International Science Index

International Journal of Chemical and Molecular Engineering

1481
60130
The Preparation of High Surface Area Ni/MgAl2O4 Catalysts for Syngas Methanation
Abstract:
High surface area MgAl2O4 supported Nickel catalysts with PVA loadings varying from 0% to 15% were prepared by precipitation and impregnation method. The catalysts were characterized by low temperature N2 adsorption/desorption, X-ray diffraction and H2 temperature programmed reduction. Compared with Ni/γ-Al2O3 catalyst, Ni/MgAl2O4 catalysts exhibited higher activity and selectivity in high temperature. Among the catalysts, Ni/MgAl2O4-5P with 5 wt% PVA showed the best performance, and achieved 95% CO conversion and 96% CH4 selectivity at 600°C, 2.0 MPa, and a WHSV of 12,000 mL·g⁻¹.h⁻¹. It also maintained good stability in 50h life test.
1480
58412
Sustainable Separation of Nicotine from Its Aqueous Solutions
Abstract:
Within this study, the separation of nicotine from its aqueous solutions, using inorganic salt sodium chloride or ionic liquid (molten salt) ECOENG212® as salting-out media, was carried out. Thus, liquid-liquid equilibria of the ternary solutions (nicotine+water+NaCl) and (nicotine+water+ECOENG212®) were determined at ambient pressure, 0.1 MPa, at three temperatures. The related phase diagrams were constructed in two manners: by adding the determined cloud-points and by the chemical analysis of phases in equilibrium (tie-line data). The latter were used to calculate two important separation parameters - partition coefficients of nicotine and separation factors. The impacts of the initial compositions of the mother solutions and of temperature on the liquid-liquid phase separation and partition coefficients were analyzed and discussed. The results obtained clearly showed that both investigated salts are good salting-out media for the efficient and sustainable separation of nicotine from its solutions with water. However, when compared, sodium chloride exhibited much better separation performance than the ionic liquid.
1479
59790
Pd-Ga/Al2O3 as a Highly Active Catalyst for Tail-End Acetylene Selective Hydrogenation
Abstract:
Mono-metallic Pd/Al2O3 and bi-metallic Pd-Ga/Al2O3 catalysts were synthesized by impregnation method and evaluated in tail-end acetylene selective hydrogenation process at 60°C, 10bar and GHSV of 4000h⁻¹. Feed mixture contained 1mol.% C2H2, 1.5mol.% H2, 30mol.% N2 and C2H4 as balance. Fresh samples were characterized by FE-SEM and TPD-CO and used ones were characterized by TG. It is observed that all samples had egg-shell distribution for active phase and promoter. TPD-CO analysis proved that due to incorporation of Ga, higher isolated Pd sites, which is favorable for improving ethylene selectivity, was formed. Catalytic performance tests proved that incorporation of Ga improved acetylene conversion and ethylene selectivity.
1478
58409
Investigation of Green Dye-Sensitized Solar Cells Based on Natural Dyes
Abstract:
Natural dyes, extracted from black carrot and bramble, were utilized as photosensitizers to prepare dye-sensitized solar cells (DSSCs). Spectrophotometric studies of the natural dyes in solution and on a titanium dioxide substrate were carried out in order to assess changes in the status of the dyes. The results show that the bathochromic shift has been seen on the photoelectrode substrate. The chemical binding of the natural dyes at the surface photoelectrode can be increment by the chelating effect of the Ti(IV) ions. The cyclic voltammetry results showed that all extracts are suitable for performed in DSSCs. Finally, photochemical performance and stability of DSSCs based on natural dyes were studied. Such evaluations demonstrate short circuit photocurrent, open circuit voltage and conversion efficiencies of 1.14 mAcm-2, 0.55 V, 0.33% and 2.23 mAcm-2, 0.54 V, 0.69% for black carrot and bramble extract, respectively. The power conversion efficiency was obtained from the mixed dyes in DSSCs. The DSSCs sensitized by a mixed extract had a conversion efficiency of around the average value of those sensitized with black carrot and bramble extracts.
1477
59943
Quantum Confinement in LEEH Capped CDS Nanocrystalline
Abstract:
LEEH (L-cysteine ethyl ester hydrochloride) capped CdS semiconductor nanocrystals are grown at 800C using a simple chemical route. Photoluminescence (PL), Optical absorption (UV) and Transmission Electron Microscopy (TEM) have been carried out to evaluate the structural and optical properties of the nanocrystal. Optical absorption studies have been carried out to optimize the sample. XRD and TEM analysis shows that the nanocrystal belongs to FCC structure having average size of 3nm while a bandgap of 2.84eV is estimated from Photoluminescence analysis. The nanocrystal emits bluish light when excited with 355nm LASER.
1476
60222
A Density Functional Theory Study of Metal-Porphyrin Graphene for CO2 Hydration
Abstract:
Electronic structure calculations of hydrogen terminated metal-porphyrin graphene were carried out to explore the catalytic activity for CO2 hydration reaction. A ruthenium atom was substituted in place of carbon atom of graphene and ruthenium chelated carbon atoms were replaced by four nitrogen atoms in metal-porphyrin graphene system. Ruthenium atom created the active site for CO2 hydration reaction. Ruthenium-porphyrin graphene followed the mechanism of carbonic anhydrase enzyme for CO2 conversion to HCO3- ion. CO2 hydration reaction over ruthenium-porphyrin graphene proceeded via the elementary steps: OH- formation from H2O dissociation, CO2 bending in presence of nucleophilic attack of OH- ion, HCO3- ion formation from proton migration, HCO3- ion desorption by H2O addition. Proton transfer to yield HCO3- ion was observed as a rate limiting step from free energy landscape.
1475
60474
C59Pd: A Novel Heterogeneous Catalytic Material for Heck Coupling Reaction
Abstract:
Density functional theory calculations were carried out for identification of an active heterogeneous catalyst to carry out Heck coupling reaction which is of pharmaceutical importance. One of the carbonaceous nanomaterials, heterofullerene, was designed for the reaction. Stability and reactivity of the proposed heterofullerenes (C59M, M = Pd/Ni) were established with insights into the metal-carbon bond, electron affinity and chemical potential. Adsorbent potentials of both the heterofullerenes were examined from the adsorption study of four halobenzenes (C6H5F, C6H5Cl, C6H5Br and C6H5I). Oxidative addition activities of all four halobenzenes were investigated by developing free energy landscapes over both the heterofullerenes for rate determining step (oxidative addition). C6H5I showed a good catalytic activity for the rate determining step. Thus, C6H5I was proposed as a suitable halobenzene and complete free energy landscapes for Heck coupling reaction were developed over C59Pd and C59Ni. Smaller activation barriers observed over C59Pd in comparison with C59Ni put us in a position to propose C59Pd to be an efficient heterofullerene for carrying Heck coupling reaction.
1474
60016
Improvement of Sentinel Lymph Node Detection after Radiopharmaceutical Injection of 99mTc Phytate Colloid
Abstract:
A sentinel lymph node (SLN) is defined as the lymph node to which it is most likely cancer cells will spread from a primary tumor. Although lymphoscintigraphy is a useful method of detecting malignancy in a sentinel node, conventional lymphoscintigraphy does not determine the exact anatomical location of that node. Breast cancer has the property of spreading to the whole body through the lymph nodes around the breast. If lymph node metastases are negative, a large lymphadenectomy is generally unnecessary. However, in lympho- scintigraphy with a radiopharmaceutical, the image may be less than ideal. We investigated three methods of image improvement for lymphoscintigraphy of breast cancer. Lymphoscintigraphy was performed 12 hours after injection of 37 MBq of 99mTc phytate colloid into the peritumoral region. The particle size of 99mTc-phytate was 150-200 nm (labeling after 15 min). Images were obtained with dual-energy windows of 140±10 keV for the primary image and 90±20 keV for the scatter image. Image processing employed the Annular Background Subtraction (ABS) method and logarithmic analysis. In brief, first the dosage site was obliterated automatically, and then the background was removed. Next, the logarithm of each pixel value was taken to improve image contrast. Third, a binarization was employed for the pixels in the scatter image, and an outline was extracted. Three kinds of logarithmic processing were used in the three versions of image processing in attempting to improve the detection of the SLN. In addition, it was not necessary to cover the injection position with lead and metastasis of the injection position neighborhood was detected well.
1473
58032
Catalytic Deoxygenation of Propionic Acid in the Vapour Phase
Abstract:
The gas-phase deoxygenation of propionic acid was investigated in the presence of Co-Mo catalysts in N2 or H2 flow at 200-400 °C. In the presence of N2 the main product was 3-pentanone with other deoxygenates and some light gases: ethane and ethene. Using H2 flow, the catalyst was active for decarboxylation and decarbonylation of acid and the yields of ethane and ethene. The decarboxylation and decarbonylation reactions increased with increasing temperature. Cobalt-molybdenum supported on alumina showed better performance than bulk catalyst, especially at 400 °C in the presence of N2 for the ketonisation of propionic acid to form 3-pentanone as the main product. Bulk and supported catalysts were characterized by surface area porosity (BET), thermogravimetric analysis (TGA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of pyridine adsorption.
1472
57521
Thermal Analysis of Automobile Radiator Using Nanofluids
Abstract:
As the technology is emerging day by day, there is a need for some better methodology which will enhance the performance of radiator. Nanofluid is the one area which has promised the enhancement of the radiator performance. Currently, nanofluid has got a well effective solution for enhancing the performance of the automobile radiators. Suspending the nano sized particle in the base fluid, which has got better thermal conductivity value when compared to a base fluid, is preferably considered for nanofluid. In the current work, at first mathematical formulation has been carried out, which will govern the performance of the radiator. Current work is justified by plotting the graph for different parameters. Current work justifies the enhancement of radiator performance using nanofluid.
1471
57906
Li2S Nanoparticles Impact on the First Charge of Li-ion/Sulfur Batteries: An Operando XAS/XES Coupled With XRD Analysis
Abstract:
With their high theoretical energy density (~2600 Wh.kg-1), lithium/sulfur (Li/S) batteries are highly promising, but these systems are still poorly understood due to the complex mechanisms/equilibria involved. Replacing S8 by Li2S as the active material allows the use of safer negative electrodes, like silicon, instead of lithium metal. S8 and Li2S have different conductivity and solubility properties, resulting in a profoundly changed activation process during the first cycle. Particularly, during the first charge a high polarization and a lack of reproducibility between tests are observed. Differences observed between raw Li2S material (micron-sized) and that electrochemically produced in a battery (nano-sized) may indicate that the electrochemical process depends on the particle size. Then the major focus of the presented work is to deepen the understanding of the Li2S material charge mechanism, and more precisely to characterize the effect of the initial Li2S particle size both on the mechanism and the electrode preparation process. To do so, Li2S nanoparticles were synthetized according to two ways: a liquid path synthesis and a dissolution in ethanol, allowing Li2S nanoparticles/carbon composites to be made. Preliminary chemical and electrochemical tests show that starting with Li2S nanoparticles could effectively suppress the high initial polarization but also influence the electrode slurry preparation. Indeed, it has been shown that classical formulation process - a slurry composed of Polyvinylidone Fluoride polymer dissolved in N-methyle-2-pyrrolidone - cannot be used with Li2S nanoparticles. This reveals a complete different Li2S material behavior regarding polymers and organic solvents when going at the nanometric scale. Then the coupling between two operando characterizations such as X-Ray Diffraction (XRD) and X-Ray Absorption and Emission Spectroscopy (XAS/XES) have been carried out in order to interpret the poorly understood first charge. This study discloses that initial particle size of the active material has a great impact on the working mechanism and particularly on the different equilibria involved during the first charge of the Li2S based Li-ion batteries. These results explain the electrochemical differences and particularly the polarization differences observed during the first charge between micrometric and nanometric Li2S-based electrodes. Finally, this work could lead to a better active material design and so to more efficient Li2S-based batteries.
1470
57911
Recycling the Lanthanides from Permanent Magnets by Electrochemistry in Ionic Liquid
Abstract:
Thanks to their high magnetization and low mass, permanent magnets (NdFeB and SmCo) have quickly became essential for new energies (wind turbines, electrical vehicles…). They contain large quantities of neodymium, samarium and dysprosium, that have been recently classified as critical elements and that therefore need to be recycled. Electrochemical processes including electrodissolution followed by electrodeposition are an elegant and environmentally friendly solution for the recycling of such lanthanides contained in permanent magnets. However, electrochemistry of the lanthanides is a real challenge as their standard potentials are highly negative (around -2.5V vs ENH). Consequently, non-aqueous solvents are required. Ionic liquids (IL) are novel electrolytes exhibiting physico-chemical properties that fulfill many requirements of the sustainable chemistry principles, such as extremely low volatility and non-flammability. Furthermore, their chemical and electrochemical properties (solvation of metallic ions, large electrochemical windows, etc.) render them very attractive media to implement alternative and sustainable processes in view of integrated processes. All experiments that will be presented were carried out using butyl-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide. Linear sweep, cyclic voltammetry and potentiostatic electrochemical techniques were used. The reliability of electrochemical experiments, performed without glove box, for the classic three electrodes cell used in this study has been assessed. Deposits were obtained by chronoamperometry and were characterized by scanning electron microscopy and energy-dispersive X-ray spectroscopy. The IL cathodic behavior under different constraints (argon, nitrogen, oxygen atmosphere or water content) and using several electrode materials (Pt, Au, GC) shows that with argon gas flow and gold as a working electrode, the cathodic potential can reach the maximum value of -3V vs Fc+/Fc; thus allowing a possible reduction of lanthanides. On a gold working electrode, the reduction potential of samarium and neodymium was found to be -1.8V vs Fc+/Fc while that of dysprosium was -2.1V vs Fc+/Fc. The individual deposits obtained were found to be porous and presented some significant amounts of C, N, F, S and O atoms. Selective deposition of neodymium in presence of dysprosium was also studied and will be discussed. Next, metallic Sm, Nd and Dy electrodes were used in replacement of Au, which induced changes in the reduction potential values and the deposit structures of lanthanides. The individual corrosion potentials were also measured in order to determine the parameters influencing the electrodissolution of these metals. Finally, a full recycling process was investigated. Electrodissolution of a real permanent magnet sample was monitored kinetically. Then, the sequential electrodeposition of all lanthanides contained in the IL was investigated. Yields, quality of the deposits and consumption of chemicals will be discussed in depth, in view of the industrial feasibility of this process for real permanent magnets recycling.
1469
51710
The Prospect of Producing Hydrogen by Electrolysis of Idle Discharges of Water from Reservoirs and Recycling of Waste-Gas Condensates
Abstract:
Among problems that the whole world faces, it is climate change that poses a serious threat for all natural and economic complexes, including water and land resources. It is obvious that in processes of global climate change the key factor is a concentration of greenhouse gases in the atmosphere. The main pollutants of the Central Asia Region atmosphere are the weighed particles (35%) and SO2 (31%), CO2 (14 %) and nitrogen oxides (10 %). In the present work, there are problems in the use of water resources from upstream countries of the Central Asian Transboundary Rivers and the surplus of the electric power during the summer period for production of hydrogen by electrolysis and the possibility of storage and hydrogen transportation for long distances are considered. Gaseous hydrogen is transportable and can be stored in huge quantities in natural underground storehouses. An identical section pressure passes through the pipelines in the form of hydrogen or methane with the same quantity of energy. Transportation through pipelines in the form of hydrogen is approximately 4 times more favorable, in comparison with the transfer of the same energy in the form of electricity. In Tajikistan 15 Billion kWt/h, hydropower is produced and used, which increases in the summer period. However, nowadays condition of hydropower use is not purposeful. With acceptance in the reform of hydropower, raising the effectiveness of hydropower decreased the demand up to 25%. We can own the valuable hydropower 6 billion kWt/h only for the production of hydrogen gas. In the future, Tajikistan is building two large hydropower stations Rogun (3600 MWt) and Sangtuda (670 MWt) are continued, the hydropower source can increase. Use of these two stations will bring an additional 20 billion kWt of hydropower annually. The electrodes from stainless steel and copper for an electrolysis are used. The subject of electrolysis was river water and the water after electro-sedimentation. If you use river water without pre-treatment were found deposition on the electrodes conglomerates of complex composition and process for the electrolysis of water was not almost observed. To release the gas bubbles from the electrodes was used to mechanical vibration. Pyrolysis of gas condensate in nitric plasma has shown about the basic possibility of production of no limiting hydrocarbons and cyanic hydrogen. Essential influence of cooling processes and training on the target products exit established. The dependence of a percentage parity of the no limiting hydrocarbons and cyanic hydrogen exits from the plasma stream specific power and time of stay of raw materials in a plasma stream specifies in possibilities of management of the process of pyrolysis on maintenance of the maximum exit of separate components of products of the reaction is shown.
1468
57794
The Prospect of Producing Hydrogen by Electrolysis of Idle Discharges of Water from Reservoirs and Recycling of Waste-Gas Condensates
Abstract:
The results of studies of hydrogen production by application of water electrolysis and plasma-chemical processing of gas condensate - waste of natural gas production methods are presented. Thin coating covers the electrode surfaces in processes of water electrolysis. Therefore, previously water for electrolysis was exposed to electrosedimentation. The threshold voltage is shifted to a lower value compared with the use of electrodes made of stainless steel. At electrolysis of electrosedimented water by use of electrodes from stainless steel, a significant number of hydrogen is formed. The pyrolysis of gascondensate with a molecular weight of 140 (C10H20) with an average boiling point of about 55°С. Pyrolysis of gas condensates in the atmosphere of a nitrogen was followed by formation of acetylene (3-7 vol. %), ethylene (4-8 vol. %) and pyrolysis carbon (10-15 weight %).
1467
59596
Carbon Dioxide Hydrogenation to Methanol over Cu/ZnO-SBA-15 Catalyst: Effect of Metal Loading
Abstract:
Utilization of CO2 as a carbon source to produce valuable chemicals is one of the important ways to reduce the global warming caused by increasing CO2 in the atmosphere. Supported metal catalysts are crucial for the production of clean and renewable fuels and chemicals from the stable CO2 molecules. The catalytic conversion of CO2 into methanol is recently under increased scrutiny as an opportunity to be used as a low-cost carbon source. Therefore, series of the bimetallic Cu/ZnO-based catalyst supported by SBA-15 were synthesized via impregnation technique with different total metal loading and tested in the catalytic hydrogenation of CO2 to methanol. The morphological and textural properties of the synthesized catalysts were determined by transmission electron microscopy (TEM), temperature programmed desorption, reduction, oxidation and pulse chemisorption (TPDRO), and N2-adsorption. The CO2 hydrogenation reaction was performed in microactivity fixed-bed system at 250 °C, 2.25 MPa, and H2/CO2 ratio of 3. Experimental results showed that the catalytic structure and performance was strongly affected by the loading of the active site. Where, the catalytic activity, methanol selectivity as well as the space-time yield increased with increasing the metal loading until it reaches the maximum values at a metal loading of 15 wt% while further addition of metal inhibits the catalytic performance. The higher catalytic activity of 14 % and methanol selectivity of 92 % were obtained over Cu/ZnO-SBA-15 catalyst with total bimetallic loading of 15 wt%. The excellent performance of 15 wt% Cu/ZnO-SBA-15 catalyst is attributed to the presence of well disperses active sites with small particle size, higher Cu surface area, and lower catalytic reducibility.
1466
58728
Highly Efficient Iron Oxide-Sulfonated Graphene Oxide Catalyst for Esterification and Trans-Esterification Reactions
Abstract:
Esterification of free fatty acid (oleic acid) and transesterification of waste cooking oil (WCO) with ethanol over graphene oxide (GO), GO-Fe2O3, sulfonated GO (GO-SO3H), and Fe2O3/GO-SO3H catalysts were examined in the present study. Iron oxide supported graphene-based acid catalyst (Fe2O3/GO-SO3H) exhibited highest catalytic activity. GO was prepared by modified Hummer’s process. The GO-Fe2O3 nanocomposites were prepared by the addition of NaOH to a solution containing GO and FeCl3. Sulfonation was done using concentrated sulfuric acid. Transmissionelectron microscopy (TEM) and atomic force microscopy (AFM) imaging revealed the presence of Fe2O3 particles having size in the range of 50-200 nm. Crystal structure was analyzed by XRD and defect states of graphene were characterized using Raman spectroscopy. The effects of the reaction variables such as catalyst loading, ethanol to acid ratio, reaction time and temperature on the conversion of fatty acids were studied. The optimum conditions for the esterification process were molar ratio of alcohol to oleic acid at 12:1 with 5 wt% of Fe2O3/GO-SO3H at 1000C with a reaction time of 4h yielding 99% of ethyl oleate. This is because metal oxide supported solid acid catalysts have advantages of having both strong Brønsted as well as Lewis acid properties. The biodiesel obtained by transesterification of WCO was characterized by 1H NMR and Gas Chromatography techniques. XRD patterns of the recycled catalyst evidenced that the catalyst structure was unchanged up to the 5th cycle, which indicated the long life of the catalyst.
1465
58905
Association of Non Synonymous SNP in DC-SIGN Receptor Gene with Tuberculosis (Tb)
Abstract:
Mycobacterium tuberculosis is a communicable chronic illness. This disease is being highly focused by researchers as it is present approximately in one third of world population either in active or latent form. The genetic makeup of a person plays an important part in producing immunity against disease. And one important factor association is single nucleotide polymorphism of relevant gene. In this study, we have studied association between single nucleotide polymorphism of CD-209 gene (encode DC-SIGN receptor) and patients of tuberculosis. Dry lab (in silico) and wet lab (RFLP) analysis have been carried out. GWAS catalogue and GEO database have been searched to find out previous association data. No association study has been found related to CD-209 nsSNPs but role of CD-209 in pulmonary tuberculosis have been addressed in GEO database.Therefore, CD-209 has been selected for this study. Different databases like ENSEMBLE and 1000 Genome Project has been used to retrieve SNP data in form of VCF file which is further submitted to different software to sort SNPs into benign and deleterious. Selected SNPs are further annotated by using 3-D modeling techniques using I-TASSER online software. Furthermore, selected nsSNPs were checked in Gujrat and Faisalabad population through RFLP analysis. In this study population two SNPs are found to be associated with tuberculosis while one nsSNP is not found to be associated with the disease.
1464
56286
Poly(3-Ethylenedioxythiophene) Polystyrenesulfonate (PEDOT-PSS) Electrodes for Thermo-Electrochemical Cells
Abstract:
Interest in thermo-electrochemical cell has grown due to the concern over the climate change connected to CO2 release and the inefficient usage of fossil fuel. Importantly more than 60% of fossil fuel energy is lost in the form of heat, which motivates the exploration of new technologies converting waste heat into electricity to achieve future sustainable energy systems. Thermo-electrochemical cell is an electrochemical device which allows direct conversion of thermal energy to electrical energy. It consists of an electrolyte with a redox couple and two identical electrodes set at different temperatures. Thermo-electrochemical cells are attractive alternative to harvest waste heat generated from industrial process and household usage due to simplicity, low cost and flexibility of device structure. The most studied Thermo-electrochemical cell is made of an electrolyte containing aqueous 0.4 M ferri/ferrocyanide redox couple with platinum electrodes. In this system, the temperature difference creates a difference in the redox potential of the ferri/ferrocyanide electrolyte at the platinum electrodes allowing to generate power. Conducting polymer is one of the promising candidate electrode for Thermo-electrochemical cells due to high stability and electrochemical activity. Furthermore conducting polymers can be synthesized with high conductivity, stability and porosity. Eventually, these properties facilitate extracting of larger current densities between electrode and electrolyte. We have shown that the power generation of the thermo-electrochemical cell increases with the conductivity of the conducting. Polymer poly(3-ethylenedioxythiophene)-polystyrenesulfonate (PEDOT-PSS) electrode. The conductivity of the PEDOT-PSS electrode is tuned by addition of well a defined concentration of dimethyl sulfoxide (DMSO). Furthermore, the power generation is further enhanced with the increase of PEDOT-PSS electrode thickness and reaches values similar to a flat platinum electrode.
1463
57069
Cost-Effective Soft Lithography of Organic Semiconductors in Organic Field-Effect Transistors (OFETs)
Authors:
Abstract:
We demonstrate repurposing linear micropatterns on the CD as a master mold to fabricate TIPS-PEN microwires. From the micropatterns on CDs, we replicated polyurethane acrylate (PUA) templates which are robust and flexible until submicrometer scale patterns. Subsequently, 1.5 μm TIPS-PEN microwires separated by 1.5 μm were grown. Using crystal analysis tools with polarized optical microscopy and X-ray diffraction measurement, it was revealed that each TIPS-PEN microwires are highly crystalline and uniform compared to spin-coated films. It is attributed to the template-guided growth of TIPS-PEN crystals along the linear template, thus the OFETs comprised of TIPS-PEN microwires displayed the high field-effect mobility.
1462
55924
Surface Sensing of Atomic Behavior of Polymer Nanofilms via Molecular Dynamics Simulation
Authors:
Abstract:
Surface-sensing devices such as atomic force microscope have been widely used to characterize the surface structure and properties of nanoscale polymer films. However, using molecular dynamics simulations, we show that there is intrinsic and unavoidable inelastic deformation at polymer surfaces induced by the sensing tip. For linear chain polymers like perfluoropolyether, such tip-induced deformation derives from the differences in the atomic interactions which are atomic specie-based Van der Waals interactions, and resulting in atomic shuffling and causing inelastic alternation in both molecular structures and mechanical properties at the regions of the polymer surface. For those aromatic chain polymers like epoxy, the intrinsic deformation is depicted as the intra-chain rotation of aromatic rings and kinking of linear atomic connections. The present work highlights the need to reinterpret the data obtained from surface-sensing tests by considering this intrinsic inelastic deformation occurring at polymer surfaces.
1461
56543
European Standardization in Nanotechnologies and Relation with International Work: The Standardization Can Help Industry and Regulators in Developing Safe Products
Abstract:
Nanotechnologies have enormous potential to contribute to human flourishing in responsible and sustainable ways. They are rapidly developing field of science, technology and innovation. As enabling technologies, their full scope of applications is potentially very wide. Major implications are expected in many areas, e.g. healthcare, information and communication technologies, energy production and storage, materials science/chemical engineering, manufacturing, environmental protection, consumer products, etc. However, nanotechnologies are unlikely to realize their full potential unless their associated societal and ethical issues are adequately attended. Namely nanotechnologies and nanoparticles may expose humans and the environment to new health risks, possibly involving quite different mechanisms of interference with the physiology of human and environmental species. One of the building blocks of the ‘safe, integrated and responsible’ approach is standardization. Both the Economic and Social Committee and the European Parliament have highlighted the importance to be attached to standardization as a means to accompany the introduction on the market of nanotechnologies and nanomaterials, and a means to facilitate the implementation of regulation. ISO and CEN have respectively started in 2005 and 2006 to deal with selected topics related to this emerging and enabling technology. In the beginning of 2010, EC DG ‘Enterprise and Industry’ addressed the mandate M/461 to CEN, CENELEC and ETSI for standardization activities regarding nanotechnologies and nanomaterials. Thus CEN/TC 352 ‘Nanotechnologies’ has been asked to take the leadership for the coordination in the execution of M/461 (46 topics to be standardized) and to contact relevant European and International Technical committees and interested stakeholders as appropriate (56 structures have been identified). Prior requests from M/461 deal with characterization and exposure of nanomaterials and any matters related to Health, Safety and Environment. Answers will be given to: - What are the structures and how they work? - Where are we right now and how work is going from now onwards? - How CEN’s work and targets deal with and interact with global matters in this field?
1460
57403
Study of Nanocrystalline Scintillator for Alpha Particles Detection
Abstract:
We report on the synthesis of cesium-iodide nanoparticles using sol-gel technique. The structural properties of CsI nanoparticles were characterized by X-ray diffraction and Scanning Electron Microscope (SEM) Also, optical properties were followed by optical absorption and UV–vis fluorescence. Intense photoluminescence is also observed, with some spectral tuning possible with ripening time getting a range of emission photon wavelength approximately from 366 to 350 nm. The size effect on CsI luminescence leads to an increase in scintillation light yield, a redshift of the emission bands of the on_center and off_center self_trapped excitons (STEs) and an increase in the contribution of the off_center STEs to the net intrinsic emission yield. The energy transfer from the matrix to CsI nanoparticles is a key characteristic for scintillation detectors. So the scintillation spectra to alpha particles of sample were monitored.
1459
55765
Development of Materials Based on Phosphates of NaZr2(PO4)3 with Low Thermal Expansion
Abstract:
NaZr2(PO4)3 (NZP) and their structural analogues are characterized by a peculiar behaviors on heating – they have different expansion and contraction along different crystallographic directions due to specific arrangements of crystal structure in these compounds. An important feature of such structures is the ability to incorporate into their structural analogues wide variety of metal cations having different size and oxidation states, with different combinations and concentrations. These cations are located in different crystallographic non-equivalent positions of octahedral tetrahedral crystal framework as well as in inter-framework cavities. Through, due to iso- and hetero-valent isomorphism of the cations (and the anions) in NZP, it becomes possible to tuning the compositions and to obtain the compounds with ‘on a plan’ properties. For the design of compounds with low and ultra-low thermal expansion including those with tailored thermal expansion properties, the following crystallochemical principles it seems are promising: 1) Insertion into crystal M1 position the cations having different sizes and, 2) the variation in the composition of compounds, providing different occupation of crystal M1 position. Following these principles we have designed and synthesized the next NZP-type phosphates series: a) where radii of the cations in the M1 crystal position was varied: Zr1/4Zr2(PO4)3 - Th1/4Zr2(PO4)3 (series I); R1/3Zr2(PO4)3 where R= Nd, Eu, Er (series II), b) where the occupation of M1 crystal position was varied: Zr1/4Zr2(PO4)3-Er1/3Zr2(PO4)3 (series III) and Zr1/4Zr2(PO4)3-Sr1/2Zr2(PO4)3 (series IV). The thermal expansion parameters were determined over the range of 25-800ºC. For each series the minimum axial coefficient of thermal expansion αa = αb, αc and their anisotropy Δα = Iαa - αcI, 10-6 K-1 was found as next: -1.51, 1.07, 2.58 for Th1/4Zr2(PO4)3 (series I); -0.72, 0.10, 0.81 for Nd1/3Zr2(PO4)3 (series II); -2.78, 1.35, 4.12 for Er1/6Zr1/8Zr2(PO4)3 (series III); 2.23, 1.32, 0.91 for Sr1/2Zr2(PO4)3 (series IV). The measured tendencies of the thermal expansion of crystals were in good agreement with predicted ones. For one of the members from the studied phosphates namely Th1/16Zr3/16Zr2(PO4)3 structural refinement have been carried out at 25, 200, 600, and 800°C. The dependencies of the structural parameters with the temperature have been determined.
1458
56156
Determination of Gold in Microelectronics Waste Pieces
Abstract:
Gold can be determined in natural objects and manufactured articles of different origin. The up-to-date status of research and problems of high gold level determination in alloys and manufactured articles are described in detail in the literature. No less important is the task of this metal determination in minerals, process products and waste pieces. The latters, as objects of gold content chemical analysis, are most hard-to-study for two reasons: Because of high requirements to accuracy of analysis results and because of difference in chemical and phase composition. As a rule, such objects are characterized by compound, variable and very often unknown matrix composition that leads to unpredictable and uncontrolled effect on accuracy and other analytical characteristics of analysis technique. In this paper, the methods for the determination of gold are described, using flame atomic-absorption spectrophotometry and gravimetric analysis technique. The techniques are aimed at gold determination in a solution for gold etching (KJ+J2), in the technological mixture formed after cleaning stainless steel members of vacuum-deposit installation with concentrated nitric and hydrochloric acids as well as in gold-containing powder resulted from liquid wastes reprocessing. Optimal conditions for sample preparation and analysis of liquid and solid waste specimens of compound and variable matrix composition were chosen. The boundaries of relative resultant error were determined for the methods within the range of gold mass concentration from 0.1 to 30g/dm3 in the specimens of liquid wastes and mass fractions from 3 to 80% in the specimens of solid wastes.
1457
57417
Toxicological Interactions of Silver Nanoparticles and Non-Essential Metals in Human Hepatocarcinoma Cell Line
Abstract:
Synergetic and antagonistic effects of drugs are well-known concerns in pharmacological assessments of dose and toxicity. Similar approach should be used in assessing cellular uptake and cytotoxicity of nanoparticles. Since nanoparticles are released into the aquatic environment they may interact with existing xenobiotics. Here we used biochemical assays and quantitative proteomics to assess the cytotoxicity of silver nanoparticles (AgNP) when human hepatoma HepG2 cells were co-exposed to 2 nm AgNP together with either Cd2+ or Hg2+ ions. Time-course experiments (2h, 4h, and 24h) were conducted to assess the first response to the exposure studies. The general trend was that a synergetic toxicological response was observed in cells exposed to both AgNP and Cd2+ or Hg2+, with AgNP and Cd2+ being more toxic. This was observed by a significant increase in the ROS and superoxide level of >35% in the case of AgNP+Cd2+ compared to the sum of responses of AgNP and Cd2+, individually. Metabolic activity and viability also dropped more for AgNP+Cd2+ (>10%) than for AgNP and Cd2+ combined. We used inductively coupled plasma mass spectrometry to investigate if AgNP facilitates larger influx of toxic metal ions into HepG2 cells. Only Hg2+ ions was found to be more efficiently engulfed as the concentration of Hg2+ was found 2.8 times larger compared to exposure experiments with only Hg2+. This effect was not observed for Cd2+. We now continue with deep proteomics studies to obtain wider details on the mechanism of the toxicity related to AgNP, Cd2+, and AgNP+Cd2+, respectively.
1456
60159
Facile Synthetic Process for Lamivudine and Emtricitabine
Abstract:
Cis-Nucleosides mainly lamivudine (3TC) and emtricitabine (FTC) are an important tool in the treatment of Human immune deficiency virus (HIV), Hepatitis B virus (HBV) and Human T-Lymotropoic virus (HTLV). Lamivudine and emtricitabine are potent nucleoside analog reverse transcriptase inhibitors (nRTI). These two drugs are synthesized by a four-stage process from the starting materials: menthyl glyoxylate hydrate and 1,4-dithane-2,5-diol to produce the 5-hydroxy oxathiolane which upon acetylation with acetic anhydride to yield 5-acetoxy oxathiolane. Then glycosylation of this acetyl product with silyl protected nucleoside to produce the intermediate. The reduction of this intermediates can provide the final targets. Although there are several different methods reported for the synthesis of lamivudine and emtricitabine as a single enantiomer, we required an efficient route, which was suitable for large-scale synthesis to support the development of these compounds. In this process, we successfully prepared the intermediates of lamivudine and emtricitabine without using any solvents and catalyst, thus promoting the green synthesis. All the synthesized compound were confirmed by TLC, GC, Mass, NMR and 13C NMR spectroscopy.
1455
57082
Calcium Complexing Properties of Isosaccharinate Ion in Highly Alkaline Environment
Abstract:
In this study the behavior of alpha-D-isosaccharinate (2-hydroxymethyl-3-deoxy-D-erythro-pentonate, ISA−) in alkaline medium in the presence of calcium was studied. At first the Ca–ISA system was studied by Ca-ion selective electrode (Ca-ISE) in neutral medium at T = 25 °C and I = 1 M NaCl to determine the formation constant of the CaISA+ monocomplex, which was found to be logK = 1.01 ± 0.01 for the reaction of Ca2+ + ISA– = CaISA+. In alkaline medium pH potentiometric titrations were carried out to determine the composition and stability constant of the complex(es) formed. It was found that in these systems above pH = 12.5 the predominant species is the CaISAOH complex. Its formation constant was found to be logK = 3.04 ± 0.05 for the reaction of Ca2+ + ISA– + H2O = CaISAOH + H+ at T = 25 °C and I = 1 M NaCl. Solubility measurements resulted in data consistent with those of the potentiometric titrations. Temperature dependent NMR spectra showed that the slow exchange range between the complex and the free ligand is below 5 °C. It was also showed that ISA– acts as a multidentate ligand forming macrochelate Ca-complexes. The structure of the complexes was determined by using ab initio quantum chemical calculations.
1454
58754
Iron-MOFs: Potential Application as Theranostics for Inhalable Therapy of Tuberculosis
Abstract:
MOF (Metal-Organic Frameworks) belong to a new group of porous coordination polymers with a hybrid organic-inorganic construction. Their well-developed surface and possibility to build MOF of biocompatible components let to use them as potential drug carriers. Forming MOF structure from cations possessing paramagnetic properties (e.g. iron cations) allows to use them as MRI (Magnetic Resonance Imaging) contrast agents and monitoring the distribution of the active substance after administration in real time. The aim of the study was to investigate the possibility of applying iron-MOF as inhalable theranostics (combining carring active substance and monitoring its distribution) particulate system for the first-line anti-tuberculose antibiotic–isoniazid. The drug content and its incorporation into the channel system of Fe-MIL-101-NH2 were evaluated by infrared spectrometry which showed high loading of the drug–ca. 50% wt. Possibility of Fe-MIL-101-NH2 application as the MRI contrast agent was demonstrated by magnetic resonance tomografy. MOF micronization via ultrasound was evaluated by XRD, nitrogen adsorption, FTIR, SEM imaging and did not influence their crystal shape. MOF cytotoxicity was evaluated in in vitro test on L929 fibroblast. After 24h no inhibition of cell proliferation was observed. All results proved potential possibility of application of iron-MOF as an isoniazid carrier and as MRI contrast agent in inhalatory treatment of tuberculosis. We gratefully acknowledge the National Science Center Poland for providing financial support, grant no 2014/15/B/ST5/04498
1453
57076
Atmospheric CO2 Capture via Temperature/Vacuum Swing Adsorption in SIFSIX-3-Ni
Abstract:
Carbon dioxide capture has attracted the attention of many governments, industries and scientists over the last few decades, due to the rapid increase in atmospheric CO2 composition, with several studies being conducted in this area over the last few years. In many of these studies, CO2 capture in complex Pressure Swing Adsorption (PSA) cycles has been associated with high energy consumption despite the promising capture performance of such processes. The purpose of this study is the economic capture of atmospheric carbon dioxide for its transformation into a clean type of energy. A single column Temperature /Vacuum Swing Adsorption (TSA/VSA) process is proposed as an alternative option to multi column Pressure Swing Adsorption (PSA) processes. The proposed adsorbent is SIFSIX-3-Ni, a newly developed MOF (Metal Organic Framework), with extended CO2 selectivity and capacity. There are three stages involved in this paper: (i) SIFSIX-3-Ni is synthesized and pelletized and its physical and chemical properties are examined before and after the pelletization process, (ii) experiments are designed and undertaken for the estimation of the diffusion and adsorption parameters and limitations for CO2 undergoing capture from the air; and (iii) the CO2 adsorption capacity and dynamical characteristics of SIFSIX-3-Ni are investigated both experimentally and mathematically by employing a single column TSA/VSA, for the capture of atmospheric CO2. This work is further supported by a technical-economical study for the estimation of the investment cost and the energy consumption of the single column TSA/VSA process. The simulations are performed using gProms.
1452
55863
Surface Characterization and Femtosecond-Nanosecond Transient Absorption Dynamics of Bioconjugated Gold Nanoparticles: Insight into the Warfarin Drug-Binding Site of Human Serum Albumin
Abstract:
We studied the spectroscopy of 25-nm diameter gold nanoparticles (AuNPs), coated with human serum albumin (HSA) as a model drug carrier. The morphology and coating of the AuNPs were examined using transmission electron microscopy and dynamic light scattering. Resonance energy transfer from the sole tryptophan of HSA (Trp214) to the AuNPs was observed in which the fluorescence quenching of Trp214 is dominated by a static mechanism. Using fluorescein (FL) to probe the warfarin drug-binding site in HSA revealed the unchanged nature of the binding cavity on the surface of the AuNPs, indicating the stability of the protein structure on the metal surface. The transient absorption results of the surface plasmonic resonance (SPR) band of the AuNPs show three ultrafast dynamics that are involved in the relaxation process after excitation at 460 nm. The three decay components were assigned to the electron-electron (~ 400 fs), electron-phonon (~ 2.0 ps) and phonon-phonon (200–250 ps) interactions. These dynamics were not changed upon coating the AuNPs with HSA which indicates the chemical and physical stability of the AuNPs upon bioconjugation. Binding of FL in HSA did not have any measurable effect on the bleach recovery dynamics of the SPR band, although both FL and AuNPs were excited at 460 nm. The current study is important for a better understanding of the physical and dynamical properties of protein-coated metal nanoparticles which are expected to help in optimizing their properties for critical applications in nanomedicine.