieces of farmed fish and 1075 mediterranean clams divided into 215 pools, and each pool contained 5 pieces). Once purchased, all samples were incubated in tubes containing peptone salt broth for 24 to 48h at 37°C. After incubation, overnight cultures were isolated on selective MacConkey agar plates supplemented with either imipenem or cefotaxime, identified using API20E test strips (bioMérieux, Marcy-l’Étoile, France) and confirmed by Maldi-TOF MS. Antimicrobial susceptibility was determined by the disk diffusion method on Mueller-Hinton agar plates and results were interpreted according to CA-SFM 2021. ESBL-producing Enterobacterales were detected using the Double Disc Synergy Test (DDST). Carbapenem-resistance was detected using an ertapenem disk and was respectively confirmed using the ROSCO KPC/MBL and OXA-48 Confirm Kit (ROSCO Diagnostica, Taastrup, Denmark). DNA was extracted using a NucleoSpin Microbial DNA extraction kit (Macherey-Nagel, Hoerdt, France), according to the manufacturer’s instructions. Resistance genes were determined using the CGE online tools. The replicon content and plasmid formula were identified from the WGS data using PlasmidFinder 2.0.1 and pMLST 2.0. From farmed fishes, nine ESBL-producing strains (9/641, 1.4%) were isolated, which were identified as E. coli (n=6) and K. pneumoniae (n=3). Among the 215 pools of 5 clams analyzed, 18 ESBL-producing isolates were identified, including 14 E. coli and 4 K. pneumoniae. A low isolation rate of ESBL-producing Enterobacterales was detected 1.6% (18/1075) in clam pools. In fish, the ESBL phenotype was due to the presence of the blaCTX-M-15 gene in all nine isolates, but no carbapenemase gene was identified. In clams, the predominant ESBL phenotype was blaCTX-M-1 (n=6/18). blaCPE (NDM1, OXA48) was detected only in 3 isolates ‘K. pneumoniae isolates’. Replicon typing on the strains carring the ESBL and carbapenemase gene revelead that the major type plasmid carried ESBL were IncF (42.3%) [n=11/26]. In all, our results suggest that seafood can be a reservoir of multi-drug resistant bacteria, most probably of human origin but also by the selection pressure of antibiotic. Our findings raise concerns that seafood bought for consumption may serve as potential reservoirs of AMR genes and pose serious threat to public health.

Keywords: BLSE, carbapenemase, enterobacterales, tunisian seafood

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44 Polarization as a Proxy of Misinformation Spreading

Authors: Michela Del Vicario, Walter Quattrociocchi, Antonio Scala, Ana Lucía Schmidt, Fabiana Zollo

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Information, rumors, and debates may shape and impact public opinion heavily. In the latest years, several concerns have been expressed about social influence on the Internet and the outcome that online debates might have on real-world processes. Indeed, on online social networks users tend to select information that is coherent to their system of beliefs and to form groups of like-minded people –i.e., echo chambers– where they reinforce and polarize their opinions. In this way, the potential benefits coming from the exposure to different points of view may be reduced dramatically, and individuals' views may become more and more extreme. Such a context fosters misinformation spreading, which has always represented a socio-political and economic risk. The persistence of unsubstantiated rumors –e.g., the hypothetical and hazardous link between vaccines and autism– suggests that social media do have the power to misinform, manipulate, or control public opinion. As an example, current approaches such as debunking efforts or algorithmic-driven solutions based on the reputation of the source seem to prove ineffective against collective superstition. Indeed, experimental evidence shows that confirmatory information gets accepted even when containing deliberately false claims while dissenting information is mainly ignored, influences users’ emotions negatively and may even increase group polarization. Moreover, confirmation bias has been shown to play a pivotal role in information cascades, posing serious warnings about the efficacy of current debunking efforts. Nevertheless, mitigation strategies have to be adopted. To generalize the problem and to better understand social dynamics behind information spreading, in this work we rely on a tight quantitative analysis to investigate the behavior of more than 300M users w.r.t. news consumption on Facebook over a time span of six years (2010-2015). Through a massive analysis on 920 news outlets pages, we are able to characterize the anatomy of news consumption on a global and international scale. We show that users tend to focus on a limited set of pages (selective exposure) eliciting a sharp and polarized community structure among news outlets. Moreover, we find similar patterns around the Brexit –the British referendum to leave the European Union– debate, where we observe the spontaneous emergence of two well segregated and polarized groups of users around news outlets. Our findings provide interesting insights into the determinants of polarization and the evolution of core narratives on online debating. Our main aim is to understand and map the information space on online social media by identifying non-trivial proxies for the early detection of massive informational cascades. Furthermore, by combining users traces, we are finally able to draft the main concepts and beliefs of the core narrative of an echo chamber and its related perceptions.

Keywords: information spreading, misinformation, narratives, online social networks, polarization

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43 Microbial Analysis of Street Vended Ready-to-Eat Meat around Thohoyandou Area, Vhembe District, Limpopo Province, RSA

Authors: Tshimangadzo Jeanette Raedani, Edgar Musie, Afsatou Traore

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Background: Street-vended meats, including chicken, pork, and beef, are popular in urban areas worldwide due to their convenience and affordability. However, these meats often pose a significant risk of foodborne diseases. The high water activity, protein content, and nearly neutral pH of meat create conditions conducive to the growth of pathogenic bacteria. Street foods, particularly meats, are frequently linked to outbreaks of foodborne illnesses due to potential contamination from improper handling and preparation. This study aimed to assess the microbial quality and safety of street-vended ready-to-eat meat sold in the Thohoyandou area. Method: The study involved collecting 168 samples of street-vended meat, split evenly between chicken (n=84) and beef (n=84), from various vendors around Thohoyandou. The samples were randomly selected and transported in sterile conditions to the Department of Food Microbiology at the University of Venda for analysis. Each 10-gram sample was cultured in selective media: MSA for Staphylococcus aureus, EMB for E. coli O157, XLD agar for Salmonella, and Sorbitol McConkey for Shigella. After initial culturing, the presumptive colonies were sub-cultured for purification and identified through Gram staining and biochemical tests, including Catalase, API 20E, Klingler Iron Agar Test, and Vitek 2 system. Antibiotic susceptibility was tested using agents such as Ampicillin, Chloramphenicol, Penicillin, Neomycin, Tetracycline, Streptomycin, and Amoxicillin. Molecular characterization was performed to identify E. coli pathotypes using multiplex PCR. Results: Out of 168 samples tested, 32 (19%) were positive for Staphylococcus spp., with the highest prevalence found in cooked chicken meat. The most common staphylococcus species identified were S. xylosus (13.2%) and S. saprophyticus (10.5%). E. coli was present in 29 (19.3%) of the samples, with the highest prevalence in fried chicken. Antibiotic susceptibility testing showed that 100% of E. coli isolates were resistant to Ampicillin, Tetracycline, and Penicillin, but 100% were susceptible to Neomycin. Staphylococcus spp. isolates were also 100% resistant to Ampicillin and 100% susceptible to Neomycin. The study detected a range of virulence genes in E. coli, with prevalence rates from 13.33% to 86.67%. The identified pathotypes included EPEC, EHEC, ETEC, EAEC, and EIEC, with many isolates showing mixed pathotypes. Conclusion: The study highlighted that the microbial quality and safety of street-vended meats in Thohoyandou are inadequate, rendering them unsafe for consumption. The presence of pathogenic microorganisms in both beef and chicken samples indicates significant risks associated with poor personal hygiene and food preparation practices. This underscores the need for improved monitoring and stricter food safety measures to prevent foodborne diseases and ensure consumer safety.

Keywords: meat, microbial analysis, street vendors, E. coli

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42 Mondoc: Informal Lightweight Ontology for Faceted Semantic Classification of Hypernymy

Authors: M. Regina Carreira-Lopez

Abstract:

Lightweight ontologies seek to concrete union relationships between a parent node, and a secondary node, also called "child node". This logic relation (L) can be formally defined as a triple ontological relation (LO) equivalent to LO in ⟨LN, LE, LC⟩, and where LN represents a finite set of nodes (N); LE is a set of entities (E), each of which represents a relationship between nodes to form a rooted tree of ⟨LN, LE⟩; and LC is a finite set of concepts (C), encoded in a formal language (FL). Mondoc enables more refined searches on semantic and classified facets for retrieving specialized knowledge about Atlantic migrations, from the Declaration of Independence of the United States of America (1776) and to the end of the Spanish Civil War (1939). The model looks forward to increasing documentary relevance by applying an inverse frequency of co-ocurrent hypernymy phenomena for a concrete dataset of textual corpora, with RMySQL package. Mondoc profiles archival utilities implementing SQL programming code, and allows data export to XML schemas, for achieving semantic and faceted analysis of speech by analyzing keywords in context (KWIC). The methodology applies random and unrestricted sampling techniques with RMySQL to verify the resonance phenomena of inverse documentary relevance between the number of co-occurrences of the same term (t) in more than two documents of a set of texts (D). Secondly, the research also evidences co-associations between (t) and their corresponding synonyms and antonyms (synsets) are also inverse. The results from grouping facets or polysemic words with synsets in more than two textual corpora within their syntagmatic context (nouns, verbs, adjectives, etc.) state how to proceed with semantic indexing of hypernymy phenomena for subject-heading lists and for authority lists for documentary and archival purposes. Mondoc contributes to the development of web directories and seems to achieve a proper and more selective search of e-documents (classification ontology). It can also foster on-line catalogs production for semantic authorities, or concepts, through XML schemas, because its applications could be used for implementing data models, by a prior adaptation of the based-ontology to structured meta-languages, such as OWL, RDF (descriptive ontology). Mondoc serves to the classification of concepts and applies a semantic indexing approach of facets. It enables information retrieval, as well as quantitative and qualitative data interpretation. The model reproduces a triple tuple ⟨LN, LE, LT, LCF L, BKF⟩ where LN is a set of entities that connect with other nodes to concrete a rooted tree in ⟨LN, LE⟩. LT specifies a set of terms, and LCF acts as a finite set of concepts, encoded in a formal language, L. Mondoc only resolves partial problems of linguistic ambiguity (in case of synonymy and antonymy), but neither the pragmatic dimension of natural language nor the cognitive perspective is addressed. To achieve this goal, forthcoming programming developments should target at oriented meta-languages with structured documents in XML.

Keywords: hypernymy, information retrieval, lightweight ontology, resonance

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41 Vascular Targeted Photodynamic Therapy Monitored by Real-Time Laser Speckle Imaging

Authors: Ruth Goldschmidt, Vyacheslav Kalchenko, Lilah Agemy, Rachel Elmoalem, Avigdor Scherz

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Vascular Targeted Photodynamic therapy (VTP) is a new modality for selective cancer treatment that leads to the complete tumor ablation. A photosensitizer, a bacteriochlorophyll derivative in our case, is first administered to the patient and followed by the illumination of the tumor area, by a near-IR laser for its photoactivation. The photoactivated drug releases reactive oxygen species (ROS) in the circulation, which reacts with blood cells and the endothelium leading to the occlusion of the blood vasculature. If the blood vessels are only partially closed, the tumor may recover, and cancer cells could survive. On the other hand, excessive treatment may lead to toxicity of healthy tissues nearby. Simultaneous VTP monitoring and image processing independent of the photoexcitation laser has not yet been reported, to our knowledge. Here we present a method for blood flow monitoring, using a real-time laser speckle imaging (RTLSI) in the tumor during VTP. We have synthesized over the years a library of bacteriochlorophyll derivatives, among them WST11 and STL-6014. Both are water soluble derivatives that are retained in the blood vasculature through their partial binding to HSA. WST11 has been approved in Mexico for VTP treatment of prostate cancer at a certain drug dose, and time/intensity of illumination. Application to other bacteriochlorophyll derivatives or other cancers may require different treatment parameters (such as light/drug administration). VTP parameters for STL-6014 are still under study. This new derivative mainly differs from WST11 by its lack of the central Palladium, and its conjugation to an Arg-Gly-Asp (RGD) sequence. RGD is a tumor-specific ligand that is used for targeting the necrotic tumor domains through its affinity to αVβ3 integrin receptors. This enables the study of cell-targeted VTP. We developed a special RTLSI module, based on Labview software environment for data processing. The new module enables to acquire raw laser speckle images and calculate the values of the laser temporal statistics of time-integrated speckles in real time, without additional off-line processing. Using RTLSI, we could monitor the tumor’s blood flow following VTP in a CT26 colon carcinoma ear model. VTP with WST11 induced an immediate slow down of the blood flow within the tumor and a complete final flow arrest, after some sporadic reperfusions. If the irradiation continued further, the blood flow stopped also in the blood vessels of the surrounding healthy tissue. This emphasizes the significance of light dose control. Using our RTLSI system, we could prevent any additional healthy tissue damage by controlling the illumination time and restrict blood flow arrest within the tumor only. In addition, we found that VTP with STL-6014 was the most effective when the photoactivation was conducted 4h post-injection, in terms of tumor ablation success in-vivo and blood vessel flow arrest. In conclusion, RTSLI application should allow to optimize VTP efficacy vs. toxicity in both the preclinical and clinical arenas.

Keywords: blood vessel occlusion, cancer treatment, photodynamic therapy, real time imaging

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40 Nanoparticle Supported, Magnetically Separable Metalloporphyrin as an Efficient Retrievable Heterogeneous Nanocatalyst in Oxidation Reactions

Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

Abstract:

Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

Procedia PDF Downloads 296
39 Overcoming the Challenges of Subjective Truths in the Post-Truth Age Through a CriticalEthical English Pedagogy

Authors: Farah Vierra

Abstract:

Following the 2016 US presidential election and the advancement of the Brexit referendum, the concept of “post-truth”, defined by Oxford Dictionary as “relating to or denoting circumstances in which objective facts are less influential in shaping public opinion than appeals to emotion and personal belief”, came into prominent use in public, political and educational circles. What this essentially entails is that in this age, individuals are increasingly confronted with subjective perpetuations of truth in their discourse spheres that are informed by beliefs and opinions as opposed to any form of coherence to the reality of those who these truth claims concern. In principle, a subjective delineation of truth is progressive and liberating – especially considering its potential in providing marginalised groups in the diverse communities of our globalised world with the voice to articulate truths that are representative of themselves and their experiences. However, any form of human flourishing that seems to be promised here collapses as the tenets of subjective truths initially in place to liberate has been distorted through post-truth to allow individuals to purport selective and individualistic truth claims that further oppress and silence certain groups within society without due accountability. The evidence of which is prevalent through the conception of terms such as "alternative facts" and "fake news" that we observe individuals declare when their problematic truth claims are questioned. Considering the pervasiveness of post-truth and the ethical issues that accompany it, educators and scholars alike have increasingly noted the need to adapt educational practices and pedagogies to account for the diminishing objectivity of truth in the twenty-first century, especially because students, as digital natives, find themselves in the firing line of post-truth; engulfed in digital societies that proliferate post-truth through the surge of truth claims allowed in various media sites. In an attempt to equip students with the vital skills to navigate the post-truth age and oppose its proliferation of social injustices, English educators find themselves having to devise instructional strategies that not only teach students the ways they can critically and ethically scrutinise truth claims but also teach them to mediate the subjectivity of truth in a manner that does not undermine the voices of diverse communities. In hopes of providing educators with the roadmap to do so, this paper will first examine the challenges that confront students as a result of post-truth. Following which, the paper will elucidate the role English education can play in helping students overcome the complex ramifications of post-truth. Scholars have consistently touted the affordances of literary texts in providing students with imagined spaces to explore societal issues through a critical discernment of language and an ethical engagement with its narrative developments. Therefore, this paper will explain and demonstrate how literary texts, when used alongside a critical-ethical post-truth pedagogy that equips students with interpretive strategies informed by literary traditions such as literary and ethical criticism, can be effective in helping students develop the pertinent skills to comprehensively examine truth claims and overcome the challenges of the post-truth age.

Keywords: post-truth, pedagogy, ethics, English, education

Procedia PDF Downloads 71
38 Overcoming the Challenges of Subjective Truths in the Post-Truth Age Through a Critical-Ethical English Pedagogy

Authors: Farah Vierra

Abstract:

Following the 2016 US presidential election and the advancement of the Brexit referendum, the concept of “post-truth,” defined by the Oxford Dictionary as “relating to or denoting circumstances in which objective facts are less influential in shaping public opinion than appeals to emotion and personal belief,” came into prominent use in public, political and educational circles. What this essentially entails is that in this age, individuals are increasingly confronted with subjective perpetuations of truth in their discourse spheres that are informed by beliefs and opinions as opposed to any form of coherence to the reality of those to who this truth claims concern. In principle, a subjective delineation of truth is progressive and liberating – especially considering its potential to provide marginalised groups in the diverse communities of our globalised world with the voice to articulate truths that are representative of themselves and their experiences. However, any form of human flourishing that seems to be promised here collapses as the tenets of subjective truths initially in place to liberate have been distorted through post-truth to allow individuals to purport selective and individualistic truth claims that further oppress and silence certain groups within society without due accountability. The evidence of this is prevalent through the conception of terms such as "alternative facts" and "fake news" that we observe individuals declare when their problematic truth claims are being questioned. Considering the pervasiveness of post-truth and the ethical issues that accompany it, educators and scholars alike have increasingly noted the need to adapt educational practices and pedagogies to account for the diminishing objectivity of truth in the twenty-first century, especially because students, as digital natives, find themselves in the firing line of post-truth; engulfed in digital societies that proliferate post-truth through the surge of truth claims allowed in various media sites. In an attempt to equip students with the vital skills to navigate the post-truth age and oppose its proliferation of social injustices, English educators find themselves having to contend with a complex question: how can the teaching of English equip students with the ability to critically and ethically scrutinise truth claims whilst also mediating the subjectivity of truth in a manner that does not undermine the voices of diverse communities. In order to address this question, this paper will first examine the challenges that confront students as a result of post-truth. Following this, the paper will elucidate the role English education can play in helping students overcome the complex demands of the post-truth age. Scholars have consistently touted the affordances of literary texts in providing students with imagined spaces to explore societal issues through a critical discernment of language and an ethical engagement with its narrative developments. Therefore, this paper will explain and demonstrate how literary texts, when used alongside a critical-ethical post-truth pedagogy that equips students with interpretive strategies informed by literary traditions such as literary and ethical criticism, can be effective in helping students develop the pertinent skills to comprehensively examine truth claims and overcome the challenges of the post-truth age.

Keywords: post-truth, pedagogy, ethics, english, education

Procedia PDF Downloads 66
37 Case Report on Anaesthesia for Ruptured Ectopic with Severe Pulmonary Hypertension in a Mute Patient

Authors: Pamela Chia, Tay Yoong Chuan

Abstract:

Introduction: Severe pulmonary hypertension (PH) patients requiring non-cardiac surgery risk have increased mortality rates ranging. These patients are plagued with cardiorespiratory failure, dysrhythmias and anticoagulation potentially with concurrent sepsis and renal insufficiency, perioperative morbidity. We present a deaf-mute patient with severe idiopathic PH emergently prepared for ruptured ectopic laparotomy. Case Report: A 20 year-old female, 62kg (BMI 25 kg/m2) with severe idiopathic PH (2DE Ejection Fraction was 41%, Pulmonary Artery Systolic Pressure (PASP) 105 mmHg, Right ventricle strain and hypertrophy) and selective mutism was rushed in for emergency laparotomy after presenting to the emergency department for abdominal pain. The patient had an NYHA Class II with room air SpO2 93-95%. While awaiting lung transplant, the patient takes warfarin, Sildanefil, Macitentan and even Selexipag for rising PASP. At presentation, vital signs: BP 95/63, HR 119 SpO2 88% (room air). Despite decreasing haemoglobin 14 to 10g/dL, INR 2.59 was reversed with prothrombin concentrate, and Vitamin K. ECG revealed Right Bundle Branch Block with right ventricular strain and x-ray showed cardiomegaly, dilated Right Ventricle, Pulmonary Arteries, basal atelectasis. Arterial blood gas showed compensated metabolic acidosis pH 7.4 pCO2 32 pO2 53 HCO3 20 BE -4 SaO2 88%. The cardiothoracic surgeon concluded no role for Extracorporeal Membrane Oxygenation (ECMO). We inserted invasive arterial and central venous lines with blood transfusion via an 18G cannula before the patient underwent a midline laparotomy, haemostasis of ruptured ovarian cyst with 2.4L of clots under general anesthesia and FloTrac cardiac output monitoring. Rapid sequence induction was done with Midazolam/Propofol, remifentanil infusion, and rocuronium. The patient was maintained on Desflurane. Blood products and colloids were transfused for further 1.5L blood loss. Postoperatively, the patient was transferred to the intensive care unit and was extubated uneventfully 7hours later. The patient went home a week later. Discussion: Emergency hemostasis laparotomy in anticoagulated WHO Class I PH patient awaiting lung transplant with no ECMO backup poses tremendous stress on the deaf-mute patient and the anesthesiologist. Balancing hemodynamics avoiding hypotension while awaiting hemostasis in the presence of pulmonary arterial dilators and anticoagulation requires close titration of volatiles, which decreases RV contractility. We review the contraindicated anesthetic agents (ketamine, N2O), choice of vasopressors in hypotension to maintain Aortic-right ventricular pressure gradients and nitric oxide use perioperatively. Conclusion: Interdisciplinary communication with a deaf-mute moribund patient and anesthesia considerations pose many rare challenges worth sharing.

Keywords: pulmonary hypertension, case report, warfarin reversal, emergency surgery

Procedia PDF Downloads 218
36 Multi-Modality Brain Stimulation: A Treatment Protocol for Tinnitus

Authors: Prajakta Patil, Yash Huzurbazar, Abhijeet Shinde

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Aim: To develop a treatment protocol for the management of tinnitus through multi-modality brain stimulation. Methodology: Present study included 33 adults with unilateral (31 subjects) and bilateral (2 subjects) chronic tinnitus with and/or without hearing loss independent of their etiology. The Treatment protocol included 5 consecutive sessions with follow-up of 6 months. Each session was divided into 3 parts: • Pre-treatment: a) Informed consent b) Pitch and loudness matching. • Treatment: Bimanual paper pen task with tinnitus masking for 30 minutes. • Post-treatment: a) Pitch and loudness matching b) Directive counseling and obtaining feedback. Paper-pen task is to be performed bimanually that included carrying out two different writing activities in different context. The level of difficulty of the activities was increased in successive sessions. Narrowband noise of a frequency same as that of tinnitus was presented at 10 dBSL of tinnitus for 30 minutes simultaneously in the ear with tinnitus. Result: The perception of tinnitus was no longer present in 4 subjects while in remaining subjects it reduced to an intensity that its perception no longer troubled them without causing residual facilitation. In all subjects, the intensity of tinnitus decreased by an extent of 45 dB at an average. However, in few subjects, the intensity of tinnitus also decreased by more than 45 dB. The approach resulted in statistically significant reductions in Tinnitus Functional Index and Tinnitus Handicap Inventory scores. The results correlate with pre and post treatment score of Tinnitus Handicap Inventory that dropped from 90% to 0%. Discussion: Brain mapping(qEEG) Studies report that there is multiple parallel overlapping of neural subnetworks in the non-auditory areas of the brain which exhibits abnormal, constant and spontaneous neural activity involved in the perception of tinnitus with each subnetwork and area reflecting a specific aspect of tinnitus percept. The paper pen task and directive counseling are designed and delivered respectively in a way that is assumed to induce normal, rhythmically constant and premeditated neural activity and mask the abnormal, constant and spontaneous neural activity in the above-mentioned subnetworks and the specific non-auditory area. Counseling was focused on breaking the vicious cycle causing and maintaining the presence of tinnitus. Diverting auditory attention alone is insufficient to reduce the perception of tinnitus. Conscious awareness of tinnitus can be suppressed when individuals engage in cognitively demanding tasks of non-auditory nature as the paper pen task used in the present study. To carry out this task selective, divided, sustained, simultaneous and split attention act cumulatively. Bimanual paper pen task represents a top-down activity which underlies brain’s ability to selectively attend to the bimanual written activity as a relevant stimulus and to ignore tinnitus that is the irrelevant stimuli in the present study. Conclusion: The study suggests that this novel treatment approach is cost effective, time saving and efficient to vanish the tinnitus or to reduce the intensity of tinnitus to a negligible level and thereby eliminating the negative reactions towards tinnitus.

Keywords: multi-modality brain stimulation, neural subnetworks, non-auditory areas, paper-pen task, top-down activity

Procedia PDF Downloads 146
35 Additional Opportunities of Forensic Medical Identification of Dead Bodies of Unkown Persons

Authors: Saule Mussabekova

Abstract:

A number of chemical elements widely presented in the nature is seldom met in people and vice versa. This is a peculiarity of accumulation of elements in the body, and their selective use regardless of widely changed parameters of external environment. Microelemental identification of human hair and particularly dead body is a new step in the development of modern forensic medicine which needs reliable criteria while identifying the person. In the condition of technology-related pressing of large industrial cities for many years and specific for each region multiple-factor toxic effect from many industrial enterprises it’s important to assess actuality and the role of researches of human hair while assessing degree of deposition with specific pollution. Hair is highly sensitive biological indicator and allows to assess ecological situation, to perform regionalism of large territories of geological and chemical methods. Besides, monitoring of concentrations of chemical elements in the regions of Kazakhstan gives opportunity to use these data while performing forensic medical identification of dead bodies of unknown persons. Methods based on identification of chemical composition of hair with further computer processing allowed to compare received data with average values for the sex, age, and to reveal causally significant deviations. It gives an opportunity preliminary to suppose the region of residence of the person, having concentrated actions of policy for search of people who are unaccounted for. It also allows to perform purposeful legal actions for its further identification having created more optimal and strictly individual scheme of personal identity. Hair is the most suitable material for forensic researches as it has such advances as long term storage properties with no time limitations and specific equipment. Besides, quantitative analysis of micro elements is well correlated with level of pollution of the environment, reflects professional diseases and with pinpoint accuracy helps not only to diagnose region of temporary residence of the person but to establish regions of his migration as well. Peculiarities of elemental composition of human hair have been established regardless of age and sex of persons residing on definite territories of Kazakhstan. Data regarding average content of 29 chemical elements in hair of population in different regions of Kazakhstan have been systemized. Coefficients of concentration of studies elements in hair relative to average values around the region have been calculated for each region. Groups of regions with specific spectrum of elements have been emphasized; these elements are accumulated in hair in quantities exceeding average indexes. Our results have showed significant differences in concentrations of chemical elements for studies groups and showed that population of Kazakhstan is exposed to different toxic substances. It depends on emissions to atmosphere from industrial enterprises dominating in each separate region. Performed researches have showed that obtained elemental composition of human hair residing in different regions of Kazakhstan reflects technogenic spectrum of elements.

Keywords: analysis of elemental composition of hair, forensic medical research of hair, identification of unknown dead bodies, microelements

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34 Targeting Peptide Based Therapeutics: Integrated Computational and Experimental Studies of Autophagic Regulation in Host-Parasite Interaction

Authors: Vrushali Guhe, Shailza Singh

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Cutaneous leishmaniasis is neglected tropical disease present worldwide caused by the protozoan parasite Leishmania major, the therapeutic armamentarium for leishmaniasis are showing several limitations as drugs are showing toxic effects with increasing resistance by a parasite. Thus identification of novel therapeutic targets is of paramount importance. Previous studies have shown that autophagy, a cellular process, can either facilitate infection or aid in the elimination of the parasite, depending on the specific parasite species and host background in leishmaniasis. In the present study, our objective was to target the essential autophagy protein ATG8, which plays a crucial role in the survival, infection dynamics, and differentiation of the Leishmania parasite. ATG8 in Leishmania major and its homologue, LC3, in Homo sapiens, act as autophagic markers. Present study manifested the crucial role of ATG8 protein as a potential target for combating Leishmania major infection. Through bioinformatics analysis, we identified non-conserved motifs within the ATG8 protein of Leishmania major, which are not present in LC3 of Homo sapiens. Against these two non-conserved motifs, we generated a peptide library of 60 peptides on the basis of physicochemical properties. These peptides underwent a filtering process based on various parameters, including feasibility of synthesis and purification, compatibility with Selective Reaction Monitoring (SRM)/Multiple reaction monitoring (MRM), hydrophobicity, hydropathy index, average molecular weight (Mw average), monoisotopic molecular weight (Mw monoisotopic), theoretical isoelectric point (pI), and half-life. Further filtering criterion shortlisted three peptides by using molecular docking and molecular dynamics simulations. The direct interaction between ATG8 and the shortlisted peptides was confirmed through Surface Plasmon Resonance (SPR) experiments. Notably, these peptides exhibited the remarkable ability to penetrate the parasite membrane and exert profound effects on Leishmania major. The treatment with these peptides significantly impacted parasite survival, leading to alterations in the cell cycle and morphology. Furthermore, the peptides were found to modulate autophagosome formation, particularly under starved conditions, suggesting their involvement in disrupting the regulation of autophagy within Leishmania major. In vitro, studies demonstrated that the selected peptides effectively reduced the parasite load within infected host cells. Encouragingly, these findings were corroborated by in vivo experiments, which showed a reduction in parasite burden upon peptide administration. Additionally, the peptides were observed to affect the levels of LC3II within host cells. In conclusion, our findings highlight the efficacy of these novel peptides in targeting Leishmania major’s ATG8 and disrupting parasite survival. These results provide valuable insights into the development of innovative therapeutic strategies against leishmaniasis via targeting autophagy protein ATG8 of Leishmania major.

Keywords: ATG8, leishmaniasis, surface plasmon resonance, MD simulation, molecular docking, peptide designing, therapeutics

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33 Magnetic Carriers of Organic Selenium (IV) Compounds: Physicochemical Properties and Possible Applications in Anticancer Therapy

Authors: E. Mosiniewicz-Szablewska, P. Suchocki, P. C. Morais

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Despite the significant progress in cancer treatment, there is a need to search for new therapeutic methods in order to minimize side effects. Chemotherapy, the main current method of treating cancer, is non-selective and has a number of limitations. Toxicity to healthy cells is undoubtedly the biggest problem limiting the use of many anticancer drugs. The problem of how to kill cancer without harming a patient can be solved by using organic selenium (IV) compounds. Organic selenium (IV) compounds are a new class of materials showing a strong anticancer activity. They are first organic compounds containing selenium at the +4 oxidation level and therefore they eliminate the multidrug-resistance for all tumor cell lines tested so far. These materials are capable of selectively killing cancer cells without damaging the healthy ones. They are obtained by the incorporation of selenous acid (H2SeO3) into molecules of fatty acids of sunflower oil and therefore, they are inexpensive to manufacture. Attaching these compounds to magnetic carriers enables their precise delivery directly to the tumor area and the simultaneous application of the magnetic hyperthermia, thus creating a huge opportunity to effectively get rid of the tumor without any side effects. Polylactic-co-glicolic acid (PLGA) nanocapsules loaded with maghemite (-Fe2O3) nanoparticles and organic selenium (IV) compounds are successfully prepared by nanoprecipitation method. In vitro antitumor activity of the nanocapsules were evidenced using murine melanoma (B16-F10), oral squamos carcinoma (OSCC) and murine (4T1) and human (MCF-7) breast lines. Further exposure of these cells to an alternating magnetic field increased the antitumor effect of nanocapsules. Moreover, the nanocapsules presented antitumor effect while not affecting normal cells. Magnetic properties of the nanocapsules were investigated by means of dc magnetization, ac susceptibility and electron spin resonance (ESR) measurements. The nanocapsules presented a typical superparamagnetic behavior around room temperature manifested itself by the split between zero field-cooled/field-cooled (ZFC/FC) magnetization curves and the absence of hysteresis on the field-dependent magnetization curve above the blocking temperature. Moreover, the blocking temperature decreased with increasing applied magnetic field. The superparamagnetic character of the nanocapsules was also confirmed by the occurrence of a maximum in temperature dependences of both real ′(T) and imaginary ′′ (T) components of the ac magnetic susceptibility, which shifted towards higher temperatures with increasing frequency. Additionally, upon decreasing the temperature the ESR signal shifted to lower fields and gradually broadened following closely the predictions for the ESR of superparamagnetoc nanoparticles. The observed superparamagnetic properties of nanocapsules enable their simple manipulation by means of magnetic field gradient, after introduction into the blood stream, which is a necessary condition for their use as magnetic drug carriers. The observed anticancer and superparamgnetic properties show that the magnetic nanocapsules loaded with organic selenium (IV) compounds should be considered as an effective material system for magnetic drug delivery and magnetohyperthermia inductor in antitumor therapy.

Keywords: cancer treatment, magnetic drug delivery system, nanomaterials, nanotechnology

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32 Tailoring Structural, Thermal and Luminescent Properties of Solid-State MIL-53(Al) MOF via Fe³⁺ Cation Exchange

Authors: T. Ul Rehman, S. Agnello, F. M. Gelardi, M. M. Calvino, G. Lazzara, G. Buscarino, M. Cannas

Abstract:

Metal-Organic Frameworks (MOFs) have emerged as promising candidates for detecting metal ions owing to their large surface area, customizable porosity, and diverse functionalities. In recent years, there has been a surge in research focused on MOFs with luminescent properties. These frameworks are constructed through coordinated bonding between metal ions and multi-dentate ligands, resulting in inherent fluorescent structures. Their luminescent behavior is influenced by factors like structural composition, surface morphology, pore volume, and interactions with target analytes, particularly metal ions. MOFs exhibit various sensing mechanisms, including photo-induced electron transfer (PET) and charge transfer processes such as ligand-to-metal (LMCT) and metal-to-ligand (MLCT) transitions. Among these, MIL-53(Al) stands out due to its flexibility, stability, and specific affinity towards certain metal ions, making it a promising platform for selective metal ion sensing. This study investigates the structural, thermal, and luminescent properties of MIL-53(Al) metal-organic framework (MOF) upon Fe3+ cation exchange. Two separate sets of samples were prepared to activate the MOF powder at different temperatures. The first set of samples, referred to as MIL-53(Al), activated (120°C), was prepared by activating the raw powder in a glass tube at 120°C for 12 hours and then sealing it. The second set of samples, referred to as MIL-53(Al), activated (300°C), was prepared by activating the MIL-53(Al) powder in a glass tube at 300°C for 70 hours. Additionally, 25 mg of MIL-53(Al) powder was dispersed in 5 mL of Fe3+ solution at various concentrations (0.1-100 mM) for the cation exchange experiment. The suspension was centrifuged for five minutes at 10,000 rpm to extract MIL-53(Al) powder. After three rounds of washing with ultrapure water, MIL-53(Al) powder was heated at 120°C for 12 hours. For PXRD and TGA analyses, a sample of the obtained MIL-53(Al) was used. We also activated the cation-exchanged samples for time-resolved photoluminescence (TRPL) measurements at two distinct temperatures (120 and 300°C) for comparative analysis. Powder X-ray diffraction patterns reveal amorphization in samples with higher Fe3+ concentrations, attributed to alterations in coordination environments and ion exchange dynamics. Thermal decomposition analysis shows reduced weight loss in Fe3+-exchanged MOFs, indicating enhanced stability due to stronger metal-ligand bonds and altered decomposition pathways. Raman spectroscopy demonstrates intensity decrease, shape disruption, and frequency shifts, indicative of structural perturbations induced by cation exchange. Photoluminescence spectra exhibit ligand-based emission (π-π* or n-π*) and ligand-to-metal charge transfer (LMCT), influenced by activation temperature and Fe3+ incorporation. Quenching of luminescence intensity and shorter lifetimes upon Fe3+ exchange result from structural distortions and Fe3+ binding to organic linkers. In a nutshell, this research underscores the complex interplay between composition, structure, and properties in MOFs, offering insights into their potential for diverse applications in catalysis, gas storage, and luminescent devices.

Keywords: Fe³⁺ cation exchange, luminescent metal-organic frameworks (LMOFs), MIL-53(Al), solid-state analysis

Procedia PDF Downloads 64
31 Feasibility of Washing/Extraction Treatment for the Remediation of Deep-Sea Mining Trailings

Authors: Kyoungrean Kim

Abstract:

Importance of deep-sea mineral resources is dramatically increasing due to the depletion of land mineral resources corresponding to increasing human’s economic activities. Korea has acquired exclusive exploration licenses at four areas which are the Clarion-Clipperton Fracture Zone in the Pacific Ocean (2002), Tonga (2008), Fiji (2011) and Indian Ocean (2014). The preparation for commercial mining of Nautilus minerals (Canada) and Lockheed martin minerals (USA) is expected by 2020. The London Protocol 1996 (LP) under International Maritime Organization (IMO) and International Seabed Authority (ISA) will set environmental guidelines for deep-sea mining until 2020, to protect marine environment. In this research, the applicability of washing/extraction treatment for the remediation of deep-sea mining tailings was mainly evaluated in order to present preliminary data to develop practical remediation technology in near future. Polymetallic nodule samples were collected at the Clarion-Clipperton Fracture Zone in the Pacific Ocean, then stored at room temperature. Samples were pulverized by using jaw crusher and ball mill then, classified into 3 particle sizes (> 63 µm, 63-20 µm, < 20 µm) by using vibratory sieve shakers (Analysette 3 Pro, Fritsch, Germany) with 63 µm and 20 µm sieve. Only the particle size 63-20 µm was used as the samples for investigation considering the lower limit of ore dressing process which is tens to 100 µm. Rhamnolipid and sodium alginate as biosurfactant and aluminum sulfate which are mainly used as flocculant were used as environmentally friendly additives. Samples were adjusted to 2% liquid with deionized water then mixed with various concentrations of additives. The mixture was stirred with a magnetic bar during specific reaction times and then the liquid phase was separated by a centrifugal separator (Thermo Fisher Scientific, USA) under 4,000 rpm for 1 h. The separated liquid was filtered with a syringe and acrylic-based filter (0.45 µm). The extracted heavy metals in the filtered liquid were then determined using a UV-Vis spectrometer (DR-5000, Hach, USA) and a heat block (DBR 200, Hach, USA) followed by US EPA methods (8506, 8009, 10217 and 10220). Polymetallic nodule was mainly composed of manganese (27%), iron (8%), nickel (1.4%), cupper (1.3 %), cobalt (1.3%) and molybdenum (0.04%). Based on remediation standards of various countries, Nickel (Ni), Copper (Cu), Cadmium (Cd) and Zinc (Zn) were selected as primary target materials. Throughout this research, the use of rhamnolipid was shown to be an effective approach for removing heavy metals in samples originated from manganese nodules. Sodium alginate might also be one of the effective additives for the remediation of deep-sea mining tailings such as polymetallic nodules. Compare to the use of rhamnolipid and sodium alginate, aluminum sulfate was more effective additive at short reaction time within 4 h. Based on these results, sequencing particle separation, selective extraction/washing, advanced filtration of liquid phase, water treatment without dewatering and solidification/stabilization may be considered as candidate technologies for the remediation of deep-sea mining tailings.

Keywords: deep-sea mining tailings, heavy metals, remediation, extraction, additives

Procedia PDF Downloads 154
30 Effect of Fertilization and Combined Inoculation with Azospirillum brasilense and Pseudomonas fluorescens on Rhizosphere Microbial Communities of Avena sativa (Oats) and Secale Cereale (Rye) Grown as Cover Crops

Authors: Jhovana Silvia Escobar Ortega, Ines Eugenia Garcia De Salamone

Abstract:

Cover crops are an agri-technological alternative to improve all properties of soils. Cover crops such as oats and rye could be used to reduce erosion and favor system sustainability when they are grown in the same agricultural cycle of the soybean crop. This crop is very profitable but its low contribution of easily decomposable residues, due to its low C/N ratio, leaves the soil exposed to erosive action and raises the need to reduce its monoculture. Furthermore, inoculation with the plant growth promoting rhizobacteria contributes to the implementation, development and production of several cereal crops. However, there is little information on its effects on forage crops which are often used as cover crops to improve soil quality. In order to evaluate the effect of combined inoculation with Azospirillum brasilense and Pseudomonas fluorescens on rhizosphere microbial communities, field experiments were conducted in the west of Buenos Aires province, Argentina, with a split-split plot randomized complete block factorial design with three replicates. The factors were: type of cover crop, inoculation and fertilization. In the main plot two levels of fertilization 0 and 7 40-0-5 (NPKS) were established at sowing. Rye (Secale cereale cultivar Quehué) and oats (Avena sativa var Aurora.) were sown in the subplots. In the sub-subplots two inoculation treatments are applied without and with application of a combined inoculant with A. brasilense and P. fluorescens. Due to the growth of cover crops has to be stopped usually with the herbicide glyphosate, rhizosphere soil of 0-20 and 20-40 cm layers was sampled at three sampling times which were: before glyphosate application (BG), a month after glyphosate application (AG) and at soybean harvest (SH). Community level of physiological profiles (CLPP) and Shannon index of microbial diversity (H) were obtained by multivariate analysis of Principal Components. Also, the most probable number (MPN) of nitrifiers and cellulolytics were determined using selective liquid media for each functional group. The CLPP of rhizosphere microbial communities showed significant differences between sampling times. There was not interaction between sampling times and both, types of cover crops and inoculation. Rhizosphere microbial communities of samples obtained BG had different CLPP with respect to the samples obtained in the sampling times AG and SH. Fertilizer and depth of sampling also caused changes in the CLPP. The H diversity index of rhizosphere microbial communities of rye in the sampling time BG were higher than those associated with oats. The MPN of both microbial functional types was lower in the deeper layer since these microorganisms are mostly aerobic. The MPN of nitrifiers decreased in rhizosphere of both cover crops only AG. At the sampling time BG, the NMP of both microbial types were larger than those obtained for AG and SH. This may mean that the glyphosate application could cause fairly permanent changes in these microbial communities which can be considered bio-indicators of soil quality. Inoculation and fertilizer inputs could be included to improve management of these cover crops because they can have a significant positive effect on the sustainability of the agro-ecosystem.

Keywords: community level of physiological profiles, microbial diversity, plant growth promoting rhizobacteria, rhizosphere microbial communities, soil quality, system sustainability

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29 Theoretical Study of the Photophysical Properties and Potential Use of Pseudo-Hemi-Indigo Derivatives as Molecular Logic Gates

Authors: Christina Eleftheria Tzeliou, Demeter Tzeli

Abstract:

Introduction: Molecular Logic Gates (MLGs) are molecular machines that can perform complex work, such as solving logic operations. Molecular switches, which are molecules that can experience chemical changes are examples of successful types of MLGs. Recently, Quintana-Romero and Ariza-Castolo studied experimentally six stable pseudo-hemi-indigo-derived MLGs capable of solving complex logic operations. The MLG design relies on a molecular switch that experiences Z and E isomerism, thus the molecular switch's axis has to be a double bond. The hemi-indigo structure was preferred for the assembly of molecular switches due to its interaction with visible light. Z and E pseudo-hemi-indigo isomers can also be utilized for selective isomerization as they have distinct absorption spectra. Methodology: Here, the photophysical properties of pseudo-hemi-indigo derivatives are examined, i.e., derivatives of molecule 1 with anthracene, naphthalene, phenanthrene, pyrene, and pyrrole. In conjunction with some trials that were conducted, the level of theory mentioned subsequently was determined. The structures under study were optimized in both cis and trans conformations at the PBE0/6-31G(d,p) level of theory. The absorption spectra of the structures were calculated at PBE0/DEF2TZVP. In all cases, the absorption spectra of the studied systems were calculated including up to 50 singlet- and triplet-spin excited electronic states. Transition states (cis → cis, cis → trans, and trans → trans) were obtained in cases where it was possible, with PBE0/6-31G(d,p) for the optimization of the transition states and PBE0/DEF2TZVP for the respective absorption spectra. Emission spectra were obtained for the first singlet state of each molecule in cis both and trans conformations in PBE0/DEF2TZVP as well. All studies were performed in chloroform solvent that was added as a dielectric constant and the polarizable continuum model was also employed. Findings: Shifts of up to 25 nm are observed in the absorption spectra due to cis-trans isomerization, while the transition state is shifted up to about 150 nm. The electron density distribution is also examined, where charge transfer and electron transfer phenomena are observed regarding the three excitations of interest, i.e., H-1 → L, H → L and H → L+1. Emission spectra calculations were also carried out at PBE0/DEF2TZVP for the complete investigation of these molecules. Using protonation as input, selected molecules act as MLGs. Conclusion: Theoretical data so far indicate that both cis-trans isomerization, and cis-cis and trans-trans conformer isomerization affect the UV-visible absorption and emission spectra. Specifically, shifts of up to 30 nm are observed, while the transition state is shifted up to about 150 nm in cis-cis isomerization. The computational data obtained are in agreement with available experimental data, which have predicted that the pyrrole derivative is a MLG at 445 nm and 400 nm using protonation as input, while the anthracene derivative is a MLG that operates at 445 nm using protonation as input. Finally, it was found that selected molecules are candidates as MLG using protonation and light as inputs. These MLGs could be used as chemical sensors or as particular intracellular indicators, among several other applications. Acknowledgements: The author acknowledges the Hellenic Foundation for Research and Innovation for the financial support of this project (Fellowship Number: 21006).

Keywords: absorption spectra, DFT calculations, isomerization, molecular logic gates

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28 Leveraging the HDAC Inhibitory Pharmacophore to Construct Deoxyvasicinone Based Tractable Anti-Lung Cancer Agent and pH-Responsive Nanocarrier

Authors: Ram Sharma, Esha Chatterjee, Santosh Kumar Guru, Kunal Nepali

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A tractable anti-lung cancer agent was identified via the installation of a Ring C expanded synthetic analogue of the alkaloid vasicinone [7,8,9,10-tetrahydroazepino[2,1-b] quinazolin-12(6H)-one (TAZQ)] as a surface recognition part in the HDAC inhibitory three-component model. Noteworthy to mention that the candidature of TAZQ was deemed suitable for accommodation in HDAC inhibitory pharmacophore as per the results of the fragment recruitment process conducted by our laboratory. TAZQ was pinpointed through the fragment screening program as a synthetically flexible fragment endowed with some moderate cell growth inhibitory activity against the lung cancer cell lines, and it was anticipated that the use of the aforementioned fragment to generate hydroxamic acid functionality (zinc-binding motif) bearing HDAC inhibitors would boost the antitumor efficacy of TAZQ. Consistent with our aim of applying epigenetic targets to the treatment of lung cancer, a strikingly potent anti-lung cancer scaffold (compound 6) was pinpointed through a series of in-vitro experiments. Notably, the compounds manifested a magnificent activity profile against KRAS and EGFR mutant lung cancer cell lines (IC50 = 0.80 - 0.96 µM), and the effects were found to be mediated through preferential HDAC6 inhibition (IC50 = 12.9 nM). In addition to HDAC6 inhibition, the compounds also elicited HDAC1 and HDAC3 inhibitory activity with an IC50 value of 49.9 nM and 68.5 nM, respectively. The HDAC inhibitory ability of compound 6 was also confirmed from the results of the western blot experiment that revealed its potential to decrease the expression levels of HDAC isoforms (HDAC1, HDAC3, and HDAC6). Noteworthy to mention that complete downregulation of the HDAC6 isoform was exerted by compound 6 at 0.5 and 1 µM. Moreover, in another western blot experiment, treatment with hydroxamic acid 6 led to upregulation of H3 acK9 and α-Tubulin acK40 levels, ascertaining its inhibitory activity toward both the class I HDACs and Class II B HDACs. The results of other assays were also encouraging as treatment with compound 6 led to the suppression of the colony formation ability of A549 cells, induction of apoptosis, and increase in autophagic flux. In silico studies led us to rationalize the results of the experimental assay, and some key interactions of compound 6 with the amino acid residues of HDAC isoforms were identified. In light of the impressive activity spectrum of compound 6, a pH-responsive nanocarrier (hyaluronic acid-compound 6 nanoparticles) was prepared. The dialysis bag approach was used for the assessment of the nanoparticles under both normal and acidic circumstances, and the pH-sensitive nature of hyaluronic acid-compound 6 nanoparticles was confirmed. Delightfully, the nanoformulation was devoid of cytotoxicity against the L929 mouse fibroblast cells (normal settings) and exhibited selective cytotoxicity towards the A549 lung cancer cell lines. In a nutshell, compound 6 appears to be a promising adduct, and a detailed investigation of this compound might yield a therapeutic for the treatment of lung cancer.

Keywords: HDAC inhibitors, lung cancer, scaffold, hyaluronic acid, nanoparticles

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27 InAs/GaSb Superlattice Photodiode Array ns-Response

Authors: Utpal Das, Sona Das

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InAs/GaSb type-II superlattice (T2SL) Mid-wave infrared (MWIR) focal plane arrays (FPAs) have recently seen rapid development. However, in small pixel size large format FPAs, the occurrence of high mesa sidewall surface leakage current is a major constraint necessitating proper surface passivation. A simple pixel isolation technique in InAs/GaSb T2SL detector arrays without the conventional mesa etching has been proposed to isolate the pixels by forming a more resistive higher band gap material from the SL, in the inter-pixel region. Here, a single step femtosecond (fs) laser anneal of the T2SL structure of the inter-pixel T2SL regions, have been used to increase the band gap between the pixels by QW-intermixing and hence increase isolation between the pixels. The p-i-n photodiode structure used here consists of a 506nm, (10 monolayer {ML}) InAs:Si (1x10¹⁸cm⁻³)/(10ML) GaSb SL as the bottom n-contact layer grown on an n-type GaSb substrate. The undoped absorber layer consists of 1.3µm, (10ML)InAs/(10ML)GaSb SL. The top p-contact layer is a 63nm, (10ML)InAs:Be(1x10¹⁸cm⁻³)/(10ML)GaSb T2SL. In order to improve the carrier transport, a 126nm of graded doped (10ML)InAs/(10ML)GaSb SL layer was added between the absorber and each contact layers. A 775nm 150fs-laser at a fluence of ~6mJ/cm² is used to expose the array where the pixel regions are masked by a Ti(200nm)-Au(300nm) cap. Here, in the inter-pixel regions, the p+ layer have been reactive ion etched (RIE) using CH₄+H₂ chemistry and removed before fs-laser exposure. The fs-laser anneal isolation improvement in 200-400μm pixels due to spatially selective quantum well intermixing for a blue shift of ~70meV in the inter-pixel regions is confirmed by FTIR measurements. Dark currents are measured between two adjacent pixels with the Ti(200nm)-Au(300nm) caps used as contacts. The T2SL quality in the active photodiode regions masked by the Ti-Au cap is hardly affected and retains the original quality of the detector. Although, fs-laser anneal of p+ only etched p-i-n T2SL diodes show a reduction in the reverse dark current, no significant improvement in the full RIE-etched mesa structures is noticeable. Hence for a 128x128 array fabrication of 8μm square pixels and 10µm pitch, SU8 polymer isolation after RIE pixel delineation has been used. X-n+ row contacts and Y-p+ column contacts have been used to measure the optical response of the individual pixels. The photo-response of these 8μm and other 200μm pixels under a 2ns optical pulse excitation from an Optical-Parametric-Oscillator (OPO), shows a peak responsivity of ~0.03A/W and 0.2mA/W, respectively, at λ~3.7μm. Temporal response of this detector array is seen to have a fast response ~10ns followed typical slow decay with ringing, attributed to impedance mismatch of the connecting co-axial cables. In conclusion, response times of a few ns have been measured in 8µm pixels of a 128x128 array. Although fs-laser anneal has been found to be useful in increasing the inter-pixel isolation in InAs/GaSb T2SL arrays by QW inter-mixing, it has not been found to be suitable for passivation of full RIE etched mesa structures with vertical walls on InAs/GaSb T2SL.

Keywords: band-gap blue-shift, fs-laser-anneal, InAs/GaSb T2SL, Inter-pixel isolation, ns-Response, photodiode array

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26 Correlation Analysis of Reactivity in the Oxidation of Para and Meta-Substituted Benzyl Alcohols by Benzimidazolium Dichromate in Non-Aqueous Media: A Kinetic and Mechanistic Aspects

Authors: Seema Kothari, Dinesh Panday

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An observed correlation of the reaction rates with the changes in the nature of substituent present on one of the reactants often reveals the nature of transition state. Selective oxidation of organic compounds under non-aqueous media is an important transformation in synthetic organic chemistry. Inorganic chromates and dichromates being drastic oxidant and are generally insoluble in most organic solvents, a number of different chromium (VI) derivatives have been synthesized. Benzimidazolium dichromate (BIDC) is one of the recently reported Cr(VI) reagents which is neither hygroscopic nor light sensitive being, therefore, much stable. Not many reports on the kinetics of the oxidations by BIDC are seemed to be available in the literature. In the present investigation, the kinetics and mechanism of benzyl alcohol (BA) and a number of para- and meta-substituted benzyl alcohols by benzimidazolium dichromate (BIDC), in dimethyl sulphoxide, is reported. The reactions were followed spectrophotometrically at 364 nm by monitoring the decrease in [BIDC] for up to 85-90% reaction, the temperature being constant. The observed oxidation product is the corresponding benzaldehyde. The reactions were of first order with respect to each the alcohol and BIDC. The reactions are catalyzed by proton, and the dependence is of the form: kobs = a + b[H+]. The reactions thus follow both, an acid-dependent and acid-independent paths. The oxidation of [1,1 2H2]benzyl alcohol exhibited the presence of a substantial kinetic isotope effect ( kH/kD = 6.20 at 298 K ). This indicated the cleavage of a α-C-H bond in the rate-determining step. An analysis of the temperature dependence of the deuterium isotope effect showed that the loss of hydrogen proceeds through a concerted cyclic process. The rate of oxidation of BA was determined in 19 organic solvents. An analysis of the solvent effect by Swain’s equation indicated that though both the anion and cation-solvating powers of the solvent contribute to the observed solvent effect, the role of cation-solvation is major. The rates of the para and meta compounds, at 298 K, failed to exhibit a significant correlation in terms of Hammett or Brown's substituent constants. The rates were then subjected to analyses in terms of dual substituent parameter (DSP) equations. The rates of oxidation of the para-substituted benzyl alcohols show an excellent correlation with Taft's σI and σRBA values. However, the rates for the meta-substituted benzyl alcohols show an excellent correlation with σI and σR0. The polar reaction constants are negative indicating an electron-deficient transition state. Hence the overall mechanism is proposed to involve the formation of a chromate ester in a fast pre-equilibrium and then a decomposition of the ester in a subsequent slow step via a cyclic concerted symmetrical transition state, involving hydride-ion transfer, leading to the product. The first order dependence on alcohol may be accounted in terms of the small value of the formation constant of the ester intermediate. An another reaction mechanism accounting the acid-catalysis involve the formation of a protonated BIDC prior to formation of an ester intermediate which subsequently decomposes in a slow step leading to the product.

Keywords: benzimidazolium dichromate, benzyl alcohols, correlation analysis, kinetics, oxidation

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25 Application of Alumina-Aerogel in Post-Combustion CO₂ Capture: Optimization by Response Surface Methodology

Authors: S. Toufigh Bararpour, Davood Karami, Nader Mahinpey

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Dependence of global economics on fossil fuels has led to a large growth in the emission of greenhouse gases (GHGs). Among the various GHGs, carbon dioxide is the main contributor to the greenhouse effect due to its huge emission amount. To mitigate the threatening effect of CO₂, carbon capture and sequestration (CCS) technologies have been studied widely in recent years. For the combustion processes, three main CO₂ capture techniques have been proposed such as post-combustion, pre-combustion and oxyfuel combustion. Post-combustion is the most commonly used CO₂ capture process as it can be readily retrofit into the existing power plants. Multiple advantages have been reported for the post-combustion by solid sorbents such as high CO₂ selectivity, high adsorption capacity, and low required regeneration energy. Chemical adsorption of CO₂ over alkali-metal-based solid sorbents such as K₂CO₃ is a promising method for the selective capture of diluted CO₂ from the huge amount of nitrogen existing in the flue gas. To improve the CO₂ capture performance, K₂CO₃ is supported by a stable and porous material. Al₂O₃ has been employed commonly as the support and enhanced the cyclic CO₂ capture efficiency of K₂CO₃. Different phases of alumina can be obtained by setting the calcination temperature of boehmite at 300, 600 (γ-alumina), 950 (δ-alumina) and 1200 °C (α-alumina). By increasing the calcination temperature, the regeneration capacity of alumina increases, while the surface area reduces. However, sorbents with lower surface areas have lower CO₂ capture capacity as well (except for the sorbents prepared by hydrophilic support materials). To resolve this issue, a highly efficient alumina-aerogel support was synthesized with a BET surface area of over 2000 m²/g and then calcined at a high temperature. The synthesized alumina-aerogel was impregnated on K₂CO₃ based on 50 wt% support/K₂CO₃, which resulted in the preparation of a sorbent with remarkable CO₂ capture performance. The effect of synthesis conditions such as types of alcohols, solvent-to-co-solvent ratios, and aging times was investigated on the performance of the support. The best support was synthesized using methanol as the solvent, after five days of aging time, and at a solvent-to-co-solvent (methanol-to-toluene) ratio (v/v) of 1/5. Response surface methodology was used to investigate the effect of operating parameters such as carbonation temperature and H₂O-to-CO₂ flowrate ratio on the CO₂ capture capacity. The maximum CO₂ capture capacity, at the optimum amounts of operating parameters, was 7.2 mmol CO₂ per gram K₂CO₃. Cyclic behavior of the sorbent was examined over 20 carbonation and regenerations cycles. The alumina-aerogel-supported K₂CO₃ showed a great performance compared to unsupported K₂CO₃ and γ-alumina-supported K₂CO₃. Fundamental performance analyses and long-term thermal and chemical stability test will be performed on the sorbent in the future. The applicability of the sorbent for a bench-scale process will be evaluated, and a corresponding process model will be established. The fundamental material knowledge and respective process development will be delivered to industrial partners for the design of a pilot-scale testing unit, thereby facilitating the industrial application of alumina-aerogel.

Keywords: alumina-aerogel, CO₂ capture, K₂CO₃, optimization

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24 Actinomycetes from Protected Forest Ecosystems of Assam, India: Diversity and Antagonistic Activity

Authors: Priyanka Sharma, Ranjita Das, Mohan C. Kalita, Debajit Thakur

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Background: Actinomycetes are the richest source of novel bioactive secondary metabolites such as antibiotics, enzymes and other therapeutically useful metabolites with diverse biological activities. The present study aims at the antimicrobial potential and genetic diversity of culturable Actinomycetes isolated from protected forest ecosystems of Assam which includes Kaziranga National Park (26°30˝-26°45˝N and 93°08˝-93°36˝E), Pobitora Wildlife Sanctuary (26º12˝-26º16˝N and 91º58˝-92º05˝E) and Gibbon Wildlife Sanctuary (26˚40˝-26˚45˝N and 94˚20˝-94˚25˝E) which are located in the North-eastern part of India. Northeast India is a part of the Indo-Burma mega biodiversity hotspot and most of the protected forests of this region are still unexplored for the isolation of effective antibiotic-producing Actinomycetes. Thus, there is tremendous possibility that these virgin forests could be a potential storehouse of novel microorganisms, particularly Actinomycetes, exhibiting diverse biological properties. Methodology: Soil samples were collected from different ecological niches of the protected forest ecosystems of Assam and Actinomycetes were isolated by serial dilution spread plate technique using five selective isolation media. Preliminary screening of Actinomycetes for an antimicrobial activity was done by spot inoculation method and the secondary screening by disc diffusion method against several test pathogens, including multidrug resistant Staphylococcus aureus (MRSA). The strains were further screened for the presence of antibiotic synthetic genes such as type I polyketide synthases (PKS-I), type II polyketide synthases (PKS-II) and non-ribosomal peptide synthetases (NRPS) genes. Genetic diversity of the Actinomycetes producing antimicrobial metabolites was analyzed through 16S rDNA-RFLP using Hinf1 restriction endonuclease. Results: Based on the phenotypic characterization, a total of 172 morphologically distinct Actinomycetes were isolated and screened for antimicrobial activity by spot inoculation method on agar medium. Among the strains tested, 102 (59.3%) strains showed activity against Gram-positive bacteria, 98 (56.97%) against Gram-negative bacteria, 92 (53.48%) against Candida albicans MTCC 227 and 130 (75.58%) strains showed activity against at least one of the test pathogens. Twelve Actinomycetes exhibited broad spectrum antimicrobial activity in the secondary screening. The taxonomic identification of these twelve strains by 16S rDNA sequencing revealed that Streptomyces was found to be the predominant genus. The PKS-I, PKS-II and NRPS genes detection indicated diverse bioactive products of these twelve Actinomycetes. Genetic diversity by 16S rDNA-RFLP indicated that Streptomyces was the dominant genus amongst the antimicrobial metabolite producing Actinomycetes. Conclusion: These findings imply that Actinomycetes from the protected forest ecosystems of Assam, India, are a potential source of bioactive secondary metabolites. These areas are as yet poorly studied and represent diverse and largely unscreened ecosystem for the isolation of potent Actinomycetes producing antimicrobial secondary metabolites. Detailed characterization of the bioactive Actinomycetes as well as purification and structure elucidation of the bioactive compounds from the potent Actinomycetes is the subject of ongoing investigation. Thus, to exploit Actinomycetes from such unexplored forest ecosystems is a way to develop bioactive products.

Keywords: Actinomycetes, antimicrobial activity, forest ecosystems, RFLP

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23 Advantages of Matrix Solid Phase Dispersive (MSPD) Extraction Associated to MIPS versus MAE Liquid Extraction for the Simultaneous Analysis of PAHs, PCBs and Some Hydroxylated PAHs in Sediments

Authors: F. Portet-Koltalo, Y. Tian, I. Berger, C. Boulanger-Lecomte, A. Benamar, N. Machour

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Sediments are complex environments which can accumulate a great variety of persistent toxic contaminants such as polychlorobiphenyles (PCBs), polycyclic aromatic hydrocarbons (PAHs) and some of their more toxic degradation metabolites such as hydroxylated PAHs (OH-PAHs). Owing to their composition, fine clayey sediments can be more difficult to extract than soils using conventional solvent extraction processes. So this study aimed to compare the potential of MSPD (matrix solid phase dispersive extraction) to extract PCBs, PAHs and OH-PAHs, in comparison with microwave assisted extraction (MAE). Methodologies: MAE extraction with various solvent mixtures was used to extract PCBs, PAHs and OH-PAHs from sediments in two runs, followed by two GC-MS analyses. MSPD consisted in crushing the dried sediment with dispersive agents, introducing the mixture in cartridges and eluting the target compounds with an appropriate volume of selected solvents. So MSPD combined with cartridges containing MIPs (molecularly imprinted polymers) designed for OH-PAHs was used to extract the three families of target compounds in only one run, followed by parallel analyses in GC-MS for PAHs/PCBs and HPLC-FLD for OH-PAHs. Results: MAE extraction was optimized to extract from clayey sediments, in two runs, PAHs/PCBs in one hand and OH-PAHs in the other hand. Indeed, the best conditions of extractions (mixtures of extracting solvents, temperature) were different if we consider the polarity and the thermodegradability of the different families of target contaminants: PAHs/PCBs were better extracted using an acetone/toluene 50/50 mixture at 130°C whereas OH-PAHs were better extracted using an acetonitrile/toluene 90/10 mixture at 100°C. Moreover, the two consecutive GC-MS analyses contributed to double the total analysis time. A matrix solid phase dispersive (MSPD) extraction procedure was also optimized, with the first objective of increasing the extraction recovery yields of PAHs and PCBs from fine-grained sediment. The crushing time (2-10 min), the nature of the dispersing agents added for purifying and increasing the extraction yields (Florisil, octadecylsilane, 3-chloropropyle, 4-benzylchloride), the nature and the volume of eluting solvents (methylene chloride, hexane, hexane/acetone…) were studied. It appeared that in the best conditions, MSPD was a better extraction method than MAE for PAHs and PCBs, with respectively, mean increases of 8.2% and 71%. This method was also faster, easier and less expensive. But the other advantage of MSPD was that it allowed to introduce easily, just after the first elution process of PAHs/PCBs, a step permitting the selective recovery of OH-PAHs. A cartridge containing MIPs designed for phenols was coupled to the cartridge containing the dispersed sediment, and various eluting solvents, different from those used for PAHs and PCBs, were tested to selectively concentrate and extract OH-PAHs. Thereafter OH-PAHs could be analyzed at the same time than PAHs and PCBs: the OH-PAH extract could be analyzed with HPLC-FLD, whereas the PAHs/PCBs extract was analyzed with GC-MS, adding only few minutes more to the total duration of the analytical process. Conclusion: MSPD associated to MIPs appeared to be an easy, fast and low expensive method, able to extract in one run a complex mixture of toxic apolar and more polar contaminants present in clayey fine-grained sediments, an environmental matrix which is generally difficult to analyze.

Keywords: contaminated fine-grained sediments, matrix solid phase dispersive extraction, microwave assisted extraction, molecularly imprinted polymers, multi-pollutant analysis

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22 Two Component Source Apportionment Based on Absorption and Size Distribution Measurement

Authors: Tibor Ajtai, Noémi Utry, Máté Pintér, Gábor Szabó, Zoltán Bozóki

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Beyond its climate and health related issues ambient light absorbing carbonaceous particulate matter (LAC) has also become a great scientific interest in terms of its regulations recently. It has been experimentally demonstrated in recent studies, that LAC is dominantly composed of traffic and wood burning aerosol particularly under wintertime urban conditions, when the photochemical and biological activities are negligible. Several methods have been introduced to quantitatively apportion aerosol fractions emitted by wood burning and traffic but most of them require costly and time consuming off-line chemical analysis. As opposed to chemical features, the microphysical properties of airborne particles such as optical absorption and size distribution can be easily measured on-line, with high accuracy and sensitivity, especially under highly polluted urban conditions. Recently a new method has been proposed for the apportionment of wood burning and traffic aerosols based on the spectral dependence of their absorption quantified by the Aerosol Angström Exponent (AAE). In this approach the absorption coefficient is deduced from transmission measurement on a filter accumulated aerosol sample and the conversion factor between the measured optical absorption and the corresponding mass concentration (the specific absorption cross section) are determined by on-site chemical analysis. The recently developed multi-wavelength photoacoustic instruments provide novel, in-situ approach towards the reliable and quantitative characterization of carbonaceous particulate matter. Therefore, it also opens up novel possibilities on the source apportionment through the measurement of light absorption. In this study, we demonstrate an in-situ spectral characterization method of the ambient carbon fraction based on light absorption and size distribution measurements using our state-of-the-art multi-wavelength photoacoustic instrument (4λ-PAS) and Single Mobility Particle Sizer (SMPS) The carbonaceous particulate selective source apportionment study was performed for ambient particulate matter in the city center of Szeged, Hungary where the dominance of traffic and wood burning aerosol has been experimentally demonstrated earlier. The proposed model is based on the parallel, in-situ measurement of optical absorption and size distribution. AAEff and AAEwb were deduced from the measured data using the defined correlation between the AOC(1064nm)/AOC(266nm) and N100/N20 ratios. σff(λ) and σwb(λ) were determined with the help of the independently measured temporal mass concentrations in the PM1 mode. Furthermore, the proposed optical source apportionment is based on the assumption that the light absorbing fraction of PM is exclusively related to traffic and wood burning. This assumption is indirectly confirmed here by the fact that the measured size distribution is composed of two unimodal size distributions identified to correspond to traffic and wood burning aerosols. The method offers the possibility of replacing laborious chemical analysis with simple in-situ measurement of aerosol size distribution data. The results by the proposed novel optical absorption based source apportionment method prove its applicability whenever measurements are performed at an urban site where traffic and wood burning are the dominant carbonaceous sources of emission.

Keywords: absorption, size distribution, source apportionment, wood burning, traffic aerosol

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