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861.
Bulk and surface properties of the ionic liquids 1-alkyl-3-methyl-imidazolium iodides ([C(n)mim]I) were simulated by classical molecular dynamics using all atom non-polarizable force field (n = 4, butyl; 6, hexyl; 8, octyl). The structure of ionic liquids were initially optimized by density functional theory and atomic charges obtained by CHELPG method. Reduction of partial atomic charges (by 20% for simulation of density and surface tension, and by 10% for viscosity) found to improve the accuracy, while a non-polarizable force field was applied. Additionally, the simulation ensembles approach the equilibrium faster when the charge reduction is applied. By these refined force field parameters, simulated surface tensions in the range of 323-393 k are quite in agreement with the experiments. Simulation of temperature dependent surface tension of [C(4)mim]I well beyond room temperature (up to 700 K) permits prediction of the critical temperature in agreement with that predicted from experimental surface tension data. Simulated densities in the range of 298-450 K for the three ionic liquids are within 0.8% of the experimental data. Structural properties for [C(4)mim]I were found to be in agreement with the results of Car-Parrinello molecular dynamics simulation we performed, which indicates a rather well-structured cation-anion interaction and occurs essentially through the imidazolium ring cation. Diffusion coefficient changes with alkyl chain length in the order of [C(8)mim]I > [C(6)mim]I > [C(4)mim]I for the cation and the anion. Formation of a dense domain in subsurface region is quite evident, and progressively becomes denser as the alkyl chain length increases. Bivariate orientational analysis was used to determine the average orientation of molecule in ionic liquids surface, subsurface, and bulk regions. Dynamic bisector-wise and side-wise movement of the imodazolium ring cation in the surface region can be deduced from the bivariate maps. Atom-atom density profile and bivariate analysis indicate that the imidazolium cation takes a spoon like configuration in the surface region and the tilt of alkyl group is a function length of alkyl chain exposing as linear as possible to the vapor phase. 相似文献
862.
Siddiqi ZA Kumar S Khalid M Shahid M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2009,71(5):1845-1850
The dipodal ligands (Im) and (BIm) as well as complexes [FeLCl3] [L = Im (1) and BIm (2)] have been prepared and studied using spectroscopic techniques. The magnetic moment, IR, electronic (ligand field), FAB-mass and NMR spectral data indicate a hexa-coordinate geometry around high-spin state Fe3+ where the ligands coordinate as a tridentate [N,N,N] chelating agent. 57Fe-Mössbauer spectral data confirmed the presence of a ligand asymmetry around Fe3+ in a high-spin state electronic configuration (t2g3,eg2, S = 5/2) with nuclear transition Fe(±3/2 → ±1/2) exhibiting Kramer's double degeneracy. The molecular computations provided the optimum energy perspective plots for the molecular geometries giving the important structural data. 相似文献
863.
Abdul Sattar Chang Nusrat Naeem Memon Sidra Amin Fouzia Chang Umair Aftab Muhammad Ishaq Abro Ali dadChandio Aqeel Ahmed Shah Mazhar Hussain Ibupoto Muhammad Akram Ansari Zafar Hussain Ibupoto 《Electroanalysis》2019,31(7):1296-1303
In this study, we have investigated the effect of counter anions on the morphology of cobalt oxide nanostructures. The nanostructures of cobalt oxide are prepared by a low temperature aqueous chemical growth method. The morphology of cobalt oxide nanostructure material was investigated by scanning electron microscopy and the crystalline structure was studied by powder X‐ray diffraction technique. The cobalt oxide nanostructures exhibit the nanowire, lump, bundle of the nanowire and flower‐like morphologies. The XRD study has revealed a cubic phase of cobalt oxide nanostructures. The electro‐catalytic properties of cobalt oxide nanostructures were explored through cyclic voltammetry and amperometric techniques by sensing of lactic acid in the alkaline media. The cobalt oxide nanostructures prepared from cobalt nitrate have shown a well‐resolved redox peak. The proposed mechanism for the non‐enzymatic lactic acid sensor is elucidated by considering the morphology and cyclic voltammetry response. The limit of detection for the sensor was found to be 0.006 mM and it exhibits a linear range from 0.05–3 mM of lactic acid as shown by cyclic voltammetry. The amperometric response has shown the excellent current‐concentration response and the linear range of sensor was found to be 0.1 mM to 5.5 mM. The lactic acid sensor is stable, selective and can be used for practical applications. This study provides an excellent alternative analytical tool for the determination of lactic acid. 相似文献
864.
Dynamic viscoelastic properties of poly(vinyl chloride) (PVC)/bis(2-ethylhexyl) phthalate (DOP) and PVC/di-n-butyl sebacate (DBS) gels with molecular weight distribution (Mw/Mn), of 2.16 and various polymer concentrations c, have been studied as a function of temperature. These PVC gels exhibited an elastic solid at room temperature T, and gradually became liquid (sol) with increasing temperature. The sol-gel transition took place at a critical gel temperature at which the scaling law of G′(ω) ∼ G″(ω) ∝ ωn held, allowing an accurate determination of the critical gel temperature by means of the frequency ω independence of the loss tangent. In this study the scaling exponent n, was 0.75–0.77. This is in good agreement with the previous results observed at different temperatures and suggests the formation of a similar fractal structure of the PVC gels. The gel strength Sg, at the gel point increased with increasing PVC concentration. These results suggest a unique character and structure for the gel points of PVC-plasticizers. 相似文献
865.
The role of UVA radiation in the formation of human nuclear cataract is not well understood. We have previously shown that exposing guinea pigs for 5 months to a chronic low level of UVA light produces increased lens nuclear light scattering and elevated levels of protein disulfide. Here we have used the technique of dynamic light scattering (DLS) to investigate lens protein aggregation in vivo in the guinea pig/UVA model. DLS size distribution analysis conducted at the same location in the lens nucleus of control and UVA-irradiated animals showed a 28% reduction in intensity of small diameter proteins in experimental lenses compared with controls (P < 0.05). In addition, large diameter proteins in UVA-exposed lens nuclei increased five-fold in intensity compared to controls (P < 0.05). The UVA-induced increase in apparent size of lens nuclear small diameter proteins was three-fold (P < 0.01), and the size of large diameter aggregates was more than four-fold in experimental lenses compared with controls. The diameter of crystallin aggregates in the UVA-irradiated lens nucleus was estimated to be 350 nm, a size able to scatter light. No significant changes in protein size were detected in the anterior cortex of UVA-irradiated lenses. It is presumed that the presence of a UVA chromophore in the guinea pig lens (NADPH bound to zeta crystallin), as well as traces of oxygen, contributed to UVA-induced crystallin aggregation. The results indicate a potentially harmful role for UVA light in the lens nucleus. A similar process of UVA-irradiated protein aggregation may take place in the older human lens nucleus, accelerating the formation of human nuclear cataract. 相似文献
866.
E. Tazikeh Lemeski G. Rezaei Behbehani A. A. Saboury M. Monajjemi R. Zafar Mehrabian M. Ahmadi Golsefidi H. Rajabzadeh M. T. Baei S. Hasanzadeh 《Journal of solution chemistry》2011,40(4):575-586
The interaction of human growth hormone (hGH) with the divalent mercury ion was studied by isothermal titration calorimetry
at two temperatures of 27 °C and 37 °C in aqueous solutions. We found that there is a set of two identical and non-interacting
binding sites for Hg2+ ions. The intrinsic dissociation equilibrium constant and the molar enthalpy of binding are 4.2 mmol⋅L−1 and −14.8 kJ⋅mol−1 at 27 °C and 5.1 mmol⋅L−1 and −14.2 kJ⋅mol−1 at 37 °C, respectively. The results obtained indicate that the stability of the protein increases due to the binding of mercury
ions using the extended solvation theory. 相似文献
867.
R. B. Gujar S. A. Ansari A. Bhattacharyya P. K. Mohapatra A. S. Kanekar P. N. Pathak V. K. Manchanda 《Journal of Radioanalytical and Nuclear Chemistry》2011,288(2):621-627
The radiolytic stability of a branched diglycolamide extractant, namely N,N,N′,N′-tetra-2-ethylhexyl diglycolamide (T2EHDGA) dissolved in n-dodecane containing several phase modifiers, viz. N,N-dihexyloctanamide (DHOA), tri-n-butyl phosphate (TBP), 1-decanol and iso-decanol has been investigated. The distribution ratio of Am(III) decreased with
increased radiation dose studied up to 1000 kGy. Nevertheless, all the composition of extractants showed satisfactory results
up to 500 kGy, beyond which the extractants degraded drastically. The stripping behaviour of Am(III) with 0.2 M HNO3 was found to be unaffected even with the ligand solution irradiated up to 1000 kGy. Extraction of fission product and structural
elements was also investigated using the irradiated solvents and was found to be not significantly affected with increasing
absorbed dose with the exception of Mo which showed sharp rise in the distribution coefficient values. Loading of Nd in the
organic phase decreased with the irradiated solvent due to degradation of the carrier. The effect of the absorbed dose on
physical parameters such as density, viscosity and interfacial tension of the solvents has also been investigated. 相似文献
868.
Application of polyaniline as an efficient and novel adsorbent for azo dyes removal from textile wastewaters 总被引:1,自引:0,他引:1
In this work, application of polyaniline coated onto wood sawdust (PAni/SD) for the removal of methyl orange (MO) as a typical
azo dye from aqueous solutions is introduced. The effects of some important parameters such as pH, initial concentration,
sorbent dosage, and contact time on the uptake of MO solution were also investigated. In order to get a better comparison,
adsorption experiments were also carried out using commercial grade of granulated activated carbon (GAC) and sawdust without
coating (SD) at the same time. It was found that PAni/SD can be used to remove azo dyes such as MO from aqueous solutions
very efficiently. Experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Kinetic parameters
for the adsorption of MO dyes for the selected adsorbents are also reported. In order to study the possibility of desorption
for frequent application, chemical regeneration of the used adsorbents was also investigated. Desorption or recovery of dye
and regeneration of adsorbent (PAni/SD) was found to be quite possible and of high performance. Application of modified sawdust
with polyaniline for the removal of azo dye is very promising for textile wastewater treatment. 相似文献
869.
Muhammad Imran Khan Zafar Iqbal Lateef Ahmad Yasar Shah Shabnam Nazir Abbas Khan Fazli Nasir 《Chromatographia》2011,73(9-10):929-939
A highly sensitive, precise, and accurate reversed-phase high-performance liquid-chromatography/electrochemical detection method for simultaneous determination of the endogenous free ??-lipoic acid and dihydrolipoic acid in biological matrices was developed and validated. The two analytes were extracted from the samples with acetonitrile/10% metaphosphoric acid solution(aqueous) (50/50 v/v). To determine the total lipoic acid, samples were treated with tris(2-carboxyethyl)phosphine solution in phosphate buffer, pH 2.5 with 85% orthophosphoric acid prior to deproteination. The two analytes were separated on a C18 (150 × 4.6 mm, 5 ??m) analytical column using acetonitrile-50 mM phosphate buffer, pH 2.5 with 85% orthophosphoric acid (35/65 v/v) as the isocratic mobile phase pumped at a flow rate of 2.0 mL min?1 at the column oven temperature of 35 °C. The column eluents were monitored at a potential of 0.9 V. These analytes were efficiently resolved in <7 min. The present method was sufficiently robust and specific for simultaneous determination of the two analytes and demonstrated acceptable values for linearity (r 2 = 0.999 in the range of 0.1?C500 and 0.25?C1,000 ng mL?1 for ??-lipoic acid and dihydrolipoic acid, respectively), recovery (>97%), precision (RSD% <2), and sensitivity (on column limit of detection, 150 and 375 fg for ??-lipoic acid and dihydrolipoic acid, respectively and limit of quantification: 0.5 and 1.25 pg for ??-lipoic acid and dihydrolipoic acid, respectively), indicating that the proposed method was more sensitive, precise, economical, and versatile, and has higher throughput than the previously reported methods for simultaneous determination of the two analytes. 相似文献
870.
Air and moisture sensitive K5[CuO2][CO3] was prepared via the azide/nitrate route from stoichiometric mixtures of the precursors CuO, KN3, KNO3 and K2CO3. According to the single‐crystal X‐ray analysis of the crystal structure [P4/nbm, Z = 2, a = 7.4067(5), c = 8.8764(8) Å, R1 = 0.053, 433 independent reflections] K5[CuO2][CO3] represents an ordered superstructure of Na5[NiO2][CO3]. The structure contains isolated [CuO2]3– dumbbells and CO32– anions, with the latter not connected to the transition element. Raman spectroscopic measurements confirm the presence of CO32– in the structure. 相似文献