Theoretical and vibrational spectral investigation of sodium salt of acenocoumarol

The FT‐IR and FT‐Raman spectra of sodium salt of 4‐hydroxy‐3[1‐(4‐nitrophenyl)‐3‐oxobutyl]‐2H‐1‐benzopyran‐2‐one (acenocoumarol sodium salt) in solid phase have been recorded and analyzed. The optimization geometry, intramolecular hydrogen bonding, and harmonic vibrational wavenumbers of acenocoumarol sodium salt have been investigated with the help of B3LYP density functional theory (DFT) methods. The infrared and Raman spectra were predicted theoretically from the calculated intensities. Natural bond orbital (NBO) analysis indicates the presence of C H···O hydrogen bonding in the molecule. The first static hyperpolarizability of the molecule has been computed. Copyright © 2009 John Wiley & Sons, Ltd.     

First order molecular hyperpolarizabilities and intramolecular charge transfer from the vibrational spectra of NLO material: ethyl‐3‐(3, 4‐dihydroxyphenyl)‐2‐propenoate

As part of the efforts for the design of new organic nonlinear optical(NLO) materials with high efficiency for present day technological requirements, a comprehensive investigation on the intramolecular charge transfer(CT) of an efficient π‐conjugated potential push–pull NLO chromophore, ethyl‐3‐(3,4‐dihydroxyphenyl)‐2‐propenoate(EDP) to a strong electron‐acceptor group through the π‐conjugated bridge has been carried out from their vibrational spectra. The first hyperpolarizabilities of caffeic derivatives are investigated by ab initio method. The NLO efficiency is experimentally measured by powder efficiency experiment. The strongest vibrational modes contributing to the electro‐optic effect from the simultaneous infrared(IR) and Raman activities of the ring CC stretching modes, in‐plane deformation modes, and the umbrella mode of the methyl groups have been identified and analyzed unambiguously. The influence of electronic effects, hyperconjugation and backdonation, on the C H stretching vibrations of both methyl and methylene groups causing the decrease of stretching wavenumbers and IR intensities has been extensively investigated. Copyright © 2009 John Wiley & Sons, Ltd.     

NIR‐FT Raman and FT‐IR spectral investigations of the nonlinear optical chromophore p‐bromoacetanilide

Vibrational spectral analysis of the hydrogen‐bonded nonlinear optical (NLO) material p‐bromo acetanilide (PBA) was carried out using NIR‐FT‐Raman and FT‐IR spectroscopy. Ab initio molecular orbital computations were performed at HF/6‐31G (d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The lowering of the imino stretching wavenumbers suggests the existence of strong intermolecular N H···O hydrogen bonding, which was substantiated by the natural bond orbital (NBO) analysis. The vibrational spectra confirm that the charge‐transfer interaction between the  NHCOCH₃ group and—Br through phenyl ring is responsible for simultaneous strong IR and Raman activation of the ring mode 8a. Vibrational analysis indicates that the lowering of stretching wavenumbers of methyl group due to electronic effects simultaneously caused by induction and hyperconjugation is due to the presence of the oxygen atom. The presence of blue‐shifting H‐bonds of CH stretching wavenumbers, simultaneous activation of carbonyl stretching mode, the strong activity of low‐wavenumber H‐bond stretching vibrations and the role of intramolecular charge transfer in making the molecule NLO active have been analyzed on the basis of the vibrational spectral features. Copyright © 2007 John Wiley & Sons, Ltd.     

Purification and Characterization of PRL Protein Tyrosine Phosphatases

PRLs constitute a subfamily of protein tyrosine phosphatases(PTPs). In the present paper are reported the molecular cloning, expression, purification, and characterization of all the three members of the PRL enzymes in human and the only PRL in C. elegans. These enzymes were expressed as glutathione S-transferase (GST) fusion proteins in DE3pLysS E. coil cells, and the recombinant fusion proteins were purified on glutathione-Sepharose affinity columns. Having been cleaved with thrombin, GST-free enzymes were further purified on an S-100 Sepharose gel filtration column. The purified proteins show single polypeptide bands on SDS-polyacrylamide gel electrophoresis. With para-nitrophenyl phosphate(p-NPP) as a substrate, PRLs exhibit classical Michaelis-Menten kinetics with Vmax values two orders of magnitude smaller than those of classic PTPs. The responses of PRLs to ionic strength, metal ions and phosphatase inhibitors are similar to those of other characterized PTPs, but their optimal pH values are different. These data thus reveal distinct common biochemical properties of PRL subfamily PTPs as well.     

Design,Synthesis and Biological Activity of Benzimidazole and Aminophenol Based Factor Xa Inhibitors

The serine protease factor Xa (FXa) is a key enzyme in the blood coagulation cascade, acting at the convergent point of the extrinsic and intrinsic pathways. The serine protease factor Xa (FXa) is a key enzyme in the blood coagulation cascade, acting at the convergent point of the extrinsic and intrinsic pathways. In our search for Fxa inhibitors as novel anticoagulants we identified the active isomer of the published FXa inhibitor, 2,7-bis-(4-amidinobenzilidine)-cycloheptan-l-one (BABCH), as the (Z, Z) isomer (ZK-805412, FXa Ki=0.66 nM). This photochemically labile (Z, Z) isomer has served as a conformationally rigid template for the development of distinct classes of potent, selective and orally active FXa inhibitors. Template evolution, in vitro SAR studies as well as our efforts to optimize in vivo parameters will be discussed.     

Fast Algorithms to Generate Necklaces, Unlabeled Necklaces, and Irreducible Polynomials over GF(2)

Many applications call for exhaustive lists of strings subject to various constraints, such as inequivalence under group actions. A k-ary necklace is an equivalence class of k-ary strings under rotation (the cyclic group). A k-ary unlabeled necklace is an equivalence class of k-ary strings under rotation and permutation of alphabet symbols. We present new, fast, simple, recursive algorithms for generating (i.e., listing) all necklaces and binary unlabeled necklaces. These algorithms have optimal running times in the sense that their running times are proportional to the number of necklaces produced. The algorithm for generating necklaces can be used as the basis for efficiently generating many other equivalence classes of strings under rotation and has been applied to generating bracelets, fixed density necklaces, and chord diagrams. As another application, we describe the implementation of a fast algorithm for listing all degree n irreducible and primitive polynomials over GF(2).     

4f-5f heterotrimetallic complexes exhibiting electrochemical and magnetic communication

Novel 4f-5f complexes of U(IV) and Th(IV) with Yb have been prepared using a terpyridyl-functionalized ketimide linking group. These 4f-5f heterotrimetallic complexes (C5Me5)2An[-N=C(CH2C6H5)(tpyYb(C5Me5)2)]2 (where An = Th, U) exist in Yb(II/III) valence equilibria and exhibit rich electrochemical behavior consistent with electronic coupling between the actinide and Yb(II/III)tpy*- moieties. The magnetic response of the uranium complex, studied qualitatively using a subtraction method, is indicative of a coupled magnetic state between the U(IV) and Yb(III)tpy*- groups at low temperatures. Both the electrochemical and magnetic data are in agreement and are consistent with differences in participation of the actinide valence orbitals in the ketimide bonding.     

A renewable nanosensor based on a glass nanopipette

A fluorescent nanosensor based on reporter dye molecules trapped in the tip of a nanopipette has been developed. This 100 nm sized nanosensor has been shown to be capable of measuring local pH and mapping sodium concentration with a temporal resolution of a few milliseconds.     

Magnetic flux and strain effects on electron transport in a linear array of nanoscopic rings

Electron transport through a linear array of nanoscopic rings with six quantum dot sites per ring is investigated in the presence of an external magnetic flux producing an Aharonov-Bohm phase shift effect. A tight-binding model is employed to analytically calculate the transmission as a function of electron energy, external flux, and inter-site coupling parameters. Current vs. voltage relationships of the ring system are computed using a standard scattering theory of transport and shown to modulate between semiconductor and ohmic characteristics. System parameters are adjusted in order to study the effects of a longitudinal strain on the transmission properties of the linear multiple-ring array. Longitudinal strain is modeled with a Slater-Koster type theory and is demonstrated to affect the transmission properties primarily by narrowing the transmission bands and opening up additional bandgaps in the band structure. In addition, a universal resonant transmission condition as a function of flux is extended to show that the application of strain causes the resonant transmission peaks to converge towards one-half of a flux quantum.     

Surface patterning with two-dimensional porphyrin supramolecular arrays

Monolayer arrays of a series of meso-tetra-substituted porphyrins containing octadecyloxy and carboxyl (or pyridyl) groups were prepared on the highly oriented pyrolytic graphite surface at the liquid/solid interface. It was found by means of scanning tunneling microscopy that some porphyrins from this family assemble into various patterns. Specifically, slightly undulated rows are obtained from 5,10,15-tris(4-octadecyloxyphenyl)-20-(4-pyridyl)porphyrin. Meanwhile, rows with more pronounced kinks result from 5-(4-carboxyphenyl)-10,15,20-tris(4-octadecyloxyphenyl)porphyrin. The occurrence of the kinks is dependent on the arrangement of surrounding porphyrin molecules and is determined by intricate interplay between directional hydrogen-bonding interactions and packing forces, including molecule-molecule and molecule-substrate interactions. A double-layer structure is obtained from 5,10-bis(4-carboxyphenyl)-15,20-bis(4-octadecyloxyphenyl)porphyrin, probably through cyclic hydrogen bond formation. This work proves the concept that programmed surface patterning is possible by using porphyrins incorporating directional intermolecular interaction sites.