Search results for: Selective Laser Melting (SLM)
82 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
Procedia PDF Downloads 10281 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
Procedia PDF Downloads 7280 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
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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
Procedia PDF Downloads 10879 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
Procedia PDF Downloads 29078 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
Procedia PDF Downloads 2777 Mondoc: Informal Lightweight Ontology for Faceted Semantic Classification of Hypernymy
Authors: M. Regina Carreira-Lopez
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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
Procedia PDF Downloads 12576 Waveguiding in an InAs Quantum Dots Nanomaterial for Scintillation Applications
Authors: Katherine Dropiewski, Michael Yakimov, Vadim Tokranov, Allan Minns, Pavel Murat, Serge Oktyabrsky
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InAs Quantum Dots (QDs) in a GaAs matrix is a well-documented luminescent material with high light yield, as well as thermal and ionizing radiation tolerance due to quantum confinement. These benefits can be leveraged for high-efficiency, room temperature scintillation detectors. The proposed scintillator is composed of InAs QDs acting as luminescence centers in a GaAs stopping medium, which also acts as a waveguide. This system has appealing potential properties, including high light yield (~240,000 photons/MeV) and fast capture of photoelectrons (2-5ps), orders of magnitude better than currently used inorganic scintillators, such as LYSO or BaF2. The high refractive index of the GaAs matrix (n=3.4) ensures light emitted by the QDs is waveguided, which can be collected by an integrated photodiode (PD). Scintillation structures were grown using Molecular Beam Epitaxy (MBE) and consist of thick GaAs waveguiding layers with embedded sheets of modulation p-type doped InAs QDs. An AlAs sacrificial layer is grown between the waveguide and the GaAs substrate for epitaxial lift-off to separate the scintillator film and transfer it to a low-index substrate for waveguiding measurements. One consideration when using a low-density material like GaAs (~5.32 g/cm³) as a stopping medium is the matrix thickness in the dimension of radiation collection. Therefore, luminescence properties of very thick (4-20 microns) waveguides with up to 100 QD layers were studied. The optimization of the medium included QD shape, density, doping, and AlGaAs barriers at the waveguide surfaces to prevent non-radiative recombination. To characterize the efficiency of QD luminescence, low temperature photoluminescence (PL) (77-450 K) was measured and fitted using a kinetic model. The PL intensity degrades by only 40% at RT, with an activation energy for electron escape from QDs to the barrier of ~60 meV. Attenuation within the waveguide (WG) is a limiting factor for the lateral size of a scintillation detector, so PL spectroscopy in the waveguiding configuration was studied. Spectra were measured while the laser (630 nm) excitation point was scanned away from the collecting fiber coupled to the edge of the WG. The QD ground state PL peak at 1.04 eV (1190 nm) was inhomogeneously broadened with FWHM of 28 meV (33 nm) and showed a distinct red-shift due to self-absorption in the QDs. Attenuation stabilized after traveling over 1 mm through the WG, at about 3 cm⁻¹. Finally, a scintillator sample was used to test detection and evaluate timing characteristics using 5.5 MeV alpha particles. With a 2D waveguide and a small area of integrated PD, the collected charge averaged 8.4 x10⁴ electrons, corresponding to a collection efficiency of about 7%. The scintillation response had 80 ps noise-limited time resolution and a QD decay time of 0.6 ns. The data confirms unique properties of this scintillation detector which can be potentially much faster than any currently used inorganic scintillator.Keywords: GaAs, InAs, molecular beam epitaxy, quantum dots, III-V semiconductor
Procedia PDF Downloads 25675 Influence of Cryo-Grinding on Particle Size Distribution of Proso Millet Bran Fraction
Authors: Maja Benkovic, Dubravka Novotni, Bojana Voucko, Duska Curic, Damir Jezek, Nikolina Cukelj
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Cryo-grinding is an ultra-fine grinding method used in the pharmaceutical industry, production of herbs and spices and in the production and handling of cereals, due to its ability to produce powders with small particle sizes which maintain their favorable bioactive profile. The aim of this study was to determine the particle size distributions of the proso millet (Panicum miliaceum) bran fraction grinded at cryogenic temperature (using liquid nitrogen (LN₂) cooling, T = - 196 °C), in comparison to non-cooled grinding. Proso millet bran is primarily used as an animal feed, but has a potential in food applications, either as a substrate for extraction of bioactive compounds or raw material in the bakery industry. For both applications finer particle sizes of the bran could be beneficial. Thus, millet bran was ground for 2, 4, 8 and 12 minutes using the ball mill (CryoMill, Retsch GmbH, Haan, Germany) at three grinding modes: (I) without cooling, (II) at cryo-temperature, and (III) at cryo-temperature with included 1 minute of intermediate cryo-cooling step after every 2 minutes of grinding, which is usually applied when samples require longer grinding times. The sample was placed in a 50 mL stainless steel jar containing one grinding ball (Ø 25 mm). The oscillation frequency in all three modes was 30 Hz. Particle size distributions of the bran were determined by a laser diffraction particle sizing method (Mastersizer 2000) using the Scirocco 2000 dry dispersion unit (Malvern Instruments, Malvern, UK). Three main effects of the grinding set-up were visible from the results. Firstly, grinding time at all three modes had a significant effect on all particle size parameters: d(0.1), d(0.5), d(0.9), D[3,2], D[4,3], span and specific surface area. Longer grinding times resulted in lower values of the above-listed parameters, e.g. the averaged d(0.5) of the sample (229.57±1.46 µm) dropped to 51.29±1.28 µm after 2 minutes grinding without LN₂, and additionally to 43.00±1.33 µm after 4 minutes of grinding without LN₂. The only exception was the sample ground for 12 minutes without cooling, where an increase in particle diameters occurred (d(0.5)=62.85±2.20 µm), probably due to particles adhering to one another and forming larger particle clusters. Secondly, samples with LN₂ cooling exhibited lower diameters in comparison to non-cooled. For example, after 8 minutes of non-cooled grinding d(0.5)=46.97±1.05 µm was achieved, while the LN₂ cooling enabled collection of particles with average sizes of d(0.5)=18.57±0.18 µm. Thirdly, the application of intermediate cryo-cooling step resulted in similar particle diameters (d(0.5)=15.83±0.36 µm, 12 min of grinding) as cryo-milling without this step (d(0.5)=16.33±2.09 µm, 12 min of grinding). This indicates that intermediate cooling is not necessary for the current application, which consequently reduces the consumption of LN₂. These results point out the potential beneficial effects of millet bran grinding at cryo-temperatures. Further research will show if the lower particle size achieved in comparison to non-cooled grinding could result in increased bioavailability of bioactive compounds, as well as protein digestibility and solubility of dietary fibers of the proso millet bran fraction.Keywords: ball mill, cryo-milling, particle size distribution, proso millet (Panicum miliaceum) bran
Procedia PDF Downloads 14574 Intriguing Modulations in the Excited State Intramolecular Proton Transfer Process of Chrysazine Governed by Host-Guest Interactions with Macrocyclic Molecules
Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury
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Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies
Procedia PDF Downloads 12173 Synthesis and Characterization of Fibrin/Polyethylene Glycol-Based Interpenetrating Polymer Networks for Dermal Tissue Engineering
Authors: O. Gsib, U. Peirera, C. Egles, S. A. Bencherif
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In skin regenerative medicine, one of the critical issues is to produce a three-dimensional scaffold with optimized porosity for dermal fibroblast infiltration and neovascularization, which exhibits high mechanical properties and displays sufficient wound healing characteristics. In this study, we report on the synthesis and characterization of macroporous sequential interpenetrating polymer networks (IPNs) combining skin wound healing properties of fibrin with the excellent physical properties of polyethylene glycol (PEG). Fibrin fibers serve as a provisional biologically active network to promote cell adhesion and proliferation while PEG provides the mechanical stability to maintain the entire 3D construct. After having modified both PEG and Serum Albumin (used for promoting enzymatic degradability) by adding methacrylate residues (PEGDM and SAM, respectively), Fibrin/PEGDM-SAM sequential IPNs were synthesized as follows: Macroporous sponges were first produced from PEGDM-SAM hydrogels by a freeze-drying technique and then rehydrated by adding the fibrin precursors. Environmental Scanning Electron Microscopy (ESEM) and Confocal Laser Scanning Microscopy (CLSM) were used to characterize their microstructure. Human dermal fibroblasts were cultivated during one week in the constructs and different cell culture parameters (viability, morphology, proliferation) were evaluated. Subcutaneous implantations of the scaffolds were conducted on five-week old male nude mice to investigate their biocompatibility in vivo. We successfully synthesized interconnected and macroporous Fibrin/PEGDM-SAM sequential IPNs. The viability of primary dermal fibroblasts was well maintained (above 90%) after 2 days of culture. Cells were able to adhere, spread and proliferate in the scaffolds suggesting the suitable porosity and intrinsic biologic properties of the constructs. The fibrin network adopted a spider web shape that covered partially the pores allowing easier cell infiltration into the macroporous structure. To further characterize the in vitro cell behavior, cell proliferation (EdU incorporation, MTS assay) is being studied. Preliminary histological analysis of animal studies indicated the persistence of hydrogels even after one-month post implantation and confirmed the absence of inflammation response, good biocompatibility and biointegration of our scaffolds within the surrounding tissues. These results suggest that our Fibrin/PEGDM-SAM IPNs could be considered as potential candidates for dermis regenerative medicine. Histological analysis will be completed to further assess scaffold remodeling including de novo extracellular matrix protein synthesis and early stage angiogenesis analysis. Compression measurements will be conducted to investigate the mechanical properties.Keywords: fibrin, hydrogels for dermal reconstruction, polyethylene glycol, semi-interpenetrating polymer network
Procedia PDF Downloads 23672 Li2o Loss of Lithium Niobate Nanocrystals during High-Energy Ball-Milling
Authors: Laura Kocsor, Laszlo Peter, Laszlo Kovacs, Zsolt Kis
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The aim of our research is to prepare rare-earth-doped lithium niobate (LiNbO3) nanocrystals, having only a few dopant ions in the focal point of an exciting laser beam. These samples will be used to achieve individual addressing of the dopant ions by light beams in a confocal microscope setup. One method for the preparation of nanocrystalline materials is to reduce the particle size by mechanical grinding. High-energy ball-milling was used in several works to produce nano lithium niobate. Previously, it was reported that dry high-energy ball-milling of lithium niobate in a shaker mill results in the partial reduction of the material, which leads to a balanced formation of bipolarons and polarons yielding gray color together with oxygen release and Li2O segregation on the open surfaces. In the present work we focus on preparing LiNbO3 nanocrystals by high-energy ball-milling using a Fritsch Pulverisette 7 planetary mill. Every ball-milling process was carried out in zirconia vial with zirconia balls of different sizes (from 3 mm to 0.1 mm), wet grinding with water, and the grinding time being less than an hour. Gradually decreasing the ball size to 0.1 mm, an average particle size of about 10 nm could be obtained determined by dynamic light scattering and verified by scanning electron microscopy. High-energy ball-milling resulted in sample darkening evidenced by optical absorption spectroscopy measurements indicating that the material underwent partial reduction. The unwanted lithium oxide loss decreases the Li/Nb ratio in the crystal, strongly influencing the spectroscopic properties of lithium niobate. Zirconia contamination was found in ground samples proved by energy-dispersive X-ray spectroscopy measurements; however, it cannot be explained based on the hardness properties of the materials involved in the ball-milling process. It can be understood taking into account the presence of lithium hydroxide formed the segregated lithium oxide and water during the ball-milling process, through chemically induced abrasion. The quantity of the segregated Li2O was measured by coulometric titration. During the wet milling process in the planetary mill, it was found that the lithium oxide loss increases linearly in the early phase of the milling process, then a saturation of the Li2O loss can be seen. This change goes along with the disappearance of the relatively large particles until a relatively narrow size distribution is achieved in accord with the dynamic light scattering measurements. With the 3 mm ball size and 1100 rpm rotation rate, the mean particle size achieved is 100 nm, and the total Li2O loss is about 1.2 wt.% of the original LiNbO3. Further investigations have been done to minimize the Li2O segregation during the ball-milling process. Since the Li2O loss was observed to increase with the growing total surface of the particles, the influence of ball-milling parameters on its quantity has also been studied.Keywords: high-energy ball-milling, lithium niobate, mechanochemical reaction, nanocrystals
Procedia PDF Downloads 13571 Nanoparticle Supported, Magnetically Separable Metalloporphyrin as an Efficient Retrievable Heterogeneous Nanocatalyst in Oxidation Reactions
Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh
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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 29970 Overcoming the Challenges of Subjective Truths in the Post-Truth Age Through a CriticalEthical English Pedagogy
Authors: Farah Vierra
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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 7169 Caged Compounds as Light-Dependent Initiators for Enzyme Catalysis Reactions
Authors: Emma Castiglioni, Nigel Scrutton, Derren Heyes, Alistair Fielding
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By using light as trigger, it is possible to study many biological processes, such as the activity of genes, proteins, and other molecules, with precise spatiotemporal control. Caged compounds, where biologically active molecules are generated from an inert precursor upon laser photolysis, offer the potential to initiate such biological reactions with high temporal resolution. As light acts as the trigger for cleaving the protecting group, the ‘caging’ technique provides a number of advantages as it can be intracellular, rapid and controlled in a quantitative manner. We are developing caging strategies to study the catalytic cycle of a number of enzyme systems, such as nitric oxide synthase and ethanolamine ammonia lyase. These include the use of caged substrates, caged electrons and the possibility of caging the enzyme itself. In addition, we are developing a novel freeze-quench instrument to study these reactions, which combines rapid mixing and flashing capabilities. Reaction intermediates will be trapped at low temperatures and will be analysed by using electron paramagnetic resonance (EPR) spectroscopy to identify the involvement of any radical species during catalysis. EPR techniques typically require relatively long measurement times and very often, low temperatures to fully characterise these short-lived species. Therefore, common rapid mixing techniques, such as stopped-flow or quench-flow are not directly suitable. However, the combination of rapid freeze-quench (RFQ) followed by EPR analysis provides the ideal approach to kinetically trap and spectroscopically characterise these transient radical species. In a typical RFQ experiment, two reagent solutions are delivered to the mixer via two syringes driven by a pneumatic actuator or stepper motor. The new mixed solution is then sprayed into a cryogenic liquid or surface, and the frozen sample is then collected and packed into an EPR tube for analysis. The earliest RFQ instrument consisted of a hydraulic ram unit as a drive unit with direct spraying of the sample into a cryogenic liquid (nitrogen, isopentane or petroleum). Improvements to the RFQ technique have arisen from the design of new mixers in order to reduce both the volume and the mixing time. In addition, the cryogenic isopentane bath has been coupled to a filtering system or replaced by spraying the solution onto a surface that is frozen via thermal conductivity with a cryogenic liquid. In our work, we are developing a novel RFQ instrument which combines the freeze-quench technology with flashing capabilities to enable the studies of both thermally-activated and light-activated biological reactions. This instrument also uses a new rotating plate design based on magnetic couplings and removes the need for mechanical motorised rotation, which can otherwise be problematic at cryogenic temperatures.Keywords: caged compounds, freeze-quench apparatus, photolysis, radicals
Procedia PDF Downloads 20868 Overcoming the Challenges of Subjective Truths in the Post-Truth Age Through a Critical-Ethical English Pedagogy
Authors: Farah Vierra
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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 6667 Radiofrequency and Near-Infrared Responsive Core-Shell Multifunctional Nanostructures Using Lipid Templates for Cancer Theranostics
Authors: Animesh Pan, Geoffrey D. Bothun
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With the development of nanotechnology, research in multifunctional delivery systems has a new pace and dimension. An incipient challenge is to design an all-in-one delivery system that can be used for multiple purposes, including tumor targeting therapy, radio-frequency (RF-), near-infrared (NIR-), light-, or pH-induced controlled release, photothermal therapy (PTT), photodynamic therapy (PDT), and medical diagnosis. In this regard, various inorganic nanoparticles (NPs) are known to show great potential as the 'functional components' because of their fascinating and tunable physicochemical properties and the possibility of multiple theranostic modalities from individual NPs. Magnetic, luminescent, and plasmonic properties are the three most extensively studied and, more importantly biomedically exploitable properties of inorganic NPs. Although successful attempts of combining any two of them above mentioned functionalities have been made, integrating them in one system has remained challenge. Keeping those in mind, controlled designs of complex colloidal nanoparticle system are one of the most significant challenges in nanoscience and nanotechnology. Therefore, systematic and planned studies providing better revelation are demanded. We report a multifunctional delivery platform-based liposome loaded with drug, iron-oxide magnetic nanoparticles (MNPs), and a gold shell on the surface of liposomes, were synthesized using a lipid with polyelectrolyte (layersomes) templating technique. MNPs and the anti-cancer drug doxorubicin (DOX) were co-encapsulated inside liposomes composed by zwitterionic phophatidylcholine and anionic phosphatidylglycerol using reverse phase evaporation (REV) method. The liposomes were coated with positively charge polyelectrolyte (poly-L-lysine) to enrich the interface with gold anion, exposed to a reducing agent to form a gold nanoshell, and then capped with thio-terminated polyethylene glycol (SH-PEG2000). The core-shell nanostructures were characterized by different techniques like; UV-Vis/NIR scanning spectrophotometer, dynamic light scattering (DLS), transmission electron microscope (TEM). This multifunctional system achieves a variety of functions, such as radiofrequency (RF)-triggered release, chemo-hyperthermia, and NIR laser-triggered for photothermal therapy. Herein, we highlight some of the remaining major design challenges in combination with preliminary studies assessing therapeutic objectives. We demonstrate an efficient loading and delivery system to significant cell death of human cancer cells (A549) with therapeutic capabilities. Coupled with RF and NIR excitation to the doxorubicin-loaded core-shell nanostructure helped in securing targeted and controlled drug release to the cancer cells. The present core-shell multifunctional system with their multimodal imaging and therapeutic capabilities would be eminent candidates for cancer theranostics.Keywords: cancer thernostics, multifunctional nanostructure, photothermal therapy, radiofrequency targeting
Procedia PDF Downloads 12866 Case Report on Anaesthesia for Ruptured Ectopic with Severe Pulmonary Hypertension in a Mute Patient
Authors: Pamela Chia, Tay Yoong Chuan
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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 22065 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 14764 Additional Opportunities of Forensic Medical Identification of Dead Bodies of Unkown Persons
Authors: Saule Mussabekova
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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
Procedia PDF Downloads 14263 Photoluminescence of Barium and Lithium Silicate Glasses and Glass Ceramics Doped with Rare Earth Ions
Authors: Augustas Vaitkevicius, Mikhail Korjik, Eugene Tretyak, Ekaterina Trusova, Gintautas Tamulaitis
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Silicate materials are widely used as luminescent materials in amorphous and crystalline phase. Lithium silicate glass is popular for making neutron sensitive scintillation glasses. Cerium-doped single crystalline silicates of rare earth elements and yttrium have been demonstrated to be good scintillation materials. Due to their high thermal and photo-stability, silicate glass ceramics are supposed to be suitable materials for producing light converters for high power white light emitting diodes. In this report, the influence of glass composition and crystallization on photoluminescence (PL) of different silicate glasses was studied. Barium (BaO-2SiO₂) and lithium (Li₂O-2SiO₂) glasses were under study. Cerium, dysprosium, erbium and europium ions as well as their combinations were used for doping. The influence of crystallization was studied after transforming the doped glasses into glass ceramics by heat treatment in the temperature range of 550-850 degrees Celsius for 1 hour. The study was carried out by comparing the photoluminescence (PL) spectra, spatial distributions of PL parameters and quantum efficiency in the samples under study. The PL spectra and spatial distributions of their parameters were obtained by using confocal PL microscopy. A WITec Alpha300 S confocal microscope coupled with an air cooled CCD camera was used. A CW laser diode emitting at 405 nm was exploited for excitation. The spatial resolution was in sub-micrometer domain in plane and ~1 micrometer perpendicularly to the sample surface. An integrating sphere with a xenon lamp coupled with a monochromator was used to measure the external quantum efficiency. All measurements were performed at room temperature. Chromatic properties of the light emission from the glasses and glass ceramics have been evaluated. We observed that the quantum efficiency of the glass ceramics is higher than that of the corresponding glass. The investigation of spatial distributions of PL parameters revealed that heat treatment of the glasses leads to a decrease in sample homogeneity. In the case of BaO-2SiO₂: Eu, 10 micrometer long needle-like objects are formed, when transforming the glass into glass ceramics. The comparison of PL spectra from within and outside the needle-like structure reveals that the ratio between intensities of PL bands associated with Eu²⁺ and Eu³⁺ ions is larger in the bright needle-like structures. This indicates a higher degree of crystallinity in the needle-like objects. We observed that the spectral positions of the PL bands are the same in the background and the needle-like areas, indicating that heat treatment imposes no significant change to the valence state of the europium ions. The evaluation of chromatic properties confirms applicability of the glasses under study for fabrication of white light sources with high thermal stability. The ability to combine barium and lithium glass matrixes and doping by Eu, Ce, Dy, and Tb enables optimization of chromatic properties.Keywords: glass ceramics, luminescence, phosphor, silicate
Procedia PDF Downloads 31662 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
Procedia PDF Downloads 8061 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
Procedia PDF Downloads 20460 Surface Acoustic Waves Nebulisation of Liposomes Manufactured in situ for Pulmonary Drug Delivery
Authors: X. King, E. Nazarzadeh, J. Reboud, J. Cooper
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Pulmonary diseases, such as asthma, are generally treated by the inhalation of aerosols that has the advantage of reducing the off-target (e.g., toxicity) effects associated with systemic delivery in blood. Effective respiratory drug delivery requires a droplet size distribution between 1 and 5 µm. Inhalation of aerosols with wide droplet size distribution, out of this range, results in deposition of drug in not-targeted area of the respiratory tract, introducing undesired side effects on the patient. In order to solely deliver the drug in the lower branches of the lungs and release it in a targeted manner, a control mechanism to produce the aerosolized droplets is required. To regulate the drug release and to facilitate the uptake from cells, drugs are often encapsulated into protective liposomes. However, a multistep process is required for their formation, often performed at the formulation step, therefore limiting the range of available drugs or their shelf life. Using surface acoustic waves (SAWs), a pulmonary drug delivery platform was produced, which enabled the formation of defined size aerosols and the formation of liposomes in situ. SAWs are mechanical waves, propagating along the surface of a piezoelectric substrate. They were generated using an interdigital transducer on lithium niobate with an excitation frequency of 9.6 MHz at a power of 1W. Disposable silicon superstrates were etched using photolithography and dry etch processes to create an array of cylindrical through-holes with different diameters and pitches. Superstrates were coupled with the SAW substrate through water-based gel. As the SAW propagates on the superstrate, it enables nebulisation of a lipid solution deposited onto it. The cylindrical cavities restricted the formation of large drops in the aerosol, while at the same time unilamellar liposomes were created. SAW formed liposomes showed a higher monodispersity compared to the control sample, as well as displayed, a faster production rate. To test the aerosol’s size, dynamic light scattering and laser diffraction methods were used, both showing the size control of the aerosolised particles. The use of silicon superstate with cavity size of 100-200 µm, produced an aerosol with a mean droplet size within the optimum range for pulmonary drug delivery, containing the liposomes in which the medicine could be loaded. Additionally, analysis of liposomes with Cryo-TEM showed formation of vesicles with narrow size distribution between 80-100 nm and optimal morphology in order to be used for drug delivery. Encapsulation of nucleic acids in liposomes through the developed SAW platform was also investigated. In vitro delivery of siRNA and DNA Luciferase were achieved using A549 cell line, lung carcinoma from human. In conclusion, SAW pulmonary drug delivery platform was engineered, in order to combine multiple time consuming steps (formation of liposomes, drug loading, nebulisation) into a unique platform with the aim of specifically delivering the medicament in a targeted area, reducing the drug’s side effects.Keywords: acoustics, drug delivery, liposomes, surface acoustic waves
Procedia PDF Downloads 12459 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
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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 6658 Feasibility of Washing/Extraction Treatment for the Remediation of Deep-Sea Mining Trailings
Authors: Kyoungrean Kim
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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 15557 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
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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
Procedia PDF Downloads 40456 Theoretical Study of the Photophysical Properties and Potential Use of Pseudo-Hemi-Indigo Derivatives as Molecular Logic Gates
Authors: Christina Eleftheria Tzeliou, Demeter Tzeli
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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
Procedia PDF Downloads 2155 Chiral Molecule Detection via Optical Rectification in Spin-Momentum Locking
Authors: Jessie Rapoza, Petr Moroshkin, Jimmy Xu
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Chirality is omnipresent, in nature, in life, and in the field of physics. One intriguing example is the homochirality that has remained a great secret of life. Another is the pairs of mirror-image molecules – enantiomers. They are identical in atomic composition and therefore indistinguishable in the scalar physical properties. Yet, they can be either therapeutic or toxic, depending on their chirality. Recent studies suggest a potential link between abnormal levels of certain D-amino acids and some serious health impairments, including schizophrenia, amyotrophic lateral sclerosis, and potentially cancer. Although indistinguishable in their scalar properties, the chirality of a molecule reveals itself in interaction with the surrounding of a certain chirality, or more generally, a broken mirror-symmetry. In this work, we report on a system for chiral molecule detection, in which the mirror-symmetry is doubly broken, first by asymmetric structuring a nanopatterned plasmonic surface than by the incidence of circularly polarized light (CPL). In this system, the incident circularly-polarized light induces a surface plasmon polariton (SPP) wave, propagating along the asymmetric plasmonic surface. This SPP field itself is chiral, evanescently bound to a near-field zone on the surface (~10nm thick), but with an amplitude greatly intensified (by up to 104) over that of the incident light. It hence probes just the molecules on the surface instead of those in the volume. In coupling to molecules along its path on the surface, the chiral SPP wave favors one chirality over the other, allowing for chirality detection via the change in an optical rectification current measured at the edges of the sample. The asymmetrically structured surface converts the high-frequency electron plasmonic-oscillations in the SPP wave into a net DC drift current that can be measured at the edge of the sample via the mechanism of optical rectification. The measured results validate these design concepts and principles. The observed optical rectification current exhibits a clear differentiation between a pair of enantiomers. Experiments were performed by focusing a 1064nm CW laser light at the sample - a gold grating microchip submerged in an approximately 1.82M solution of either L-arabinose or D-arabinose and water. A measurement of the current output was then recorded under both rights and left circularly polarized lights. Measurements were recorded at various angles of incidence to optimize the coupling between the spin-momentums of the incident light and that of the SPP, that is, spin-momentum locking. In order to suppress the background, the values of the photocurrent for the right CPL are subtracted from those for the left CPL. Comparison between the two arabinose enantiomers reveals a preferential signal response of one enantiomer to left CPL and the other enantiomer to right CPL. In sum, this work reports on the first experimental evidence of the feasibility of chiral molecule detection via optical rectification in a metal meta-grating. This nanoscale interfaced electrical detection technology is advantageous over other detection methods due to its size, cost, ease of use, and integration ability with read-out electronic circuits for data processing and interpretation.Keywords: Chirality, detection, molecule, spin
Procedia PDF Downloads 9254 Spatial Organization of Cells over the Process of Pellicle Formation by Pseudomonas alkylphenolica KL28
Authors: Kyoung Lee
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Numerous aerobic bacteria have the ability to form multicellular communities on the surface layer of the air-liquid (A-L) interface as a biofilm called a pellicle. Pellicles occupied at the A-L interface will benefit from the utilization of oxygen from air and nutrient from liquid. Buoyancy of cells can be obtained by high surface tension at the A-L interface. Thus, formation of pellicles is an adaptive advantage in utilization of excess nutrients in the standing culture where oxygen depletion is easily set up due to rapid cell growth. In natural environments, pellicles are commonly observed on the surface of lake or pond contaminated with pollutants. Previously, we have shown that when cultured in standing LB media an alkylphenol-degrading bacteria Pseudomonas alkylphenolia KL28 forms pellicles in a diameter of 0.3-0.5 mm with a thickness of ca 40 µm. The pellicles have unique features for possessing flatness and unusual rigidity. In this study, the biogenesis of the circular pellicles has been investigated by observing the cell organization at early stages of pellicle formation and cell arrangements in pellicle, providing a clue for highly organized cellular arrangement to be adapted to the air-liquid niche. Here, we first monitored developmental patterns of pellicle from monolayer to multicellular organization. Pellicles were shaped by controlled growth of constituent cells which accumulate extracellular polymeric substance. The initial two-dimensional growth was transited to multilayers by a constraint force of accumulated self-produced extracellular polymeric substance. Experiments showed that pellicles are formed by clonal growth and even with knock-out of genes for flagella and pilus formation. In contrast, the mutants in the epm gene cluster for alginate-like polymer biosynthesis were incompetent in cell alignment for initial two-dimensional growth of pellicles. Electron microscopic and confocal laser scanning microscopic studies showed that the fully matured structures are highly packed by matrix-encased cells which have special arrangements. The cells on the surface of the pellicle lie relatively flat and inside longitudinally cross packed. HPLC analysis of the extrapolysaccharide (EPS) hydrolysate from the colonies from LB agar showed a composition with L-fucose, L-rhamnose, D-galactosamine, D-glucosamine, D-galactose, D-glucose, D-mannose. However, that from pellicles showed similar neutral and amino sugar profile but missing galactose. Furthermore, uronic acid analysis of EPS hydrolysates by HPLC showed that mannuronic acid was detected from pellicles not from colonies, indicating the epm-derived polymer is critical for pellicle formation as proved by the epm mutants. This study verified that for the circular pellicle architecture P. alkylphenolica KL28 cells utilized EPS building blocks different from that used for colony construction. These results indicate that P. alkylphenolica KL28 is a clever architect that dictates unique cell arrangements with selected EPS matrix material to construct sophisticated building, circular biofilm pellicles.Keywords: biofilm, matrix, pellicle, pseudomonas
Procedia PDF Downloads 15253 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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