Search results for: Raman spectroscopy

Authors: Mohsin Ejaz, Shiao-Wei Kuo

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The growing production and exploitation of fossil fuels have placed human society in serious environmental issues. As a result, it's critical to design efficient and eco-friendly energy production and storage techniques. Porous organic polymers (POPs) are multi-dimensional porous network materials developed through the formation of covalent bonds between different organic building blocks that possess distinct geometries and topologies. POPs have tunable porosities and high surface area making them a good candidate for an effective electrode material in energy storage applications. Herein, we prepared a fully benzoxazine-based porous organic polymers (TPA–DHTP–BZ POP) through sonogashira coupling of dihydroxyterephthalaldehyde (DHPT) and triphenylamine (TPA) containing benzoxazine (BZ) monomers. Firstly, both BZ monomers (TPA-BZ-Br and DHTP-BZ-Ea) were synthesized by three steps, including Schiff base, reduction, and mannich condensation reaction. Finally, the TPA–DHTP–BZ POP was prepared through the sonogashira coupling reaction of brominated monomer (TPA-BZ-Br) and ethynyl monomer (DHTP-BZ-Ea). Fourier transform infrared (FTIR) and solid-state nuclear magnetic resonance (NMR) spectroscopy confirmed the successful synthesis of monomers as well as POP. The porosity of TPA–DHTP–BZ POP was investigated by the N₂ absorption technique and showed a Brunauer–Emmett–Teller (BET) surface area of 196 m² g−¹, pore size 2.13 nm and pore volume of 0.54 cm³ g−¹, respectively. The TPA–DHTP–BZ POP experienced thermal ring-opening polymerization, resulting in poly (TPA–DHTP–BZ) POP having strong inter and intramolecular hydrogen bonds formed by phenolic groups and Mannich bridges, thereby enhancing CO₂ capture and supercapacitive performance. The poly(TPA–DHTP–BZ) POP demonstrated a remarkable CO₂ capture of 3.28 mmol g−¹ and a specific capacitance of 67 F g−¹ at 0.5 A g−¹. Thus, poly(TPA–DHTP–BZ) POP could potentially be used for energy storage and CO₂ capture applications.

Keywords: porous organic polymer, benzoxazine, sonogashira coupling, CO₂, supercapacitor

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Authors: Dong Xie, Jun Zhao, Yiming Weng

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One of the challenges in dental cement biomaterials is how to make a restorative with mechanical strengths and wear resistance that are comparable to contemporary dental resin composites. Currently none of the dental cement restoratives has been used in high stress-bearing sites due to their low mechanical strengths and poor wear-resistance. The objective of this study was to synthesize and characterize the poly(alkenoic acid)s with different molecular structures, use these polymers to formulate a dental cement restorative, and study the effect of molecular structures on reaction kinetics, viscosity, and mechanical strengths of the formed polymers and cement restoratives. In this study, poly(alkenoic acid)s with different molecular structures were synthesized. The purified polymers were formulated with commercial Fuji II LC glass fillers to form the experimental cement restoratives. The reaction kinetics was studied via 1HNMR spectroscopy. The formed restoratives were evaluated using compressive strength, diametral tensile strength, flexural strength, hardness and wear-resistance tests. Specimens were conditioned in distilled water at 37 oC for 24 h prior to testing. Fuji II LC restorative was used as control. The results show that the higher the arm number and initiator concentration, the faster the reaction was. It was also found that the higher the arm number and branching that the polymer had, the lower the viscosity of the polymer in water and the lower the mechanical strengths of the formed restorative. The experimental restoratives were 31-53% in compressive strength, 37-55% in compressive modulus, 80-126% in diametral tensile strength, 76-94% in flexural strength, 4-21% in fracture toughness and 53-96% in hardness higher than Fuji II LC. For wear test, the experimental restoratives were only 5.4-13% of abrasive and 6.4-12% of attritional wear depths of Fuji II LC in each wear cycle. The aging study also showed that all the experimental restoratives increased their strength continuously during 30 days, unlike Fuji II LC. It is concluded that polymer molecular structures have significant and positive impact on mechanical properties of dental cement restoratives.

Keywords: dental materials, polymers, strength, biomaterials

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Authors: Zahid Ali Ghazi

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Supercapacitors (SCs) have emerged as auspicious energy storage devices because of their fast charge-discharge characteristics and high power densities. In the current study, a simple approach is used to coat activated carbon (AC) with a thin layer of nickel (Ni) by an electroless deposition process to enhance the electrochemical performance of the SC. The synergistic combination of large surface area and high electrical conductivity of the AC, as well as the pseudocapacitive behavior of the metallic Ni, has shown great potential to overcome the limitations of traditional SC materials. First, the materials were characterized using X-ray diffraction (XRD) for crystallography, scanning electron microscopy (SEM) for surface morphology and energy dispersion X-ray (EDX) for elemental analysis. The electrochemical performance of the nickel-coated activated carbon (Ni-AC) is systematically evaluated through various techniques, including galvanostatic charge-discharge (GCD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The GCD results revealed that Ni/AC has a higher specific capacitance (1559 F/g) than bare AC (222 F/g) at 1 A/g current density in a 2 M KOH electrolyte. Even at a higher current density of 20 A/g, the Ni/AC showed a high capacitance of 944 F/g as compared to 77 F/g by AC. The specific capacitance (1318 F/g) calculated from CV measurements for Ni-AC at 10mV/sec was in close agreement with GCD data. Furthermore, the bare AC exhibited a low energy of 15 Wh/kg at a power density of 356 W/kg whereas, an energy density of 111 Wh/kg at a power density of 360 W/kg was achieved by Ni/AC-850 electrode and demonstrated a long life cycle with 94% capacitance retention over 50000 charge/discharge cycles at 10 A/g. In addition, the EIS study disclosed that the Rs and Rct values of Ni/AC electrodes were much lower than those of bare AC. The superior performance of Ni/AC is mainly attributed to the presence of excessive redox active sites, large electroactive surface area and corrosive resistance properties of Ni. We believe that this study will provide new insights into the controlled coating of ACs and other porous materials with metals for developing high-performance SCs and other energy storage devices.

Keywords: supercapacitor, cyclic voltammetry, coating, energy density, activated carbon

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Authors: Dong Tang, Yongli Zhao

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The study of the microstructure of asphalt is of great importance for the analysis of its macroscopic properties. However, the peculiarities of the chemical composition of the asphalt itself and the limitations of existing direct imaging techniques have caused researchers to face many obstacles in studying the microstructure of asphalt. The advantage of small-angle X-ray scattering (SAXS) is that it allows quantitative determination of the internal structure of opaque materials and is suitable for analyzing the microstructure of materials. Therefore, the SAXS technique was used to study the evolution of microstructures on the nanoscale during asphalt aging. And the reasons for the change in scattering contrast during asphalt aging were also explained with the help of Fourier transform infrared spectroscopy (FTIR). SAXS experimental results show that the SAXS curves of asphalt are similar to the scattering curves of scattering objects with two-level structures. The Porod curve for asphalt shows that there is no obvious interface between the micelles and the surrounding mediums, and there is only a fluctuation of the hot electron density between the two. The Beaucage model fit SAXS patterns shows that the scattering coefficient P of the asphaltene clusters as well as the size of the micelles, gradually increase with the aging of the asphalt. Furthermore, aggregation exists between the micelles of asphalt and becomes more pronounced with increasing aging. During asphalt aging, the electron density difference between the micelles and the surrounding mediums gradually increases, leading to an increase in the scattering contrast of the asphalt. Under long-term aging conditions due to the gradual transition from maltenes to asphaltenes, the electron density difference between the micelles and the surrounding mediums decreases, resulting in a decrease in the scattering contrast of asphalt SAXS. Finally, this paper correlates the macroscopic properties of asphalt with microstructural parameters, and the results show that the high-temperature rutting resistance of asphalt is enhanced and the low-temperature cracking resistance decreases due to the aggregation of micelles and the generation of new micelles. These results are useful for understanding the relationship between changes in microstructure and changes in properties during asphalt aging and provide theoretical guidance for the regeneration of aged asphalt.

Keywords: asphalt, Beaucage model, microstructure, SAXS

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Authors: Sumira Jan, Javid Iqbal Mir, Desh Beer Singh, Anil Sharma, Shafia Zaffar Faktoo

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Background and Aims: Climatic and edaphic factors immensely influence crop quality and proper development. Regardless of economic potential, Himalayan Oregano has not subjected to phytonutrient and chemometric evaluation and its relationship with environmental conditions are scarce. The central objective of this research was to investigate microclimatic variation among wild and cultivated populations located in a microclimatic gradient in north-western Himalaya, Kashmir and analyse if such disparity was related with diverse climatic and edaphic conditions. Methods: Micrometeorological, Atomic absorption spectroscopy for micro elemental analysis was carried for soil. HPLC was carried out to estimate variation in phytonutrients and phytochemicals. Results: Geographic variation in phytonutrient was observed among cultivated and wild populations and among populations diverse within regions. Cultivated populations exhibited comparatively lesser phytonutrient value than wild populations. Moreover, our results observed higher vegetative growth of O. vulgare L. with higher pH (6-7), elevated organic carbon (2.42%), high nitrogen (97.41Kg/ha) and manganese (10-12ppm) and zinc contents (0.39-0.50) produce higher phytonutrients. HPLC data of phytonutrients like quercetin, betacarotene, ascorbic acid, arbutin and catechin revealed direct relationship with UV-B flux (r2=0.82), potassium (r2=0.97) displaying parallel relationship with phytonutrient value. Conclusions: Catechin was found as predominant phytonutrient among all populations with maximum accumulation of 163.8 ppm while as quercetin exhibited lesser value. Maximum arbutin (53.42ppm) and quercetin (2.87ppm) accumulated in plants thriving under intense and high UV-B flux. Minimum variation was demonstrated by beta carotene and ascorbic acid.

Keywords: phytonutrient, ascorbic acid, beta carotene, quercetin, catechin

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Authors: Alaa Hamed Salama, Rehab Nabil Shamma

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Introduction: Polymeric micelles that can deliver drug to intended sites of the eye have attracted much scientific attention recently. The aim of this study was to review the aqueous-based formulation of drug-loaded polymeric micelles that hold significant promise for ophthalmic drug delivery. This study investigated the synergistic performance of mixed polymeric micelles made of linear and branched poly (ethylene oxide)-poly (propylene oxide) for the more effective encapsulation of Lornoxicam (LX) as a hydrophobic model drug. Methods: The co-micellization process of 10% binary systems combining different weight ratios of the highly hydrophilic poloxamers; Synperonic® PE/P84, and Synperonic® PE/F127 and the hydrophobic poloxamine counterpart (Tetronic® T701) was investigated by means of photon correlation spectroscopy and cloud point. The drug-loaded micelles were tested for their solubilizing capacity towards LX. Results: Results showed a sharp solubility increase from 0.46 mg/ml up to more than 4.34 mg/ml, representing about 136-fold increase. Optimized formulation was selected to achieve maximum drug solubilizing power and clarity with lowest possible particle size. The optimized formulation was characterized by 1HNMR analysis which revealed complete encapsulation of the drug within the micelles. Further investigations by histopathological and confocal laser studies revealed the non-irritant nature and good corneal penetrating power of the proposed nano-formulation. Conclusion: LX-loaded polymeric nanomicellar formulation was fabricated allowing easy application of the drug in the form of clear eye drops that do not cause blurred vision or discomfort, thus achieving high patient compliance.

Keywords: confocal laser scanning microscopy, Histopathological studies, Lornoxicam, micellar solubilization

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Authors: W. Jahouach-Rabai, J. Aribi, Z. Azzouz-Berriche, R. Lahsni, F. Hosni

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Gamma irradiation applied in removing pharmaceutical contaminants from wastewater is an effective advanced oxidation process (AOP), considered as an alternative to conventional water treatment technologies. In this purpose, the degradation efficiency of several detected contaminants under gamma irradiation was evaluated. In fact, radiolysis of organic pollutants in aqueous solutions produces powerful reactive species, essentially hydroxyl radical ( ·OH), able to destroy recalcitrant pollutants in water. Pharmaceuticals considered in this study are aqueous solutions of paracetamol, ibuprofen, and diclofenac at different concentrations 0.1-1 mmol/L, which were treated with irradiation doses from 3 to 15 kGy. The catalytic oxidation of these compounds by gamma irradiation was investigated using hydrogen peroxide (H₂O₂) as a convenient oxidant. Optimization of the main parameters influencing irradiation process, namely irradiation doses, initial concentration and oxidant volume (H₂O₂) were investigated, in the aim to release high degradation efficiency of considered pharmaceuticals. Significant modifications attributed to these parameters appeared in the variation of degradation efficiency, chemical oxygen demand removal (COD) and concentration of radio-induced radicals, confirming them synergistic effect to attempt total mineralization. Pseudo-first-order reaction kinetics could be used to depict the degradation process of these compounds. A sophisticated analytical study was released to quantify the detected radio-induced radicals (electron paramagnetic resonance spectroscopy (EPR) and high performance liquid chromatography (HPLC)). All results showed that this process is effective for the degradation of many pharmaceutical products in aqueous solutions due to strong oxidative properties of generated radicals mainly hydroxyl radical. Furthermore, the addition of an optimal amount of H₂O₂ was efficient to improve the oxidative degradation and contribute to the high performance of this process at very low doses (0.5 and 1 kGy).

Keywords: AOP, COD, hydroxyl radical, EPR, gamma irradiation, HPLC, pharmaceuticals

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Authors: Santimoy Khilari, Debabrata Pradhan

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Ever−increasing energy demand and growing energy crisis along with environmental issues emphasize the research on sustainable energy conversion and storage systems. Recently, supercapacitors or electrochemical capacitors emerge as a promising energy storage technology for future generation. The activity of supercapacitors generally depends on the efficiency of its electrode materials. So, the development of cost−effective efficient electrode materials for supercapacitors is one of the challenges to the scientific community. Transition metal oxides with spinel crystal structure receive much attention for different electrochemical applications in energy storage/conversion devices because of their improved performance as compared to simple oxides. In the present study, we have synthesized polypyrrole (PPy) supported manganese cobaltite nanorods (MnCo2O4 NRs) hybrid electrode material for supercapacitor application. The MnCo2O4 NRs were synthesized by a simple hydrothermal and calcination approach. The MnCo2O4 NRs/PPy hybrid was prepared by in situ impregnation of MnCo2O4 NRs during polymerization of pyrrole. The surface morphology and microstructure of as−synthesized samples was characterized by scanning electron microscopy and transmission electron microscopy, respectively. The crystallographic phase of MnCo2O4 NRs, PPy and hybrid was determined by X-ray diffraction. Electrochemical charge storage activity of MnCo2O4 NRs, PPy and MnCo2O4 NRs/PPy hybrid was evaluated from cyclic voltammetry, chronopotentiometry and electrochemical impedance spectroscopy. Significant improvement of specific capacitance was achieved in MnCo2O4 NRs/PPy hybrid as compared to the individual components. Furthermore, the mechanically mixed MnCo2O4 NRs, and PPy shows lower specific capacitance as compared to MnCo2O4 NRs/PPy hybrid suggesting the importance of in situ hybrid preparation. The stability of as prepared electrode materials was tested by cyclic charge-discharge measurement for 1000 cycles. Maximum 94% capacitance was retained with MnCo2O4 NRs/PPy hybrid electrode. This study suggests that MnCo2O4 NRs/PPy hybrid can be used as a low cost electrode material for charge storage in supercapacitors.

Keywords: supercapacitors, nanorods, spinel, MnCo2O4, polypyrrole

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Authors: Hajar Zarei, AliAkbar Zarenejadatashgah, Vuk Uskoković, Hiroshi Watabe

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The reactive oxygen species (ROS) generated by radiation in nuclear diagnostic imaging and radiotherapy could damage the structure of the proteins in noncancerous cells surrounding the tumor. The critical factor in many age-related diseases, such as Alzheimer, Parkinson, or Huntington diseases, is the oxidation of proteins by the ROS as molecular triggers of the given pathologies. Our studies by spectroscopic experiments showed doses close to therapeutic ones (1 to 5 Gy) could lead to changes of secondary and tertiary structures in BSA protein macromolecule as a protein model as well as the aggregation of polypeptide chain but without the fragmentation. For this reason, we investigated the radioprotective effects of natural (vitamin C and E) and synthetic materials (CNPs and FIOMPs) on the structural changes in BSA protein induced by gamma irradiation at a therapeutic dose (3Gy). In the presence of both vitamins and synthetic materials, the spectroscopic studies revealed that irradiated BSA was protected from the structural changes caused by ROS, according to in vitro research. The radioprotective property of CNPs and FIOMPs arises from enzyme mimetic activities (catalase, superoxide dismutase, and peroxidase) and their antioxidant capability against hydroxyl radicals. In the case of FIOMPs, a porous structure also leads to increased ROS recombination with each other in the same radiolytic track and subsequently decreased encounters with BSA. The hydrophilicity of vitamin C resulted in the major scavenging of ROS in the solvent, whereas hydrophobic vitamin E localized on the nonpolar patches of the BSA surface, where it did not only neutralize them thanks to the moderate BSA binding constant but also formed a barrier for diffusing ROS. To the best of our knowledge, there has been a persistent lack of studies investigating the radioactive effect of mentioned materials on proteins. Therefore, the results of our studies can open a new widow for application of these common dietary ingredients and new synthetic NPs in improving the safety of radiotherapy.

Keywords: reactive oxygen species, spectroscopy, bovine serum albumin, gamma radiation, radioprotection

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Authors: Bukunola K. Oguntade, Gareth M. Watkins

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The synthesis and characterization of metal-organic frameworks (MOFs) is an area of coordination chemistry which has grown rapidly in recent years. Worldwide there has been growing concerns about future energy supplies, and its environmental impacts. A good number of MOFs have been tested for the adsorption of small molecules in the vapour phase. An important issue for potential applications of MOFs for gas adsorption and storage materials is the stability of their structure upon sorption. Therefore, study on the thermal stability of MOFs upon adsorption is important. The incorporation of two or more transition metals in a coordination polymer is a current challenge for designed synthesis. This work focused on the synthesis, characterization and small molecule adsorption properties of three microporous (one zinc monometal and two bimetallics) complexes involving Cu(II), Zn(II) and 1,2,4,5-benzenetetracarboxylic acid using the ambient precipitation and solvothermal method. The complexes were characterized by elemental analysis, Infrared spectroscopy, Scanning Electron microscopy, Thermogravimetry analysis and X-ray Powder diffraction. The N2-adsorption Isotherm showed the complexes to be of TYPE III in reference to IUPAC classification, with very small pores only capable for small molecule sorption. All the synthesized compounds were observed to contain water as guest. Investigations of their inclusion properties for small molecules in the vapour phase showed water and methanol as the only possible inclusion candidates with 10.25H2O in the monometal complex [Zn4(H2B4C)2.5(OH)3(H2O)]·10H2O but not reusable after a complete structural collapse. The ambient precipitation bimetallic; [(CuZnB4C(H2O)2]·5H2O, was found to be reusable and recoverable from structure collapse after adsorption of 5.75H2O. In addition, Solvo-[CuZnB4C(H2O)2.5]·2H2O obtained from solvothermal method show two cycles of rehydration with 1.75H2O and 0.75MeOH inclusion while structure remains unaltered upon dehydration and adsorption.

Keywords: adsorption, characterization, copper, metal -organic frameworks, zinc

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Authors: Aleksandra BužArovska, Gordana Bogoeva Gaceva

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Biodegradable polymers have received significant scientific attention in tissue engineering (TE) application, in particular their composites consisting of inorganic nanoparticles. In the last 15 years, they are subject of intensive research by many groups, aiming to develop polymer scaffolds with defined biodegradability, porosity and adequate mechanical stability. The most important characteristic making these materials attractive for TE is their biodegradability, a process that could be time controlled and long enough to enable generation of a new tissue as a replacement for the degraded polymer scaffold. In this work poly(L-lactic acid) scaffolds, filled with TiO2 nanoparticles functionalized with oleic acid, have been prepared by thermally induced phase separation method (TIPS). The functionalization of TiO2 nanoparticles with oleic acid was performed in order to improve the nanoparticles dispersibility within the polymer matrix and at the same time to inhibit the cytotoxicity of the nanofiller. The oleic acid was chosen as amphiphilic molecule belonging to the fatty acid family because of its non-toxicity and possibility for mediation between the hydrophilic TiO2 nanoparticles and hydrophobic PLA matrix. The produced scaffolds were characterized with thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and mechanical compression measurements. The bioactivity for bone tissue engineering application was tested in supersaturated simulated body fluid. The degradation process was followed by Fourier transform infrared spectroscopy (FTIR). The results showed anisotropic morphology with elongated open pores (100 µm), high porosity (around 92%) and perfectly dispersed nanofiller. The compression moduli up to 10 MPa were identified independent on the nanofiller content. Functionalized TiO2 nanoparticles induced formation of hydroxyapatite clusters as much as unfunctionalized TiO2. The prepared scaffolds showed properties ideal for scaffold vascularization, cell attachment, growth and proliferation.

Keywords: biodegradation, bone tissue engineering, mineralization, PLA scaffolds

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Authors: Daniela N. Correa-Llantén, Sebastián A. Muñoz-Ibacache, Mathilde Maire, Jenny M. Blamey

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The biosynthesis of nanoparticles by microorganisms, on the contrary to chemical synthesis, is an environmentally-friendly process which has low energy requirements. In this investigation, we used the microorganism Geobacillus wiegelii, strain GWE1, an aerobic thermophile belonging to genus Geobacillus, isolated from a drying oven. This microorganism has the ability to reduce selenite evidenced by the change of color from colorless to red in the culture. Elemental analysis and composition of the particles were verified using transmission electron microscopy and energy-dispersive X-ray analysis. The nanoparticles have a defined spherical shape and a selenium elemental state. Previous experiments showed that the presence of the whole microorganism for the reduction of selenite was not necessary. The results strongly suggested that an intracellular NADPH/NADH-dependent reductase mediates selenium nanoparticles synthesis under aerobic conditions. The enzyme was purified and identified by mass spectroscopy MALDI-TOF TOF technique. The enzyme is a 1-pyrroline-5-carboxylate dehydrogenase. Histograms of nanoparticles sizes were obtained. Size distribution ranged from 40-160 nm, where 70% of nanoparticles have less than 100 nm in size. Spectroscopic analysis showed that the nanoparticles are composed of elemental selenium. To analyse the effect of pH in size and morphology of nanoparticles, the synthesis of them was carried out at different pHs (4.0, 5.0, 6.0, 7.0, 8.0). For thermostability studies samples were incubated at different temperatures (60, 80 and 100 ºC) for 1 h and 3 h. The size of all nanoparticles was less than 100 nm at pH 4.0; over 50% of nanoparticles have less than 100 nm at pH 5.0; at pH 6.0 and 8.0 over 90% of nanoparticles have less than 100 nm in size. At neutral pH (7.0) nanoparticles reach a size around 120 nm and only 20% of them were less than 100 nm. When looking at temperature effect, nanoparticles did not show a significant difference in size when they were incubated between 0 and 3 h at 60 ºC. Meanwhile at 80 °C the nanoparticles suspension lost its homogeneity. A change in size was observed from 0 h of incubation at 80ºC, observing a size range between 40-160 nm, with 20% of them over 100 nm. Meanwhile after 3 h of incubation at size range changed to 60-180 nm with 50% of them over 100 nm. At 100 °C the nanoparticles aggregate forming nanorod structures. In conclusion, these results indicate that is possible to modulate size and shape of biologically synthesized nanoparticles by modulating pH and temperature.

Keywords: genus Geobacillus, NADPH/NADH-dependent reductase, selenium nanoparticles, biosynthesis

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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: Letemariam Gebreslassie Gebrekidan

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Water pollution is one of the most feared problems in modern societies, especially in developing countries like Ethiopia. Nanoparticles with controlled size and composition are of fundamental and technological interest as they provide solutions to technological and environmental challenges in the areas of solar energy conversion, catalysis, medicine, and water treatment. The synthesis of metallic nanoparticles is an active area of academic and, more importantly, application research in nanotechnology. Adsorption is a process in which pollutants are absorbed on a solid surface. A molecule (pollutant) adhered to the solid surface is called an adsorbate, and the solid surface is an adsorbent. Adsorption is controlled by various parameters such as temperature, the nature of the adsorbate and adsorbent, and the presence of other pollutants along with the experimental conditions (pH, concentration of pollutants, contact time, particle size, and temperature). Depending on the main problem of water pollution, this research is available on the adsorption of wastewater using silver nanoparticles extracted from phytolacca Dodecandra leaf. AgNP was synthesized from a 1mM aqueous solution of silver nitrate (AgNO3) and Phytolacca Dodecandra leaf extract at room temperature. The synthesized nanoparticles were characterized using UV/visible Spectrometer, FTIR and XRD. In the UV-Vis spectrum, The Surface Plasmon resonance (SPR) peak was observed at 414 nm, which confirmed the synthesis of AgNPs. FTIR spectroscopy, recorded from 4000 cm-1 to 400 cm-1, indicated the presence of a capping agent with the nanoparticles. From the XRD results, the average crystalline size was estimated to be 20 nm Confirming the nanoparticle nature of the obtained sample. Thus, the present method leads to the formation of silver nanoparticles with well-defined dimensions. The effects of different parameters like solution pH, adsorbent dose, contact time and initial concentration of dye were studied. The concentration of MB is 0.01 mg/L and 0.002 mg/L before and after adsorption, respectively. The wastewater containing MB was well purified using AgNP adsorbent.

Keywords: wastewater, silver nanoparticle, Characterization, adsorption, parameter

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Authors: Cahya Wimar Wicaksono, Reynara Davin Chen, Alvian Kristianto Santoso

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Grasberg Cu-Au ore deposit as one of the biggest porphyry deposits located in Papua Province, Indonesia produced by several intrusion that restricted by Heavy Sulphide Zone (HSZ) in peripheral. HSZ is the rock that becomes the contact between Grassberg Igneous Complex (GIC) with sedimentary and igneous rock outside, which is rich in sulphide minerals such as pyrite ± pyrrhotite. This research is to obtain the characteristic of HSZ based on geotechnical, geochemical and mineralogy aspect and those implication for daily mining operational activities. Method used in this research are geological and alteration mapping, core logging, FAA (Fire Assay Analysis), AAS (Atomic absorption spectroscopy), RQD (Rock Quality Designation) and rock water content. Data generated from methods among RQD data, mineral composition and grade, lithological and structural geology distribution in research area. The mapping data show that HSZ material characteristics divided into three type based on rocks association, there are near igneous rocks, sedimentary rocks and on HSZ area. And also divided based on its location, north and south part of research area. HSZ material characteristic consist of rock which rich of pyrite ± pyrrhotite, and RQD range valued about 25%-100%. Pyrite ± pyrrhotite which outcropped will react with H₂O and O₂ resulting acid that generates corrosive effect on steel wire and rockbolt. Whereas, pyrite precipitation proses in HSZ forming combustible H₂S gas which is harmful during blasting activities. Furthermore, the impact of H₂S gas in blasting activities is forming poison gas SO₂. Although HSZ high grade Cu-Au, however those high grade Cu-Au rich in sulphide components which is affected in flotation milling process. Pyrite ± pyrrhotite in HSZ will chemically react with Cu-Au that will settle in milling process instead of floating.

Keywords: combustible, corrosive, heavy sulphide zone, pyrite ± pyrrhotite

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Authors: Federica Laface, Cristina Pedà, Francesco Longo, Francesca de Domenico, Riccardo Minichino, Pierpaolo Consoli, Pietro Battaglia, Silvestro Greco, Teresa Romeo

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Plastics pollution represents one of the most important threats to marine biodiversity. In the last decades, different species are investigated to evaluate the extent of the plastic ingestion phenomenon. Even if the cephalopods play an important role in the food chain, they are still poorly studied. The aim of this research was to investigate the plastic ingestion in two commercial cephalopod species from the southern Tyrrhenian Sea: the common octopus, Octopus vulgaris (n=6; mean mantle length ML 10.7 ± 1.8) and the common cuttlefish, Sepia officinalis (n=13; mean ML 13.2 ± 1.7). Plastics were extracted from the filters obtained by the chemical digestion of cephalopods gastrointestinal tracts (GITs), using 10% potassium hydroxide (KOH) solution in a 1:5 (w/v) ratio. Once isolated, particles were photographed, measured, and their size class, shape and color were recorded. A total of 81 items was isolated from 16 of the 19 examined GITs, representing a total occurrence (%O) of 84.2% with a mean value of 4.3 ± 8.6 particles per individual. In particular, 62 plastics were found in 6 specimens of O. vulgaris (%O=100) and 19 particles in 10 S. officinalis (%O=94.7). In both species, the microplastics size class was the most abundant (93.8%). Plastic items found in O. vulgaris were mainly fibers (61%) while fragments were the most frequent in S. officinalis (53%). Transparent was the most common color in both species. The analysis will be completed by Fourier transform infrared (FT-IR) spectroscopy technique in order to identify polymers nature. This study reports preliminary data on plastic ingestion events in two cephalopods species and represents the first record of plastic ingestion by the common octopus. Microplastic items detected in both common octopus and common cuttlefish could derive from secondary and/or accidental ingestion events, probably due to their behavior, feeding habits and anatomical features. Further studies will be required to assess the effect of marine litter pollution in these ecologically and commercially important species.

Keywords: cephalopods, GIT analysis, marine pollution, Mediterranean sea, microplastics

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Authors: Mohamed dammak

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Great attention has been paid to the design and synthesis of novel organic-inorganic compounds in recent decades because of their structural variety and the large diversity of atomic arrangements. In this work, the structure for the novel dimethyl aminopyridine tetrachlorocobaltate (C₇H₁₁N₂)₂CoCl₄ prepared by the slow evaporation method at room temperature has been successfully discussed. The X-ray diffraction results indicate that the hybrid material has a triclinic structure with a P space group and features a 0D structure containing isolated distorted [CoCl₄]2- tetrahedra interposed between [C7H11N²⁻]+ cations forming planes perpendicular to the c axis at z = 0 and z = ½. The effect of the synthesis conditions and the reactants used, the interactions between the cationic planes, and the isolated [CoCl4]2- tetrahedra are employing N-H...Cl and C-H…Cl hydrogen bonding contacts. The inspection of the Hirshfeld surface analysis helps to discuss the strength of hydrogen bonds and to quantify the inter-contacts. A phase transition was discovered by thermal analysis at 390 K, and comprehensive dielectric research was reported, showing a good agreement with thermal data. Impedance spectroscopy measurements were used to study the electrical and dielectric characteristics over a wide range of frequencies and temperatures, 40 Hz–10 MHz and 313–483 K, respectively. The Nyquist plot (Z" versus Z') from the complex impedance spectrum revealed semicircular arcs described by a Cole-Cole model. An electrical circuit consisting of a link of grain and grain boundary elements is employed. The real and imaginary parts of dielectric permittivity, as well as tg(δ) of (C₇H₁₁N₂)₂CoCl₄ at different frequencies, reveal a distribution of relaxation times. The presence of grain and grain boundaries is confirmed by the modulus investigations. Electric and dielectric analyses highlight the good protonic conduction of this material.

Keywords: organic-inorganic, phase transitions, complex impedance, protonic conduction, dielectric analysis

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Authors: Sanjay Singh, Karunanithi Priyanka, Ramoji Kosuru, Raju Prasad Sharma

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Herbal drugs are well known for their mixed pharmacological activities with the benefit of no harmful side effects. The use of herbal drugs is limited because of their higher dose requirement, frequent drug administration, poor bioavailability of phytochemicals and delayed onset of action. Ficus religiosa, a potent anti-oxidant plant useful in the treatment of diabetes and cancer was selected for the study. Solid lipid nanoparticles (SLN) of Ficus religiosa extract was developed for the enhancement in oral bioavailability of stigmasterol and β-sitosterol-d-glucoside, principal components present in the extract. Hot homogenization followed by ultrasonication method was used to develop extract loaded SLN. Developed extract loaded SLN were characterized for particle size, PDI, zeta potential, entrapment efficiency, in vitro drug release and kinetics, fourier transform infra-red spectroscopy, differential scanning calorimetry, powder X-ray diffractrometry and stability studies. Entrapment efficiency of optimized extract loaded SLN was found to be 68.46 % (56.13 % of stigmasterol and 12.33 % of β-sitosteryl-d-glucoside, respectively). RP HPLC method development was done for simultaneous estimation of stigmasterol and β-sitosterol-d-glucoside in Ficus religiosa extract in rat plasma. Bioavailability studies were carried out for extract in suspension form and optimized extract loaded SLN. AUC of stigmasterol and β-sitosterol-d-glucoside were increased by 6.7-folds by 9.2-folds, respectively in rats treated with extract loaded SLN compared to extract suspension. Also, Cmax of stigmasterol and β-sitosterol-d-glucoside were increased by 4.3-folds by 3.9-folds, respectively in rats treated with extract loaded SLN compared to extract suspension. Mean residence times (MRT) for stigmasterol were found to be 12.3 ± 0.67 hours from extract and 7.4 ± 2.1 hours from SLN and for β-sitosterol-d-glucoside, 10.49 ± 2.9 hours from extract and 6.4 ± 0.3 hours from SLN. Hence, it was concluded that SLN enhanced the bioavailability and reduced the MRT of stigmasterol and β-sitosterol-d-glucoside in Ficus religiosa extract which in turn may lead to reduction in dose of Ficus religiosa extract, prolonged duration of action and also enhanced therapeutic efficacy.

Keywords: Ficus religiosa, phytosterolins, bioavailability, solid lipid nanoparticles, stigmasterol and β-sitosteryl-d-glucoside

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Authors: J. W. Choi, S. Y. Cho, H. J. Lee, W. Z. Oh, S. J. Choi

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Ionic liquids (ILs), which is alternative to conventional organic solvent, were used for extraction of Cs ions. ILs, as useful environment friendly green solvents, have been recently applied as replacement for traditional volatile organic compounds (VOCs) in liquid/liquid extraction of heavy metal ions as well as organic and inorganic species and pollutants. Thus, Ionic liquids were used for extraction of Cs ions from the liquid radioactive waste. In most cases, Cs ions present in radioactive wastes in very low concentration, approximately less than 1ppm. Therefore, unlike established extraction system the required amount of ILs as extractant is comparatively very small. This extraction method involves cation exchange mechanism in which Cs ion transfers to the organic phase and binds to one crown ether by chelation in exchange of single ILs cation, IL_cation+, transfer to the aqueous phase. In this extraction system showed solid-liquid separation in which the Ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonly)imide (C2mimTf2N) and the crown ether Dicyclohexano-18-crown-6 (DCH18C6) both were used here in very little amount as solvent and as extractant, respectively. 30 mM of CsNO3 was used as simulated waste solution cesium ions. Generally, in liquid-liquid extraction, the molar ratio of CE:Cs+:ILs was 1:5~10:>100, while our applied molar ratio of CE:Cs+:ILs was 1:2:1~10. The quantity of CE and Cs ions were fixed to 0.6 and 1.2 mmol, respectively. The phenomenon of precipitation showed two kinds of separation: solid-liquid separation in the ratio of 1:2:1 and 1:2:2; solid-liquid-liquid separation (3 phase) in the ratio of 1:2:5 and 1:2:10. In the last system, 3 phases were precipitate-ionic liquids-aqueous. The precipitate was verified to consist of Cs+, DCH18C6, Tf2N- based on the cation exchange mechanism. We analyzed precipitate using scanning electron microscopy with X-ray microanalysis (SEM-EDS), an elemental analyser, Fourier transform infrared spectroscopy (FT-IR) and differential scanning calorimetry (DSC). The experimental results showed an easy extraction method and confirmed the composition of solid precipitate. We also obtained information that complex formation ratio of Cs+ to DCH18C6 is 0.88:1 regardless of C2mimTf2N quantities.

Keywords: extraction, precipitation, solid-liquid seperation, ionic liquid, precipitate

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Authors: Burcu Doymus, Fatma N. Kok, Sakip Onder

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Titanium and titanium-based materials are commonly used to replace or regenerate the injured or lost tissues because of accidents or illnesses. Hospital infections and strong bond formation at the implant-tissue interface are directly affecting the success of the implantation as weak bonding with the native tissue and hospital infections lead to revision surgery. The purpose of the presented study is to modify the surface of the titanium substrates with nano/microspheres for local drug delivery and to prevent hospital infections. Firstly, titanium surfaces were silanized with APTES (3-Triethoxysilylpropylamine) following the negatively charged oxide layer formation. Then characterization studies using Scanning Electron Microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) were done on the modified surfaces. Secondly, microspheres/nanospheres were prepared with chitosan that is a natural polymer and having valuable properties such as non-toxicity, high biocompatibility, low allergen city and biodegradability for biomedical applications. Antibiotic (ciprofloxacin) loaded micro/nanospheres have been fabricated using emulsion cross-linking method and have been immobilized onto the titanium surfaces with different immobilization techniques such as covalent bond and entrapment. Optimization studies on size and drug loading capacities of micro/nanospheres were conducted before the immobilization process. Light microscopy and SEM were used to visualize and measure the size of the produced micro/nanospheres. Loaded and released drug amounts were determined by using UV- spectrophotometer at 278 nm. Finally, SEM analysis and drug release studies on the micro/nanospheres coated Ti surfaces were done. As a conclusion, it was shown that micro/nanospheres were immobilized onto the surfaces successfully and drug release from these surfaces was in a controlled manner. Moreover, the density of the micro/nanospheres after the drug release studies was higher on the surfaces where the entrapment technique was used for immobilization. Acknowledgement: This work is financially supported by The Scientific and Technological Research Council Of Turkey (Project # 217M220)

Keywords: chitosan, controlled drug release, nanosphere, nosocomial infections, titanium

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Authors: Monalisa Pradhan, Ajana Dutta, Irshad Kariyattuparamb Abbas, Boby Joseph, T. N. Guru Row, Diptikanta Swain, Gopal K. Pradhan

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Compounds with the Vanthoffite crystal structure having general formula Na6M(SO₄)₄ (M= Mg, Mn, Ni , Co, Fe, Cu and Zn) display a variety of intriguing physical properties intimately related to their structural arrangements. The compound Na6Mn(SO4)4 shows antiferromagnetic ordering at low temperature where the in-plane Mn-O•••O-Mn interactions facilitates antiferromagnetic ordering via a super-exchange interaction between the Mn atoms through the oxygen atoms . The inter-atomic bond distances and angles can easily be tuned by applying external pressure and can be probed using high resolution X-ray diffraction. Moreover, because the magnetic interaction among the Mn atoms are super-exchange type via Mn-O•••O-Mn path, the variation of the Mn-O•••O-Mn dihedral angle and Mn-O bond distances under high pressure inevitably affects the magnetic properties. Therefore, it is evident that high pressure studies on the magnetically ordered materials would shed light on the interplay between their structural properties and magnetic ordering. This will indeed confirm the role of buckling of the Mn-O polyhedral in understanding the origin of anti-ferromagnetism. In this context, we carried out the pressure dependent X-ray diffraction measurement in a diamond anvil cell (DAC) up to a maximum pressure of 17 GPa to study the phase transition and determine equation of state from the volume compression data. Upon increasing the pressure, we didn’t observe any new diffraction peaks or sudden discontinuity in the pressure dependences of the d values up to the maximum achieved pressure of ~17 GPa. However, it is noticed that beyond 12 GPa the a and b lattice parameters become identical while there is a discontinuity in the β value around the same pressure. This indicates a subtle transition to a pseudo-monoclinic phase. Using the third order Birch-Murnaghan equation of state (EOS) to fit the volume compression data for the entire range, we found the bulk modulus (B0) to be 44 GPa. If we consider the subtle transition at 12 GPa, we tried to fit another equation state for the volume beyond 12 GPa using the second order Birch-Murnaghan EOS. This gives a bulk modulus of ~ 34 GPa for this phase.

Keywords: mineral, structural phase transition, high pressure XRD, spectroscopy

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Authors: Minhal Abidi, Moinuddin

Abstract:

Diabetes mellitus (DM) induced metabolic abnormalities causes oxidative stress which leads to the pathogenesis of complications associated with diabetes like retinopathy, nephropathy periodontitis etc. Combination of glycation and oxidation 'glycoxidation' occurs when oxidative reactions affect the early state of glycation products. Low density lipoprotein (LDL) is prone to glycoxidative attack by sugars and methylglyoxal (MGO) being a strong glycating agent may have severe impact on its structure and consequent role in diabetes. Pro-inflammatory cytokines like IL1β and TNFα produced by the action of gram negative bacteria in periodontits (PD) can in turn lead to insulin resistance. This work discusses modifications to LDL as a result of glycoxidation. The changes in the protein molecule have been characterized by various physicochemical techniques and the immunogenicity of the modified molecules was also evaluated as they presented neo-epitopes. Binding of antibodies present in diabetes patients to the native and glycated LDL has been evaluated. Role of modified epitopes in the generation of antibodies in diabetes and periodontitis has been discussed. The structural perturbations induced in LDL were analyzed by UV–Vis, fluorescence, circular dichroism and FTIR spectroscopy, molecular docking studies, thermal denaturation studies, Thioflavin T assay, isothermal titration calorimetry, comet assay. MALDI-TOF, ketoamine moieties, carbonyl content and HMF content were also quantitated in native and glycated LDL. IL1β and TNFα levels were also measured in the type 2 DM and PD patients. We report increased carbonyl content, ketoamine moieties and HMF content in glycated LDL as compared to native analogue. The results substantiate that in hyperglycemic state MGO modification of LDL causes structural perturbations making the protein antigenic which could obstruct normal physiological functions and might contribute in the development of secondary complications in diabetic patients like periodontitis.

Keywords: advanced glycation end products, diabetes mellitus, glycation, glycoxidation, low density lipoprotein, periodontitis

Procedia PDF Downloads 191

Authors: Yasaman Samani, Ali Golmohammadi

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Introduction: The degree of conversion and depth of cure affects the clinical success of resin composite restorations directly. One of the main challenges in achieving a successful composite restoration is the achievement of sufficient depth of cure. The insufficient polymerization may lead to a decrease in the physical/mechanical and biological properties of resin composites and, as a result of that, unsuccessful composite restoration. Thus, because of the importance of studying and evaluating the depth of cure and degree of conversion in bulk-fill composites, we decided to evaluate and compare the degree of conversion and depth of cure in two bulk-fill composites; x-tra fill (Voco, Germany) and Opus Bulk fill APS (FGM, Brazil). Materials and Methods: Composite resin specimens (n=10) per group were prepared as cylinder blocks (4×8 mm) with bulk-fill composites, x-tra fil (Voco, Germany) designated as Group A, and Opus Bulk fill APS (FGM, Brazil) designated as Group B. Depth of cure was determined according to “ISO 4049; Depth of Cure” method, In which each specimen were cured (iLED, Woodpecker, China) 40 seconds and FTIR spectroscopy method was used to estimate the degree of conversion of both the bulk-fill composites. The degree of conversion of monomer to polymer was estimated individually in the coronal half (Group A1 and B1) and pulpal half (Group A2 and Group B2) by dividing each specimen into two halves. The data were analyzed using a Student’s t-test and one-way ANOVA at a 5% level of significance. Results: The mean depth of cure in x-tra fil (Voco, Germany) was 3.99 (±0.16), and for Opus Bulk fill, APS (FGM, Brazil) was 2.14 (±0.3). The degree of conversion percentage in Group A1 was 82.7 (±6.1), in group A2 was 73.4 (±5.2), in group B1 was 63.3 (±4.7) and in Group B2 was 56.5 (±7.7). Statistical analysis revealed a significant difference in the depth of cure between the two bulk-fill composites with x-tra fil (Voco, Germany) higher than Opus Bulk fill APS (FGM, Brazil) (P<0.001). The degree of conversion percentage also showed a significant difference, Group A1 being higher than A2 (P=0.0085), B1, and B2 (P<0.001). Group A2 was also higher than B1 (P=0.003) and B2 (P<0.001). There was no significant difference between B1 and B2 (P=0.072). Conclusion: The results indicate that x-tra fill has more depth of cure and a higher percentage of the degree of conversion than Opus Bulk fill APS. The coronal half of x-tra fil had the highest depth of cure percentage (82.66%), and the pulpal half of Opus Bulk fill APS had the lowest percentage (56.45%). Even though both bulk-fill composite materials had an acceptable degree of conversion (55% and higher), x-tra fill has shown better results.

Keywords: depth of cure, degree of conversion, bulk-fill composite, FTIR

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Authors: M. Jerold, V. Sivasubramanian, A. George, B.S. Ashik, S. S. Kumar

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Bioethanol is a sustainable biofuel that can be used alternative to fossil fuels. Today, third generation (3G) biofuel is gaining more attention than first and second-generation biofuel. The more lignin content in the lignocellulosic biomass is the major drawback of second generation biofuels. Algae are the renewable feedstock used in the third generation biofuel production. Algae contain a large number of carbohydrates, therefore it can be used for the fermentation by hydrolysis process. There are two groups of Algae, such as micro and macroalgae. In the present investigation, Macroalgae was chosen as raw material for the production of bioethanol. Two marine algae viz. Ulva Lactuca and Sargassum swartzii were used for the experimental studies. The algal biomass was characterized using various analytical techniques like Elemental Analysis, Scanning Electron Microscopy Analysis and Fourier Transform Infrared Spectroscopy to understand the physio-Chemical characteristics. The batch experiment was done to study the hydrolysis and operation parameters such as pH, agitation, fermentation time, inoculum size. The saccharification was done with acid and alkali treatment. The experimental results showed that NaOH treatment was shown to enhance the bioethanol. From the hydrolysis study, it was found that 0.5 M Alkali treatment would serve as optimum concentration for the saccharification of polysaccharide sugar to monomeric sugar. The maximum yield of bioethanol was attained at a fermentation time of 9 days. The inoculum volume of 1mL was found to be lowest for the ethanol fermentation. The agitation studies show that the fermentation was higher during the process. The percentage yield of bioethanol was found to be 22.752% and 14.23 %. The elemental analysis showed that S. swartzii contains a higher carbon source. The results confirmed hydrolysis was not completed to recover the sugar from biomass. The specific gravity of ethanol was found to 0.8047 and 0.808 for Ulva Lactuca and Sargassum swartzii, respectively. The purity of bioethanol also studied and found to be 92.55 %. Therefore, marine algae can be used as a most promising renewable feedstock for the production of bioethanol.

Keywords: algae, biomass, bioethaol, biofuel, pretreatment

Procedia PDF Downloads 159

Authors: Luciana P. Mazur, Tatiana A. Pozdniakova, Rui A. R. Boaventura, Vitor J. P. Vilar

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The principal mechanism of metal ions sequestration by brown algae involves the formation of complexes between the metal ion and functional groups present on the cell wall of the biological material. To understand the role of functional groups on copper(II) uptake by Ascophyllum nodosum, some functional groups were chemically modified. The esterification of carboxylic groups was carried out by suspending the biomass in a methanol/HCl solution under stirring for 48 h and the blocking of the sulfonic groups was performed by repeating the same procedure for 4 cycles of 48 h. The methylation of amines was conducted by suspending the biomass in a formaldehyde/formic acid solution under shaking for 6 h and the chemical modification of sulfhydryl groups on the biomass surface was achieved using dithiodipyridine for 1 h. Equilibrium sorption studies for Cu2+ using the raw and esterified algae were performed at pH 2.0 and 4.0. The experiments were performed using an initial copper concentration of 300 mg/L and algae dose of 1.0 g/L. After reaching the equilibrium, the metal in solution was quantified by atomic absorption spectrometry. The biological material was analyzed by Fourier Transform Infrared Spectroscopy and Potentiometric Titration techniques for functional groups identification and quantification, respectively. The results using unmodified algae showed that the maximum copper uptake capacity at pH 4.0 and 2.0 was 1.17 and 0.52 mmol/g, respectively. At acidic pH values most carboxyl groups are protonated and copper sorption suffered a significant reduction of 56%. Blocking the carboxylic, sulfonic, amines and sulfhydryl functional groups, copper uptake decreased by 24/26%, 69/81%, 1/23% and 40/27% at pH 2.0/4.0, respectively, when compared to the unmodified biomass. It was possible to conclude that the carboxylic and sulfonic groups are the main functional groups responsible for copper binding (>80%). This result is supported by the fact that the adsorption capacity is directly related to the presence of carboxylic groups of the alginate polymer, and the second most abundant acidic functional group in brown algae is the sulfonic acid of fucoidan that contributes, to a lower extent, to heavy metal binding, particularly at low pH.

Keywords: biosorption, brown marine macroalgae, copper, ion-exchange

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Authors: Parvin Samadi Pakchin, Reza Saber, Hossein Ghanbari, Yadollah Omidi

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Ovarian cancer is one of the leading cause of mortality among the gynecological malignancies, and it remains the one of the most prevalent cancer in females worldwide. Tumor markers are biochemical molecules in blood or tissues which can indicates cancers occurrence in the human body. So, the sensitive and specific detection of cancer markers typically recruited for diagnosing and evaluating cancers. Recently extensive research efforts are underway to achieve a simple, inexpensive and accurate device for detection of cancer biomarkers. Compared with conventional immunoassay techniques, electrochemical immunosensors are of great interest, because they are specific, simple, inexpensive, easy to handling and miniaturization. Moreover, in the past decade nanotechnology has played a crucial role in the development of biosensors. In this study, a signal-off electrochemical immunosensor for the detection of CA125 antigen has been developed using chitosan-gold nanoparticles (CS-AuNP) and multi-wall carbon nanotubes (MWCNT) composites. Toluidine blue (TB) is used as redox probe which is immobilized on the electrode surface. CS-AuNP is synthesized by a simple one step method that HAuCl4 is reduced by NH2 groups of chitosan. The CS-AuNP-MWCNT modified electrode has shown excellent electrochemical performance compared with bare Au electrode. MWCNTs and AuNPs increased electrochemical conductivity and accelerate electrons transfer between solution and electrode surface while excessive amine groups on chitosan lead to the effective loading of the biological material (CA125 antibody) and TB on the electrode surface. The electrochemical, immobilization and sensing properties CS-AuNP-MWCNT-TB modified electrodes are characterized by cyclic voltammetry, electrochemical impedance spectroscopy, differential pulse voltammetry and square wave voltammetry with Fe(CN)63−/4−as an electrochemical redox indicator.

Keywords: signal-off electrochemical biosensor, CA125, ovarian cancer, chitosan-gold nanoparticles

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Authors: Qianying Sun, Abdelhadi Kassiba, Guorong Li

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ZnO with wurtzite structure is a well-known semiconducting oxide (SCO), being applied in thermoelectric devices, varistors, gas sensors, transparent electrodes, solar cells, liquid crystal displays, piezoelectric and electro-optical devices. Intrinsically, ZnO is weakly n-type SCO due to native defects (Znⱼ, Vₒ). However, the substitutional doping by metallic elements as (Al, Ti) gives rise to a high n-type conductivity ensured by donor centers. Under CO+N₂ sintering atmosphere, Schottky barriers of ZnO ceramics will be suppressed by lowering the concentration of acceptors at grain boundaries and then inducing a large increase in the Hall mobility, thereby increasing the conductivity. The presented work concerns ZnO based ceramics, which are fabricated with doping by TiO₂ (0.50mol%), Al₂O₃ (0.25mol%) and MgO (1.00mol%) and sintering in different atmospheres (Air (A), N₂ (N), CO+N₂(C)). We obtained uniform, dense ceramics with ZnO as the main phase and Zn₂TiO₄ spinel as a secondary and minor phase. An important increase of the conductivity was shown for the samples A, N, and C which were sintered under different atmospheres. The highest conductivity (σ = 1.52×10⁵ S·m⁻¹) was obtained under the reducing atmosphere (CO). The role of doping was investigated with the aim to identify the local environment and valence states of the doping elements. Thus, Electron paramagnetic spectroscopy (EPR) determines the concentration of defects and the effects of charge carriers in ZnO ceramics as a function of the sintering atmospheres. The relation between conductivity and defects concentration shows the opposite behavior between these parameters suggesting that defects act as traps for charge carriers. For Al ions, nuclear magnetic resonance (NMR) technique was used to identify the involved local coordination of these ions. Beyond the six and forth coordinated Al, an additional NMR signature of ZnO based TCO requires analysis taking into account the grain boundaries and the conductivity through the Knight shift effects. From the thermal evolution of the conductivity as a function of the sintering atmosphere, we succeed in defining the conditions to realize ZnO based TCO ceramics with an important thermal coefficient of resistance (TCR) which is promising for electrical safety of devices.

Keywords: ceramics, conductivity, defects, TCO, ZnO

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Authors: Lucja Rodzik, Joanna Lewandowska-Lancucka, Michal Szuwarzynski, Krzysztof Szczubialka, Maria Nowakowska

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The analysis of nucleobases is of great importance for bioscience since their abnormal concentration in body fluids suggests the deficiency and mutation of the immune system, and it is considered to be an important parameter for diagnosis of various diseases. The presented conjugate meets the need for development of the effective, selective and highly sensitive sensor for nucleobase/nucleoside detection. The novel, highly fluorescent cadmium telluride quantum dots (CdTe QDs) functionalized with thymine and stabilized with thioglycolic acid (TGA) conjugates has been developed and thoroughly characterized. Successful formation of the material was confirmed by elemental analysis, and UV–Vis fluorescence and FTIR spectroscopies. The crystalline structure of the obtained product was characterized with X-ray diffraction (XRD) method. The composition of CdTe QDs and their thymine conjugate was also examined using X-ray photoelectron spectroscopy (XPS). The size of the CdTe-thymine was 3-6 nm as demonstrated using atomic force microscopy (AFM) and high resolution transmission electron microscopy (HRTEM) imaging. The plasmon resonance fluorescence band at 540 nm on excitation at 351 nm was observed for these nanoparticles. The intensity of this band increased with the increase in the amount of conjugated thymine with no shift in its position. Based on the fluorescence measurements, it was found that the CdTe-thymine conjugate interacted efficiently and selectively not only with adenine, a nucleobase complementary to thymine, but also with nucleosides and adenine-containing modified nucleosides, i.e., 5′-deoxy-5′-(methylthio)adenosine (MTA) and 2’-O-methyladenosine, the urinary tumor markers which allow monitoring of the disease progression. The applicability of the CdTe-thymine sensor for the real sample analysis was also investigated in simulated urine conditions. High sensitivity and selectivity of CdTe-thymine fluorescence towards adenine, adenosine and modified adenosine suggest that obtained conjugate can be potentially useful for development of the biosensor for complementary nucleobase/nucleoside detection.

Keywords: CdTe quantum dots, conjugate, sensor, thymine

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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: Anna S. Tolkacheva, Sergey N. Shkerin, Kirill G. Zemlyanoi, Olga G. Reznitskikh, Pavel D. Khavlyuk

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Calcium oxovanadates with garnet related structure are multifunctional oxides in various fields like photoluminescence, microwave dielectrics, and magneto-dielectrics. For example, vanadate garnets are self-luminescent compounds. They attract attention as RE-free broadband excitation and emission phosphors and are candidate materials for UV-based white light-emitting diodes (WLEDs). Ca₅M₄(VO₄)₆ (M = Mg, Zn, Co, Ni, Mn) compounds are also considered promising for application in microwave devices as substrate materials. However, the relation between their structure, composition and physical/chemical properties remains unclear. Given the above-listed observations, goals of this study are to synthesise Ca₅M₄(VO₄)₆ (M = Mg, Zn, Ni) and to study their thermal and electrical properties. Solid solutions Ca₅Mg₄₋ₓMₓ(VO₄)₆ (0 ≤ x ≤ 4) where M is Zn and Ni have been synthesized by sol-gel method. The single-phase character of the final products was checked by powder X-ray diffraction on a Rigaku D/MAX-2200 X-ray diffractometer using Cu Kα radiation in the 2θ range from 15° to 70°. The dependence of thermal properties on chemical composition of solid solutions was studied using simultaneous thermal analyses (DSC and TG). Thermal analyses were conducted in a Netzch simultaneous analyser STA 449C Jupiter, in Ar atmosphere, in temperature range from 25 to 1100°C heat rate was 10 K·min⁻¹. Coefficients of thermal expansion (CTE) were obtained by dilatometry measurements in air up to 800°C using a Netzsch 402PC dilatometer; heat rate was 1 K·min⁻¹. Impedance spectra were obtained via the two-probe technique with an impedance meter Parstat 2273 in air up to 700°C with the variation of pH₂O from 0.04 to 3.35 kPa. Cation deficiency in Ca and Mg sublattice under the substitution of MgO with ZnO up to 1/6 was observed using Rietveld refinement of the crystal structure. Melting point was found to decrease with x changing from 0 to 4 in Ca₅Mg₄₋ₓMₓ(VO₄)₆ where M is Zn and Ni. It was observed that electrical conductivity does not depend on air humidity. The reported study was funded by the RFBR Grant No. 17–03–01280. Sample attestation was carried out in the Shared Access Centers at the IHTE UB RAS.

Keywords: garnet structure, electrical conductivity, thermal expansion, thermal properties

Procedia PDF Downloads 155