Semiempirical evaluation of the global hardness of the atoms of 103 elements of the periodic table using the most probable radii as their size descriptors

Relying upon the fact that the density functional computation of the global hardness of the atoms of the elements are still at large and there is some mathematical in congruency between the theory and operational formula of finite difference approximation, we have suggested a radial‐dependent ansatz for evaluating global hardness of atoms as: η=a(7.2/r)+b (in eV), where, “a” and “b” are the constants and r is the absolute radius of atoms in angstrom unit. The ansatz is invoked to evaluate the global hardness of atoms of 103 element of the periodic table. The evaluated new set of global hardness is found to satisfy the sine qua non of a reasonable scale of hardness by exhibiting perfect periodicity of periods and groups and correlating the gross physicochemical properties of elements. The inertness of Hg and extreme reactivity Cs atoms are nicely correlated. The chemical reactivity and its variation in small steps in the series of lanthanide elements are also nicely reproduced. The results of the present semiempirical calculation also have strong correlation with the result of some sophisticated DFT calculation for a set of atoms. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010     

Influence of accelerated ageing on the physico-mechanical properties of alkali-treated industrial hemp fibre reinforced poly(lactic acid) (PLA) composites

30 wt% aligned untreated long hemp fibre/PLA (AUL) and aligned alkali treated long hemp fibre/PLA (AAL) composites were produced by film stacking and subjected to accelerated ageing. Accelerated ageing was carried out using UV irradiation and water spray at 50 °C for four different time intervals (250, 500, 750 and 1000 h). After accelerated ageing, tensile strength (TS), flexural strength, Young's modulus (YM), flexural modulus and mode I fracture toughness (K_Ic) were found to decrease and impact strength (IS) was found to increase for both AUL and AAL composites. AUL composites had greatest overall reduction in mechanical properties than that for AAL composites upon exposure to accelerated ageing environment. FTIR analysis and crystallinity contents of the accelerated aged composites support the results of the deterioration of mechanical properties upon exposure to accelerated ageing environment.     

Directed immobilization of reduced antibody fragments onto a novel SAM on gold for myoglobin impedance immunosensing

The successful construction of an immunosensor depends on having an effective procedure for immobilising the bio-recognition element to the transducer surface. In the present study, an amino-terminated 4-aminothiophenol (ATP) self-assembled monolayer (SAM) was modified with heterobifunctional crosslinker sulfosuccinimidyl 4-[N-maleimidomethyl] cyclohexane-1-carboxylate to couple reduced anti-myoglobin half-antibody fragments. The disulphide groups present in the hinge region of IgG molecules were selectively cleaved by 2-mercaptoethylamine to produce reduced half-antibody fragments with free sulphydryl groups. The maleimide terminated 4-ATP SAM modified surface was coupled to these reduced antibody fragments to produce highly oriented immobilization of the half-antibody via its Fc domain and to allow free access to the Fv bindings sites. This represents an improvement by comparison with biotin/avidin mediated IgG attachment which is essentially randomly oriented. Functional immunosensors were able to detect myoglobin in both phosphate buffered saline and whole serum over the range of concentrations from 10(-13)M to 10(-6)M, and order of magnitude better than avidin/biotin linked immunosensors. In addition, atomic force microscopy (AFM) was carried out to elucidate the nanotopology of the immunosensor surface at different stages of fabrication; the images demonstrate that half antibodies bind as described and show structural changes on subsequent antigen binding.     

Multiple silicon-hydrogen bond activations at adjacent rhodium and iridium centers

The reaction of 1 equiv of primary silanes, SiH(3)R (R = Ph, Mes), with [RhIr(CO)(3)(dppm)(2)] yields mono(silylene)-bridged complexes of the type [RhIr(H)(2)(CO)(2)(μ-SiHR)(dppm)(2)] (R = Ph or Mes), while for R = Ph the addition of 2 equiv yields the bis(silylene)-bridged complexes, [RhIr(CO)(2)(μ-SiHPh)(2)(dppm)(2)]. The kinetic isomer of this bis(silylene)-bridged product has the phenyl substituent axial on one silylene unit and equatorial on the other, and in the presence of excess silane this rearranges to the thermodynamically preferred "axial-axial" isomer, in which the phenyl substituents on each bridging silylene unit are axial and parallel to one another. The reaction of 1 equiv of diphenylsilane with [RhIr(CO)(3)(dppm)(2)] produces the mono(silylene)-bridged product, [RhIr(H)(2)(CO)(2)(μ-SiPh(2))(dppm)(2)], and the subsequent addition of silane in the presence of CO yields the silyl/silylene product [RhIr(H)(SiPh(2)H)(CO)(3)(κ(1)-dppm)(μ-SiPh(2))(dppm)]. The reaction of [RhIr(CO)(3)(dppm)(2)] with 2 equiv of SiH(2)Me(2) yields the analogous product [RhIr(H)(SiMe(2)H)(CO)(3)(κ(1)-dppm)(μ-SiMe(2))(dppm)]. Low-temperature NMR spectroscopic observation of some key intermediates, such as [RhIr(H)(SiH(2)Ph)(CO)(2)(μ-CO)(dppm)(2)], formed during the formation of the mono(silylene)-bridged species provides evidence for a mechanism involving initial Si-H bond activation at Rh, followed by the subsequent Si-H bond activation at Ir. The Si-H bond activation of a second equivalent of silane seems to be initiated by dissociation of the Rh-bound end of one diphosphine. The reaction of diphenylsilane with the cationic complex [RhIr(CH(3))(CO)(2)(dppm)(2)][CF(3)SO(3)] gives rise to a different reactivity pattern in which Si-H bond activation is initiated at Ir. In this case, the cationic silyl-bridged species, [RhIr(CH(3))(CO)(2)(κ(1):η(2)-SiHPh(2))(dppm)(2)][CF(3)SO(3)], contains an agostic Si-H interaction with Rh. In solution, at ambient temperature, this complex converts to two species, [RhIr(H)(COCH(3))(CO)(μ-H)(μ-SiPh(2))(dppm)(2)][CF(3)SO(3)] and [RhIr(CO)(2)(μ-H)(μ-SiPh(2))(dppm)(2)] [CF(3)SO(3)], formed by the competing methyl migration to CO and reductive elimination of methane, respectively. In the diphenylsilylene dihydride product, a weak interaction between the bridging silicon and the terminal Ir-bound hydride is proposed on the basis of NMR evidence.     

Sensitivity enhancement of CE and CE-MS for the analysis of peptides by a dynamic pH junction

An analytical method of CE-MS and CE with an online preconcentration technique induced by a dynamic pH junction, addition of organic solvent and large volume injection was developed for sensitive determination of peptides in biological samples. Leucine enkephalin, methionine enkephalin, dynorphin A, β-endorphin and angiotensin II were used as model peptides. The optimal online preconcentration conditions were obtained at a sample matrix consisting of 100?mM borate buffer (pH 10.0) with 50% v/v acetonitrile and a BGE containing 1?M formic acid at pH 2.0, along with a 25-cm injection length. Under the optimized conditions, a 4.0×10(3)-1.1×10(4)-fold increase in peak intensity was achieved without degrading the peak shape. This online preconcentration method was applied to analyze the intracellular angiotensin II within the peptides extracted from HL1 cells and approximately increase of 1×10(4)-fold sensitivity was achieved compared to normal condition. Thus, the developed method could be applied to the analysis of various peptides for peptidomics study in biological samples.     

Redox-active ionic-liquid-assisted one-step general method for preparing gold nanoparticle thin films: applications in refractive index sensing and catalysis

We describe a general one-step facile method for depositing gold nanoparticle (GNP) thin films onto any type of substrates by the in situ reduction of AuCl(3) using a newly designed redox-active ionic liquid (IL), tetrabutylphosphonium citrate ([TBP][Ci]). Various substrates such as positively charged glass, negatively charged glass/quartz, neutral hydrophobic glass, polypropylene, polystyrene, plain paper, and cellophane paper are successfully coated with a thin film of GNPs. This IL ([TBP][Ci]) is prepared by the simple neutralization of tetrabutylphosphonium hydroxide with citric acid. We also demonstrate that the [TBP][Ci] ionic liquid can be successfully used to generate GNPs in an aqueous colloidal suspension in situ. The deposited GNP thin films on various surfaces are made up of mostly discrete spherical GNPs that are well distributed throughout the film, as confirmed by field-emission scanning electron microscopy. However, it seems that some GNPs are arranged to form arrays depending on the nature of surface. We also characterize these GNP thin films via UV-vis spectroscopy and X-ray diffractometry. The as-formed GNP thin films show excellent stability toward solvent washing. We demonstrate that the thin film of GNPs on a glass/quartz surface can be successfully used as a refractive index (RI) sensor for different polar and nonpolar organic solvents. The as-formed GNP thin films on different surfaces show excellent catalytic activity in the borohydride reduction of p-nitrophenol.     

Synthesis and characterization of a polymer-anchored palladium(II) Schiff base complex and its catalytic efficiency in phosphine-free Sonogashira coupling reactions

A polymer-anchored Pd(II) Schiff base complex has been synthesized by reacting a polymeric amine with 2-pyridinecarboxaldehyde to get the polymer-anchored Schiff base, which was then reacted with palladium acetate. The catalyst was characterized by physicochemical and spectroscopic methods. It shows excellent catalytic activity in the Sonogashira coupling of phenylacetylene with aryl halides using triethylamine as a base and copper iodide as a co-catalyst in water under open air at 70 °C. We have also studied the effects of base and solvent on the coupling reaction. Sonogashira reactions of phenylacetylene with a variety of functionalized aryl halides were performed under the optimized reaction conditions. This catalyst gives excellent yields without the use of phosphine ligands. Further experiments showed that the catalyst can be used five times without much loss in the catalytic activity.     

Determination of PuO2% in power reactor mixed oxide fuel blends (0.4–44% PuO2) by neutron well co-incidence counting technique

Neutron Well Coincidence Counting has been explored as a non destructive assay technique for determining the percentage of PuO₂ in blended mixture of UO₂ and PuO₂ powders. The method has been applied to MOX blends having PuO₂ content varying from 0.4 to 44% for both thermal and fast reactors. The use of Neutron Well Coincidence Counting technique is validated as a process control step for determining PuO₂ content in the fabrication of MOX fuel by comparing it with chemical analysis of sintered pellets. It has been used at Advanced Fuel fabrication Facility, Bhabha Atomic Research Centre, Tarapur during the manufacture of MOX fuel of various types for thermal and fast reactors.     

Experimental design optimization of the capillary electrophoresis separation of leucine enkephalin and its immune complex

To optimize the capillary electrophoretic separation conditions for leucine enkephalin (LE) and the immune complex of the LE and anti-LE reaction, an analysis using a three-level, three-factorial Box-Behnken design was performed. Three separation parameters, buffer pH (X(1)), buffer concentration (X(2)), and applied voltage (X(3)), were chosen to observe the effect on separation responses. The responses were theoretical plate number, migration time of the LE peak, and resolution between the peaks. The optimum conditions and process validation were determined using statistical regression analysis and surface plot diagrams. The capillary electrophoresis optimum separation conditions were established to be 75 mM phosphate buffer at pH 7.00 with an applied separation voltage of 15 kV. By using the analysis technique, the prediction of responses was satisfactory and process verification yielded values within the +/-5% range of the predicted efficiency.