Electron paramagnetic resonance studies of some ternary oxides of copper (II)

The electron paramagnetic resonance (EPR) of ternary oxides of Cu(II) has been studied between 4.2 and 300 K. The systems include those with 180 degrees Cu-O-Cu interactions (such as Ln2CuO4, Sr2CuO2Cl2, Sr2CuO3 and Ca2CuO3) or 90 degrees Cu-O-Cu interactions (such as Y2Cu2O5 or BaCuO2) as well as those in which the Cu2+ ions are isolated (such as Y2BaCuO5, La1.8Ba1.2Cu0.9O4.8 and Bi2CuO4). The change in the EPR susceptibility as a function of temperature is compared with that of the DC magnetic susceptibility. Compounds with extended 180 degrees Cu-O-Cu interactions which have a low susceptibility also do not give EPR signals below room temperature. For compounds such as Ca2CuO3 with one-dimensional 180 degrees Cu-O-Cu interactions a weak EPR signal is found the temperature dependence of which is very different from that of the DC susceptibility. For Y2BaCuO5 as well as for La1.8Ba1.2Cu0.9O4.8 the EPR susceptibility as well as its temperature variation are comparable with those of the static susceptibility near room temperature but very different at low temperatures. Bi2CuO4 also shows a similar behaviour. In contrast, for Y2Cu2O5, in which the copper ions have a very distorted nonsquare-planar configuration, the EPR and the static susceptibility show very similar temperature dependences. In general, compounds in which the copper ions have a square-planar geometry give no EPR signal in the ground state (0 K) while those with a distortion from square-planar geometry do give a signal. The results are analysed in the light of recent MS Xalpha calculations on CuO46- square-planar clusters with various Cu-O distances as well as distortions. It is suggested that in square-planar geometry the ground state has an unpaired electron in anionic orbitals which is EPR inactive. Competing interactions from other cations, an increase in Cu-O distance or distortions from square-planar geometry stabilise another state which has considerably more Cu 3d character. These states are EPR active. Both these states, however, are magnetic. For isolated CuO46- clusters the magnetic interactions seem to involve only the states which have mainly anionic character.

Conformations of synthetic alamethicin fragments. Evidence for 310 helical folding from 270-MHz hydrogen-1 nuclear magnetic resonance and circular dichroism studies

IH NMR studies at 270 MHz on the synthetic alamethicin fragments Z-Aib-Pro-Aib-Ala-Aib-Ala-OMe (1-6), Boc-Gln-Aib-Val-Aib-Gly-Leu-Aib-OMe (7-1 3), Boc-Leu-Aib-Pro-Val-Aib-OMe (1 2-16), and Boc-Gly-Leu- Aib-Pro-Val-Aib-OMe (1 1-16) have been carried out in CDC13 and (CD3)2S0. The intramolecularly hydrogen bonded amide hydrogens in these peptides have been delineated by using solvent titration experiments and temperature coefficientsof NH chemical shifts in (CD3)+30. All the peptides adopt highly folded structures, characterized by intramolecular 4 - 1 hydrogen bonds. The 1-6 fragment adopts a 310 helical conformation with four hydrogen bonds, in agreement with earlier studies (Rao, Ch. P., Nagaraj, R., Rao, C. N. R., & Balaram, P. (1980) Biochemistry 19, 425-4311. The 7-13

High-resolution methyl edited GFT NMR experiments for protein resonance assignments and structure determination

Three-dimensional (3D) structure determination of proteins is benefitted by long-range distance constraints comprising the methyl groups, which constitute the hydrophobic core of proteins. However, in methyl groups (of Ala, Ile, Leu, Met, Thr and Val) there is a significant overlap of C-13 and H-1 chemical shifts. Such overlap can be resolved using the recently proposed (3,2)D HCCH-COSY, a G-matrix Fourier transform (GFT) NMR based experiment, which facilitates editing of methyl groups into distinct spectral regions by combining their C-13 chemical shifts with that of the neighboring, directly attached, C-13 nucleus. Using this principle, we present three GFT experiments: (a) (4,3)D NOESY-HCCH, (b) (4,3)D H-1-TOCSY-HCCH and (c) (4,3)D C-13-TOCSY-HCCH. These experiments provide unique 4D spectral information rapidly with high sensitivity and resolution for side-chain resonance assignments and NOE analysis of methyl groups. This is exemplified by (4,3)D NOESY-HCCH data acquired for 17.9 kDa non-deuterated cytosolic human J-protein co-chaperone, which provided crucial long-range distance constraints for its 3D structure determination.

An EQCM Investigation of Electrochemical Precipitation of Mn(OH)(2) and Its Capacitance Behavior

Electrochemical quartz crystal microbalance (EQCM) has been used to study the electrochemical precipitation of Mn(OH)(2) on a Au crystal and its capacitance properties. From the EQCM data, it is inferred that NO3- ions get adsorbed on the Au crystal and then undergo reduction, resulting in an increase in pH near the electrode surface. Precipitation of Mn2+ occurs as Mn(OH)(2), with an increase in mass of the Au crystal. Mn(OH)(2) undergoes oxidation to MnO2, which exhibits electrochemical supercapacitor behavior on subjecting to electrochemical cycling in a Na2SO4 electrolyte. EQCM data indicate mass variations corresponding to surface insertion/extraction of Na+ ions during discharge/charge cycling. (C) 2010 The Electrochemical Society. DOI: 10.1149/1.3479665] All rights reserved.

Effects of Parasitics and Interface Traps on Ballistic Nanowire FET in the Ultimate Quantum Capacitance Limit

In this paper, we focus on the performance of a nanowire field-effect transistor in the ultimate quantum capacitance limit (UQCL) (where only one subband is occupied) in the presence of interface traps (D-it), parasitic capacitance (C-L), and source/drain series resistance (R-s,R-d), using a ballistic transport model and compare the performance with its classical capacitance limit (CCL) counterpart. We discuss four different aspects relevant to the present scenario, namely: 1) gate capacitance; 2) drain-current saturation; 3) subthreshold slope; and 4) scaling performance. To gain physical insights into these effects, we also develop a set of semianalytical equations. The key observations are as follows: 1) A strongly energy-quantized nanowire shows nonmonotonic multiple-peak C-V characteristics due to discrete contributions from individual subbands; 2) the ballistic drain current saturates better in the UQCL than in the CCL, both in the presence and absence of D-it and R-s,R-d; 3) the subthreshold slope does not suffer any relative degradation in the UQCL compared to the CCL, even with Dit and R-s,R-d; 4) the UQCL scaling outperforms the CCL in the ideal condition; and 5) the UQCL scaling is more immune to R-s,R-d, but the presence of D-it and C-L significantly degrades the scaling advantages in the UQCL.

High-frequency capacitance-voltage characteristics of amorphous (undoped)/crystalline silicon heterostructures

A numerical procedure is presented for calculating high-frequency capacitance variation with bias in amorphous (undoped)/crystalline silicon heterojunction. The results of the model calculations using this procedure have been reported, for different p silicon substrates. These have been compared with the corresponding capacitance variations in the other limiting case, in which the heterostructure acts like an MIS structure. The effect of interface states on the capacitance characteristics has also been studied. In the second part, we report the results of 1 MHz capacitance measurements on various amorphous (undoped)/crystalline silicon heterostructures.

Nuclear-quadrupole resonance in coordination chemistry- identification of bridiging and therminal chlorines in the mercuric chloride-4-picoline n-oxide complex

The temperature dependence of the chlorine-35 n.q.r. in the mercuric chloride-4-picoline N-oxide complex has been studied from 77 K to room temperature, and the results are used to assign the observed frequencies to terminal and bridging chlorines.

Infrared and Nuclear Quadrupole Resonance Studies of the Phase Transitions of Para-dichlorobenzene

The α→γ→α→β transitions of para-dichlorobenzene have been studied by employing infrared and n.q.r. spectroscopy as well as differential scanning calorimetry. The γ phase is associated with considerably higher values of some of the intramolecular vibration frequencies. The α→γ transition shows athermal nucleation behaviour as in martensitic transitions. Intermolecular vibration bands around 46 and 85 cm–1 present in γ and α phases disappear in the β phase. The α→β transition seems to be associated with some orientational disorder.

Time-Resolved Resonance Raman Studies on Proton-Induced Electron-Transfer Reaction from Triplet Excited State of 2-Methoxynaphthalene to Decafluorobenzophenone

In this paper time-resolved resonance Raman (TR3) spectra of intermediates generated by proton induced electron-transfer reaction between triplet 2-methoxynaphthalene ((ROMe)-R-3) and decafluorobenzophenone (DFBP) are presented The TR3 vibrational spectra and structure of 2-methoxynaphthalene cation radical (ROMe+) have been analyzed by density functional theory (DFT) calculation It is observed that the structure of naphthalene ring of ROMe+ deviates from the structure of cation radical of naphthalene

13 C nuclear magnetic resonance studies of the binding of alkali and alkaline earth metal salts to amides

13 C resonances of carbonyl and methyl groups in amides are shifted down-field on interaction with alkali and alkaline earth metal salts. The magnitude of the shift depends on the ionic potential of the cation. Ions like Li+ bind to the amide carbonyl group both in neat amide solutions as well as in concentrated salt solutions in water.

Proton Magnetic-Resonance Study of Cycloheximide-Ribosome Interactions

Cycloheximide-ribosome interactions from sensitive and resistant organisms were studied by proton magnetic resonance spectroscopic techniques. The two methyl resonances of cycloheximide upon interaction with ribosomes from Saccharomyces cerevisiae showed preferential broadening. Comparison of cycloheximide line broadening as effected by ribosomes from S. cerevisiae (sensitive) and Microsporum canis (resistant) revealed that less cycloheximide is bound to the M. canis ribosomes. From the decrease in line broadening observed with increasing temperature it may be concluded that cycloheximide-ribosome interaction is a fast exchange reaction. Tetracycline did not compete with cycloheximide for binding site(s) on the ribosomes of S. cerevisiae.

Circular dichroism and 13C nuclear magnetic resonance spectroscopy of pennisetin from pearl millet

The conformation and stability of pearl millet prolamin (pennisetin) were examined by using circular dichroism and C-13 nuclear magnetic resonance spectroscopy. The far UV spectrum of pennisetin in 70% (v/v) aqueous ethanol showed the presence of predominant alpha-helical structure and its occurrence in the alpha + beta class of protein. The far and near UV spectra of pennisetin in ethanol: trifluoroethanol also supported this observation. However pennisetin showed the presence of some helical structure in 8 M urea which is known to be a highly unordered structure forming solvent. A decrease in alpha helical content of native pennisetin was observed with rise in temperature from 5-75-degrees-C and this effect of temperature was found to be reversible. A C-13 NMR spectrum of pennisetin in 70% ethanol suggested a high degree of molecular mobility in ethanol. Comparison of the cross polarization spectrum with the single pulse excitation spectrum suggested pennisetin to be a heterogeneous protein.

A Feature-Based Solution to Forward Problem in Electrical Capacitance Tomography of Conductive Materials

A new feature-based technique is introduced to solve the nonlinear forward problem (FP) of the electrical capacitance tomography with the target application of monitoring the metal fill profile in the lost foam casting process. The new technique is based on combining a linear solution to the FP and a correction factor (CF). The CF is estimated using an artificial neural network (ANN) trained using key features extracted from the metal distribution. The CF adjusts the linear solution of the FP to account for the nonlinear effects caused by the shielding effects of the metal. This approach shows promising results and avoids the curse of dimensionality through the use of features and not the actual metal distribution to train the ANN. The ANN is trained using nine features extracted from the metal distributions as input. The expected sensors readings are generated using ANSYS software. The performance of the ANN for the training and testing data was satisfactory, with an average root-mean-square error equal to 2.2%.