Pulsed laser deposition film of a donor-acceptor-donor polymer as possible active layer in devices

A molecule having a ketone group between two thiophene groups was synthesized. Presence of alternating electron donating and accepting moieties gives this material a donor-acceptor-donor (DAD) architecture. PolyDAD was synthesized from DAD monomer by oxidative polymerization. Device quality films of polyDAD were fabricated using pulsed laser deposition technique. X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectra (FTIR) data of both as synthesized and film indicate the material does not degrade during ablation. Optical band gap was determined to be about 1.45 eV. Four orders of magnitude increase in conductivity was observed from as synthesized to pulsed laser deposition (PLD) fabricated film of polyDAD. Annealing of polyDAD films increase conductivity, indicating better ordering of the molecules upon heating. Rectifying devices were fabricated from polyDAD, and preliminary results are discussed.

The role of lysine-41 in RNase A catalysis - A quantum chemical study on the active site ligand complex

Several mechanisms have been proposed to explain the action of enzymes at the atomic level. Among them, the recent proposals involving short hydrogen bonds as a step in catalysis by Gerlt and Gassman [1] and proton transfer through low barrier hydrogen bonds (LBHBs) [2, 3] have attracted attention. There are several limitations to experimentally testing such hypotheses, Recent developments in computational methods facilitate the study of active site-ligand complexes to high levels of accuracy, Our previous studies, which involved the docking of the dinucleotide substrate UpA to the active site of RNase A [4, 5], enabled us to obtain a realistic model of the ligand-bound active site of RNase A. From these studies, based on empirical potential functions, we were able to obtain the molecular dynamics averaged coordinates of RNase A, bound to the ligand UpA. A quantum mechanical study is required to investigate the catalytic process which involves the cleavage and formation of covalent bonds. In the present study, we have investigated the strengths of some of the hydrogen bonds between the active site residues of RNase A and UpA at the ab initio quantum chemical level using the molecular dynamics averaged coordinates as the starting point. The 49 atom system and other model systems were optimized at the 3-21G level and the energies of the optimized systems were obtained at the 6-31G* level. The results clearly indicate the strengthening of hydrogen bonds between neutral residues due to the presence of charged species at appropriate positions. Such a strengthening manifests itself in the form of short hydrogen bonds and a low barrier for proton transfer. In the present study, the proton transfer between the 2'-OH of ribose (from the substrate) and the imidazole group from the H12 of RNase A is influenced by K41, which plays a crucial role in strengthening the neutral hydrogen bond, reducing the barrier for proton transfer.

Hyperexpression of biologically active human chorionic gonadotropin using the methylotropic yeast, Pichia pastoris

Human chorionic gonadotropin (hCG), a heterodimeric glycoprotein hormone, is composed of an alpha subunit noncovalentlv associated with the hormone-specific beta subunit. The objective of the present study was recombinant expression of properly folded, biologically active hCG and its subunits using an expression system that could be used for structure-function studies while providing adequate quantities of the hormone for immunocontraceptive studies. We report here expression of biologically active hCG and its subunits using a yeast expression system, Pichia pastoris. The recombinant hGG alpha and hCG beta subunits were secreted into the medium and the levels of expression achieved at shake culture level were 24 and 2.7-3 mg/l secretory medium respectively. Go-expression of both subunits in the same cell resulted in secretion of heterodimeric hGG into the medium. The pichia-expressed hCG was immunologically similar to the native hormone, capable of binding to the LH receptors and stimulating a biological response in vitro. Surprisingly, the maximal response obtained was twice that obtained with the native hGG. The le level of expression of hCG achieved was 12-16 mg/l secretory medium and is expected to increase several-fold in a fermenter. Thus the Pichia expression system is capable of hyperexpressing properly folded, biologically active hGG and is suitable for structure-function studies of the hormone.

Infrared spectroscopic study of the rotation of the NH 4+ ion in ammonium halides

Infrared correlation functions, have been obtained from the analysis of band shapes of the 1400 cm−1 bending mode of NH4Cl, NH4Br and NH4I in both the Pm3m and Fm3m phases. The NH 4 + ion seems to undergo relatively free rotation in the high temperature Fm3m phases of these halides.

Infrared Spectra and Conformation of N-Acetylthiourea

Infrared spectra of N-acetylthiourea (ATU) and its N,N,N′-trideuterated compound have been examined in the range 4000–50 cm−1. A complete vibrational assignment with a normal coordinate treatment based on a Urey-Bradley type intramolecular potential function supplemented with valence force function for the out of plane and torsional modes is proposed and the feature of the thioureido vibrations explained. A molecular orbital study by the CNDO/2 method of ATU and its oxygen analog is undertaken and the results are analyzed for a comparative study of the molecular electronic structure and conformation.

A 1h And 13c Magnetic Resonance And Infrared Spectroscopic Study Of Coordinated 2-Aminocyclopentene-1-Dithiocarboxylic Acid And Its S-Methyl Ester

The ligating properties of 2-aminocyclopentene-1-dithiocarboxylic acid and its S-methyl esters were investigated. Complexes with Zn(II), Cd(II) and Hg(II) halides were synthesized and characterized by infrared and proton and carbon-13 NMR studies. The results are concordant with a bidentate coordination of the -CS2 group to the metal ions

Molecular conformation of N,N -diarylthioureas: An assessment by 1H NMR and infrared spectroscopy

Several N,N -dipyridyl- and N-phenyl-N -pyridyl-thioureas were examined in different solvents at various temperatures by 1H NMR in order to study their conformational properties. The influence of concentration and the methyl substituent in the pyridine ring on the chemical shifts of the NH and pyridine groups was investigated. The observed chemical shifts are analysed in terms of the conformational properties of the molecules. Free energy barriers to the internal rotation about the C N bonds have been determined. Infrared spectra have been measured to supplement the NMR studies. Intramolecular hydrogen bonding played a major role in the preferred conformation of pyridylthioureas. The data further revealed an interesting dynamic exchange phenomenon occurring in symmetric N,N -dipyridylthioureas between two intramolecularly hydrogen bonded conformers.

Optically active gossypol as a circular dichroism probe of interactions with serum albumins

The (+)-enantiomer of the polyphenolic binaphthyl gossypol, has been shown to be a useful CD probe of interactions with human and bovine serum albumin. (+)-Gossypol binds to albumin with same affinity as recemic (±)-gossypol, as shown by fluorescence quenching, and also displaces bilirubin from its albumin binding site. The CD characteristics of bound gossypol are different in the case of the two proteins.

Calorimetric, infrared and ESR studies of the plastically crystalline state of organic compounds

Enthalpy changes of the crystal-plastic and plastic-liquid transitions are related to the temperature range of stability of the plastic phase. Thermodynamics of the plastic state of binary mixtures have been examined. Infrared correlation times, τc, and activation energies have been measured for a few molecules in the plastic state. Molecular tumbling times, τt, have also been measured employing ESR spectra of a spin-probe. Plots of log τc(τt) 1/T are continuous through the plastic-liquid transition. Activation energies for molecular motion seem to vary in the same direction as the ΔH of the plastic-crystal transition. Infrared correlation times of solute molecules in binary solutions in the plastic and the liquid states show interesting variations with solute concentration.

Transient pulse evolution of active mode locking in an intracavity frequency-doubled laser

The theory of transient mode locking for an active modulator in an intracavity frequency-doubled laser is presented. The theory is applied to mode-locked and intracavity frequency-doubled Nd:YAG laser and the mode-locked pulse width is plotted as a function of number of round trips inside the cavity. It is found that the pulse compression is faster and the system takes a very short time to approach the steady state in the presence of a second harmonic generating crystal inside the laser cavity. The effect of modulation depth and the second harmonic conversion efficiency on the temporal behavior of the pulse width is discussed. Journal of Applied Physics is copyrighted by The American Institute of Physics.

An infrared spectroscopic study of the incommensurate transitions and related phase changes in K2Pb[Cu(NO2)6] and [N(CH3)4]2MX4 (M = Mn, Co, Cu or Zn and X = Cl or Br)

K2Pb[Cu(NO2)6] and [N(CH3)4]2MX4 (M = Mn, Co, Cu or Zn and X = Cl or Br) undergo phase transitions which involve incommensurate phases. The transitions have been investigated by examining the changes in the NO2 and CH3 vibration bands in the i.r. spectra. Splitting and broadening of some of the bands across the incommensurate transitions are discussed in the context of geometrical restrictions in the incommensurate phases. The phase transitions have also been characterized using differential scanning calorimetry.

Conformational Characterization of S-Methyl Dithiocarbazate by Infrared Spectra and Vibrational Assignments

Infrared spectra are recorded for S-methyl dithiocarbazate and its N-deuterated compound in two molecular conformations in the solid state and in solution between 4000 and 30 cm−1. The assignments have been supported from a complete normal coordinate analysis; the conformation sensitive bands of the –CSNHNH2 grouping are discussed. The assignments are compared with those of related molecules to check the internal consistency and to obtain the pattern of the characteristic bands of thiocarbazoyl (–CSNHNH2) group. The magnitudes of the C–N and S–CH3 torsional barriers are estimated from the force constants.

Sensible heat fluxes during the active and break phases of the southwest monsoon over the Indian region

Based on the theory given by Saltzman and Ashe (1976), sensible heat fluxes are calculated for the active and break phases of the southwest monsoon over the Indian region. The conclusion drawn is that the sensible heat flux is generally larger during the break monsoon situation when compared with that for the active monsoon situation. The synoptic heat flux is negligible when compared with mean and diurnal heat fluxes over the Indian region even during the monsoon season.

An infrared spectroscopic study of the phase transitions of crystalline aromatic donor-acceptor complexes involving a pseudoplastic state

Variable temperature i.r. spectroscopic studies of weak pi-donor-pi-acceptor complexes in the crystalline state indicate that the complexes undergo order-disorder transitions, the disorder being caused by molecular motion. Thermodynamic data on the phase transitions along with the spectral data suggest that the high-temperature crystalline forms of the complexes are likely to be pseudoplastic.