Search results for: polymeric precursors

Authors: Lucas Viani, Benedetta Mennucci, Soo Young Park, Johannes Gierschner

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Organic semiconductors have attracted the attention of the scientific community in the past decades due to their unique physicochemical properties, allowing new designs and alternative device fabrication methods. Until today, organic electronic devices are largely based on conjugated polymers mainly due to their easy processability. In the recent years, due to moderate ET and CT efficiencies and the ill-defined nature of polymeric systems the focus has been shifting to small conjugated molecules with well-defined chemical structure, easier control of intermolecular packing, and enhanced CT and ET properties. It has led to the synthesis of new small molecules, followed by the growth of their crystalline structure and ultimately by the device preparation. This workflow is commonly followed without a clear knowledge of the ET and CT properties related mainly to the macroscopic systems, which may lead to financial and time losses, since not all materials will deliver the properties and efficiencies demanded by the current standards. In this work, we present a theoretical workflow designed to predict the key properties of ET of these new materials prior synthesis, thus speeding up the discovery of new promising materials. It is based on quantum mechanical, hybrid, and classical methodologies, starting from a single molecule structure, finishing with the prediction of its packing structure, and prediction of properties of interest such as static and averaged excitonic couplings, and exciton diffusion length.

Keywords: organic semiconductor, organic crystals, energy transport, excitonic couplings

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Authors: Nguyen-Tri Phuong, Triki Ennouri, Gauvin Chantal, Tuduri Ludovic, Vu-Khanh Toan

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Hand injuries due to mechanical hazards such as cuts and punctures are major risks and concerns for several occupational groups, particularly for workers in the metal manufacturing sector and mechanical automotive services. Personal protective equipment such as gloves or clothing is necessary for many professionals to protect against a variety of occupational hazards, which arise daily in their work environments. In many working places such as metal manufacturing or automotive services, mechanical hazards often occur together with industrial contaminants, particularly metalworking fluids (MWFs). The presence of these contaminants could modify the properties of gloves made from polymeric materials and thus increase the risk of hand injuries for workers. The focus of this study is to determine the swelling characteristics and the resistance of six polymer membranes when they are contaminated with several industrial metalworking fluids. These polymer membranes, commonly used in protective gloves, are nitrile, neoprene, vinyl, butyl, polyurethane and latex rubbers. Changes swelling index were continuously followed during the contamination procedure to compare the performance of each polymer under different conditions. The modification of the samples surface, tensile properties during the contamination process was also investigated. The effect of temperature on mechanical properties and morphology of material was also examined.

Keywords: metalworking fluid, swelling behavior, protective glove materials, elastomers

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Authors: María del Carmen Recio-Ruiz, Ramiro Ruiz-Rosas, Juana María Rosas, José Rodríguez-Mirasol, Tomás Cordero

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Nowadays, fossil resources are main precursors for fuel production. Due to their contribution to the greenhouse effect and their future depletion, there is a constant search for environmentally friendly feedstock alternatives. Biomass residues constitute an interesting replacement for fossil resources because of their zero net CO₂ emissions. One of the main routes to convert biomass into energy and chemicals is pyrolysis. In this work, conventional pyrolysis of different biomass residues highly available such as almond shells, hemp hurds, olive stones, and Kraft lignin, was studied. In a typical experiment, the biomass was crushed and loaded into a fixed bed reactor under continuous nitrogen flow. The influence of temperature (400-800 ºC) and heating rate (10 and 20 ºC/min) on the pyrolysis yield and composition of the different fractions has been studied. In every case, the mass yields revealed that the solid fraction decreased with temperature, while liquid and gas fractions increased due to depolymerization and cracking reactions at high temperatures. The composition of every pyrolysis fraction was studied in detail. The results showed that the composition of the gas fraction was mainly CO, CO₂ when working at low temperatures, and mostly CH₄ and H₂at high temperatures. The solid fraction developed an incipient microporosity, with narrow micropore volume of 0.21 cm³/g. Regarding the liquid fraction, pyrolysis of almond shell, hemp hurds, and olive stones led mainly to a high content in aliphatic acids and furans, due to the high volatile matter content of these biomass (>74 %wt.), and phenols to a lesser degree, which were formed due to the degradation of lignin at higher temperatures. However, when Kraft lignin was used as bio-oil precursor, the presence of phenols was very prominent, and aliphatic compounds were also detected in a lesser extent.

Keywords: Bio-oil, biomass, conventional pyrolysis, lignocellulosic

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Authors: Jolanta Jaskowska, Anna Drabczyk, Sonia Kudlacik, Agnieszka Sobczak-Kupiec, Bozena Tyliszczak

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The aim of the study was to select the best conditions for the synthesis of Beetosan's hydrogels with yellow tea. The study determined recipe hydrogel matrix by selecting the appropriate ratio of substrates and to investigate the effect of yellow tea, on the structure and properties of the hydrogel materials. The scope of the research included both to obtain of raw materials required for the synthesis of hydrogel materials, as well as an assessment of their properties. In the first stage of research Beetosan (chitosan derived from bees), and extract the yellow tea China Kekecha was obtained. The second stage was synthesis hydrogels modified by yellow tea. The synthesis of polymeric matrix was preparation under UV radiation. Obtained hydrogel materials were investigated extensively using incubation investigations, absorption capacity, and spectroscopic (FT-IR) and X-ray diffraction (XRD) methods. Moreover, there was also performed the surface wettability test and a photomicrograph of the structure using scanning electron microscope. Analysis of the obtained results confirms that presence of yellow tea does not significantly affect the behavior of the hydrogels in the incubation fluids. The results show that hydrogel materials exhibit compatibility with the incubatory solutions and they also retain the stability in the tested liquids. Hydrogels obtained in this method might be applied in the cosmetics industry and in the field of medicine. This is possible due to the many interesting properties of tea and biocompatibility and non-toxicity hydrogel materials. The authors would like to thank the The National Centre for Research and Development (Grant no: LIDER/033/697/L-5/13/NCBR/2014) for providing financial support to this project.

Keywords: Beetosan, hygrogels, materials, yellow tea

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Authors: S. S. Singh, A. Bhattacharya, S. Bhattacharya

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The eukaryotic exosome complex plays a pivotal role in RNA biogenesis, maturation, surveillance and differential expression of various RNAs in response to varying environmental signals. The exosome is composed of evolutionary conserved nine core subunits and the associated exonucleases Rrp6 and Rrp44. Rrp6p is crucial for the processing of rRNAs, other non-coding RNAs, regulation of polyA tail length and termination of transcription. Rrp6p, a 3’-5’ exonuclease is required for degradation of 5’-external transcribed spacer (ETS) released from the rRNA precursors during the early steps of pre-rRNA processing. In the parasitic protist Entamoeba histolytica in response to growth stress, there occurs the accumulation of unprocessed pre-rRNA and 5’ ETS sub fragment. To understand the processes leading to this accumulation, we looked for Rrp6 and the exosome subunits in E. histolytica, by in silico approaches. Of the nine core exosomal subunits, seven had high percentage of sequence similarity with the yeast and human. The EhRrp6 homolog contained exoribonuclease and HRDC domains like yeast but its N- terminus lacked the PMC2NT domain. EhRrp6 complemented the temperature sensitive phenotype of yeast rrp6Δ cells suggesting conservation of biological activity. We showed 3’-5’ exoribonuclease activity of EhRrp6p with in vitro-synthesized appropriate RNAs substrates. Like the yeast enzyme, EhRrp6p degraded unstructured RNA, but could degrade the stem-loops slowly. Furthermore, immunolocalization revealed that EhRrp6 was nuclear-localized in normal cells but was diminished from nucleus during serum starvation, which could explain the accumulation of 5’ETS during stress. Our study shows functional conservation of EhRrp6p in E.histolytica, an early-branching eukaryote, and will help to understand the evolution of exosomal components and their regulatory function.

Keywords: entamoeba histolytica, exosome complex, rRNA processing, Rrp6

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Authors: Srutirekha Giri, Manoranjan Sahoo, Anuradha Das, Pravanjan Mallick, Biswajit Mallick

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Ion Beam (IB) technique is a very powerful experimental technique for both material synthesis and material modifications. In this work, 3MeV proton beam was generated using the 3MV Tandem machine of the Institute of Physics, Bhubaneswar and extracted into air for the irradiation-induced modification purpose[1]. The polymeric material can be modeled for a three-phase system viz. crystalline(I), amorphous(II) and mesomorphic(III). So far, our knowledge is concerned. There are only few techniques reported for the synthesis of this third-phase(III) of polymer. The IB induced technique is one of them and has been reported very recently [2-4]. It was observed that by irradiating polyethylene terephthalate (PET) fiber at very low proton fluence, 10¹⁰ - 10¹² p/s, possess 2D mesophase structure. This was confirmed using X-ray diffraction technique. A low-intensity broad peak was observed at small angle of about 2θ =6º, when the fiber axis was mounted parallel to the X-ray direction. Such peak vanished in the diffraction spectrum when the fiber axis was mounted perpendicular to the beam direction. The appearance of this extra peak in a particular orientation confirms that the phase is 2-dimensionally oriented (mesophase). It is well known that the mesophase is a 2-dimensionally ordered structure but 3-dimensionally disordered. Again, the crystallite of the mesophase peak particle was measured about 3nm. The MeV proton-induced 2D mesophase patterning of nanocrystallites (3nm) of PET due to irradiation was observed within the above low fluence range and failed in high proton fluence. This is mainly due to the breaking of crystallites, radiation-induced thermal degradation, etc.

Keywords: Ion irradiation, mesophase, nanocrystallites, polymer

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Authors: Mazita Mohd Diah, Anton V. Dolzhenko, Tin Wui Wong

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Nanoparticles, being small with a large specific surface area, increase solubility, enhance bioavailability, improve controlled release and enable precision targeting of the entrapped compounds. In this study, chitosan as polymeric permeation enhancer was conjugated to a polar pro-drug, carboxymethyl-5-fluorouracil (CMFU) to increase the skin drug permeation. Chitosan-CMFU conjugate was synthesized using chemical conjugation process through succinate linker. It was then transformed into nanoparticles via spray drying method. The conjugation was elucidated using Fourier Transform Infrared and Proton Nuclear Magnetic Resonance techniques. The nanoparticle size, size distribution, zeta potential, drug content, skin permeation and retention profiles were characterized. The conjugation was denoted using 1H NMR by new peaks at signal δ = 4.184 ppm (singlet, 2H for CH2) and 7.676-7.688 ppm (doublet, 1H for C6) attributed to CMFU in chitosan-CMFU NMR spectrum. The nanoparticles had profiles of particle size: 93.97 ±35.11 nm, polydispersity index: 0.40 ± 0.14, zeta potential: +18.25 ±2.95 mV and drug content: 6.20 ± 1.98 % w/w. Almost 80 % w/w CMFU in the form of nanoparticles permeated through the skin in 24 hours and close to 50 % w/w permeation occurred in first 1-2 hours. Without conjugation to chitosan and nanoparticulation, less than 40 % w/w CMFU permeated through the skin in 24 hours. The skin drug retention likewise was higher with chitosan-CMFU nanoparticles (15.34 ± 5.82 % w/w) than CMFU (2.24 ± 0.57 % w/w). CMFU, through conjugation with chitosan permeation enhancer and processed in nanogeometry, had its skin permeation and retention degree promoted.

Keywords: carboxymethyl-5-fluorouracil, chitosan, conjugate, skin permeation, skin retention

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Authors: Benhui Fan, Fahmi Bedoui, Jinbo Bai

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Incorporated carbon nanotube-BaTiO₃ hybrids (H-CNT-BT) with core-shell structure, a better dispersion of CNTs can be achieved in a semi-crystalline polymeric matrix, polyvinylidene fluoride (PVDF). Carried by BT particles, CNTs are easy to mutually connect which helps to obtain an extremely low percolation threshold (fc). After thermal treatments, the dielectric constants (ε’) of samples further increase which depends on the conditions of thermal treatments such as annealing temperatures, annealing durations and cooling ways. Thus, in order to study more comprehensively about the influence of thermal treatments on composite’s dielectric behaviors, in situ synchrotron X-ray is used to detect re-crystalline behavior of PVDF. Results of wide-angle X-ray diffraction (WAXD) and small-angle X-ray scattering (SAXS) show that after the thermal treatment, the content of β polymorph (the polymorph with the highest ε’ among all the polymorphs of PVDF’s crystalline structure) has increased nearly double times at the interfacial region of CNT-PVDF, and the thickness of amorphous layers (La) in PVDF’s long periods (Lp) has shrunk around 10 Å. The evolution of CNT’s network possibly occurs in the procedure of La shrinkage, where the strong interfacial polarization may be aroused and increases ε’ at low frequency. Moreover, an increase in the thickness of crystalline lamella may also arouse more orientational polarization and improve ε’ at high frequency.

Keywords: dielectric properties, thermal treatments, carbon nanotubes, crystalline structure

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Authors: Muhammad R. Islam, Mohammad Dalour H. Beg, Saidatul S. Jamari

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Considering palm oil as non-drying oil owing to its low iodine value, an attempt was taken to increase the unsaturation in the fatty acid chains of palm oil for the preparation of alkyds. To increase the unsaturation in the palm oil, sulphuric acid (SA) and para-toluene sulphonic acid (PTSA) was used prior to alcoholysis for the dehydration process. The iodine number of the oil samples was checked for the unsaturation measurement by Wijs method. Alkyd resin was prepared using the dehydrated palm oil by following alcoholysis and esterification reaction. To improve the film properties 0.5 wt% multi-wall carbon nano tubes (MWCNTs) were used to manufacture polymeric film. The properties of the resins were characterized by various physico-chemical properties such as density, viscosity, iodine value, acid value, saponification value, etc. Structural elucidation was confirmed by Fourier transform of infrared spectroscopy and proton nuclear magnetic resonance; surfaces of the cured films were observed by scanning electron microscopy. In addition, pencil hardness and chemical resistivity was also measured by using standard methods. The effect of enhancement of the unsaturation in the fatty acid chain found significant and motivational. The resin prepared with dehydrated palm oil showed improved properties regarding hardness and chemical resistivity testing. The incorporation of MWCNTs enhanced the thermal stability and hardness of the films as well.

Keywords: alkyd resin, nano-coatings, dehydration, palm oil

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Authors: Leticia Leandro Rade, Amanda Silva de Sousa, Suman Das, Wesley Generoso, Mayara Chagas Ávila, Plinio Salmazo Vieira, Antonio Bonomi, Gabriela Persinoti, Mario Tyago Murakami, Thomas Michael Makris, Leticia Maria Zanphorlin

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Alkenes have an economic appeal, especially in the biofuels field, since they are precursors for drop-in biofuels production, which have similar chemical and physical properties to the conventional fossil fuels, with no oxygen in their composition. After the discovery of the first P450 CYP152 OleTJE in 2011, reported with its unique property of decarboxylating fatty acids (FA), by using hydrogen peroxide as a cofactor and producing 1-alkenes as the main product, the scientific and technological interest in this family of enzymes vastly increased. In this context, the present work presents a new decarboxylase (OleTRN) with low similarity with OleTJE (32%), its biochemical characterization, and structure elucidation. As main results, OleTRN presented a high yield of expression and purity, optimum reaction conditions at 35 °C and pH from 6.5 to 8.0, and higher specificity for oleic acid. Besides that, structure-guided mutations were performed and according to the functional characterizations, it was observed that some mutations presented different specificity and chemoselectivity by varying the chain-length of FA substrates from 12 to 20 carbons. These results are extremely interesting from a biotechnological perspective as those characteristics could diversify the applications and contribute to designing better cytochrome P450 decarboxylases. Considering that peroxygenases have the potential activity of decarboxylating and hydroxylating fatty acids and that the elucidation of the intriguing mechanistic involved in the decarboxylation preferential from OleTJE is still a challenge, the elucidation of OleTRN structure and the functional characterizations of OleTRN and its mutants contribute to new information about CYP152. Besides that, the work also contributed to the discovery of a new decarboxylase with a different selectivity profile from OleTJE, which allows a wide range of applications.

Keywords: P450, decarboxylases, alkenes, biofuels

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Authors: Hiroyuki Aoki

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Polymeric materials are often used in a form of thin film such as food wrap and surface coating. In such the applications, polymer films thinner than 100 nm have been often used. The thickness of such the ultra-thin film is less than the unperturbed size of a polymer chain; therefore, the polymer chain in an ultra-thin film is strongly constrained. However, the details on the constrained dynamics of polymer molecules in ultra-thin films are still unclear. In the current study, the segmental dynamics of single polymer chain was directly investigated by fluorescence microscopy. The individual chains of poly(alkyl methacrylate) labeled by a perylenediimide dye molecule were observed by a highly sensitive fluorescence microscope in a defocus condition. The translational and rotational diffusion of the center segment in a single polymer chain was directly analyzed. The segmental motion in a thin film with a thickness of 10 nm was found to be suppressed compared to that in a bulk state. The detailed analysis of the molecular motion revealed that the diffusion rate of the in-plane rotation was similar to the thin film and the bulk; on the other hand, the out-of-plane motion was restricted in a thin film. This result indicates that the spatial restriction in an ultra-thin film thinner than the unperturbed chain dimension alters the dynamics of individual molecules in a polymer system.

Keywords: polymer materials, single molecule, molecular motion, fluorescence microscopy, super-resolution techniques

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Authors: Vidia A. Nuraini, Eugene M. H. Yee, Mohan Bhadbhade, David StC. Black, Naresh Kumar

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Flavonoids are naturally occurring compounds that have been shown to exhibit a wide range of biological properties including anticancer and anti-inflammatory activities. However, flavonoids suffer from low bioavailability, which limits their overall utility for therapeutic applications. One of the methods to overcome this limitation is through structural modification of natural flavonoids. In this study, flavanone, isoflavanone, and isoflavene, were structurally modified through the introduction of additional fused-ring systems via ortho-quinone methide intermediates (o-QMs). These intermediates can readily undergo a [4+2] cycloaddition through an inverse-electron-demand Diels–Alder reaction with electron-rich dienophiles. A regioselective Mannich reaction using bis-(N,N-dimethylamino)methane was employed to generate the o-QM precursors of flavanone, isoflavanone, and isoflavene. The o-QM intermediates were subsequently generated in situ through thermal elimination of the dimethylamine functionality and reacted with a variety of dienophiles to produce novel flavonoids with fused-ring systems. A total of 21 novel flavonoid analogs were successfully synthesized. The X-ray crystal structure of cycloaddition adducts, particularly those derived from 3,4-dihydro-2H-pyran and p-methoxystyrene revealed a special case of enantiomeric disorder, where two enantiomers in equal amounts superpose with one another, with the exception for atoms that have opposite configuration. The anticancer properties of fused-ring systems derived from isoflavene were evaluated against the neuroblastoma SKN-BE(2)C, the triple negative breast cancer MDA-MB-231, and the glioblastoma U87 cancer cell lines. One of these cycloaddition adducts had displayed improved anti-proliferative activity against MDA-MB-231 and U87 cancer cell lines as compared to the parent compound. Further anticancer and anti-inflammatory activities of the flavanone and isoflavanone analogs are currently being investigated.

Keywords: Diels-Alder reaction, flavonoids, Mannich reaction, ortho-quinone methide.

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Authors: Viriyavudh Sim, SeungHyun Kim, JungKyu Choi, WooYoung Jung

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Glass Fiber Reinforced Polymer (GFRP) is a major evolution for energy dissipation when used as infill material for seismic retrofitting of steel frame, a basic PMC infill wall system consists of two GFRP laminates surrounding an infill of foam core. This paper presents numerical analysis in terms of buckling resistance of GFRP sandwich infill panels system under the influence of environment temperature and stacking sequence of laminate skin. Mode of failure under in-plane compression is studied by means of numerical analysis with ABAQUS platform. Parameters considered in this study are contact length between infill and frame, laminate stacking sequence of GFRP skin and variation of mechanical properties due to increment of temperature. The analysis is done with four cases of simple stacking sequence over a range of temperature. The result showed that both the effect of temperature and stacking sequence alter the performance of entire panel system. The rises of temperature resulted in the decrements of the panel’s strength. This is due to the polymeric nature of this material. Additionally, the contact length also displays the effect on the performance of infill panel. Furthermore, the laminate stiffness can be modified by orientation of laminate, which can increase the infill panel strength. Hence, optimal performance of the entire panel system can be obtained by comparing different cases of stacking sequence.

Keywords: buckling resistance, GFRP infill panel, stacking sequence, temperature dependent

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Authors: Salah Al-Enezi, Rashed Al-Zufairi, Naseer Ahmad

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A Thermo-mechanical technique was developed to determine softening point temperature/glass transition temperature (Tg) of polystyrene exposed to high pressures. The design utilizes the ability of carbon dioxide to lower the glass transition temperature of polymers and acts as plasticizer. In this apparatus, the sorption of carbon dioxide to induce softening of polymers as a function of temperature/pressure is performed and the extent of softening is measured in three-point-flexural-bending mode. The polymer strip was placed in the cell in contact with the linear variable differential transformer (LVDT). CO₂ was pumped into the cell from a supply cylinder to reach high pressure. The results clearly showed that full softening point of the samples, accompanied by a large deformation on the polymer strip. The deflection curves are initially relatively flat and then undergo a dramatic increase as the temperature is elevated. It was found that increasing the pressure of CO₂ causes the temperature curves to shift from higher to lower by increment of about 45 K, over the pressure range of 0-120 bars. The obtained experimental Tg values were validated with the values reported in the literature. Finally, it is concluded that the defection model fits consistently to the generated experimental results, which attempts to describe in more detail how the central deflection of a thin polymer strip affected by the CO₂ diffusions in the polymeric samples.

Keywords: softening, high-pressure, polystyrene, CO₂ diffusions

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Authors: Ali Bayram, Remzi Yiğiter

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Objective: Alzheimer's disease (AD), the most common cause of dementia, is a progressive neurodegenerative disease. At present, diagnosis of AD is rather late in the disease. Therefore, we attempted to find peripheral biomarkers for the early diagnosis of AD. Herein, we conducted a study to investigate the unc-51 like autophagy activating kinase-1 (ULK1) mRNA expression levels in human peripheral blood mononuclear cells from patients with Alzheimer's disease. Method: To determine whether ULK1 gene expression are altered in AD patients, we measured their gene expression in human peripheral blood cell in 50 patients with AD and 50 age and gender matched healthy controls by quantitative real-time PCR technique. Results: We found that both ULK1 gene expression in peripheral blood cell were significantly decreased in patients with AD as compared with controls (p <0.05). Lower levels of ULK1 gene expression were significantly associated with the increased risk for AD. Conclusions: Serine/threonine-protein kinase involved in autophagy in response to starvation. Acts upstream of phosphatidylinositol 3-kinase PIK3C3 to regulate the formation of autophagophores, the precursors of autophagosomes. Part of regulatory feedback loops in autophagy: acts both as a downstream effector and negative regulator of mammalian target of rapamycin complex 1 (mTORC1) via interaction with RPTOR. Activated via phosphorylation by AMPK and also acts as a regulator of AMPK by mediating phosphorylation of AMPK subunits PRKAA1, PRKAB2, and PRKAG1, leading to negatively regulate AMPK activity. May phosphorylate ATG13/KIAA0652 and RPTOR; however such data need additional evidences. Plays a role early in neuronal differentiation and is required for granule cell axon formation. Alzheimer is the most common neurodegenerative disease. Our results provide useful information that the ULK1 gene expression is decreased in the neurodegeneration and AD patients with, indicating their possible systemic involvement in AD.

Keywords: Alzheimer’s sisease, ULK1, mRNA expression, RT-PCR

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Authors: Claudiu Marcu, Cristina Paul, Adelina Andelescu, Corneliu Mircea Davidescu, Francisc Péter

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Heavy metal pollution has become a more serious environmental problem in the last several decades as a result of its toxicity and insusceptibility to the environment. Methods for removing metal ions from aqueous solution mainly consist of physical, chemical and biochemical procedures. Biosorption is defined as the removal of metal or metalloid species, compounds and particulates from solution by a biological material. Biosorption represents a very attractive method for the removal of toxic metal ions from aqueous effluents because it uses the ability of various biomass to bind the metal ions without the risk of releasing other toxic chemical compounds into the environment. The problem with using biomass or living cells as biosorbents is that their regeneration/reuse is often either impossible or very laborious. One of the most common chelating group found in biosorbents is the thiol group in cysteine. Therefore, we immobilized cysteine using covalent binding using glutaraldehyde as a linker on a synthetic sol-gel support obtained using 3-amino-propyl-trimetoxysilane and trimetoxysilane as precursors. The obtained adsorbents were used for removal of cadmium from aqueous solutions and the removal capacity was investigated in relation to the composition of the sol-gel hybrid composite, the loading of the biomolecule and the physical parameters of the biosorption process. In the same conditions, the bare sol-gel support without cysteine had no Cd removal effect, while the adsorbent with cysteine had an adsorption capacity up to 25.8 mg Cd/g adsorbent at pH 2.0 and 119 mg Cd/g adsorbent at pH 6.6, depending on cadmium concentration and adsorption conditions. We used atomic adsorption spectrometry to assess the cadmium concentration in the samples after the biosorbtion process. The parameters for the Freundlich and Langmuir adsorption isotherms where calculated from plotting the results of the adsorption experiments. The results for cysteine immobilization show a good loading capacity of the sol-gel support which indicates it could be used to immobilize metal binding proteins and by doing so boosting the heavy metal adsorption capacity of the biosorbent.

Keywords: biosorbtion, cadmium, cysteine covalent binding, sol-gel

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Authors: Baburao Ganpat Apte, Gajodhar

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Introduction: diopathic Parkinson’s disease (PD) is the most common neurodegenerative disorder. Early PD may present a diagnostic challenge with broad differential diagnoses that are not associated with striatal dopamine deficiency. This test was performed by using special type of radioactive precursor which was made available through our logistics. 131I-TOPA L-6-[131I] Iodo-3,4-Trihydroxyphenylalnine (131I -TOPA) is a positron emission tomography (PET) agent that measures the uptake of dopamine precursors for assessment of presynaptic dopaminergic integrity and has been shown to accurately reflect the sign of nervous mind going in patients suffers from monoaminergic disturbances in PD. Both qualitative and quantitative analyses of the scans were performed. Therefore, the early clinical diagnosis alone may be accurate and this reinforces the importance of functional imaging targeting the patholigically of the disease process. The patient’s medical records were then assessed for length of follow-up, response to levotopa, clinical course of sickness, and usually though of symptoms at time of 131I -TOPA PET. A respective analysis was carried out for all patients that gone through 131I -TOPA PET brain scan for motor symptoms suspicious for PD between 2000 - 2006. The eventual diagnosis by the referring neurologist, movement therapist, physiotherapist, was used as the accurate measurements in standard for further analysis. In this study, our goal to illustrate our local experience to determine the accuracy of 131I -TOPA PET for diagnosis of PD. We studied a total of 48 patients. Of the 25 scans, it found that one was a false negative, 40 were true positives, and 7 were true negatives. The resultant values are Sensitivity 90.4% (95% CI: 100%-71.3%), Specificity 100% (92% CI: 100%-58.0%), PPV 100% (91% CI 100%-75.7%), and NPV 80.5% (95% CI: 92.5%-48.5%). Result: Twenty-three patients were found in the initial query, and 1 were excluded (2 uncertain diagnosis, 2 inadequate follow-up). Twenty-eight patients (28 scans) remained with 15 males (62%) and 8 females (30%). All the patients had a clinical follow-up of at least 3 years, however the median length of follow-up was 5.5 years (range: 2-8 years). The median age at scan time was 51.2 years (range: 35-75)

Keywords: 18F-TOPA, petct, parkinson’s disease, cardiac

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Authors: Mazyar Ahrari, Ramin Khajavi, Mehdi Kamali Dolatabadi, Tayebeh Toliyat, Abosaeed Rashidi

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Fabric as the first and most common layer that is in permanent contact with human skin is a very good interface to provide coverage, as well as heat and cold insulation. Phase change materials (PCMs) are organic and inorganic compounds which have the capability of absorbing and releasing noticeable amounts of latent heat during phase transitions between solid and liquid phases at a low temperature range. PCMs come across phase changes (liquid-solid and solid-liquid transitions) during absorbing and releasing thermal heat; so, in order to use them for a long time, they should have been encapsulated in polymeric shells, so-called microcapsules. Microencapsulation and nanoencapsulation methods have been developed in order to reduce the reactivity of a PCM with outside environment, promoting the ease of handling, decreasing the diffusion and evaporation rates. Methods of incorporation of PCMs in textiles such as electrospinning and determining thermal properties had been summarized. Paraffin waxes catch a lot of attention due to their high thermal storage density, repeatability of phase change, thermal stability, small volume change during phase transition, chemical stability, non-toxicity, non-flammability, non-corrosive and low cost and they seem to play a key role in confronting with climate change and global warming. In this article, we aimed to review the researches concentrating on the characteristics of PCMs and new materials and methods of microencapsulation.

Keywords: thermoregulation, microencapsulation, phase change materials, thermal energy storage, nanoencapsulation

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Authors: Lucky Malise, Hilary Rutto, Tumisang Seodigeng

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Heavy metal contamination in waste water is a very serious issue affecting a lot of industrialized countries due to the health and environmental impact of these heavy metals on human life and the ecosystem. Adsorption using activated carbon is the most promising method for the removal of heavy metals from waste water but commercial activated carbon is expensive which gives rise to the need for alternatively activated carbon derived from cheap precursors, agricultural wastes, or byproducts from other processes. In this study activated bio-carbon derived from the carbonaceous material obtained from the pyrolysis of Marula nut shells was chemically activated and used as an adsorbent for the removal of lead (II) and copper (II) ions from aqueous solution. The surface morphology and chemistry of the adsorbent before and after chemical activation with zinc chloride impregnation were studied using SEM and FTIR analysis respectively and the results obtained indicate that chemical activation with zinc chloride improves the surface morphology of the adsorbent and enhances the intensity of the surface oxygen complexes on the surface of the adsorbent. The effect of process parameters such as adsorbent dosage, pH value of the solution, initial metal concentration, contact time, and temperature on the adsorption of lead (II) and copper (II) ions onto Marula nut activated carbon were investigated, and their optimum operating conditions were also determined. The experimental data was fitted to both the Langmuir and Freundlich isotherm models, and the data fitted best on the Freundlich isotherm model for both metal ions. The adsorption kinetics were also evaluated, and the experimental data fitted the pseudo-first order kinetic model better than the pseudo second-order kinetic model. The adsorption thermodynamics were also studied and the results indicate that the adsorption of lead and copper ions is spontaneous and exothermic in nature, feasible, and also involves a dissociative mechanism in the temperature range of 25-45 °C.

Keywords: adsorption, isotherms, kinetics, marula nut shells activated carbon, thermodynamics

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Authors: Suzanne Ahmed

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Nanomotors, also commonly referred to as nanorobotics or nanomachines, have garnered considerable research attention due to their numerous potential applications in biomedicine, including drug delivery and microsurgery. Nanomotors typically consist of inorganic or polymeric particles that are powered to undergo motion. These artificial, man-made nanoscale motors operate in the low Reynolds number regime and typically have no moving parts. Several methods have been developed to actuate the motion of nanomotors including magnetic fields, electrical fields, electromagnetic waves, and chemical fuel. Since their introduction in 2012, ultrasonically powered nanomotors have been explored in biocompatible fluids and even within living cells. Due to the common use of ultrasound within the biomedical community for both imaging and therapeutics, the introduction of ultrasonically propelled nanomotors holds significant potential for biomedical applications. In this work, metallic nanomotors are electrochemically plated within porous anodic alumina templates to have a diameter of 300 nm and a length that is 2-4 µm. Nanomotors are placed within an acoustic chamber capable of producing bulk acoustic waves in the ultrasonic range. The motion of nanomotors within biomimetic confines is explored. The control over nanomotor motion is exerted by virtue of the properties of the acoustic signal within these biomimetic confines to control speed, modes of motion and directionality of motion. To expand the range of control over nanorod motion within biomimetic confines, external forces from biocompatible magnetic fields, are exerted onto the acoustically propelled nanomotors.

Keywords: nanomotors, nanomachines, nanorobots, ultrasound

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Authors: Eva Ujaczki, Rama Krishna Chinnam, Ronan Courtney, Syed A. M. Tofail, Lisa O'Donoghue

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Concrete is the second most widely used material in the world and is made of cement, sand, and aggregates. Cement is a hydraulic binder which reacts with water to form a solid material. In the cement manufacturing process, the right mix of minerals from mined natural rocks, e.g., limestone is melted in a kiln at 1450 °C to form a new compound, clinker. In the final stage, the clinker is milled into a fine cement powder. The principal cement types manufactured in Ireland are: 1) CEM I – Portland cement; 2) CEM II/A – Portland-fly ash cement; 3) CEM II/A – Portland-limestone cement and 4) CEM III/A – Portland-round granulated blast furnace slag (GGBS). The production of eco-efficient, blended cement (CEM II, CEM III) reduces CO₂ emission and improves energy efficiency compared to traditional cements. Blended cements are produced locally in Ireland and more than 80% of produced cement is blended. These eco-efficient, blended cements are a relatively new class of construction materials and a kind of geopolymer binders. From a terminological point of view, geopolymer cement is a binding system that is able to harden at room temperature. Geopolymers do not require calcium-silicate-hydrate gel but utilize the polycondensation of SiO₂ and Al₂O₃ precursors to achieve a superior strength level. Geopolymer materials are usually synthesized using an aluminosilicate raw material and an activating solution which is mainly composed of NaOH or KOH and Na₂SiO₃. Cement is the essential ingredient in concrete which is vital for economic growth of countries. The challenge for the global cement industry is to reach to increasing demand at the same time recognize the need for sustainable usage of resources. Therefore, in this research, we investigated the potential for Irish wastes to be used in geopolymer cement type applications through a national stakeholder workshop with the Irish construction sector and relevant stakeholders. This paper aims at summarizing Irish stakeholder’s perspective for introducing new secondary raw materials, e.g., bauxite residue or increasing the fly ash addition into cement for eco-efficient cement production.

Keywords: eco-efficient, cement, geopolymer, blending

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Authors: Mosaad Attia Elkasaby

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The crude oil contains paraffines, aromatics, and asphaltenes in addition to some organic impurities, with increasing demands to reduce the cost of crude oil production, the uses of a pour point depressant is mandatory to maintain good flow rate. The wax materials cause many problems during production, storage, and transport, especially at low temperature, as these waxes tend, at low temperatures, to precipitate on the wall lines, thus leads to the high viscosity of crude oil and impede the flow rate, which represents an additional burden for crude oil pumping system from the place of production to the refinery. There are many ways to solve this problem, including, but not limited to, heat the crude and the use of organic solvents. But one of the most important disadvantages of these methods is the high economic cost. The aim of this innovation is to manufacture some polymeric materials (polymers based on aniline) that are processed locally that can be used as a pour point depressant of crude oil. For the first time, polymer based on aniline is modified and used with a number of organic solvents and tested with solvent (Styrene). It was found that the polymer based on aniline, when modified, had full solubility in styrene, unlike other organic solvent that was used in the past, such as chloroform and toluene. We also used a new solvent (PONA) that is obtained from the process of hydrotreating and separation of straight run naphtha to dissolve polymer based on aniline as a pour point depressant of crude oil. This innovative include studies conducted on highly paraffinic crude oil (C.O.1 and C.O.2). On using concentration (2500 ppm) of polymer based on aniline, the pour point of crude oil has decreased from +33 to - 9°C in case of crude oil (C.O.1) and from + 42 to – 6°C in case crude oil (C.O.2) at the same concentration.

Keywords: PPD, aniline, paraffinic crude oils, polymers

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Authors: Mazouzi Nourdjihane, K. Boutemak, A. Haddad, Y. Chegreouche

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In the last decades, biodegradable polymers have been considered as one of the most popular options for the delivery of drugs and various conventional doses. The film forming system (FFS) can be used in topical, transdermal, ophthalmic, oral and gastric applications. Recently this system has focused on improving drug delivery, which can promote drug release. In this context, the aim of this study is to create polymeric film-forming systems for the stomach and to evaluate and test their gastroprotective effects, comparing the effects of changes in composition on film characteristics. It uses a plant-derived polyphenol extract extracted from fennel to demonstrate anti-inflammatory activity in the film. The films are made from hydroxypropyl methylcellulose polymer and different types of plastic, glycerol and polyethylene glycol. The ffs properties show that MgO-glycerol-reinforced hydroxypropylmethylcellulose (HPMC-MgO-Gly) is better than that based on MgO-PEG-reinforced hydroxypropylmethylcellulose (HPMC-MgO-PEG). It is durable, has a faster drying time and allows for maximum recovery. Water vapor strength and blowing speed and other additions show another advantage of HPMC-MgO-Gly compared to HPMC-MgO-PEG, indicating good adhesion between the support (top) and film production. In this study, the gastroprotective effect of fennel phenol extract was found, showing that this plant material has a gastroprotective effect on ulcers and that the film can absorb the active substance.

Keywords: film formin system, hydroxypropyl methylcellulose, magnesium oxide, in vivo

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Authors: Saba Atefyekta

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Aim: Control of bacterial bioburden in wounds is an important step for minimizing the risk of wound infection. An antimicrobial hydrogel wound dressing is developed out of soft polymeric hydrogels that contain antimicrobial peptides (AMPs). Such wound dressings can bind and kill all types of bacteria, even the resistance types at the wound site. Methods: AMPs are permanently bonded onto a soft nanostructured polymer via covalent attachment and physical entanglement. This improves stability, rapid antibacterial activity, and, most importantly, prevents the leaching of AMPs. Major Findings: Antimicrobial analysis of antimicrobial hydrogels using in-vitro wound models confirmed >99% killing efficiency against multiple bacterial trains, including MRSA, MDR, E. Coli. Furthermore, the hydrogel retained its antibacterial activity for up to 4 days when exposed to human serum. Tests confirmed no release of AMPs, and it was proven non-toxic to mammalian cells. An in-vivo study on human intact skin showed a significant reduction of bacteria for part of the subject’s skin treated with antibacterial hydrogels. A similar result was detected through a qualitative study in veterinary trials on different types of surgery wounds in cats, dogs, and horses. Conclusions: Antimicrobial hydrogels wound dressings developed by permanent attachment of AMPs can effectively and rapidly kill bacteria in contact. Such antibacterial hydrogel wound dressings are non-toxic and do not release any substances into the wound.

Keywords: antibacterial wound dressing, antimicrobial peptides, post-surgical wounds, infection

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Authors: Mohamed Majrashi, Patricia Connolly, Terry Gourlay

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Cardiopulmonary bypass is known to cause inflammatory response during open heart surgery. It includes the initiation of different cascades such as coagulation, complement system and cytokines. Although the immune system is body’s key defense mechanism against external assault, when overexpressed, it can be injurious to the patient, particularly in a cohort of patients in which there is a heightened and uncontrolled response. The inflammatory response develops in these patients to an exaggerated level resulting in an autoimmune injury and may lead to poor postoperative outcomes (systemic inflammatory response syndrome and multi-organs failure). Previous studies by this group have suggested a correlation between the level of IL6 measured in patient’s blood before surgery and after polymeric activation and the observed inflammatory response during surgery. Based upon these findings, the present work is aimed at using this response to develop a test which can be used prior to the open heart surgery to identify the high-risk patients before their operation. The work will be accomplished via three main clinical phases including some pilot in-vitro studies, device development and clinical investigation. Current findings from studies using animal blood, employing DEHP and DEHP plasticized PVC materials as the activator, support the earlier results in patient samples. Having established this relationship, ongoing work will focus on developing an activated lateral flow strip technology as a screening device for heightened inflammatory propensity.

Keywords: cardiopulmonary bypass, cytokines, inflammatory response, overexpression

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Authors: Flavia Laffleur

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Summary: Biomaterials have gained immense interest in the pharmaceutical research in the last decades. Hyaluronic acid a carbohydrate and mucopolysaccharide was chemically modified in order to achieve and establish a promising platform for buccal drug delivery. Aim: Novel biomaterial was tested for its potential for buccal drug delivery. Background: Polysaccharide hyaluronic acid (HA) was chemically modified with cysteine ethyl ether (CYS). By immobilization of the thiol-bearing ligand on the polymeric backbone the thiolated bioconjugate HA-CYS was obtained. Methodology: Mucoadhesive, permeation enhancing and stability potential as well as mechanical, physicochemical properties further mucoadhesive strength, swelling index and residence time were investigated. The developed thiolated bioconjugate displayed enhanced mucoadhesiveness on buccal mucosa as well as permeation behavior and polymer stability. The near neutral pH and negative cytotoxicity studies indicated their non-irritability and biocompatible nature with biological tissues. Further, the model drug sulforhodamine 101 was incorporated to determine its drug release profiles. Results: The synthesized thiomer showed no toxicity. The mucoadhesion of thiolated hyaluronic acid on buccal mucosa was significantly improved in comparison to unmodified one. The biomaterial showed 2.5-fold higher stability in polymer structure. The release of sulforhodamine in the presence of thiolated hyaluronic acid was 2.3-fold increased compared to hyaluronic acid. Conclusion: Thus, the promising results encourage further investigations and exploitation of this versatile polysaccharide. So far, hyaluronic acid was not evaluated for buccal drug delivery.

Keywords: buccal delivery, hyaluronic acid, mucoadhesion, thiomers

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Authors: Samaneh Nabavi, Hadi Shirzad, Arash Ghoorchian, Maryam Shanesaz, Reza Naderi

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Morphine (MO), the most effective painkiller, is considered the reference by which analgesics are assessed. It is very necessary for the biomedical applications to detect and maintain the MO concentrations in the blood and urine with in safe ranges. To date, there are many expensive techniques for detecting MO. Recently, many electrochemical sensors for direct determination of MO were constructed. The molecularly imprinted polymer (MIP) is a polymeric material, which has a built-in functionality for the recognition of a particular chemical substance with its complementary cavity.This paper reports a sensor for MO using a combination of a molecularly imprinted polymer (MIP) and differential-pulse voltammetry (DPV). Electropolymerization of MO doped polypyrrole yielded poor quality, but a well-doped, nanostructure and increased impregnation has been obtained in the pH=12. Above a pH of 11, MO is in the anionic forms. The effect of various experimental parameters including pH, scan rate and accumulation time on the voltammetric response of MO was investigated. At the optimum conditions, the concentration of MO was determined using DPV in a linear range of 7.07 × 10−6 to 2.1 × 10−4 mol L−1 with a correlation coefficient of 0.999, and a detection limit of 13.3 × 10-8 mol L−1, respectively. The effect of common interferences on the current response of MO namely ascorbic acid (AA) and uric acid (UA) is studied. The modified electrode can be used for the determination of MO spiked into urine samples, and excellent recovery results were obtained. The nanostructured polypyrrole films were characterized by field emission scanning electron microscopy (FESEM) and furrier transforms infrared (FTIR).

Keywords: morphine detection, sensor, polypyrrole, nanostructure, molecularly imprinted polymer

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Authors: Reema Tiwari, U. C. Kulshrestha

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As a key regulator of atmospheric oxidative capacity and secondary aerosol formations, the signatures of reactive nitrogen (Nr) emissions are becoming increasingly evident in the cascade of air pollution, acidification, and eutrophication of the ecosystem. However, their accurate estimates in N budget remains limited by the photochemical conversion processes where occurrence of differential atmospheric residence time of gaseous (NOₓ, HNO₃, NH₃) and particulate (NO₃⁻, NH₄⁺) Nr species becomes imperative to their spatio temporal evolution on a synoptic scale. The present study attempts to quantify such interactions under tropical conditions when low anticyclonic winds become favorable to the advections from west during winters. For this purpose, a diurnal sampling was conducted using low volume sampler assembly where ambient concentrations of Nr trace gases along with their ionic fractions in the aerosol samples were determined with UV-spectrophotometer and ion chromatography respectively. The results showed a spatial gradient of the gaseous precursors with a much pronounced inter site variability (p < 0.05) than their particulate fractions. Such observations were confirmed for their limited photochemical conversions where less than 1 ratios of day and night measurements (D/N) for the different Nr fractions suggested an influence of boundary layer dynamics at the background site. These phase conversion processes were further corroborated with the molar ratios of NOₓ/NOᵧ and NH₃/NHₓ where incomplete titrations of NOₓ and NH₃ emissions were observed irrespective of their diurnal phases along the sampling transect. Their calculations with equilibrium based approaches for an NH₃-HNO₃-NH₄NO₃ system, on the other hand, were characterized by delays in equilibrium attainment where plots of their below deliquescence Kₘ and Kₚ values with 1000/T confirmed the role of lower temperature ranges in NH₄NO₃ aerosol formation. These results would help us in not only resolving the changing atmospheric inputs of reduced (NH₃, NH₄⁺) and oxidized (NOₓ, HNO₃, NO₃⁻) Nr estimates but also in understanding the dependence of Nr mixing ratios on their local meteorological conditions.

Keywords: diurnal ratios, gas-aerosol interactions, spatial gradient, thermodynamic equilibrium

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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: Danila Merino, Leandro N. Ludueña, Vera A. Alvarez

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Clays are commonly used to reinforce polymeric materials. In order to modify them, long-chain quaternary-alkylammonium salts have been widely employed. However, the application of these clays in biological fields is limited by the toxicity and poor biocompatibility presented by these modifiers. Meanwhile, soy lecithin, acts as a natural biosurfactant and environment-friendly biomodifier. In this report, we analyse the effect of content of soy lecithin-modified bentonite on the properties of polycaprolactone (PCL) nanocomposites. Commercial grade PCL (CAPA FB 100) was supplied by Perstorp, with Mw = 100000 g/mol. Minarmco S.A. and Melar S.A supplied bentonite and soy lecithin, respectively. Clays with 18, 30 and 45 wt% of organic content were prepared by exchanging 4 g of Na-Bent with 1, 2 and 4 g of soy lecithin aqueous and acid solution (pH=1, with HCl) at 75ºC for 2 h. Then, they were washed and lyophilized for 72 h. Samples were labeled A, B and C. Nanocomposites with 1 and 2 wt.% of each clay were prepared by melt-intercalation followed by compression-moulding. An intensive Brabender type mixer with two counter-rotating roller rotors was used. Mixing temperature was 100 ºC; speed of rotation was 100 rpm. and mixing time was 10 min. Compression moulding was carried out in a hydraulic press under 75 Kg/mm2 for 10 minutes at 100 ºC. The thickness of the samples was about 1 mm. Thermal and mechanical properties were analysed. PCL nanocomposites with 1 and 2% of B presented the best mechanical properties. It was observed that an excessive organic content produced an increment on the rigidity of PCL, but caused a detrimental effect on the tensile strength and elongation at break of the nanocomposites. Thermogravimetrical analyses suggest that all reinforced samples have higher resistance to degradation than neat PCL.

Keywords: chemical modification, clay, nanocomposite, characterization

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