Synthesis and properties of mononuclear and binuclear molybdenum complexes derived from bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone

The monomer molybdenum(VI) complex [MoO(2)(napoxlhH(2))].2H(2)O (1) has been synthesized from the reaction of MoO(2)(acac)(2) with bis(2-hydroxy-1-naphthaldehyde)oxaloyldihydrazone (napoxlhH(4)) in 1:1 molar ratio in ethanol under reflux. This complex on reaction with pyridine/3-picoline/4-picoline yielded the dimer molybdenum(VI) complexes [Mo(2)O(4)(napoxlhH(2))(2)(A)(2)].2H(2)O (A=py (2), 3-pic (3), 4-pic (4)), whereas reaction with isonicotinoylhydrazine (inhH(3)) and salicyloylhydrazine (sylshH(3)) lead to the reduction of the metal centre yielding monomeric molybdenum(V) complexes [Mo(napoxlhH(2))(hzid)].2H(2)O (where hzidH(3)=inhH(3) (5) and sylshH(3) (6)). The complexes have been characterized by elemental analyses, molecular weight determinations, molar conductance data, magnetic moment data, electronic, IR, ESR and (1)H NMR spectroscopic studies. The complexes (5) and (6) are paramagnetic to the extent of one unpaired electron. The electronic spectra of the complexes are dominated by strong charge transfer bands. In all of the complexes, the principal dihydrazone ligand has been suggested to coordinate to the metal centres in the anti-cis-configuration. The complexes (1), (5) and (6) are suggested to have six-coordinate octahedral stereochemistry around molybdenum(VI) and molybdenum(V) metal centres, respectively, while the complexes (2)-(4) are suggested to have eight coordinate dodecahedral stereochemistry around molybdenum(VI) metal centre.     

Highly Conjugated Bis(benzo[b]phosphole)-P-oxides: Synthesis and Electrochemical,Optical, and Computational Studies

The first examples of a π-conjugated benzo[b]phosphole P-oxide in which two phosphole P-oxide units are connected by a carbon-carbon double bond are described. The molecules are synthesized as E isomers with respect to the carbon-carbon double bond and exist as stable cis and trans isomers (chiral and meso one respectively) relatively to the two stereogenic P atoms. The optical and electrochemical properties of both isomers have been investigated by experiment and computations.     

Mechanical properties of cellulose nanomaterials studied by contact resonance atomic force microscopy

Quantification of the mechanical properties of cellulose nanomaterials is key to the development of new cellulose nanomaterial based products. Using contact resonance atomic force microscopy we measured and mapped the transverse elastic modulus of three types of cellulosic nanoparticles: tunicate cellulose nanocrystals, wood cellulose nanocrystals, and wood cellulose nanofibrils. These modulus values were calculated with different contact mechanics models exploring the effects of cellulose geometry and thickness on the interpretation of the data. While intra-particle variations in modulus are detected, we did not observe a measureable difference in modulus between the three types of cellulose particles. Improved practices and experimental complications for the characterization of cellulosic nanomaterials with atomic force microscopy are discussed.     

Measurement of vibration with Young's fringe modulated speckle patterns in a photorefractive correlator

A technique has been proposed to analyze small in-plane component of vibrations by measuring the fringe shift, and analysing the correlation output of captured vibrating Young's fringes with a photorefractive correlator. Fringes are formed due to interference between the reconstructed speckled beam recorded for stationary object beam, and vibrated speckled beam transmitting through a BaTiO₃ crystal after introducing a small shift in the diffuser position. The correlation peak intensity is affected due to mismatch of vibrations between two piezo-mirrors in the object beam. High correlation output gives an indication of the frequency matching of known reference and unknown vibrations, thus giving information on the frequency of vibration. Vibration amplitudes of the order of a wavelength of light have been measured by counting the number of fringes passing past a line in the observation plane.     

Propagation velocity of the reaction front in addition polymerization systems

Traveling polymerization fronts in unstirred solutions of methylmethacrylate, methacrylic acid, or acrylamide with some free radicals initiators (through thermal decomposition) have been observed experimentally. A local heating of the initial reactant mixture, under suitable conditions, leads to a reaction front that propagates along the space coordinate with a constant velocity. In this article, a physical interpretation of this phenomenon is provided through a mathematical model that accounts for the depolimerization reaction and is based on the constant pattern approach. Moreover, an approximate explicit analytic expression for the velocity of propagation of the polymerization front is proposed. The theoretical values are compared with those measured experimentally as a function of the initiator concentration for different addition polymerization systems. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35:1047–1059, 1997     

Enrichment of Zinc and Iron Micronutrients in Lentil (Lens culinaris Medik.) through Biofortification

Biofortification of pulse crops with Zn and Fe is a viable approach to combat their widespread deficiencies in humans. Lentil (Lens culinaris Medik.) is a widely consumed edible crop possessing a high level of Zn and Fe micronutrients. Thus, the present study was conducted to examine the influence of foliar application of Zn and Fe on productivity, concentration, uptake and the economics of lentil cultivation (LL 931). For this, different treatment combinations of ZnSO₄·7H₂O (0.5%) and FeSO₄·7H₂O (0.5%), along with the recommended dose of fertilizer (RDF), were applied to the lentil. The results of study reported that the combined foliar application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at pre-flowering (S1) and pod formation (S2) stages was most effective in enhancing grain and straw yield, Zn and Fe concentration, and uptake. However, the outcome of this treatment was statistically on par with the results obtained under the treatment ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. A single spray of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage enhanced the grain and straw yield up to 39.6% and 51.8%, respectively. Similarly, Zn and Fe concentrations showed enhancement in grain (10.9% and 20.4%, respectively) and straw (27.5% and 27.6% respectively) of the lentil. The increase in Zn and Fe uptake by grain was 54.8% and 68.0%, respectively, whereas uptake by straw was 93.6% and 93.7%, respectively. Also the benefit:cost was the highest (1.96) with application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. Conclusively, the combined use of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage can contribute significantly towards yield, Zn and Fe concentration, as well as uptake and the economic returns of lentil to remediate the Zn and Fe deficiency.     

Bio-inspired dual surface modification to improve tribological properties at small-scale

In miniaturized devices like micro/nano-electro-mechanical systems (MEMS/NEMS), the critical forces, namely adhesion and friction restrict the smooth operation of the elements that are in relative motion. MEMS/NEMS are traditionally made of silicon, whose tribological properties are not good. In this paper, we present an investigation on the approach of dual surface modification of silicon surfaces and their tribological properties at micro-scale. The dual surface modification is a combination of topographical and chemical modifications. As the topographical modification, micro-patterns with varying shapes of pillars and channels were fabricated on Si(1 0 0) wafer surfaces using photolithography method. Chemical modification included the coating of micro-patterns with diamond-like carbon (DLC) and Z-DOL (perfluoropolyether, PFPE) thin films. The surfaces with combined modification were evaluated for their micro-friction behavior in comparison with those of bare Si(1 0 0) flat surfaces and the topographically/chemically modified silicon surfaces. Results showed that the surfaces with dual modification exhibited superior tribological properties. These results indicate that a combination of topographical and chemical modification is very effective in enhancing tribological properties at small-scale. The combined surface treatments such as the ones investigated in the current work could be useful for tribological applications in small-scale devices such as MEMS/NEMS. The motivation for undertaking the dual modification approach comes from an earlier observation made on the significant influence of the surface characteristics of lotus leaf on its micro-friction behavior.     

Investigations of effect of target thickness and detector collimation on 662 keV multiply backscattered gamma photons

The present studies aimed to investigate the effects of detector collimation and target thickness on multiply backscattered gamma photons. The numbers of multiply backscattered events, having energy the same as in singly scattered distribution, are found to be increasing with target thickness, and saturate for a particular thickness known as saturation thickness. The saturation thickness is not altered by the variation in the collimator opening. The number and energy albedos, characterizing the reflection probability of a material, are also evaluated. Monte Carlo calculations support the present experimental work.     

On the Two Species Asymmetric Exclusion Process with Semi-Permeable Boundaries

We investigate the structure of the nonequilibrium stationary state (NESS) of a system of first and second class particles, as well as vacancies (holes), on L sites of a one-dimensional lattice in contact with first class particle reservoirs at the boundary sites; these particles can enter at site 1, when it is vacant, with rate α, and exit from site L with rate β. Second class particles can neither enter nor leave the system, so the boundaries are semi-permeable. The internal dynamics are described by the usual totally asymmetric exclusion process (TASEP) with second class particles. An exact solution of the NESS was found by Arita. Here we describe two consequences of the fact that the flux of second class particles is zero. First, there exist (pinned and unpinned) fat shocks which determine the general structure of the phase diagram and of the local measures; the latter describe the microscopic structure of the system at different macroscopic points (in the limit L→∞) in terms of superpositions of extremal measures of the infinite system. Second, the distribution of second class particles is given by an equilibrium ensemble in fixed volume, or equivalently but more simply by a pressure ensemble, in which the pair potential between neighboring particles grows logarithmically with distance. We also point out an unexpected feature in the microscopic structure of the NESS for finite L: if there are n second class particles in the system then the distribution of first class particles (respectively holes) on the first (respectively last) n sites is exchangeable.