NMR spectra of oriented biologically important molecules - The structure of and the internal rotation in N,N'-dimethyluracil

From the proton NMR spectra of Nfl-dimethyluracil oriented in two different nematic solvents, the internal rotation of the methyl groups about the N-C bonds is studied. It has been observed that the preferred conformation of the methyl group having one carbonyl in the vicinity is the one where a C-H bond is in the ring plane pointing toward the carbonyl group. The results are not sensitive to the mode of rotation of the other methyl group. These data are interpreted in terms of the bond polarizations.

NMR Investigations on Di- and Tri-Azanaphthalenes Oriented in Liquid Crystals

Proton NMR spectra of 1,3-diazanaphthalene and 1,2,4-triazanaphthalene have been investigated in the nematic phase of three liquid crystals. The spectral analysis provided direct dipole-dipole couplings which have been used to derive the molecular structure. Geometry of the phenyl ring in both the molecules deviates from the regular hexagonal structure. Signs of the order parameter of the largest magnitude are opposite in liquid crystals with positive diamagetic anisotropies.

Scheme of squares: Part I. Systems formalism for potentiostatic studies

The so-called “Scheme of Squares”, displaying an interconnectivity of heterogeneous electron transfer and homogeneous (e.g., proton transfer) reactions, is analysed. Explicit expressions for the various partial currents under potentiostatic conditions are given. The formalism is applicable to several electrode geometries and models (e.g., semi-infinite linear diffusion, rotating disk electrodes, spherical or cylindrical systems) and the analysis is exact. The steady-state (t→∞) expressions for the current are directly given in terms of constant matrices whereas the transients are obtained as Laplace transforms that need to be inverted by approximation of numerical methods. The methodology employs a systems approach which replaces a system of partial differential equations (governing the concentrations of the several electroactive species) by an equivalent set of difference equations obeyed by the various partial currents.

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

Lanthanide perchlorate complexes of 4-nitroquinoline-1-oxide and 5-nitroisoquinoline-2-oxide

Novel complexes of lanthanide perchlorates with 4-nitroquinoline-1-oxide (NQNO) and 5-nitroisoquinoline-2-oxide (NIQNO) have been prepared and characterized. The complexes have the general formulaeLn(NQNO)8(ClO4)3 (whereLn=La-Nd), Ln(NQNO)7(ClO4)3 (whereLn=Gd-Yb),Ln(NIQNO)9(ClO4)3 (whereLn=La-Nd), andLn(NIQNO)7(ClO4)3 (whereLn=Gd-Yb). The IR, proton NMR spectral data indicate the coordination of the N—O group of the ligands to he lanthanide ions.

Molecular complexes of metallo tetraphenyl porphyrins with 2,4,5,7-tetranitro fluorenone

The interactions of mesotetraphenyl porphyrin and its metallo derivatives with 2,4,5,7-tetra nitrofluorenone have been studied using spectroscopic methods. The association constants (K) for 1:1 complexes in Ch2Cl2Cl2 follow the order Pd+2>Co+2> Cu+2>VO+2>Ni+2>Zn+2. The values of K are accounted in terms of stereochemistry of MTPPs and the electronic configuration of the metal ions. The magnitude and direction of the proton NMR shifts of the acceptor and donor in the complexes and their ESR parameter furnish information as to the possible structures of these complexes in solution.

The effect of composition, electron irradiation and quenching on ionic conductivity in a new solid polymer electrolyte: (PEG) (x) NH4I

We have prepared, characterized and investigated a new PEG-2000 based solid polymer electrolyte (PEG) x NH4I. Ionic conductivity measurements have been made as a function of salt concentration as well as temperature in the range 265–330 K. Selected compositions of the electrolyte were exposed to a beam of 8 MeV electrons to an accumulated dose of 10 kGy to study the effect on ionic conductivity. The electrolyte samples were also quenched at liquid nitrogen temperature and conductivity measurements were made. The ionic conductivity at room temperature exhibits a characteristic double peak for the composition x = 20 and 70. Both electron beam irradiation and quenching at low temperature have resulted in an increase in conductivity by 1–2 orders of magnitude. The enhancement of conductivity upon irradiation and quenching is interpreted as due to an increase in amorphous region and decrease in crystallinity of the electrolyte. DSC and proton NMR measurements also support this conclusion.

Co-assembly of a Nafion-Mesoporous Zirconium Phosphate Composite Membrane for PEM Fuel Cells

Synthesis of mesoporous zirconium phosphate (MZP) by co-assembly of a tri-block copolymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide and phosphorous trichloride as inorganic precursors is reported. MZP with a specific surface area of 84 m(2) g(-1) average pore diameter of about 17 nm and pore volume of 0.35 cm(3) g(-1) has been prepared, and characterised by X-ray diffraction (XRD) and transmission electron microscopy. Nafion-MZP composite membrane is obtained by employing MZP as a surface-functionalised solid-super-acid-proton-conducting medium as well as all inorganic filler with high affinity to absorb water and fast proton-transport across the electrolyte membrane even under low relative humidity (RH) conditions. The composite membranes have been evaluated in H-2/O-2 polymer electrolyte fuel cells (PEFCs) at varying RH values between 18 and 100%; a peak power density of 355 mW cm(-2) at a load current density of 1,100 mA cm(-2) is achieved with the PEFC employing Nafion-MZP composite membrane while operating at optimum temperature (70 degrees C) under 18% RH and ambient pressure. On operating the PEFC employing Nafion-MZP membrane electrolyte with hydrogen and air feeds at ambient pressure and a RH value of 18%, a peak power density of 285 mW cm(-2) at the optimum temperature (60 degrees C) is achieved. In contrast, operating under identical conditions, a peak power density of only similar to 170 mW cm(-2) is achieved with the PEFC employing Nafion-1135 membrane electrolyte.

NMR relaxation study of disorder in the mixed system BP x GPI(1-x) and the low temperature transition from classical to quantum rotation

1H NMR spin-lattice relaxation time (T1) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BPxGPI(1-x)), to study the effects of disorder on the proton group dynamics. Analysis of T1 data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (Ea) and the torsional energy gap (E01). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.

Co-induction of sucrose transport and invertase activities in a thermophilic fungus,Thermomyces lanuginosus

The incorporation of sucrose into the thermophilic fungus,Thermomyces lanuginosus, occurred only in mycelia previously exposed to sucrose or raffinose. Sucrose uptake and invertase were inducible. Both activities appeared in sucrose-induced mycelia at about the same time. Both activities declined almost simultaneously following the exhaustion of sucrose in the medium. The sucrose-induced uptake system was specific for \beta -fructofuranosides as revealed by competition with various sugars. The induction of sucrose uptake system was blocked by cycloheximide, showing that it was dependent on new protein synthesis. Transport of sucrose did not seem to be dependent on ATP. Rather, uptake of this sugar seemed to be driven by a proton gradient across the plasma membrane. The uptake system showed Michaelis-Menten kinetics.

1H NMR study of [N(CH3)4]2ZnCI4 at high pressures and low temperatures

Wide-line proton NMR studies on polycrystalline tetramethylammonium tetrachlorozincate have been carried out at high hydrostatic pressures up to 15 kbar in the temperature range 77-300 K and at ambient pressure down to 4.2 K. A second-moment transition is observed to occur starting around 161 K, the temperature for the V-VI phase transition. This transition temperature is seen to have a negative pressure coefficient up to 2 kbar, beyond which it changes sign. At 77 K the second moment decreases to 4 kbar and then increases again as a function of pressure. The results are explained in terms of the dynamics of the N(CH3)4 groups.

The ethyl, 1- and 2-propyl, and other simple alky carbanions do not exist

A combination of experimental data and theoretical calculations has been used to estimate the electron affinities of simple primary, secondary, and tertiary alkyl radicals and the proton affinities of the corresponding anions. With the exception of cyclopropyl, such carbanionsâ are indicated to be unstable towards loss of an electron and are not expected to exist as long-lived species in the gas phase.

13c And 1h Nmr Study Of Complexes Of 2-Pyridinethione And 4-Pyridinethione With Zn(Ii), Cd(Ii) And Hg(Ii) Halides

Proton and carbon-13 NMR has been used to study complexes of 2-pyridinethione (in its basic and deprotonated forms) and 4-pyridinethione with zinc(II), cadmium(II) and mercury(II) halides. The variations in the carbon-13 and proton chemical shifts are discussed.

An eels study of water, methanol, formaldehyde and formic acid adsorbed on clean and oxygen-covered zinc(0001) surfaces

Water adsorbs molecularly on a clean Zn(0001) surface; on a surface covered with atomic oxygen, however, hydroxyl species is produced due to proton abstraction by the surface oxygen atoms. Methanol, molecularly adsorbed on a clean surface at 80 K, transforms to methoxy species above 110 K. On an atomic oxygen-covered surface, adsorbed methanol gives rise to methoxy species and water, the latter arising from proton abstraction. HCHO adsorbs molecularly at 80 K on both clean as well as oxygen-covered surfaces and polymerizes at higher temperatures. Formic acid does not adsorb on a clean Zn surface, but on an oxygen-covered surface gives rise to formate and hydroxyl species.

A nuclear magnetic resonance study of tetramethylammonium tribromocadmate

Proton spin lattice relaxation (T1) in (CH3)4NCdBr3 at different Larmor frequencies (10, 20 and 30 MHz) has been studied in the temperature range 77 to 400 K. The variations in T1 at high temperature are independent of frequency and show a maximum due to spin rotation- interaction. The other features are interpreted as being due to isotropic tumbling of the tetramethylammonium ion and random reorientation of the CH3 group. The CW spectrum remained narrow up to 77 K and develops a wing structure at low temperatures. This observation is attributed to a possible tunnelling motion of the CH3 group, which has rather low activation energy as demonstrated by the study of T1.