Search results for: endothermic reaction

Authors: Sonam Chorol, Sharvan Kumar, Pritam Mukhopadhyay

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In biology, supramolecular systems require the use of chemical fuels to stay in sustained nonequilibrium steady states termed dissipative self-assembly in contrast to synthetic self-assembly. Biomimicking these natural dynamic systems, some studies have demonstrated artificial self-assembly under nonequilibrium utilizing various forms of energies (fuel) such as chemical, redox, and pH. Naphthalene diimides (NDIs) are well-known organic molecules in supramolecular architectures with high electron affinity and have applications in controlled electron transfer (ET) reactions, etc. Herein, we report the endergonic ET from tetraphenylborate to highly electron-deficient phosphonium NDI²+ dication to generate NDI•+ radical. The formation of radicals was confirmed by UV-Vis-NIR absorption spectroscopy. Electron-donor and electron-acceptor energy levels were calculated from experimental electrochemistry and theoretical DFT analysis. The HOMO of the electron donor locates below the LUMO of the electro-acceptor. This indicates that electron transfer is endergonic (ΔE°ET = negative). The endergonic ET from NaBPh₄ to NDI²+ dication was achieved thermodynamically by the formation of coupled biphenyl product confirmed by GC-MS analysis. NDI molecule bearing octyl phosphonium at the core and H-bond forming imide moieties at the axial position forms a gel. The rheological properties of purified radical ion NDI⦁+ gels were evaluated. The atomic force microscopy studies reveal the formation of large branching-type networks with a maximum height of 70-80 nm. The endergonic ET from NaBPh₄ to NDI²+ dication was used to design the assembly and disassembly redox reaction cycle using reducing (NaBPh₄) and oxidizing agents (Br₂) as chemical fuels. A part of NaBPh₄ is used to drive assembly, while a fraction of the NaBPh₄ is dissipated by forming a useful product. The system goes back to the disassembled NDI²+ dication state with the addition of Br₂. We think bioinspired dissipative self-assembly is the best approach to developing future lifelike materials with autonomous behavior.

Keywords: Ionic-gel, redox-cycle, self-assembly, useful product

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Authors: A. Pascual Ramsay

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Accounts of the management of the economic and euro crisis in Spain have been dominated by an emphasis on external constraints. However, this approach leaves unanswered important questions about the role of domestic political factors. Using systematic qualitative primary research and employing elite interviewing and process tracing, this paper aims to fill this gap for the period of the Partido Socialista Obrero Español (PSOE) administration. The paper shows that domestic politics played a crucial role in the management of the crisis, most importantly by determining the shape of the measures undertaken. In its three distinct stages – downplaying/inaction, reaction/stimulus, and austerity/reform – the PSOE's response was certainly constrained by external factors, most notably EMU membership and the actions of sovereign-bond investors, the ECB and Germany. Yet while these external constraints forced the government to act, domestic political factors fundamentally shaped the content of key measures: the fiscal stimulus, the labour, financial and pension reforms, the refusal to accept a bailout or the reform of the Constitution. Seven factors were particularly influential: i) electoral and political cost, ii) party and partisanship, iii) organised interests, iv) domestic institutions, v) ideological preferences, vi) ineffective decision-making, and vii) judgement and personal characteristics of decision-makers. In conclusion, domestic politics played an important role in the management of the crisis, a role that has been underestimated by dominant approaches focusing on external constraints and weak domestic policy autonomy. The findings provide empirical evidence to support research agendas that identify significant state discretion in the face of international economic integration and an important role for domestic political factors such as institutions, material interests, partisanship and ideology in shaping economic outcomes.

Keywords: economic crisis, Euro, PSOE, Spain

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Authors: Maryam Ghareh Chaei, Masuzyo Chilwesa, Ali Akbarnezhad, Arnaud Castel, Redmond Lloyd, Stephen Foster

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Cement hydration is an exothermic chemical reaction generally leading to a rise in concrete’s temperature. This internal heating of concrete may, in turn, lead to a temperature difference between the hotter interior and the cooler exterior of concrete and thus differential thermal stresses in early ages which could be particularly significant in mass concrete. Such differential thermal stresses result in early age thermal cracking of concrete when exceeding the concrete’s tensile strength. The extent of temperature rise and thus early age differential thermal stresses is generally a function of hydration heat intensity, thermal properties of concrete and size of the concrete element. Both hydration heat intensity and thermal properties of concrete may vary considerably with variations in the type cementitious materials and other constituents. With this in mind, partial replacement of cement with supplementary cementitious materials including fly ash and ground granulated blast furnace slag has been investigated widely as an effective strategy to moderate the heat generation rate and thus reduce the risk of early age thermal cracking of concrete. However, there is currently a lack of adequate literature on effect of partial replacement of cement with fly ash and/or ground granulated blast furnace slag on the thermal properties of concrete. This paper presents the results of an experimental conducted to evaluate the effect of addition of varying percentages of fly ash (up to 60%) and ground granulated blast furnace slag (up to 50%) on the heat capacity and thermal conductivity of early age cement paste. The water to cementitious materials ratio is kept 0.45 for all the paste samples. The results of the experimental studies were used in a numerical analysis performed using Comsol Multiphysics to highlight the effects of variations in the thermal properties of concrete, due to variations in the type of aggregate and content of supplemenraty cementitious materials, on the risk of early age cracking of a concrete raft.

Keywords: thermal diffusivity, early age thermal cracking, concrete, supplementary cementitious materials

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Authors: Amatulraheem Al-Abassi, K. Khanafer, Ibrahim Deiab

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The coronary artery stent is a promising technology that can treat various coronary diseases. Materials used for manufacturing medical stents should have high biocompatible properties. Stent alloys, in particular, are remarkably promising good clinical outcomes, however, there is threaten of restenosis (reoccurring of artery narrowing due to fatty plaque), stent recoiling, or in long-term the occurrence of stent fracture. However, stents that are made of Nickel-titanium (Nitinol) can bare extensive plastic deformation and resist restenosis. This shape memory alloy has outstanding mechanical properties. Nitinol is a unique shape memory alloy as it has unique mechanical properties such as; biocompatibility, super-elasticity, and recovery to original shape under certain loads. Stent failure may cause complications in vascular diseases and possibly blockage of blood flow. Thus, studying the behaviors of the stent under different medical conditions will help the doctors and cardiologists to predict when it is necessary to change the stent in order to prevent any severe morbidity outcomes. To the best of our knowledge, there are limited published papers that analyze the stent behavior with regards to the contact surfaces of plaque layer and blood vessel. Thus, stent material properties will be discussed in this investigation to highlight the mechanical and clinical differences between various stents. This research analyzes the performance of Nitinol stent in well-known stent design to determine its bearing with stress and its dislocation in blood vessels, in comparison to stents made of different biocompatible materials. In addition, a study of its performance will be represented in the system. Finite Element Analysis is the core of this study. Thus, a physical representative model will be discussed to show the distribution of stress and strain along the interaction surface between the stent and the artery. The reaction of vascular tissue to the stent will be evaluated to predict the possibility of restenosis within the treated area.

Keywords: shape memory alloy, stent, coronary artery, finite element analysis

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Authors: Kinga Mylkie, Pawel Nowak, Marta Z. Borowska

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The most important proteins in human serum responsible for drug binding are human serum albumin (HSA) and α1-acid glycoprotein (AGP). The AGP molecule is a glycoconjugate containing a single polypeptide chain composed of 183 amino acids (the core of the protein), and five glycan branched chains (sugar part) covalently linked by an N-glycosidic bond with aspartyl residues (Asp(N) -15, -38, -54, -75, - 85) of polypeptide chain. This protein plays an important role in binding alkaline drugs, a large group of drugs used in psychiatry, some acid drugs (e.g., coumarin anticoagulants), and neutral drugs (steroid hormones). The main goal of the research was to obtain magnetic nanoparticles coated with biopolymers in a chemically modified form, which will have highly reactive functional groups able to effectively immobilize the glycoprotein (acid α1-glycoprotein) without losing the ability to bind active substances. The first phase of the project involved the chemical modification of biopolymer starch. Modification of starch was carried out by methods of organic synthesis, leading to the preparation of a polymer enriched on its surface with aldehyde groups, which in the next step was coupled with 3-aminophenylboronic acid. Magnetite nanoparticles coated with starch were prepared by in situ co-precipitation and then oxidized with a 1 M sodium periodate solution to form a dialdehyde starch coating. Afterward, the reaction between the magnetite nanoparticles coated with dialdehyde starch and 3-aminophenylboronic acid was carried out. The obtained materials consist of a magnetite core surrounded by a layer of modified polymer, which contains on its surface dihydroxyboryl groups of boronic acids which are capable of binding glycoproteins. Magnetic nanoparticles obtained as carriers for plasma protein immobilization were fully characterized by ATR-FTIR, TEM, SEM, and DLS. The glycoprotein was immobilized on the obtained nanoparticles. The amount of mobilized protein was determined by the Bradford method.

Keywords: glycoproteins, immobilization, magnetic nanoparticles, polysaccharides

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Authors: V. P. Muhamed Shajudheen, K. Viswanathan, K. Anitha Rani, A. Uma Maheswari, S. Saravana Kumar

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In this paper, a simple chemical precipitation route for the preparation of titanium dioxide nanoparticles, synthesized by using titanium tetra isopropoxide as a precursor and polyvinyl pyrrolidone (PVP) as a capping agent, is reported. The Differential Scanning Calorimetry (DSC) and Thermo Gravimetric Analysis (TGA) of the samples were recorded and the phase transformation temperature of titanium hydroxide, Ti(OH)₄ to titanium oxide, TiO₂ was investigated. The as-prepared Ti(OH)₄ precipitate was annealed at 800°C to obtain TiO₂ nanoparticles. The thermal, structural, morphological and textural characterizations of the TiO₂ nanoparticle samples were carried out by different techniques such as DSC-TGA, X-Ray Diffraction (XRD), Fourier Transform Infra-Red spectroscopy (FTIR), Micro Raman spectroscopy, UV-Visible absorption spectroscopy (UV-Vis), Photoluminescence spectroscopy (PL) and Field Effect Scanning Electron Microscopy (FESEM) techniques. The as-prepared precipitate was characterized using DSC-TGA and confirmed the mass loss of around 30%. XRD results exhibited no diffraction peaks attributable to anatase phase, for the reaction products, after the solvent removal. The results indicate that the product is purely rutile. The vibrational frequencies of two main absorption bands of prepared samples are discussed from the results of the FTIR analysis. The formation of nanosphere of diameter of the order of 10 nm, has been confirmed by FESEM. The optical band gap was found by using UV-Visible spectrum. From photoluminescence spectra, a strong emission was observed. The obtained results suggest that this method provides a simple, efficient and versatile technique for preparing TiO₂ nanoparticles and it has the potential to be applied to other systems for photocatalytic activity.

Keywords: TiO2 nanoparticles, chemical precipitation route, phase transition, Fourier Transform Infra-Red spectroscopy (FTIR), micro-Raman spectroscopy, UV-Visible absorption spectroscopy (UV-Vis), Photoluminescence Spectroscopy (PL) and Field Effect Scanning electron microscopy (FESEM)

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Authors: Annika Stechemesser, Rachel Pounds, Emma Lucas, Chris Dawson, Julia Lipecki, Pavle Vrljicak, Jan Brosens, Sean Kehoe, Jason Yap, Lawrence Young, Sascha Ott

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Advances in technology make it now possible to retrieve the genetic information of thousands of single cancerous cells. One of the key challenges in single cell analysis of cancerous tissue is to determine the number of different cell types and their characteristic genes within the sample to better understand the tumors and their reaction to different treatments. For this analysis to be possible, it is crucial to filter out background noise as it can severely blur the downstream analysis and give misleading results. In-depth analysis of the state-of-the-art filtering methods for single cell data showed that they do, in some cases, not separate noisy and normal cells sufficiently. We introduced an algorithm that filters and clusters single cell data simultaneously without relying on certain genes or thresholds chosen by eye. It detects communities in a Shared Nearest Neighbor similarity network, which captures the similarities and dissimilarities of the cells by optimizing the modularity and then identifies and removes vertices with a weak clustering belonging. This strategy is based on the fact that noisy data instances are very likely to be similar to true cell types but do not match any of these wells. Once the clustering is complete, we apply a set of evaluation metrics on the cluster level and accept or reject clusters based on the outcome. The performance of our algorithm was tested on three datasets and led to convincing results. We were able to replicate the results on a Peripheral Blood Mononuclear Cells dataset. Furthermore, we applied the algorithm to two samples of ovarian cancer from the same patient before and after chemotherapy. Comparing the standard approach to our algorithm, we found a hidden cell type in the ovarian postchemotherapy data with interesting marker genes that are potentially relevant for medical research.

Keywords: cancer research, graph theory, machine learning, single cell analysis

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Authors: Mohammed Alasel, Michael Keusgen

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Gold is a noble metal; in its nano-scale level (e.g. spherical nanoparticles), the conduction electrons are triggered to collectively oscillate with a resonant frequency when certain wavelengths of electromagnetic radiation interact with its surface; this phenomenon is known as surface plasmon resonance (SPR). SPR is responsible for giving the gold nanoparticles its intense red color depending mainly on its size, shape and distance between nanoparticles. A decreased distance between gold nanoparticles results in aggregation of them causing a change in color from red to blue. This aggregation enables gold nanoparticles to serve as a sensitive biosensoric indicator. In the proposed work, gold nanoparticles were modified with two proteins: i) Borrelia antigen, variable lipoprotein surface-exposed protein (VlsE), and ii) protein A. VlsE antigen induces a strong antibody response against Lyme disease and can be detected from early to late phase during the disease in humans infected with Borrelia. In addition, it shows low cross-reaction with the other non-pathogenic Borrelia strains. The high specificity of VlsE antigen to anti-Borrelia antibodies, combined simultaneously with the high specificity of protein A to the Fc region of all IgG human antibodies, was utilized to develop a rapid test for serological point of care diagnosis of borreliosis in human serum. Only in the presence of anti-Borrelia antibodies in the serum probe, an aggregation of gold nanoparticles can be observed, which is visible by a concentration-dependent colour shift from red (low IgG) to blue (high IgG). Experiments showed it is clearly possible to distinguish between positive and negative sera samples using a simple suspension of the two-protein modified gold nanoparticles in a very short time (30 minutes). The proposed work showed the potential of using such modified gold nanoparticles generally for serological diagnosis. Improved specificity and reduced assay time can be archived in applying increased salt concentrations combined with decreased pH values (pH 5).

Keywords: gold nanoparticles, gold aggregation, serological diagnosis, protein A, lyme borreliosis

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Authors: Manish Chand, Subhrojit Bagchi, R. Kumar

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A new dry tube (DT) has been installed in the tank of KAMINI research reactor, Kalpakkam India. This tube will be used for neutron activation analysis of small to large samples and testing of neutron detectors. DT tube is 375 cm height and 7.5 cm in diameter, located 35 cm away from the core centre. The experimental thermal flux at various axial positions inside the tube has been measured by irradiating the flux monitor (¹⁹⁷Au) at 20kW reactor power. The measured activity of ¹⁹⁸Au and the thermal cross section of ¹⁹⁷Au (n,γ) ¹⁹⁸Au reaction were used for experimental thermal flux measurement. The flux inside the tube varies from 10⁹ to 10¹⁰ and maximum flux was (1.02 ± 0.023) x10¹⁰ n cm⁻²s⁻¹ at 36 cm from the bottom of the tube. The Au and Zr foils without and with cadmium cover of 1-mm thickness were irradiated at the maximum flux position in the DT to find out the irradiation specific input parameters like sub-cadmium to epithermal neutron flux ratio (f) and the epithermal neutron flux shape factor (α). The f value was 143 ± 5, indicates about 99.3% thermal neutron component and α value was -0.2886 ± 0.0125, indicates hard epithermal neutron spectrum due to insufficient moderation. The measured flux profile has been validated using theoretical model of KAMINI reactor through Monte Carlo N-Particle Code (MCNP). In MCNP, the complex geometry of the entire reactor is modelled in 3D, ensuring minimum approximations for all the components. Continuous energy cross-section data from ENDF-B/VII.1 as well as S (α, β) thermal neutron scattering functions are considered. The neutron flux has been estimated at the corresponding axial locations of the DT using mesh tally. The thermal flux obtained from the experiment shows good agreement with the theoretically predicted values by MCNP, it was within ± 10%. It can be concluded that this MCNP model can be utilized for calculating other important parameters like neutron spectra, dose rate, etc. and multi elemental analysis can be carried out by irradiating the sample at maximum flux position using measured f and α parameters by k₀-NAA standardization.

Keywords: neutron flux, neutron activation analysis, neutron flux shape factor, MCNP, Monte Carlo N-Particle Code

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Authors: Denis Mustafov, Emmanouil Karteris, Maria Braoudaki

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Glioblastoma multiform (GBM) is a heterogenous primary brain tumour that kills most affected patients. To the authors best knowledge, despite all research efforts there is no early diagnostic biomarker for GBM. MicroRNAs (miRNAs) are short non-coding RNA molecules which are deregulated in many cancers. The aim of this research was to determine miRNAs with a diagnostic impact and to potentially identify promising therapeutic targets for glioblastoma multiform. In silico analysis was performed to identify deregulated miRNAs with diagnostic relevance for glioblastoma. The expression profiles of the chosen miRNAs were then validated in vitro in the human glioblastoma cell lines A172 and U-87MG. Briefly, RNA extraction was carried out using the Trizol method, whilst miRNA extraction was performed using the mirVANA miRNA isolation kit. Quantitative Real-Time Polymerase Chain Reaction was performed to verify their expression. The presence of five target proteins within the A172 cell line was evaluated by Western blotting. The expression of the CORO1C protein within 32 GBM cases was examined via immunohistochemistry. The miRNAs identified in silico included miR-21-5p, miR-34a and miR-128a. These miRNAs were shown to target deregulated GBM genes, such as CDK6, E2F3, BMI1, JAG1, and CORO1C. miR-34a and miR-128a showed low expression profiles in comparison to a control miR-RNU-44 in both GBM cell lines suggesting tumour suppressor properties. Opposing, miR-21-5p demonstrated greater expression indicating that it could potentially function as an oncomiR. Western blotting revealed expression of all five proteins within the A172 cell line. In silico analysis also suggested that CORO1C is a target of miR-128a and miR-34a. Immunohistochemistry demonstrated that 75% of the GBM cases showed moderate to high expression of CORO1C protein. Greater understanding of the deregulated expression of miR-128a and the upregulation of CORO1C in GBM could potentially lead to the identification of a promising diagnostic biomarker signature for glioblastomas.

Keywords: non-coding RNAs, gene expression, brain tumours, immunohistochemistry

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Authors: Ploenpit Boochathum, Pitchayanad Kaolim, Phimjutha Srisangkaew

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In general, rubber foam is produced based on the sulfur curing system. However, the remaining sulfur in the rubber product waste is burned to sulfur dioxide gas causing the environment pollution. To avoid using sulfur as curing agent in the rubber foam products, this research work proposes non-sulfur curing system by using corn starch as a curing agent. The ether crosslinks were proposed to be produced via the functional bonding between hydroxyl groups of the starch molecules and chloroacetate groups added on the natural rubber molecules. The chloroacetated natural rubber (CNR) latex was prepared via the epoxidation reaction of the concentrated natural rubber latex, subsequently, epoxy rings were attacked by chloroacetic acid to produce hydroxyl groups and chloroacetate groups on the rubber molecules. Foaming agent namely NaHCO3 was selected to add in the CNR latex due to the low decomposition temperature at about 50°C. The appropriate curing temperature was assigned to be 90°C that is above gelatinization temperature; 60-70°C, of starch. The effect of weight ratio of starch, i.e., 0 phr, 3 phr and 5 phr, on the physical properties of CNR rubber foam was investigated. It was found that density reduced from 0.81 g/cm3 for 0 phr to 0.75 g/cm3 for 3 phr and 0.79 g/cm3 for 5 phr. The ability to return to its original thickness after prolonged compressive stresses of CNR rubber foam cured with starch loading of 5 phr was found to be considerably better than that of CNR rubber foam cured with starch 3 phr and CNR rubber foam without addition of starch according to the compression set that was determined to decrease from 66.67% to 40% and 26.67% with the increase loading of starch. The mechanical properties including tensile strength and modulus of CNR rubber foams cured using starch were determined to increase except that the elongation at break was found to decrease. In addition, all mechanical properties of CNR rubber foams cured with the starch 3 phr and 5 phr were found to be slightly different and drastically higher than those of CNR rubber foam without the addition of starch. This research work indicates that starch can be applicable as a curing agent for CNR rubber. This is confirmed by the increase of the elastic modulus (G') of CNR rubber foams that was cured with the starch over the CNR rubber foam without curing agent. This type of rubber foam is believed to be one of the biodegradable and environment-friendly product that can be cured at low temperature of 90°C.

Keywords: chloroacetated natural rubber, corn starch, non-sulfur curing system, rubber foam

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Authors: Nur Syahidatul Idany Abdul Ghani, Rahizar Ramli, Jamilah Mohamad, Ahmad Saifizul, Mohamed Rehan Karim

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Increasing fatalities in road accidents in Malaysia over the last 10 years are quite alarming. Based on Malaysian Institute of Road Safety Research (Miros) latest research ‘Predicting Malaysian Road Fatalities for year 2020; it is predicted that road fatalities in Malaysia for 2015 is 8,780 and 10,716 for the year 2020 which 30 percent of fatalities were caused by accidents involving commercial vehicles. Government, related agencies and NGOs have continuously and persistently work to reduce the statistics through enforcement, educating the public, training to drivers, road safety campaigns, advertisements etc. However, the trend of casualties does not show encouraging pattern but instead, steadily growing. Thus, this comparative study reviews the literature pertaining on method of measurement used to evaluate commercial drivers competency. In several studies driving competency has been assessed with different assessment based on the license procedures and requirements according to the country regulation. The assessment criteria that has been establish for commercial drivers generally focus on driving tasks and assessment e.g. theory test, medical test and road assessment rather than driving competency test or physical test. Realizing the importance of specific assessment test for drivers competency this comparative study reviews the most discussed literature related to competency assessment method to identify competency of the drivers include (1. judgement and reaction, 2. skill of drivers, 3. experiences and fatigue). The concluding analysis of this paper is a comparative table for assessment methodology to access driver’s competency. A comparative study is a further discussion reviewing past literature to provide an overview on existing assessment test and potential subject matters that can be identified for further studies to increase awareness of the drivers, passengers as well as the authorities about the importance of competent drivers in order to improve safety in commercial vehicles.

Keywords: commercial vehicles, driver’s competency, specific assessment

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Authors: Elias L. Souza, Noeli Sellin, Cintia Marangoni, Ozair Souza

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Among the different forms of reuse and recovery of agro-residual waste is the production of biofuels. The production of second-generation ethanol has been evaluated and proposed as one of the technically viable alternatives for this purpose. This research work employed the banana pseudostem as biomass. Two different chemical pre-treatment methods (acid hydrolisis with H2SO4 2% w/w and alkaline hydrolysis with NaOH 3% w/w) of dry and milled biomass (70 g/L of dry matter, ms) were assessed, and the corresponding reducing sugars yield, AR, (YAR), after enzymatic saccharification, were determined. The effect on YAR by increasing the dry matter (ms) from 70 to 100 g/L, in dry and milled biomass and also fresh, were analyzed. Changes in cellulose crystallinity and in biomass surface morphology due to the different chemical pre-treatments were analyzed by X-ray diffraction and scanning electron microscopy. The acid pre-treatment resulted in higher YAR values, whether related to the cellulose content under saccharification (RAR = 79,48) or to the biomass concentration employed (YAR/ms = 32,8%). In a comparison between alkaline and acid pre-treatments, the latter led to an increase in the cellulose content of the reaction mixture from 52,8 to 59,8%; also, to a reduction of the cellulose crystallinity index from 51,19 to 33,34% and increases in RAR (43,1%) and YAR/ms (39,5%). The increase of dry matter (ms) bran from 70 to 100 g/L in the acid pre-treatment, resulted in a decrease of average yields in RAR (43,1%) and YAR/ms (18,2%). Using the pseudostem fresh with broth removed, whether for 70 g/L concentration or 100 g/L in dry matter (ms), similarly to the alkaline pre-treatment, has led to lower average values in RAR (67,2% and 42,2%) and in YAR/ms (28,4% e 17,8%), respectively. The acid pre-treated and saccharificated biomass broth was detoxificated with different activated carbon contents (1,2 and 4% w/v), concentrated up to AR = 100 g/L and fermented by Saccharomyces cerevisiae. The yield values (YP/AR) and productivity (QP) in ethanol were determined and compared to those values obtained from the fermentation of non-concentrated/non-detoxificated broth (AR = 18 g/L) and concentrated/non-detoxificated broth (AR = 100 g/L). The highest average value for YP/AR (0,46 g/g) was obtained from the fermentation of non-concentrated broth. This value did not present a significant difference (p<0,05) when compared to the YP/RS related to the broth concentrated and detoxificated by activated carbon 1% w/v (YP/AR = 0,41 g/g). However, a higher ethanol productivity (QP = 1,44 g/L.h) was achieved through broth detoxification. This value was 75% higher than the average QP determined using concentrated and non-detoxificated broth (QP = 0,82 g/L.h), and 22% higher than the QP found in the non-concentrated broth (QP = 1,18 g/L.h).

Keywords: biofuels, biomass, saccharification, bioethanol

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Authors: R. Sekula

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Epoxy composites are broadly used as an electrical insulation for the high voltage applications since only such materials can fulfill particular mechanical, thermal, and dielectric requirements. However, properties of the final product are strongly dependent on proper manufacturing process with minimized material failures, as too large shrinkage, voids and cracks. Therefore, application of proper materials (epoxy, hardener, and filler) and process parameters (mold temperature, filling time, filling velocity, initial temperature of internal parts, gelation time), as well as design and geometric parameters are essential features for final quality of the produced components. In this paper, an approach for three-dimensional modeling of all molding stages, namely filling, curing and post-curing is presented. The reactive molding simulation tool is based on a commercial CFD package, and include dedicated models describing viscosity and reaction kinetics that have been successfully implemented to simulate the reactive nature of the system with exothermic effect. Also a dedicated simulation procedure for stress and shrinkage calculations, as well as simulation results are presented in the paper. Second part of the paper is dedicated to recent developments on formulations of functional composites for electrical insulation applications, focusing on thermally conductive materials. Concepts based on filler modifications for epoxy electrical composites have been presented, including the results of the obtained properties. Finally, having in mind tough environmental regulations, in addition to current process and design aspects, an approach for product re-design has been presented focusing on replacement of epoxy material with the thermoplastic one. Such “design-for-recycling” method is one of new directions associated with development of new material and processing concepts of electrical products and brings a lot of additional research challenges. For that, one of the successful products has been presented to illustrate the presented methodology.

Keywords: curing, epoxy insulation, numerical simulations, recycling

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Authors: Krasimira N. Zhilkova, Mariya K. Kyulavska, Roza P. Mateva

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The anionic polymerization of -caprolactam (CL) with bifunctional activators has been extensively studied as an effective and beneficial method of improving chemical and impact resistances, elasticity and other mechanical properties of polyamide (PA6). In presence of activators or macroactivators (MAs) also called polymeric activators (PACs) the anionic polymerization of lactams proceeds rapidly at a temperature range of 130-180C, well below the melting point of PA-6 (220C) permitting thus the direct manufacturing of copolymer product together with desired modifications of polyamide properties. Copolymers of PA6 with an elastic polypropylene glycol (PPG) middle block into main chain were successfully synthesized via activated anionic ring opening polymerization (ROP) of CL. Using novel PACs based on PPG polyols (with differ molecular weight) the anionic ROP of CL was realized and investigated in the presence of a basic initiator sodium salt of CL (NaCL). The PACs were synthesized as N-carbamoyllactam derivatives of hydroxyl terminated PPG functionalized with isophorone diisocyanate [IPh, 5-Isocyanato-1-(isocyanatomethyl)-1,3,3-trimethylcyclohexane] and blocked then with CL units via an addition reaction. The block copolymers were analyzed and proved with 1H-NMR and FT-IR spectroscopy. The influence of the CL/PACs ratio in feed, the length of the PPG segments and polymerization conditions on the kinetics of anionic ROP, on average molecular weight, and on the structure of the obtained block copolymers were investigated. The structure and phase behaviour of the copolymers were explored with differential scanning calorimetry, wide-angle X-ray diffraction, thermogravimetric analysis and dynamic mechanical thermal analysis. The crystallinity dependence of PPG content incorporated into copolymers main backbone was estimate. Additionally, the mechanical properties of the obtained copolymers were studied by notched impact test. From the performed investigation in this study could be concluded that using PPG based PACs at the chosen ROP conditions leads to obtaining well-defined PA6-b-PPG-b-PA6 copolymers with improved impact resistance.

Keywords: anionic ring opening polymerization, caprolactam, polyamide copolymers, polypropylene glycol

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Authors: Sunil K. Jena, Sanjaya K. Samal, Mahesh Chand, Abhay T. Sangamwar

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Tamoxifen (TMX) and its analogues are approved as a first line therapy for the treatment of estrogen receptor-positive tumors. However, clinical development of TMX has been hampered by its low bioavailability and severe hepatotoxicity. Herein, we attempt to design a new drug delivery vehicle that could enhance the pharmacokinetic performance of TMX. Initially, high-molecular weight carboxymethyl chitosan was hydrolyzed to low-molecular weight carboxymethyl chitosan (LMW CMC) with hydrogen peroxide under the catalysis of phosphotungstic acid. Amphiphilic block copolymers of LMW CMC were synthesized via amidation reaction between the carboxyl group of α-tocopherol succinate (TS) and an amine group of LMW CMC. These amphiphilic block copolymers were self-assembled to nanosize core-shell-structural micelles in the aqueous medium. The critical micelle concentration (CMC) decreased with the increasing substitution of TS on LMW CMC, which ranged from 1.58 × 10-6 to 7.94 × 10-8 g/mL. Maximum TMX loading up to 8.08 ± 0.98% was achieved with Cmc-TS4.5 (TMX/Cmc-TS4.5 with 1:8 weight ratio). Both blank and TMX-loaded polymeric micelles (TMX-PM) of Cmc-TS4.5 exhibits spherical shape with the particle size below 200 nm. TMX-PM has been found to be stable in the gastrointestinal conditions and released only 44.5% of the total drug content by the first 72 h in simulated gastric fluid (SGF), pH 1.2. However, the presence of pepsin does not significantly increased the TMX release in SGF, pH 1.2, released only about 46.2% by the first 72 h suggesting its inability to cleave the peptide bond. In contrast, the release of TMX from TMX-PM4.5 in SIF, pH 6.8 (without pancreatin) was slow and sustained, released only about 10.43% of the total drug content within the first 30 min and nearly about 12.41% by the first 72 h. The presence of pancreatin in SIF, pH 6.8 led to an improvement in drug release. About 28.09% of incorporated TMX was released in the presence of pancreatin in 72 h. A cytotoxicity study demonstrated that TMX-PM exhibited time-delayed cytotoxicity in human MCF-7 breast cancer cells. Pharmacokinetic studies on Sprague-Dawley rats revealed a remarkable increase in oral bioavailability (1.87-fold) with significant (p < 0.0001) enhancement in AUC0-72 h, t1/2 and MRT of TMX-PM4.5 than that of TMX-suspension. Thus, the results suggested that CMC-TS micelles are a promising carrier for TMX delivery.

Keywords: carboxymethyl chitosan, d-α-tocopherol succinate, pharmacokinetic, polymeric micelles, tamoxifen

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Authors: Venkataraman Sivasankar, Kiyoshi Omine, Hideaki Sano

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The leaching of fluoride from Plaster Board Waste (PBW) is quite feasible in soil and water environments. The Ministry of Environment, Japan recommended the standard limit of 0.8 mgL⁻¹ or less for fluoride. Although the utilization of PBW as a substitute for cement is rather meritorious, its fluoride leaching behavior deteriorates the quality of soil and water and therefore envisaged as a demerit. In view of this fluoride leaching problem, the present research is focused on immobilizing fluoride in PBW. The immobilization experiments were conducted with four chemical systems operated by DAHP (diammonium hydrogen phosphate) and phosphoric acid carbonization of bamboo mass coupled with certain inorganic reactions using reagents such as calcium hydroxide, sodium hydroxide, and aqueous ammonia. The fluoride immobilization was determined after shaking the reactor contents including the plaster board waste for 24 h at 25˚C. In the DAHP system, the immobilization of fluoride was evident from the leaching of fluoride in the range 0.071-0.12 mgL⁻¹, 0.026-0.14 mgL⁻¹ and 0.068-0.12 mgL⁻¹ for the reaction temperatures at 30˚C, 50˚C, and 90˚C, respectively, with final pH of 6.8. The other chemical systems designated as PACCa, PACAm, and PACNa could immobilize fluoride in PBW, and the resulting solution was analyzed with the fluoride less than the Japanese environmental standard of 0.8 mgL⁻¹. In the case of PACAm and PACCa systems, the calcium concentration was found undetectable and witnessed the formation of phosphate compounds. The immobilization of fluoride was found inversely proportional to the increase in the volume of leaching solvent and dose of PBW. Characterization studies of PBW and the solid after fluoride immobilization was done using FTIR (Fourier transform infrared spectroscopy), Raman spectroscopy, FE-SEM ( Field Emission Scanning Electron Microscopy) with EDAX (Energy Dispersive Spectroscopy), XRD (X-ray diffraction), and XPS (X-ray photoelectron spectroscopy). The results revealed the formation of new calcium phosphate compounds such as apatite, monetite, and hydroxylapatite. The participation of such new compounds in fluoride immobilization seems indispensable through the exchange mechanism of hydroxyl and fluoride groups. Acknowledgment: First author thanks to Japanese Society for the Promotion of Science (JSPS) for the award of the fellowship (ID No. 16544).

Keywords: characterization, fluoride, immobilization, plaster board waste

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Authors: Lotfollah Rezagholizadeh

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Background and Aim: Diabetes mellitus is related to high mortality and morbidity caused by the early development of atherosclerosis correlated to diabetic macroangiopathy. The endothelium-derived vasodilator, nitric oxide (NO) has been implicated in the development of vascular complications via the regulation of blood flow, and various antiatherosclerotic actions. Patients with type 2 diabetes (T2D) have a decreased level of endothelial nitric oxide release. In this study we aimed to examine the effect of aquatic seed extract of Cichorium intybus L. (chicory) and metformin (a known prescription drug for diabetes) on NO levels in T2D rats. Methods: Five groups of adult male Wistar rats were used (n=6): Non-diabetic controls without extract treatment (Control), Non-diabetic controls with extract treatment (Chicory-control), T2D rats without extract treatment (NIA/STZ), T2D rats treated with the extract (Chicory-NIA/STZ), and T2D groups that received metformin (100 mg/kg) but no extract (Metformin-NIA/STZ). T2D was induced with intraperitoneal (i.p) injection of niacinamide (NIA, 200 mg/kg), 15 min after an i.p administration of streptozotocin (STZ, 55 mg/kg). Lyophilized chicory extract (125 mg/kg) was dissolved in 0.2 ml normal saline and administered one dose a day. The experiments lasted for 3 weeks after the diabetes induction. NO analysis was performed by assay based on the Griess reaction. Data were reported as the mean ± SD and statistical analysis was performed by ANOVA. Results: Serum nitric oxide levels decreased significantly in NIA/STZ group compared with Control and Chicory-control. Treatment with chicory extract caused a significant increase in serum levels of NO in Chicory-NIA/STZ group compare to NIA/STZ group (p<05). Metformin-NIA/STZ group did not show considerable difference when compared with NIA/STZ, with respect to NO levels. In a group of rats made diabetic by STZ alone (type 1 diabetic rats, T1D), chicory did not have a significant ameliorating effect. Conclusion: In this study, we clearly showed a relationship between low serum nitric oxide levels and diabetes mellitus in rats. The increase in serum nitric oxide by chicory extract is an indication of antiatherogenic effect of this plant. Chicory seed extract was more efficient than metformin in improving the NO levels in NO-deficient T2D diabetic rats.

Keywords: type 2 diabetes mellitus, nitric oxide, chicory, metformin

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Authors: J. Das, T. S. Mahule, V. V. Srinivasu

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Electron spin resonance (ESR) study at 9.45 GHz and a field modulation frequency of 100Hz was performed on bulk polycrystalline samples of Mn:TM (Fe/Ni) and Mn:RE (Gd/Sm) co doped ZnO samples with composition Zn1-xMn:TM/RE)xO synthesised by solid state reaction route and sintered at 500 0C temperature. The room temperature microwave absorption data collected by sweeping the DC magnetic field from -500 to 9500 G for the Mn:Fe and Mn:Ni co doped ZnO samples exhibit a rarely reported non resonant low field absorption (NRLFA) in addition to a strong absorption at around 3350G, usually associated with ferromagnetic resonance (FMR) satisfying Larmor’s relation due to absorption in the full saturation state. Observed low field absorption is distinct to ferromagnetic resonance even at low temperature and shows hysteresis. Interestingly, it shows a phase opposite with respect to the main ESR signal of the samples, which indicates that the low field absorption has a minimum value at zero magnetic field whereas the ESR signal has a maximum value. The major resonance peak as well as the peak corresponding to low field absorption exhibit asymmetric nature indicating magnetic anisotropy in the sample normally associated with intrinsic ferromagnetism. Anisotropy parameter for Mn:Ni codoped ZnO sample is noticed to be quite higher. The g values also support the presence of oxygen vacancies and clusters in the samples. These samples have shown room temperature ferromagnetism in the SQUID measurement. However, in rare earth (RE) co doped samples (Zn1-x (Mn: Gd/Sm)xO), which show paramagnetic behavior at room temperature, the low field microwave signals are not observed. As microwave currents due to itinerary electrons can lead to ohmic losses inside the sample, we speculate that more delocalized 3d electrons contributed from the TM dopants facilitate such microwave currents leading to the loss and hence absorption at the low field which is also supported by the increase in current with increased micro wave power. Besides, since Fe and Ni has intrinsic spin polarization with polarisability of around 45%, doping of Fe and Ni is expected to enhance the spin polarization related effect in ZnO. We emphasize that in this case Fe and Ni doping contribute to polarized current which interacts with the magnetization (spin) vector and get scattered giving rise to the absorption loss.

Keywords: co-doping, electron spin resonance, hysteresis, non-resonant microwave absorption

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Authors: Roghaye Behroozi

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The development of functionalized metal complexes and nanomaterials has gained significant attention due to their potential in catalyzing selective oxidation and coupling reactions. These catalysts play a crucial role in various industrial and pharmaceutical processes, enhancing the efficiency, selectivity, and sustainability of chemical reactions. This research aims to design and synthesize new functionalized metal complexes and nanomaterials to explore their catalytic applications in the selective oxidation of alcohols and coupling reactions, focusing on improving yield, selectivity, and catalyst reusability. The study involves the synthesis of a nickel Schiff base complex stabilized within 41-MCM as a heterogeneous catalyst. A Schiff base ligand derived from glycine was used to create a tin (IV) metal complex characterized through spectroscopic techniques and computational analysis. Additionally, iron-based magnetic nanoparticles functionalized with melamine were synthesized for catalytic evaluation. Lastly, a palladium (IV) complex was prepared, and its oxidative stability was analyzed. The nickel Schiff base catalyst showed high selectivity in converting primary and secondary alcohols to aldehydes and ketones, with yields ranging from 73% to 90%. The tin (IV) complex demonstrated accurate structural and electronic properties, with consistent results between experimental and computational data. The melamine-functionalized iron nanoparticles exhibited efficient catalytic activity in producing triazoles, with enhanced reaction speed and reusability. The palladium (IV) complex displayed remarkable stability and low reactivity towards C–C bond formation due to its symmetrical structure. The synthesized metal complexes and nanomaterials demonstrated significant potential as efficient, selective, and reusable catalysts for oxidation and coupling reactions. These findings pave the way for developing environmentally friendly and cost-effective catalytic systems for industrial applications.

Keywords: catalysts, Schiff base complexes, metal-organic frameworks, oxidation reactions, nanoparticles, reusability

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Authors: Nurcihan Kiris

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Restricted sleep is common in young adults and adolescents. The results of a few objective studies of sleep deprivation on cognitive performance were not clarified. In particular, the effect of sleep deprivation on the cognitive functions associated with frontal lobe such as attention, executive functions, working memory is not well known. The aim of this study is to investigate the effect of partial sleep deprivation experimentally in adolescents on the cognitive tasks of frontal lobe including working memory, strategic thinking, simple attention, continuous attention, executive functions, and cognitive flexibility. Subjects of the study were recruited from voluntary students of Cukurova University. Eighteen adolescents underwent four consecutive nights of monitored sleep restriction (6–6.5 hr/night) and four nights of sleep extension (10–10.5 hr/night), in counterbalanced order, and separated by a washout period. Following each sleep period, cognitive performance was assessed, at a fixed morning time, using a computerized neuropsychological battery based on frontal lobe functions task, a timed test providing both accuracy and reaction time outcome measures. Only the spatial working memory performance of cognitive tasks was found to be statistically lower in a restricted sleep condition than the extended sleep condition. On the other hand, there was no significant difference in the performance of cognitive tasks evaluating simple attention, constant attention, executive functions, and cognitive flexibility. It is thought that especially the spatial working memory and strategic thinking skills of adolescents may be susceptible to sleep deprivation. On the other hand, adolescents are predicted to be optimally successful in ideal sleep conditions, especially in the circumstances requiring for the short term storage of visual information, processing of stored information, and strategic thinking. The findings of this study may also be associated with possible negative functional effects on the processing of academic social and emotional inputs in adolescents for partial sleep deprivation. Acknowledgment: This research was supported by Cukurova University Scientific Research Projects Unit.

Keywords: attention, cognitive functions, sleep deprivation, working memory

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Authors: A. Sezai Sarac

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Acrylonitrile (AN) copolymers with typical comonomers of vinyl acetate (VAc) or methyl acrylate (MA) exhibit better mechanical behaviors than its homopolymer. To increase processability of conjugated polymer, and to obtain a hybrid nano-structure multi-stepped emulsion polymerization was applied. Such products could be used in, i.e., drug-delivery systems, biosensors, gas-sensors, electronic compounds, etc. Incorporation of a number of flexible comonomers weakens the dipolar interactions among CN and thereby decreases melting point or increases decomposition temperatures of the PAN based copolymers. Hence, it is important to consider the effect of comonomer on the properties of PAN-based copolymers. Acrylonitrile vinylacetate (AN–VAc ) copolymers have the significant effect to their thermal behavior and are also of interest as precursors in the production of high strength carbon fibers. AN is copolymerized with one or two comonomers, particularly with vinyl acetate The copolymer of AN and VAc can be used either as a plastic (VAc > 15 wt %) or as microfibers (VAc < 15 wt %). AN provides the copolymer with good processability, electrochemical and thermal stability; VAc provides the mechanical stability. The free radical copolymerization of AN and VAc copolymer and core Shell structure of polyprrole composites,and nanofibers of poly(m-anthranilic acid)/polyacrylonitrile blends were recently studied. Free radical copolymerization of acrylonitrile (AN) – with different comonomers, i.e. acrylates, and styrene was realized using ammonium persulfate (APS) in the presence of a surfactant and in-situ polymerization of conjugated polymers was performed in this reaction medium to obtain core-shell nano particles. Nanofibers of such nanoparticles were obtained by electrospinning. Morphological properties of nanofibers are investigated by scanning electron microscopy (SEM) and atomic force spectroscopy (AFM). Nanofibers are characterized using Fourier Transform Infrared - Attenuated Total Reflectance spectrometer (FTIR-ATR), Nuclear Magnetic Resonance Spectroscopy (1H-NMR), differential scanning calorimeter (DSC), thermal gravimetric analysis (TGA), and Electrochemical Impedance Spectroscopy. The electrochemical Impedance results of the nanofibers were fitted to an equivalent curcuit by modelling (ECM).

Keywords: core shell nanoparticles, nanofibers, ascrylonitile copolymers, hybrid nanostructures

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Authors: Sadaf Moeez, Madiha Khalid, Zoya Khalid, Sania Shaheen, Sumbul Khalid

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Background: Inter-individual variation in response to metformin, which has been considered as a first line therapy for T2DM treatment is considerable. In the current study, it was aimed to investigate the impact of two genetic variants Leu125Phe (rs77474263) and Gly64Asp (rs77630697) in gene SLC47A1 on the clinical efficacy of metformin in T2DM Pakistani patients. Methods: The study included 800 T2DM patients (400 metformin responders and 400 metformin non-responders) along with 400 ethnically matched healthy individuals. The genotypes were determined by allele-specific polymerase chain reaction. In-silico analysis was done to confirm the effect of the two SNPs on the structure of genes. Association was statistically determined using SPSS software. Results: Minor allele frequency for rs77474263 and rs77630697 was 0.13 and 0.12. For SLC47A1 rs77474263 the homozygotes of one mutant allele ‘T’ (CT) of rs77474263 variant were fewer in metformin responders than metformin non-responders (29.2% vs. 35.5 %). Likewise, the efficacy was further reduced (7.2% vs. 4.0 %) in homozygotes of two copies of ‘T’ allele (TT). Remarkably, T2DM cases with two copies of allele ‘C’ (CC) had 2.11 times more probability to respond towards metformin monotherapy. For SLC47A1 rs77630697 the homozygotes of one mutant allele ‘A’ (GA) of rs77630697 variant were fewer in metformin responders than metformin non-responders (33.5% vs. 43.0 %). Likewise, the efficacy was further reduced (8.5% vs. 4.5%) in homozygotes of two copies of ‘A’ allele (AA). Remarkably, T2DM cases with two copies of allele ‘G’ (GG) had 2.41 times more probability to respond towards metformin monotherapy. In-silico analysis revealed that these two variants affect the structure and stability of their corresponding proteins. Conclusion: The present data suggest that SLC47A1 Leu125Phe (rs77474263) and Gly64Asp (rs77630697) polymorphisms were associated with the therapeutic response of metformin in T2DM patients of Pakistan.

Keywords: diabetes, T2DM, SLC47A1, Pakistan, polymorphism

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Authors: Naveen Kumar B. T., Anuj Tyagi, Prabjeet Singh, Shanthanagouda A. H., Sumeet Rai

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Inland saline water resources are gaining the importance in expanding the aquaculture activities to mitigate the nutritional and food security issues of the world. For profitable and sustainable aquaculture practices, scientific farming, biosecurity measure, and best fish health management should be the integral part of developmental activities. Keeping in line with global awareness and trends, the Indian government has taken an innovative step to conduct disease surveillance and awareness programme for aquatic disease through network project. This ‘National Surveillance Programme for Aquatic Animal Diseases (NSPAAD)’ is being implemented in collaboration of national institutes and state agriculture universities with funding support from National Fisheries Development Board (NFDB), Govt. of India. Guru Angad Dev Veterinary and Animal Sciences University (GADVASU), Ludhiana, an NSPAAD collaborator, has been actively engaged in disease surveillance in the Indian state of Punjab. Shrimp farming in inland saline areas of Punjab is expanding at a tremendous pace under the guidance of GADVASU along with the support of State Fisheries Department. Under this national disease surveillance programme, we reported Enterocytozoon hepatopenaei (EHP) infection in the Litopenaeus vannamei cultured in the inland saline waters. Polymerase chain reaction (PCR) based diagnosis was carried out using the OIE (World Organisation for Animal Health) protocol. It was observed that out of 20 shrimp farms, two farms were 1st step PCR positive and two more farms were nested PCR positive. All the EHP positive ponds had shown the white faeces along with mortalities at very low rate. Therefore, implementation of biosecurity and continuous surveillance and monitoring program for finfish and shellfish aquaculture are in need of the hour to prevent and control the large-scale disease outbreaks and subsequent economic losses.

Keywords: disease, EHP, inland saline water, shrimp culture

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Authors: Sarre Nzaba, Bulelwa Ntsendwana, Bekkie Mamba, Alex Kuvarega

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The discharge of azo dyes such as Brilliant black (BB) into the water bodies has carcinogenic and mutagenic effects on humankind and the ecosystem. Conventional water treatment techniques fail to degrade these dyes completely thereby posing more problems. Advanced oxidation processes (AOPs) are promising technologies in solving the problem. Anatase type nitrogen-platinum (N, Pt) co-doped TiO₂ photocatalysts were prepared by a modified sol-gel method using amine terminated polyamidoamine generation 1 (PG1) as a template and source of nitrogen. The resultant photocatalysts were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X‐ray photoelectron spectroscopy (XPS), UV‐Vis diffuse reflectance spectroscopy, photoluminescence spectroscopy (PL), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy (RS), thermal gravimetric analysis (TGA). The results showed that the calcination atmosphere played an important role in the morphology, crystal structure, spectral absorption, oxygen vacancy concentration, and visible light photocatalytic performance of the catalysts. Anatase phase particles ranging between 9- 20 nm were also confirmed by TEM, SEM, and analysis. The origin of the visible light photocatalytic activity was attributed to both the elemental N and Pd dopants and the existence of oxygen vacancies. Co-doping imparted a shift in the visible region of the solar spectrum. The visible light photocatalytic activity of the samples was investigated by monitoring the photocatalytic degradation of brilliant black dye. Co-doped TiO₂ showed greater photocatalytic brilliant black degradation efficiency compared to singly doped N-TiO₂ or Pd-TiO₂ under visible light irradiation. The highest reaction rate constant of 3.132 x 10-2 min⁻¹ was observed for N, Pd co-doped TiO₂ (2% Pd). The results demonstrated that the N, Pd co-doped TiO₂ (2% Pd) sample could completely degrade the dye in 3 h, while the commercial TiO₂ showed the lowest dye degradation efficiency (52.66%).

Keywords: brilliant black, Co-doped TiO₂, polyamidoamine generation 1 (PAMAM G1), photodegradation

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Authors: Julius K. Gane, Mohamad N. Nahil, Paul T. Williams

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In today’s world of rapid population growth and a changing climate, one way to mitigate various negative effects is via renewable energy solutions. Energy and power as basic requirements in almost all human endeavours are also the banes of the changing climate and the impacts thereof. Thus it is crucial to develop innovative and environmentally friendly energy options to ameliorate various negative repercussions. Upgrading of fast pyrolysis bio-oil via hydro-treatment offers such opportunities, as quality renewable liquid transportation fuels can be produced. The process, however, is typically accompanied by bio-char formation as a by-product. The goal of this work was to study the yield and some properties of bio-chars formed from a hydrotreatment process, with an overall aim to promote the valuable utilization of wastes or by-products from renewable energy technologies. It is assumed that bio-chars that have comparable energy contents with coals will be more desirable as solid energy materials due to renewability and environmental friendliness. Therefore, the analytical work in this study focused mainly on determining the higher heating value (HHV) of the chars. The method involved the reaction of bio-oil in an autoclave supplied by the Parr Instrument Company, IL, USA. Two main parameters (different temperatures and resident times) were investigated. The chars were characterized using a Thermo EA2000 CHNS analyser, then oxygen contents and HHVs computed based on the literature. From the results, these bio-chars can readily serve as feedstocks for the production of renewable solid fuels. Their HHVs ranged between 29.26-39.18 MJ/kg, affected by different temperatures and retention times. There was an inverse relationship between the oxygen content and the HHVs of the chars. It can, therefore, be concluded that it is possible to optimize the process efficiency of the hydrotreatment process used through the production of renewable energy materials from the 'waste’ char by-products. Future work should consider developing a suitable balance between the primary objective of bio-oil upgrading processes (which is to improve the quality of the liquid fuels) and the conversion of its solid wastes into value-added products such as smokeless briquettes.

Keywords: bio-char, renewable solid biofuels, valorisation, waste-to-energy

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Authors: Çisem Gündüz Arabacı

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Deliberation has been seen one of the most important components of democratic ideals especially since liberal democratic attributions have been under fire. Deliberative democracy advocates that people should participate in collective decision-making processes by other mechanisms rather than conventional ones in order to reach legitimate decisions. Deliberative democratic theory makes emphasis on deliberative communication between people and encourages them not to merely express their political opinions (through surveys and referendum) but to form those opinions through public debates. This paper focuses on deliberative democratic visions of Gezi Park Public Forums by taking deliberative democracy as theoretical basis and examining Gezi Park Public Forums in the light of core elements of deliberative democracy. Gezi Movement started on 28 May 2013 in İstanbul as a reaction to local government's revision plans for Taksim Gezi Park, spread throughout the country and created new zones in public sphere which are called Public Park Forums. During the summer of 2013, especially in İstanbul but also in other cities, people gathered in public parks, discussed and took collective decisions concerning actions which they will take. It is worth to mention that since 3 and half years some Public Park Forums are still continuing their meetings regularly in city of İzmir. This paper analyzes four 'Public Park Forums' in İzmir which are called Bornova Public Forum; Karşıyaka Public Forum, Foça Public Forum and Güzelyalı Public Forum. These Forums are under investigation in terms of their understanding of democracy and the values that support that understanding. Participant observation and in-depth interview methods are being used as research methods. Core element of deliberative democracy are being collected under three main category: common interest versus private interest, membership, rational argument and these values are being questioning within one of each Forum in order to draw an overall picture and also make comparison between them. Discourse analysis is being used in order to examine empirical data and paper aims to reveal how participants of public forums perceive deliberative democratic values and whether they give weight to these values.

Keywords: deliberative democracy, Gezi Park movement, public forums, social movement

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Authors: Sarah Gounden, Mukesh Dheda, Boikhutso Tlou, Elizabeth Ojewole, Frasia Oosthuizen

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Background: Antiretroviral therapy (ART) has been effective in the reduction of mortality and resulted in an improvement in the prognosis of HIV-infected patients. However, treatment with antiretrovirals (ARVs) has led to the development of many adverse drug reactions (ADRs). It is, therefore, necessary to determine the safety profile of these medicines in a South African population in order to ensure safe and optimal medicine use. Objectives: The aim of this study was to quantify ADRs experienced with the different ARVs currently used in South Africa, to determine the safety profile of ARV medicine in South Africa based on reported ADRs, and to determine the ARVs with the lowest risk profile based on specific patient populations. Methodology: This was a quantitative study. Individual case safety reports for the period January 2010 – December 2013 were obtained from the National Pharmacovigilance Center; these reports contained information on ADRs, ARV medicine, and patient demographics. Data was analysed to find associations that may exist between ADRs experienced, ARV medicines used and patient demographics. Results: A total of 1916 patient reports were received of which 1534 met the inclusion criteria for the study. The ARV with the lowest risk of ADRs were found to be lamivudine (0.51%, n=12), followed by lopinavir/ritonavir combination (0.8%, n=19) and abacavir (0.64%, n=15). A higher incidence of ADRs was observed in females compared to males. The age group 31–50 years and the weight group 61–80 kg had the highest incidence of ADRs reported. Conclusion: This study found that the safest ARVs to be used in a South African population are lamivudine, abacavir, and the lopinavir/ritonavir combination. Gender differences play a significant role in the occurrence of ADRs and both anatomical and physiological differences account for this. An increased BMI (body mass index) in both men and women showed an increase in the incidence of ADRs associated with ARV therapy.

Keywords: adverse drug reaction, antiretrovirals, HIV/AIDS, pharmacovigilance, South Africa

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Authors: Abdul Mutalib Md Jani, Abdul Hadi Mahmud, Mohd Tajuddin Mohd Ali

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The rapid growth of interest in surface modification of nanostructures materials that exhibit improved structural and functional properties is attracting more researchers. The unique properties of highly ordered nanoporous anodic aluminium oxide (NAAO) membrane have been proposed as a platform for biosensing applications. They exhibit excellent physical and chemical properties with high porosity, high surface area, tunable pore sizes and excellent chemical resistance. In this study, NAAO was functionalized with 3-aminopropyltriethoxysilane (APTES) to prepared silane-modified NAAO. Amine functional groups are formed on the surface of NAAO during silanization and were characterized using Fourier Transform Infrared spectroscopy (FTIR). The synthesis of multi segment of peptide on NAAO surfaces can be realized by changing the surface chemistry of the NAAO membrane via click chemistry. By click reactions, utilizing alkyne terminated with amino group, various peptides tagged on NAAO can be envisioned from chiral natural or unnatural amino acids using standard coupling methods (HOBt, EDCI and HBTU). This strategy seemly versatile since coupling strategy of dipeptide with another amino acids, leading to tripeptide, tetrapeptide or pentapeptide, can be synthesized without purification. When an appropriate terminus is selected, multiple segments of amino acids can be successfully synthesized on the surfaces. The immobilized NAAO should be easily separated from the reaction medium by conventional filtration, thus avoiding complicated purification methods. Herein, we proposed to synthesize multi fragment peptide as a model for capturing and attaching various small biomolecules on NAAO surfaces and can be also applied as biosensing device, drug delivery systems and biocatalyst.

Keywords: nanoporous anodic aluminium oxide, silanization, peptide synthesise, click chemistry

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Authors: Héctor González Espinosa, Ricardo Ivan Cordova Chávez, Alejandra Contreras Ramos, Itzia Irene Padilla Martínez, José Guadalupe Trujillo Ferrara, Marvin Antonio Soriano Ursúa

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Boronic acids are able to create diester bonds with carbohydrates because of their hydroxyl groups; in nature, there are some organoborates with these characteristics, such as the calcium fructoborate, formed by the union of two fructose molecules and a boron atom, synthesized by plants. In addition, it has been observed that, in animal cells only the compounds with cis-diol functional groups are capable of linking to boric or boronic acids. The formation of these organoboron compounds could impair the physical and chemical properties of the precursors, even their acute toxicity. In this project, two carbohydrate-derived boron-containing compounds from D-fructose and D-arabinose and phenylboronic acid are analyzed by different spectroscopy techniques such as Raman, Infrared with Fourier Transform Infrared (FT-IR), Nuclear Magnetic Resonance (NMR) and X-ray diffraction crystallography to describe their chemical characteristics. Also, an acute toxicity test was performed to determine their LD50 using the Lorke’s method. It was confirmed by multiple spectra the formation of the adducts by the generation of the diester bonds with a β-D-pyranose of fructose and arabinose. The most prominent findings were the presence of signals corresponding to the formation of new bonds, like the stretching of B-O bonds, or the absence of signals of functional groups like the hydroxyls presented in the reagents used for the synthesis of the adducts. The NMR spectra yielded information about the stereoselectivity in the synthesis reaction, observed by the interaction of the protons and their vicinal atoms in the anomeric and second position carbons; but also, the absence of a racemic mix by the finding of just one signal in the range for the anomeric carbon in the 13C NMR spectra of both adducts. The acute toxicity tests by the Lorke’s method showed that the LD50 value for both compounds is 1265 mg/kg. Those results let us to propose these adducts as highly safe agents for further biological evaluation with medical purposes.

Keywords: acute toxicity, adduct, boron, carbohydrate, diester bond

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