Search results for: gold clusters

Authors: Jahangir Ahmad Rather, Emad A. Khudaish, Ahsanulhaq Qurashi, Palanisamy Kannan

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Chemical modification and assembling of fullerenes are fundamentally important for the application of fullerenes as functional molecules and in molecular devices and organic electronic devices. We have synthesized fullerene nanorods C60NRs conjugate via liquid-liquid interface and the synthesized C60NRs was characterized by FTIR spectroscopy, field emission electron microscopy (FESEM) and X-ray diffraction techniques. The C60NRs were immobilized on glassy carbon electrode via surface bound diazonium salts as an impact strategy. This method involves electrografting of p–nitrophenyl to give GCE–Ph–NO2 and then the terminal nitro-group was chemically reduced to GCE–Ph–NH2 in a presence of sodium borohydride/gold–polyaniline nanocomposite (NaBH4/Au–PANI). The Au–PANI composite was synthesized and characterized by FTIR, UV-vis, SEM and EDX techniques. The C60NRs were immobilized on GCE–Ph–NH2 via amination reaction which involves N-H addition across a π-bond on [60] fullerene. The immobilized C60NRs/GCE was subjected to electrochemical reduction in 1.0 M KOH to yield ERC60NRs/GCE sensor. The developed sensor shows high electrocatalytic activity for the detection of ethylparaben (EP) over a concentration range from 0.01 to 0.52 µM with a detection limit (LOD) 3.8 nM. The amount of EP present in the nourishing repair cream (OlAY®) was determined by standard addition method at the developed ERC60NRs/GCE sensor. The total concentration of EP was found to be 0.011 µM (0.1%) and is within the permissible limit of 0.19 % EP in cosmetics according to the European scientific committee (SCCS) on consumer safety on 22 March 2011 (SCCS/1348/11).

Keywords: diazonium salt reduction, ethylparaben (EP), endocrine disruptor, fullerene nanorods (C60NRs), gold–polyaniline nanocomposite (Au–PANI)

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Authors: Gysele Lima Ricci, Jose Miguel Rodriguez Anton

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Companies in the tourism sector need to achieve competitive advantages for their survival in the market. In this way, the models based on association, cooperation, complementarity, distribution, exchange and mutual assistance arise as a possibility of organizational development, taking as reference the concept of networks. Many companies seek to partner in local networks as clusters to act together and associate. The main objective of the present research is to identify the specificities of management and the practices of cooperation in the tourist destination of São Paulo - Brazil, and to propose a new management model with possible cluster of tourism. The empirical analysis was carried out in three phases. As a first phase, a research was made by the companies, associations and tourism organizations existing in São Paulo, analyzing the characteristics of their business. In the second phase, the management specificities and cooperation practice used in the tourist destination. And in the third phase, identifying the possible strengths and weaknesses that potential or potential tourist cluster could have, proposing the development of the management model of the same adapted to the needs of the companies, associations and organizations. As a main result, it has been identified that companies, associations and organizations could be looking for synergies with each other and collaborate through a Hiperred organizational structure, in which they share their knowledge, try to make the most of the collaboration and to benefit from three concepts: flexibility, learning and collaboration. Finally, it is concluded that, the proposed tourism cluster management model is viable for the development of tourism destinations because it makes it possible to strategically address agents which are responsible for public policies, as well as public and private companies and organizations in their strategies competitiveness and cooperation.

Keywords: cluster, management model, networks, tourism sector

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Authors: Anindita Sen

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Oral fluid is a promising diagnostic matrix for drugs of abuse compared to urine and serum. Detection of methamphetamine in oral fluid would pave way for the easy evaluation of impairment in drivers during roadside drug testing as well as ensure safe working environments by facilitating evaluation of impairment in employees at workplaces. A membrane-based point-of-care (POC) friendly pre-treatment technique has been developed which aided elimination of interferences caused by salivary proteins and facilitated the demonstration of methamphetamine detection in saliva using a gold nanoparticle based colorimetric aptasensor platform. It was found that the colorimetric response in saliva was always suppressed owing to the matrix effects. By navigating the challenging interfering issues in saliva, we were successfully able to detect methamphetamine at nanomolar levels in saliva offering immense promise for the translation of these platforms for on-site diagnostic systems. This subsequently motivated the development of a handheld portable light meter device that can reliably transduce the aptasensors colorimetric response into absorbance, facilitating quantitative detection of analyte concentrations on-site. This is crucial due to the prevalent unreliability and sensitivity problems of the conventional drug testing kits. The fabricated light meter device response was validated against a standard UV-Vis spectrometer to confirm reliability. The portable and cost-effective handheld detector device features sensitivity comparable to the well-established UV-Vis benchtop instrument and the easy-to-use device could potentially serve as a prototype for a commercial device in the future.

Keywords: aptasensors, colorimetric gold nanoparticle assay, point-of-care, oral fluid

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Authors: Ranjita Ghoshmoulick, Aswathi Madhavan, Subhavna Juneja, Prasenjit Sen, Jaydeep Bhattacharya

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Type 2 diabetes mellitus (T2DM) is a very complex and multifactorial metabolic disease where the blood sugar level goes up. One of the major consequence of this elevated blood sugar is the formation of AGE (Advance Glycation Endproducts), from a series of chemical or biochemical reactions. AGE are detrimental because it leads to severe pathogenic complications. They are a group of structurally diverse chemical compounds formed from nonenzymatic reactions between the free amino groups (-NH2) of proteins and carbonyl groups (>C=O) of reducing sugars. The reaction is known as Maillard Reaction. It starts with the formation of reversible schiff’s base linkage which after sometime rearranges itself to form Amadori Product along with dicarbonyl compounds. Amadori products are very unstable hence rearrangement goes on until stable products are formed. During the course of the reaction a lot of chemically unknown intermediates and reactive byproducts are formed that can be termed as Early Glycation Products. And when the reaction completes, structurally stable chemical compounds are formed which is termed as Advanced Glycation Endproducts. Though all glycation products have not been characterized well, some fluorescence compounds e.g pentosidine, Malondialdehyde (MDA) or carboxymethyllysine (CML) etc as AGE and α-dicarbonyls or oxoaldehydes such as 3-deoxyglucosone (3-DG) etc as the intermediates have been identified. In this work Gold NanoParticle (GNP) was used as an optical indicator of glycation products. To achieve faster glycation kinetics and high AGE accumulation, fructose was used instead of glucose. Hemoglobin A0 (HbA0) was fructosylated by in-vitro method. AGE formation was measured fluorimetrically by recording emission at 450nm upon excitation at 350nm. Thereafter this fructosylated HbA0 was fractionated by column chromatography. Fractionation separated the proteinaceous substance from the AGEs. Presence of protein part in the fractions was confirmed by measuring the intrinsic protein fluorescence and Bradford reaction. GNPs were synthesized using the templates of chromatographically separated fractions of fructosylated HbA0. Each fractions gave rise to GNPs of varying color, indicating the presence of distinct set of glycation products differing structurally and chemically. Clear solution appeared due to settling down of particles in some vials. The reactive groups of the intermediates kept the GNP formation mechanism on and did not lead to a stable particle formation till Day 10. Whereas SPR of GNP showed monotonous colour for the fractions collected in case of non fructosylated HbA0. Our findings accentuate the use of GNPs as a simple colorimetric sensing platform for the identification of intermediates of glycation reaction which could be implicated in the prognosis of the associated health risk due to T2DM and others.

Keywords: advance glycation endproducts, glycation, gold nano particle, sensor

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Authors: Ofelia Loani Elvir Lazo, Roya Yumul, David Chernobylsky, Omar Durra

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Background: It is crucial to detect the patient’s existing anxiety to assist patients in a perioperative setting which is to be caused by the fear associated with surgical and anesthetic complications. However, the current gold standard for assessing patient anxiety, the STAI, is problematic to use in the preoperative setting, given the duration and concentration required to complete the 40-item questionnaire. Our primary aim in the study is to investigate the correlation of the Yumul Visual Facial Anxiety Scale (VFAS) and Numerical Verbal Rating Scale (NVRS) to State-Trait Anxiety Inventory (STAI) to determine the optimal anxiety scale to use in the perioperative setting. Methods: A clinical study of patients undergoing various surgeries was conducted utilizing each of the preoperative anxiety scales. Inclusion criteria included patients undergoing elective surgeries, while exclusion criteria included patients with anesthesia contraindications, inability to comprehend instructions, impaired judgement, substance abuse history, and those pregnant or lactating. 293 patients were analyzed in terms of demographics, anxiety scale survey results, and anesthesia data via Spearman Coefficients, Chi-Squared Analysis, and Fischer’s exact test utilized for comparative analysis. Results: Statistical analysis showed that VFAS had a higher correlation to STAI than NVRS (rs=0.66, p<0.0001 vs. rs=0.64, p<0.0001). The combined VFAS-Categorization Scores showed the highest correlation with the gold standard (rs=0.72, p<0.0001). Subgroup analysis showed similar results. STAI evaluation time (247.7 ± 54.81 sec) far exceeds VFAS (7.29 ± 1.61 sec), NVRS (7.23 ± 1.60 sec), and Categorization scales (7.29 ± 1.99 sec). Patients preferred VFAS (54.4%), Categorization (11.6%), and NVRS (8.8%). Anesthesiologists preferred VFAS (63.9%), NVRS (22.1%), and Categorization Scales (14.0%). Of note, the top five causes of preoperative anxiety were determined to be waiting (56.5%), pain (42.5%), family concerns (40.5%), no information about surgery (40.1%), or anesthesia (31.6%). Conclusıons: Both VFAS and Categorization tests also take significantly less time than STAI, which is critical in the preoperative setting. Combined VFAS-Categorization Score (VCS) demonstrates the highest correlation to the gold standard, STAI. Among both patients and anesthesiologists, VFAS was the most preferred scale. This forms the basis of the Yumul Faces Anxiety Scale, designed for quick quantization and assessment in the preoperative setting while maintaining a high correlation to the golden standard. Additional studies using the formulated Yumul Faces Anxiety Scale are merited.

Keywords: numerical verbal anxiety scale, preoperative anxiety, state-trait anxiety inventory, visual facial anxiety scale

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Authors: Muhammad Solikhudin Nafi, Wahyu Afif Mufida, Mita Erna Wati, Fitri Setyani Rokim, M. Al-Rizqi Dharma Fauzi

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High dose activity without any pre-exercise will impact Delayed Onset Muscle Soreness (DOMS). DOMS known as delayed pain post-exercise and induce skeletal injury which will decrease athletes’ performances. From now on, post-exercise muscle damage can be detected by measuring skeletal troponin I (sTnI) concentration in serum using ELISA but this method needs more time and cost. To prevent decreased athletes performances, screening need to be done rapidly. We want to introduce our new prototype to detect DOMS acutely. Rapid detection tests are based on immunological reaction between skeletal troponin I antibodies and sTnI in human serum or whole blood. Chemical methods that are used in the manufacture of diagnostic test is lateral flow immunoassay. The material used is rat monoclonal antibody sTnI, colloidal gold, anti-mouse IgG, nitrocellulose membrane, conjugate pad, sample pad, wick and backing card. The procedure are made conjugate (colloidal gold and mAb sTnI) and insert into the conjugate pad, gives spray sTnI mAb and anti-mouse IgG into nitrocellulose membrane, and assemble RDT. RDT had been evaluated by measuring the sensitivity of positive human serum (n = 30) and negative human serum (n = 30). Overall sensitivity value was 93% and specificity value was 90%. ADCOR as the first rapid detection test qualitatively showed antigen-antibody reaction and showed good overall performances for screening of muscle damage. Furthermore, these finding still need more improvements to get best results.

Keywords: DOMS, sTnI, rapid detection test, ELISA

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Authors: Mohamed Farhat O. Hameed, Yasamin K. A. Alrayk, A. A Shaalan, S. S. A. Obayya

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The surface plasmon resonance (SPR) sensors are widely used due to its high sensitivity with molecular labels free. The commercial SPR sensors depend on the conventional prism-coupled configuration. However, this type of configuration suffers from miniaturization and integration. Therefore, the search for compact, portable and highly sensitive SPR sensors becomes mandatory.In this paper, sensitivity enhancement of a novel photonic crystal fiber biosensoris introduced and studied. The suggested design has microstructure of air holes in the core region surrounded by two large semicircular metallized channels filled with the analyte. The inner surfaces of the two channels are coated by a silver layer followed by a gold layer.The simulation results are obtained using full vectorial finite element methodwith perfect matched layer (PML) boundary conditions. The proposed design depends on bimetallic configuration to enhance the biosensor sensitivity. Additionally, the suggested biosensor can be used for multi-channel/multi-analyte sensing. In this study, the sensor geometrical parameters are studied to maximize the sensitivity for the two polarized modes. The numerical results show that high refractive index sensitivity of 4750 nm/RIU (refractive index unit) and 4300 nm/RIU can be achieved for the quasi (transverse magnetic) TM and quasi (transverse electric) TE modes of the proposed biosensor, respectively. The reportedbiosensor has advantages of integration of microfluidics setup, waveguide and metallic layers into a single structure. As a result, compact biosensor with better integration compared to conventional optical fiber SPR biosensors can be obtained.

Keywords: photonic crystal fibers, gold, silver, surface plasmon, biosensor

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Authors: Dmitry Kukushkin

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Lineaments form complex grids on Earth's surface. Currently, one particular object of study for many researchers is the analysis and geological interpretation of maps of lineament density in an attempt to locate various geological structures. But lineament grids are made up of global, regional and local components, and this superimposition of lineament grids of various scales (global, regional, and local) renders this method less effective. Besides, the erosion processes and the erosional resistance of rocks lying on the surface play a significant role in the formation of lineament grids. Therefore, specific lineament density map is characterized by poor contrast (most anomalies do not exceed the average values by more than 30%) and unstable relation with local geological structures. Our method allows to confidently determine the location and boundaries of local geological structures that are likely to contain mineral deposits. Maps of the fields of lineament distortion (residual specific density) created by our method are characterized by high contrast with anomalies exceeding the average by upward of 200%, and stable correlation to local geological structures containing mineral deposits. Our method considers a lineament grid as a general lineaments field – surface manifestation of stress and strain fields of Earth associated with geological structures of global, regional and local scales. Each of these structures has its own field of brittle dislocations that appears on the surface of its lineament field. Our method allows singling out local components by suppressing global and regional components of the general lineaments field. The remaining local lineament field is an indicator of local geological structures.The following are some of the examples of the method application: 1. Srednevilyuiskoye gas condensate field (Yakutia) - a direct proof of the effectiveness of methodology; 2. Structure of Astronomy (Taimyr) - confirmed by the seismic survey; 3. Active gold mine of Kadara (Chita Region) – confirmed by geochemistry; 4. Active gold mine of Davenda (Yakutia) - determined the boundaries of the granite massif that controls mineralization; 5. Object, promising to search for hydrocarbons in the north of Algeria - correlated with the results of geological, geochemical and geophysical surveys. For both Kadara and Davenda, the method demonstrated that the intensive anomalies of the local lineament fields are consistent with the geochemical anomalies and indicate the presence of the gold content at commercial levels. Our method of suppression of global and regional components results in isolating a local lineament field. In early stages of a geological exploration for oil and gas, this allows determining boundaries of various geological structures with very high reliability. Therefore, our method allows optimization of placement of seismic profile and exploratory drilling equipment, and this leads to a reduction of costs of prospecting and exploration of deposits, as well as acceleration of its commissioning.

Keywords: lineaments, mineral exploration, oil and gas, remote sensing

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Authors: Yuxiang Pan, Yong Qiu, Chenlei Gu, Ping Wang

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In the past decade, three-dimensional (3D) tumor cell models have attracted increasing interest in the field of drug screening due to their great advantages in simulating more accurately the heterogeneous tumor behavior in vivo. Drug sensitivity testing based on 3D tumor cell models can provide more reliable in vivo efficacy prediction. The gold standard fluorescence staining is hard to achieve the real-time and label-free monitoring of the viability of 3D tumor cell models. In this study, micro-groove impedance sensor (MGIS) was specially developed for dynamic and non-invasive monitoring of 3D cell viability. 3D tumor cells were trapped in the micro-grooves with opposite gold electrodes for the in-situ impedance measurement. The change of live cell number would cause inversely proportional change to the impedance magnitude of the entire cell/matrigel to construct and reflect the proliferation and apoptosis of 3D cells. It was confirmed that 3D cell viability detected by the MGIS platform is highly consistent with the standard live/dead staining. Furthermore, the accuracy of MGIS platform was demonstrated quantitatively using 3D lung cancer model and sophisticated drug sensitivity testing. In addition, the parameters of micro-groove impedance chip processing and measurement experiments were optimized in details. The results demonstrated that the MGIS and 3D cell-based biosensor and would be a promising platform to improve the efficiency and accuracy of cell-based anti-cancer drug screening in vitro.

Keywords: micro-groove impedance sensor, 3D cell-based biosensors, 3D cell viability, micro-electromechanical systems

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Authors: Nadia El Alami El Hassani, Soukaina Motia, Benachir Bouchikhi, Nezha El Bari

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Doxycycline (DXy) is a cycline antibiotic, most frequently prescribed to treat bacterial infections in veterinary medicine. However, its broad antimicrobial activity and low cost, lead to an intensive use, which can seriously affect human health. Therefore, its spread in the food products has to be monitored. The scope of this work was to synthetize a sensitive and very selective molecularly imprinted polymer (MIP) for DXy detection in honey samples. Firstly, the synthesis of this biosensor was performed by casting a layer of carboxylate polyvinyl chloride (PVC-COOH) on the working surface of a gold screen-printed electrode (Au-SPE) in order to bind covalently the analyte under mild conditions. Secondly, DXy as a template molecule was bounded to the activated carboxylic groups, and the formation of MIP was performed by a biocompatible polymer by the mean of polyacrylamide matrix. Then, DXy was detected by measurements of differential pulse voltammetry (DPV). A non-imprinted polymer (NIP) prepared in the same conditions and without the use of template molecule was also performed. We have noticed that the elaborated biosensor exhibits a high sensitivity and a linear behavior between the regenerated current and the logarithmic concentrations of DXy from 0.1 pg.mL⁻¹ to 1000 pg.mL⁻¹. This technic was successfully applied to determine DXy residues in honey samples with a limit of detection (LOD) of 0.1 pg.mL⁻¹ and an excellent selectivity when compared to the results of oxytetracycline (OXy) as analogous interfering compound. The proposed method is cheap, sensitive, selective, simple, and is applied successfully to detect DXy in honey with the recoveries of 87% and 95%. Considering these advantages, this system provides a further perspective for food quality control in industrial fields.

Keywords: doxycycline, electrochemical sensor, food control, gold nanoparticles, honey, molecular imprinted polymer

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Authors: Marc Evenst Jn Jacques, Sophie Bernard

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Electrical and electronic applications, as well as rechargeable batteries, are common in any economy. They also contain a number of important and valuable metals. It is critical to investigate the impact of these new materials or volume sources on the metal market dynamics. This paper investigates the impact of responsible recycling within the European region on metal price volatility. As far as we know, no empirical studies have been conducted to assess the role of metal recycling in metal market price volatility. The goal of this paper is to test the claim that metal recycling helps to cushion price volatility. A set of circular economy indicators/variables, namely, 1) annual total trade values of recycled metals, 2) annual volume of scrap traded and 3) circular material use rate, and 4) information about recycling, are used to estimate the volatility of monthly spot prices of regular metals. A combination of the GARCH-MIDAS model for mixed frequency data sampling and a simple GARCH (1,1) model for the same frequency variables was adopted to examine the potential links between each variable and price volatility. We discovered that from 2010 to 2019, except for Nickel, scrap consumption (Millions of tons), Scrap Trade Values, and Recycled Material use rate had no significant impact on the price volatility of standard metals (Aluminum, Lead) and precious metals (Gold and Platinum). Worldwide interest in recycling has no impact on returns or volatility. Specific interest in metal recycling did have a link to the mean return equation for Aluminum, Gold and to the volatility equation for lead and Nickel.

Keywords: recycling, circular economy, price volatility, GARCH, mixed data sampling

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Authors: Hongquan Zhang

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Inspired by endogenous protein motors, researchers have constructed various synthetic DNA motors based on the specificity and predictability of Watson-Crick base pairing. However, the application of DNA motors to signal amplification and biosensing is limited because of low mobility and difficulty in real-time monitoring of the walking process. The objective of our work was to construct a new type of DNA motor termed target-triggered DNA motors that can walk for hundreds of steps in response to a single target binding event. To improve the mobility and processivity of DNA motors, we used gold nanoparticles (AuNPs) as scaffolds to build high-density, three-dimensional tracks. Hundreds of track strands are conjugated to a single AuNP. To enable DNA motors to respond to specific protein and nucleic acid targets, we adapted the binding-induced DNA assembly into the design of the target-triggered DNA motors. In response to the binding of specific target molecules, DNA motors are activated to autonomously walk along AuNP, which is powered by a nicking endonuclease or DNAzyme-catalyzed cleavage of track strands. Each moving step restores the fluorescence of a dye molecule, enabling monitoring of the operation of DNA motors in real time. The motors can translate a single binding event into the generation of hundreds of oligonucleotides from a single nanoparticle. The motors have been applied to amplify the detection of proteins and nucleic acids in test tubes and live cells. The motors were able to detect low pM concentrations of specific protein and nucleic acid targets in homogeneous solutions without the need for separation. Target-triggered DNA motors are significant for broadening applications of DNA motors to molecular sensing, cell imagining, molecular interaction monitoring, and controlled delivery and release of therapeutics.

Keywords: biosensing, DNA motors, gold nanoparticles, signal amplification

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Authors: Yuriy A. Knirel

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Enteric bacteria Escherichia coli is the predominant facultative anaerobe of the colonic flora, and some specific serotypes are associated with enteritis, hemorrhagic colitis, and hemolytic uremic syndrome. Shigella spp. are human pathogens that cause diarrhea and bacillary dysentery (shigellosis). They are in effect E. coli with a specific mode of pathogenicity. Strains of Salmonella enterica are responsible for a food-borne infection (salmonellosis), and specific serotypes cause typhoid fever and paratyphoid fever. All these bacteria are closely related in respect to structure and genetics of the lipopolysaccharide, including the O-polysaccharide part (O‑antigen). Being exposed to the bacterial cell surface, the O antigen is subject to intense selection by the host immune system and bacteriophages giving rise to diverse O‑antigen forms and providing the basis for typing of bacteria. The O-antigen forms of many bacteria are unique, but some are structurally and genetically related to others. The sequenced O-antigen gene clusters between conserved galF and gnd genes were analyzed taking into account the O-antigen structures established by us and others for all S. enterica and Shigella and most E. coli O-serogroups. Multiple genetic mechanisms of diversification of the O-antigen forms, such as lateral gene transfer and mutations, were elucidated and are summarized in the present paper. They include acquisition or inactivation of genes for sugar synthesis or transfer or recombination of O-antigen gene clusters or their parts. The data obtained contribute to our understanding of the origins of the O‑antigen diversity, shed light on molecular evolutionary relationships between the O-antigens of enteric bacteria, and open a way for studies of the role of gene polymorphism in pathogenicity.

Keywords: enteric bacteria, O-antigen gene cluster, polysaccharide biosynthesis, polysaccharide structure

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Authors: Eder Amayuelas, Begoña Bazán, M. Karmele Urtiaga, Gotzone Barandika, María I. Arriortua

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Metal Organic Frameworks (MOFs) have attracted great interest in recent years, taking a lead role in the field of catalysis, drug delivery, sensors and absorption. In the past decade, promising results have been reported specifically in the field of adsorption, based on the topology and chemical features of this type of porous material. Thus, its application in industry and environment for the adsorption of pollutants is presented as a response to an increasingly important need. In this area, organic dyes are nowadays widely used in many industries including medicine, textile, leather, printing and plastics. The consequence of this fact is that dyes are present as emerging pollutants in soils and water where they remain for long periods of time due to their high stability, with a potential risk of toxicity in wildlife and in humans. On the other hand, the presence of iodine in soils, water and gas as a nuclear activity pollutant product or its extended use as a germicide is still a problem in many countries, which indicates the imperative need for its removal. In this context, this work presents the characterization as an adsorbent of the activated compound αMOP@Ei2-1 obtained from the already reported [Cu₂₄(m-BDC)₂₄(DMF)₂₀(H₂O)₄]•24DMF•40H₂O (MOP@Ei2-1), where m-BDC is the 1,3-benzenedicarboxylic ligand and DMF is N,N′-dimethylformamide. The structure of MOP@Ei2-1 consists of Cu24 clusters arranged in such a way that 12 paddle-wheels are connected through m-BDC ligands. The clusters exhibit an internal cavity where crystallization molecules of DMF and water are located. Adsorption of dyes and iodine as pollutant examples has been carried out, focusing attention on the kinetics of the rapid process.

Keywords: adsorption, organic dyes, iodine, metal organic frameworks

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Authors: Goksel Ezgi Guzey, Bihrat Onoz

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The scarcity of streamflow gauging stations and the increasing effects of global warming cause designing water management systems to be very difficult. This study is a significant contribution to assessing regional regression models for estimating streamflow. In this study, simulated meteorological data was related to the observed streamflow data from 1971 to 2020 for 33 stream gauging stations of the Euphrates-Tigris Basin. Ordinary least squares regression was used to predict flow for 2020-2100 with the simulated meteorological data. CORDEX- EURO and CORDEX-MENA domains were used with 0.11 and 0.22 grids, respectively, to estimate climate conditions under certain climate scenarios. Twelve meteorological variables simulated by two regional climate models, RCA4 and RegCM4, were used as independent variables in the ordinary least squares regression, where the observed streamflow was the dependent variable. The variability of streamflow was then calculated with 5-6 meteorological variables and watershed characteristics such as area and height prior to the application. Of the regression analysis of 31 stream gauging stations' data, the stations were subjected to a clustering analysis, which grouped the stations in two clusters in terms of their hydrometeorological properties. Two streamflow equations were found for the two clusters of stream gauging stations for every domain and every regional climate model, which increased the efficiency of streamflow estimation by a range of 10-15% for all the models. This study underlines the importance of homogeneity of a region in estimating streamflow not only in terms of the geographical location but also in terms of the meteorological characteristics of that region.

Keywords: hydrology, streamflow estimation, climate change, hydrologic modeling, HBV, hydropower

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Authors: Amgad A. Farghal, Dina I. El Desouki

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Energy consumption and users’ satisfaction were compared in three LEED certified office buildings in turkey and an office building in Egypt. The field studies were conducted in summer 2012. The measured environmental parameters in the four buildings were indoor air temperature, relative humidity, CO2 percentage and light intensity. The traditional building is located in Smart Village in Abu Rawash, Cairo, Egypt. The building was studied for 7 days resulting in 84 responds. The three rated buildings are in Istanbul; Turkey. A Platinum LEED certified office building is owned by BASF and gained a platinum certificate for new construction and major renovation. The building was studied for 3 days resulting in 13 responds. A Gold LEED certified office building is owned by BASF and gained a gold certificate for new construction and major renovation. The building was studied for 2 days resulting in 10 responds. A silver LEED certified office building is owned by Unilever and gained a silver certificate for commercial interiors. The building was studied for 7 days resulting in 84 responds. The results showed that all buildings had no significant difference regarding occupants’ satisfaction with the amount of lighting, noise level, odor and access to the outdoor view. There was significant difference between occupants’ satisfaction in LEED certified buildings and the traditional building regarding the thermal environment and the perception of the general environment (colors, carpet and decoration. The findings suggest that careful design could lead to a certified building that enhances the thermal environment and the perception of the indoor environment leading to energy consumption without scarifying occupants’ satisfaction.

Keywords: energy consumption, occupants’ satisfaction, rating systems, office buildings

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Authors: Shaima A. Al Mansoori

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Eco-cities have become part of the broader and universal discourse and embrace of sustainable communities. Given the ideals and ‘potential’ benefits of eco-cities for people, the environment and prosperity, hardly can an argument be made against the desirability of eco-cities. Yet, this paper posits that it is necessary for urban scholars, technocrats and policy makers to engage in discussions of the pragmatism of implementing the ideals of eco-cities, for example, from the political, budgetary, cultural and other dimensions. In the context of such discourse, this paper examines the feasibility of one of the cardinal principles and goals of eco-cities, which is the reduction or elimination of pollution through various creative and innovative initiatives, in the UAE. This paper contends and argues that, laudable and desirable as this goal is, it is a polylemma and, therefore, overly ambitious and practically unattainable in the UAE. The paper uses the mixed method research strategy, in which data is sourced from secondary and general sources through desktop research, from public records in governmental agencies, and from the conceptual academic and professional literature. Information from these sources will be used, first, to define and review pollution as a concept and multifaceted phenomenon with multidimensional impacts. Second, the paper will use society’s five goal clusters as a framework to identify key causes and impacts of pollution in the UAE. Third, the paper will identify and analyze specific public policies, programs and projects that make pollution in the UAE a polylemma. Fourth, the paper will argue that the phenomenal rates of population increase, urbanization, economic growth, consumerism and development in the UAE make pollution an inevitable product and burden that society must live with. This ‘reality’ makes the goal and desire of pollution-free cities pursuable but unattainable. The paper will conclude by identifying and advocating creative and innovative initiatives that can be taken by the various stakeholders in the country to reduce and mitigate pollution in the short- and long-term.

Keywords: goal clusters, pollution, polylemma, sustainable communities

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Authors: Rekaya A. Shabbir, Marco Mingarelli, Glenn Flux, Ananya Choudhury, Tim A. D. Smith

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Introduction: Heterogeneity of dose distributions across a tumour is problematic for targeted radiotherapy. Gold nanoparticles (AuNPs) enhance dose-distributions of targeted radionuclides. The aim of this study is to demonstrate if tumour dose-distribution of targeted AuNPs radiolabelled with either of two radioisotopes (¹⁷⁷Lu and ⁹⁰Y) in breast cancer cells produced homogeneous dose distributions. Moreover, in vitro and in vivo studies were conducted to study the importance of receptor level on cytotoxicity of EGFR-targeted AuNPs in breast and colorectal cancer cells. Methods: AuNPs were functionalised with DOTA and OPPS-PEG-SVA to optimise labelling with radionuclide tracers and targeting with Erbitux. Radionuclides were chelated with DOTA, and the uptake of the radiolabelled AuNPs and targeted activity in vitro in both cell lines measured using liquid scintillation counting. Cells with medium (HCT8) and high (MDA-MB-468) EGFR expression were incubated with targeted ¹⁷⁷Lu-AuNPs for 4h, then washed and allowed to form colonies. Nude mice bearing tumours were used to study the biodistribution by injecting ¹⁷⁷Lu-AuNPs or ⁹⁰Y-AuNPs via the tail vein. Heterogeneity of dose-distribution in tumours was determined using autoradiography. Results: Colony formation (% control) was 81 ± 4.7% (HCT8) and 32 ± 9% (MDA-MB-468). High uptake was observed in the liver and spleen, indicating hepatobiliary excretion. Imaging showed heterogeneity in dose-distributions for both radionuclides across the tumours. Conclusion: The cytotoxic effect of EGFR-targeted AuNPs is greater in cells with higher EGFR expression. Dose-distributions for individual radiolabelled nanoparticles were heterogeneous across tumours. Further strategies are required to improve the uniformity of dose distribution prior to clinical trials.

Keywords: cancer cells, dose distributions, radionuclide therapy, targeted gold nanoparticles

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Authors: Nir Schreiber, Reuven Cohen, Simi Haber

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The Potts model has been widely explored in the literature for the last few decades. While many analytical and numerical results concern with the traditional two site interaction model in various geometries and dimensions, little is yet known about models where more than two spins simultaneously interact. We consider a ferromagnetic four site interaction Potts model on the square lattice (FFPS), where the four spins reside in the corners of an elementary square. Each spin can take an integer value 1,2,...,q. We write the partition function as a sum over clusters consisting of monochromatic faces. When the number of faces becomes large, tracing out spin configurations is equivalent to enumerating large lattice animals. It is known that the asymptotic number of animals with k faces is governed by λᵏ, with λ ≈ 4.0626. Based on this observation, systems with q < 4 and q > 4 exhibit a second and first order phase transitions, respectively. The transition nature of the q = 4 case is borderline. For any q, a critical giant component (GC) is formed. In the finite order case, GC is simple, while it is fractal when the transition is continuous. Using simple equilibrium arguments, we obtain a (zero order) bound on the transition point. It is claimed that this bound should apply for other lattices as well. Next, taking into account higher order sites contributions, the critical bound becomes tighter. Moreover, for q > 4, if corrections due to contributions from small clusters are negligible in the thermodynamic limit, the improved bound should be exact. The improved bound is used to relate the critical point to the finite correlation length. Our analytical predictions are confirmed by an extensive numerical study of FFPS, using the Wang-Landau method. In particular, the q=4 marginal case is supported by a very ambiguous pseudo-critical finite size behavior.

Keywords: entropic sampling, lattice animals, phase transitions, Potts model

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Authors: Peng Hou

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Natural products produced from marine bacteria serve as an immense reservoir for anti-infective drugs and therapeutic agents. Nowadays, heterologous expression of gene clusters of interests has been widely adopted as an effective strategy for natural product discovery. Briefly, the heterologous expression flowchart would be: biosynthetic gene cluster identification, pathway construction and expression, and product detection. However, gene cluster capture using traditional Transformation-associated recombination (TAR) protocol is low-efficient (0.5% positive colony rate). To make things worse, most of these putative new natural products are only predicted by bioinformatics analysis such as antiSMASH, and their corresponding natural products biosynthetic pathways are either not expressed or expressed at very low levels under laboratory conditions. Those setbacks have inspired us to focus on seeking new technologies to efficiently edit and refractor of biosynthetic gene clusters. Recently, two cutting-edge techniques have attracted our attention - the CRISPR-Cas9 and Gibson Assembly. By now, we have tried to pretreat Brevibacillus laterosporus strain genomic DNA with CRISPR-Cas9 nucleases that specifically generated breaks near the gene cluster of interest. This trial resulted in an increase in the efficiency of gene cluster capture (9%). Moreover, using Gibson Assembly by adding/deleting certain operon and tailoring enzymes regardless of end compatibility, the silent construct (~80kb) has been successfully refactored into an active one, yielded a series of analogs expected. With the appearances of the novel molecular tools, we are confident to believe that development of a high throughput mature pipeline for DNA assembly, transformation, product isolation and identification would no longer be a daydream for marine natural product discovery.

Keywords: biosynthesis, CRISPR-Cas9, DNA assembly, refactor, TAR cloning

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Authors: Getachew Weldemichael, Sentayehu Alamerew, Leta Tulu, Gezahegn Berecha

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Coffee quality improvement program is becoming the focus of coffee research, as the world coffee consumption pattern shifted to high-quality coffee. However, there is limited information on the genetic variation of C. Arabica for quality improvement in potential specialty coffee growing areas of Ethiopia. Therefore, this experiment was conducted with the objectives of determining the magnitude of variation among 105 coffee accessions collected from east Wollega coffee growing areas and assessing correlations between the different coffee qualities attributes. It was conducted in RCRD with three replications. Data on green bean physical characters (shape and make, bean color and odor) and organoleptic cup quality traits (aromatic intensity, aromatic quality, acidity, astringency, bitterness, body, flavor, and overall standard of the liquor) were recorded. Analysis of variance, clustering, genetic divergence, principal component and correlation analysis was performed using SAS software. The result revealed that there were highly significant differences (P<0.01) among the accessions for all quality attributes except for odor and bitterness. Among the tested accessions, EW104 /09, EW101 /09, EW58/09, EW77/09, EW35/09, EW71/09, EW68/09, EW96 /09, EW83/09 and EW72/09 had the highest total coffee quality values (the sum of bean physical and cup quality attributes). These genotypes could serve as a source of genes for green bean physical characters and cup quality improvement in Arabica coffee. Furthermore, cluster analysis grouped the coffee accessions into five clusters with significant inter-cluster distances implying that there is moderate diversity among the accessions and crossing accessions from these divergent inter-clusters would result in hetrosis and recombinants in segregating generations. The principal component analysis revealed that the first three principal components with eigenvalues greater than unity accounted for 83.1% of the total variability due to the variation of nine quality attributes considered for PC analysis, indicating that all quality attributes equally contribute to a grouping of the accessions in different clusters. Organoleptic cup quality attributes showed positive and significant correlations both at the genotypic and phenotypic levels, demonstrating the possibility of simultaneous improvement of the traits. Path coefficient analysis revealed that acidity, flavor, and body had a high positive direct effect on overall cup quality, implying that these traits can be used as indirect criteria to improve overall coffee quality. Therefore, it was concluded that there is considerable variation among the accessions, which need to be properly conserved for future improvement of the coffee quality. However, the variability observed for quality attributes must be further verified using biochemical and molecular analysis.

Keywords: accessions, Coffea arabica, cluster analysis, correlation, principal component

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Authors: Manjula Weerasekera, Chris Sissons, Lisa Wong, Sally Anderson, Ann Holmes, Richard Cannon

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The aim of this study was to characterize bacterial population and yeasts in saliva by Polymerase chain reaction followed by denaturing gradient gel electrophoresis (PCR-DGGE) and measure yeast levels by culture. PCR-DGGE was performed to identify oral bacteria and yeasts in 24 saliva samples. DNA was extracted and used to generate DNA amplicons of the V2–V3 hypervariable region of the bacterial 16S rDNA gene using PCR. Further universal primers targeting the large subunit rDNA gene (25S-28S) of fungi were used to amplify yeasts present in human saliva. Resulting PCR products were subjected to denaturing gradient gel electrophoresis using Universal mutation detection system. DGGE bands were extracted and sequenced using Sanger method. A potential relationship was evaluated between groups of bacteria identified by cluster analysis of DGGE fingerprints with the yeast levels and with their diversity. Significant interpersonal variation of salivary microbiome was observed. Cluster and principal component analysis of the bacterial DGGE patterns yielded three significant major clusters, and outliers. Seventeen of the 24 (71%) saliva samples were yeast positive going up to 10³ cfu/mL. Predominately, C. albicans, and six other species of yeast were detected. The presence, amount and species of yeast showed no clear relationship to the bacterial clusters. Microbial community in saliva showed a significant variation between individuals. A lack of association between yeasts and the bacterial fingerprints in saliva suggests the significant ecological person-specific independence in highly complex oral biofilm systems under normal oral conditions.

Keywords: bacteria, denaturing gradient gel electrophoresis, oral biofilm, yeasts

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Authors: M. Mohan, J. P. Roise, G. P. Catts

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Despite living in an era where conservation zones are de-facto the central element in any sustainable wildlife management strategy, we still find ourselves grappling with several pareto-optimal situations regarding resource allocation and area distribution for the same. In this paper, a multi-objective decision making (MODM) model is presented to answer the question of whether or not we can establish mutual relationships between these contradicting objectives. For our study, we considered a Red-cockaded woodpecker (Picoides borealis) habitat conservation scenario in the coastal plain of North Carolina, USA. Red-cockaded woodpecker (RCW) is a non-migratory territorial bird that excavates cavities in living pine trees for roosting and nesting. The RCW groups nest in an aggregation of cavity trees called ‘cluster’ and for our model we use the number of clusters to be established as a measure of evaluating the size of conservation zone required. The case study is formulated as a linear programming problem and the objective function optimises the Red-cockaded woodpecker clusters, carbon retention rate, biofuel, public safety and Net Present Value (NPV) of the forest. We studied the variation of individual objectives with respect to the amount of area available and plotted a two dimensional dynamic graph after establishing interrelations between the objectives. We further explore the concept of interdependency by integrating the MODM model with GIS, and derive a raster file representing carbon distribution from the existing forest dataset. Model results demonstrate the applicability of interdependency from both linear and spatial perspectives, and suggest that this approach holds immense potential for enhancing environmental investment decision making in future.

Keywords: conservation, interdependency, multi-objective decision making, red-cockaded woodpecker

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Authors: Getiye Dejenu Kibret, Daniel Demant, Andrew Hayen

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Introduction: In Ethiopia, more than half of newborn babies do not have access to Emergency Obstetric and Neonatal Care (EmONC) services. Understanding the effect of distance to health facilities on service use and neonatal survival is crucial to recommend policymakers and improve resource distribution. We aimed to investigate the effect of distance to health services on maternal service use and neonatal mortality. Methods: We implemented a data linkage method based on geographic coordinates and calculated straight-line (Euclidean) distances from the Ethiopian 2016 demographic and health survey clusters to the closest health facility. We computed the distance in ESRI ArcGIS Version 10.3 using the geographic coordinates of DHS clusters and health facilities. Generalised Structural Equation Modelling (GSEM) was used to estimate the effect of distance on neonatal mortality. Results: Poor geographic accessibility to health facilities affects maternal service usage and increases the risk of newborn mortality. For every ten kilometres (km) increase in distance to a health facility, the odds of neonatal mortality increased by 1.33% (95% CI: 1.06% to 1.67%). Distance also negatively affected antenatal care, facility delivery and postnatal counselling service use. Conclusions: A lack of geographical access to health facilities decreases the likelihood of newborns surviving their first month of life and affects health services use during pregnancy and immediately after birth. The study also showed that antenatal care use was positively associated with facility delivery service use and that both positively influenced postnatal care use, demonstrating the interconnectedness of the continuum of care for maternal and neonatal care services. Policymakers can leverage the findings from this study to improve accessibility barriers to health services.

Keywords: acessibility, distance, maternal health service, neonatal mortality

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Authors: Kasra Majbouri Yazdi, Adel Majbouri Yazdi, Saeid Khodayi, Jingyu Hou, Wanlei Zhou, Saeed Saedy

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Fake news and false information are big challenges of all types of media, especially social media. There is a lot of false information, fake likes, views and duplicated accounts as big social networks such as Facebook and Twitter admitted. Most information appearing on social media is doubtful and in some cases misleading. They need to be detected as soon as possible to avoid a negative impact on society. The dimensions of the fake news datasets are growing rapidly, so to obtain a better result of detecting false information with less computation time and complexity, the dimensions need to be reduced. One of the best techniques of reducing data size is using feature selection method. The aim of this technique is to choose a feature subset from the original set to improve the classification performance. In this paper, a feature selection method is proposed with the integration of K-means clustering and Support Vector Machine (SVM) approaches which work in four steps. First, the similarities between all features are calculated. Then, features are divided into several clusters. Next, the final feature set is selected from all clusters, and finally, fake news is classified based on the final feature subset using the SVM method. The proposed method was evaluated by comparing its performance with other state-of-the-art methods on several specific benchmark datasets and the outcome showed a better classification of false information for our work. The detection performance was improved in two aspects. On the one hand, the detection runtime process decreased, and on the other hand, the classification accuracy increased because of the elimination of redundant features and the reduction of datasets dimensions.

Keywords: clustering, fake news detection, feature selection, machine learning, social media, support vector machine

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Authors: Frodouard Minani

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Since last decade, wireless sensor networks (WSNs) have been used in many areas like health care, agriculture, defense, military, disaster hit areas and so on. Wireless Sensor Networks consist of a Base Station (BS) and more number of wireless sensors in order to monitor temperature, pressure, motion in different environment conditions. The key parameter that plays a major role in designing a protocol for Wireless Sensor Networks is energy efficiency which is a scarcest resource of sensor nodes and it determines the lifetime of sensor nodes. Maximizing sensor node’s lifetime is an important issue in the design of applications and protocols for Wireless Sensor Networks. Clustering sensor nodes mechanism is an effective topology control approach for helping to achieve the goal of this research. In this paper, the researcher presents an energy efficiency protocol to prolong the network lifetime based on Energy efficient clustering algorithm. The Low Energy Adaptive Clustering Hierarchy (LEACH) is a routing protocol for clusters which is used to lower the energy consumption and also to improve the lifetime of the Wireless Sensor Networks. Maximizing energy dissipation and network lifetime are important matters in the design of applications and protocols for wireless sensor networks. Proposed system is to maximize the lifetime of the Wireless Sensor Networks by choosing the farthest cluster head (CH) instead of the closest CH and forming the cluster by considering the following parameter metrics such as Node’s density, residual-energy and distance between clusters (inter-cluster distance). In this paper, comparisons between the proposed protocol and comparative protocols in different scenarios have been done and the simulation results showed that the proposed protocol performs well over other comparative protocols in various scenarios.

Keywords: base station, clustering algorithm, energy efficient, sensors, wireless sensor networks

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Authors: M. F. Mamabolo

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Mining activities are identified as the most significant source of heavy metal contamination in river basins, due to inadequate disposal of mining waste thus resulting in acid mine drainage. Waste materials generated from gold mining and processing have severe and widespread impacts on water resources. Therefore, a total of 30 water samples were collected from Fig Tree Creek, Kaapriver, Sheba mine stream & Sauid kaap river to investigate the impact of gold mines on the Kaap River system. Physicochemical parameters (pH, EC and TDS) were taken using a BANTE 900P portable water quality meter. The concentration of Fe, Cu, Co, and SO₄²⁻ in water samples were analysed using Inductively Coupled Plasma-Mass spectrophotometry (ICP-MS) at 0.01 mg/L. The results were compared to the regulatory guideline of the World Health Organization (WHO) and the South Africa National Standards (SANS). It was found that Fe, Cu and Co were below the guideline values while SO₄²⁻ detected in Sheba mine stream exceeded the 250 mg/L limit for both seasons, attributed by mine wastewater. SO₄²⁻ was higher in wet season due to high evaporation rates and greater interaction between rocks and water. The pH of all the streams was within the limit (≥5 to ≤9.7), however EC of the Sheba mine stream, Suid Kaap River & where the tributary connects with the Fig Tree Creek exceeded 1700 uS/m, due to dissolved material. The TDS of Sheba mine stream exceeded 1000 mg/L, attributed by high SO₄²⁻ concentration. While the tributary connecting to the Fig Tree Creek exceed the value due to pollution from household waste, runoff from agriculture etc. In conclusion, the water from all sampled streams were safe for consumption due to low concentrations of physicochemical parameters. However, elevated concentration of SO₄²⁻ should be monitored and managed to avoid water quality deterioration in the Kaap River system.

Keywords: Kaap river system, mines, heavy metals, sulphate

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Authors: Jaehong Yu, Seoung Bum Kim

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Clustering analysis can facilitate the extraction of intrinsic patterns in a dataset and reveal its natural groupings without requiring class information. For effective clustering analysis in high dimensional datasets, unsupervised dimensionality reduction is an important task. Unsupervised dimensionality reduction can generally be achieved by feature extraction or feature selection. In many situations, feature selection methods are more appropriate than feature extraction methods because of their clear interpretation with respect to the original features. The unsupervised feature selection can be categorized as feature subset selection and feature ranking method, and we focused on unsupervised feature ranking methods which evaluate the features based on their importance scores. Recently, several unsupervised feature ranking methods were developed based on ensemble approaches to achieve their higher accuracy and stability. However, most of the ensemble-based feature ranking methods require the true number of clusters. Furthermore, these algorithms evaluate the feature importance depending on the ensemble clustering solution, and they produce undesirable evaluation results if the clustering solutions are inaccurate. To address these limitations, we proposed an ensemble-based feature ranking method with random subspace and multiple-k ensemble (FRRM). The proposed FRRM algorithm evaluates the importance of each feature with the random subspace ensemble, and all evaluation results are combined with the ensemble importance scores. Moreover, FRRM does not require the determination of the true number of clusters in advance through the use of the multiple-k ensemble idea. Experiments on various benchmark datasets were conducted to examine the properties of the proposed FRRM algorithm and to compare its performance with that of existing feature ranking methods. The experimental results demonstrated that the proposed FRRM outperformed the competitors.

Keywords: clustering analysis, multiple-k ensemble, random subspace-based feature evaluation, unsupervised feature ranking

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Authors: Zhiguo Yang, Xiangan Yue, Minglu Shao, Yue Yang, Rongjie Yan

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It is difficult to realize deep profile control because of the small pore-throats and easy water channeling in low-permeability heterogeneous reservoir, and the traditional polymer microspheres have the contradiction between injection and plugging. In order to solve this contradiction, the controllable self-aggregating colloidal particles (CSA) containing amide groups on the surface of microspheres was prepared based on emulsion polymerization of styrene and acrylamide. The dispersed solution of CSA colloidal particles, whose particle size is much smaller than the diameter of pore-throats, was injected into the reservoir. When the microspheres migrated to the deep part of reservoir, , these CSA colloidal particles could automatically self-aggregate into large particle clusters under the action of the shielding agent and the control agent, so as to realize the plugging of the water channels. In this paper, the morphology, temperature resistance and self-aggregation properties of CSA microspheres were studied by transmission electron microscopy (TEM) and bottle test. The results showed that CSA microspheres exhibited heterogeneous core-shell structure, good dispersion, and outstanding thermal stability. The microspheres remain regular and uniform spheres at 100℃ after aging for 35 days. With the increase of the concentration of the cations, the self-aggregation time of CSA was gradually shortened, and the influence of bivalent cations was greater than that of monovalent cations. Core flooding experiments showed that CSA polymer microspheres have good injection properties, CSA particle clusters can effective plug the water channels and migrate to the deep part of the reservoir for profile control.

Keywords: heterogeneous reservoir, deep profile control, emulsion polymerization, colloidal particles, plugging characteristic

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Authors: Shahed Vahedi, Mohd Salmi Md Noorani

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This paper investigates cluster synchronization phenomena between community networks. We focus on the situation where a variety of dynamics occur in the clusters. In particular, we show that different synchronization states simultaneously occur between the networks. The controller is designed having an adaptive control gain, and theoretical results are derived via Lyapunov stability. Simulations on well-known dynamical systems are provided to elucidate our results.

Keywords: cluster synchronization, adaptive control, community network, simulation

Procedia PDF Downloads 453