Pyrrolidine ring conformations in prolyl peptides from 13C spin-lattice relaxation times

A method was developed in the framework of a bistable jump model to obtain the pyrrolidine ring conformations in proline peptides from 13C spin-lattice relaxation times. Equations are presented expressing the ring torsions in terms of the 13C spin-lattice relaxation times of the ring carbons. This method was applied to 26 pyrrolidine ring systems and acceptable conformations were obtained.

Antiferromagnetic spin-wave states in a linear chain with nearest- and next-nearest-neighbour interactions

The spectrum of short-closed chains up to N=12 are studied by exact diagonalization to obtain the spin-wave spectrum of the Hamiltonian H=2J Sigma i=1Nsi.si+1+2J alpha Sigma i=1Nsi.si+2, -1.0spin-wave spectrum is fairly well described for small alpha by the spin-wave formula obtained by the Anderson approximation (1952). The results of short chains indicate that S=0 bound magnon states lie partly below the spin-wave states with S=1 only for alpha >or=0.3 and alpha

Simplified theory of optical nonlinearities in spin-polarized semiconductors

The spin degree of freedom is largely disregarded in existing theories of the density-dependent optical properties of an interacting electron-hole plasma in quasiequilibrium. Here, we extended the pair equation, which is applicable to a bulk semiconductor at elevated temperatures, to calculate optical nonlinearities due to a spin-polarized plasma. We obtained agreement with recent circular dichroism data in laser-excited GaAs by using the plasma density alone as the fitting parameter. The simplicity of our theory, based on the analytical pair-equation formula, makes it ideal for conveniently modelling absorption in a carrier spin-polarized semiconductor.

Observation of the intense de-pairing effect in YBa2Cu3O7-delta due to the spin injection from La0.5Sr0.5CoO3

We report experimental evidence for a huge pair breaking effect induced by spin polarized quasiparticles in a YBa2Cu3O7-delta/La0.5Sr0.5CoO3 bi-layer fabricated by pulsed laser deposition. The temperature dependent magnetization measurements show evidence for the presence of both ferromagnetic and diamagnetic phases in the bi-layer. The current dependent electrical transport studies in the bi-layer exhibit a significant reduction in the superconducting transition temperature with the increase in applied current as compared to a single YBa2Cu3O7-delta layer and it follows a I-2/3 dependence in accordance with the pair breaking effect. Here, we find that the current driven from a ferromagnetic electrode with low spin polarization, such as La0.5Sr0.5CoO3 (-11%), into the superconductor can act as a strong pair breaker. This indicates that the spin polarization of the injecting electrode is not the only criterion in determining the pair breaking effect, rather the transparency of the interface for the spin polarization may also be significant. More interestingly, the spin diffusion length for YBa2Cu3O7-delta has a much longer length scale than that reported earlier in the study of ferromagnetic/superconducting heterostructures.

Spin-Probe ESR Studies on Nanocomposite Polymer Electrolytes

The possibility of using spin-probe electron spin resonance (ESR) as a tool to study glass transition temperature, T g, of polymer electrolytes is explored in 4 hydroxy 2,2,6,6 tetramethylpiperidine N oxyl (TEMPOL) doped composite polymer electrolyte (PEG)46LiClO4 dispersed with nanoparticles of hydrotalcite. The T g is estimated from the measured values of T 50G, the temperature at which the extrema separation 2A zz of the broad powder spectrum decreases to 50 G. In another method, the correlation time τc for the spin probe dynamics was determined by computer simulation of the ESR spectra and T g has been identified as the temperature at which τc begins to show temperature dependence. While both methods give values of T g close to those obtained from differential scanning calorimetry, it is concluded that more work is required to establish spin-probe ESR as a reliable technique for the determination of T g.

Vitrification, relaxation and free volume in glycerol-water binary liquid mixture:Spin probe ESR studies

Glass transition and relaxation of the glycerol-water (G-W) binary mixture system have been studied over the glycerol concentration range of 5-85 mol% by using the highly sensitive technique of electron spin resonance (ESR). For the water rich mixture the glass transition,sensed by the dissolved spin probe, arises from the vitrified mesoscopic portion of the binary system. The concentration dependence of the glass transition temperature manifests a closely related molecular level cooperativity in the system. A drastic change in the mesoscopic structure of the system at the critical concentration of 40 mol is confirmed by an estimation of the spin probe effective volume in a temperature range where the tracer reorientation is strongly coupled to the system dynamics.

Nonspecifically bound proteins spin while diffusing along DNA

It is known that DNA-binding proteins can slide along the DNA helix while searching for specific binding sites, but their path of motion remains obscure. Do these proteins undergo simple one-dimensional (1D) translational diffusion, or do they rotate to maintain a specific orientation with respect to the DNA helix? We measured 1D diffusion constants as a function of protein size while maintaining the DNA-protein interface. Using bootstrap analysis of single-molecule diffusion data, we compared the results to theoretical predictions for pure translational motion and rotation-coupled sliding along the DNA. The data indicate that DNA-binding proteins undergo rotation-coupled sliding along the DNA helix and can be described by a model of diffusion along the DNA helix on a rugged free-energy landscape. A similar analysis including the 1D diffusion constants of eight proteins of varying size shows that rotation-coupled sliding is a general phenomenon. The average free-energy barrier for sliding along the DNA was 1.1 +/- 0.2 k(B)T. Such small barriers facilitate rapid search for binding sites.

Highly efficient spin-conversion effect leading to energy up-converted electroluminescence in singlet fission photovoltaics

Free charge generation in donor-acceptor (D-A) based organic photovoltaic diodes (OPV) progresses through formation of charge-transfer (CT) and charge-separated (CS) states and excitation decay to the triplet level is considered as a terminal loss. On the other hand a direct excitation decay to the triplet state is beneficial for multiexciton harvesting in singlet fission photovoltaics (SF-PV) and the formation of CT-state is considered as a limiting factor for multiple triplet harvesting. These two extremes when present in a D-A system are expected to provide important insights into the mechanism of free charge generation and spin-character of bimolecular recombination in OPVs. Herein, we present the complete cycle of events linked to spin conversion in the model OPV system of rubrene/C60. By tracking the spectral evolution of photocurrent generation at short-circuit and close to open-circuit conditions we are able to capture spectral changes to photocurrent that reveal the triplet character of CT-state. Furthermore, we unveil an energy up-conversion effect that sets in as a consequence of triplet population build-up where triplet-triplet annihilation (TTA) process effectively regenerates the singlet excitation. This detailed balance is shown to enable a rare event of photon emission just above the open-circuit voltage (VOC) in OPVs.

The incongruous observation of magnetic phase separation in La0.85Sr0.15CoO3 spin glass system

Phase separation (PS) in hole-doped cobaltites (La1-xSrxCoxO3) is drawing renewed interest recently. In particular, the magnetic behavior of La0.85Sr0.15CoO3 has been subjected to a controversial debate for the past several years; while some groups show evidence for magnetic PS, others show spin glass (SG) behavior. Here, an attempt is made to resolve the controversy related to ``PS versus SG'' behavior in this compound. We present the results of a comprehensive investigation of the dc magnetization, ac susceptibility, and the magnetotransport properties of La0.85Sr0.15CoO3 samples. We contemplate that the magnetic PS in La0.85Sr0.15CoO3 is neither intrinsic nor inherent, but it is a consequence of the preparation conditions. It is realized that a low temperature annealed (LTA) sample shows PS whereas the high temperature annealed (HTA) sample shows SG behavior. The Brillouin-like behavior of field cooled dc magnetization and apparently no frequency dependent peak shift in ac susceptibility for the LTA sample characterize it to be of ferromagneticlike whereas a kink in field cooled dc magnetization and a considerable amount (similar to 3 K) of frequency dependent peak shift in the ac susceptibility for the HTA sample characterize it to be of SG state. The magnetotransport properties show that the HTA sample is more semiconducting as compared to the LTA sample. This is interpreted in terms of the presence of isolated as well as coalescing metallic ferromagnetic clusters in the case of LTA sample. The magnetoresistance (MR) at 10 K for the HTA sample exhibits a huge value (similar to 65%) as compared to the LTA sample, and it monotonically decreases with the rise in temperature. Such a high value of MR in the case of HTA sample is strongly believed to be due to the spin dependent part of random potential distribution. Further, the slow decay of remnant magnetization with progress of time and the existence of hysteresis at higher temperatures (up to 200 K) in the case of LTA sample as compared to the HTA sample clearly unveil different magnetic states associated with them.

Recognition and alignment of homologous DNA sequences between minichromosomes and single-stranded DNA promoted by RecA protein

The incorporation of DNA into nucleosomes and higher-order forms of chromatin in vivo creates difficulties with respect to its accessibility for cellular functions such as transcription, replication, repair and recombination. To understand the role of chromatin structure in the process of homologous recombination, we have studied the interaction of nucleoprotein filaments, comprised of RecA protein and ssDNA, with minichromosomes. Using this paradigm, we have addressed how chromatin structure affects the search for homologous DNA sequences, and attempted to distinguish between two mutually exclusive models of DNA-DNA pairing mechanisms. Paradoxically, we found that the search for homologous sequences, as monitored by unwinding of homologous or heterologous duplex DNA, was facilitated by nucleosomes, with no discernible effect on homologous pairing. More importantly, unwinding of minichromosomes required the interaction of nucleoprotein filaments and led to the accumulation of circular duplex DNA sensitive to nuclease P1. Competition experiments indicated that chromatin templates and naked DNA served as equally efficient targets for homologous pairing. These and other findings suggest that nucleosomes do not impede but rather facilitate the search for homologous sequences and establish, in accordance with one proposed model, that unwinding of duplex DNA precedes alignment of homologous sequences at the level of chromatin. The potential application of this model to investigate the role of chromosomal proteins in the alignment of homologous sequences in the context of cellular recombination is considered.

Tetragonal bismuth bilayer: A stable and robust quantum spin hall insulator

Topological insulators (TIs) exhibit novel physics with great promise for new devices, but considerable challenges remain to identify TIs with high structural stability and large nontrivial band gap suitable for practical applications. Here we predict by first-principles calculations a two-dimensional (2D) TI, also known as a quantum spin Hall (QSH) insulator, in a tetragonal bismuth bilayer (TB-Bi) structure that is dynamically and thermally stable based on phonon calculations and finite-temperature molecular dynamics simulations. Density functional theory and tight-binding calculations reveal a band inversion among the Bi-p orbits driven by the strong intrinsic spin-orbit coupling, producing a large nontrivial band gap, which can be effectively tuned by moderate strains. The helical gapless edge states exhibit a linear dispersion with a high Fermi velocity comparable to that of graphene, and the QSHphase remains robust on a NaCl substrate. These remarkable properties place TB-Bi among the most promising 2D TIs for high-speed spintronic devices, and the present results provide insights into the intriguing QSH phenomenon in this new Bi structure and offer guidance for its implementation in potential applications.

Uncoupled surface spin induced exchange bias in α-MnO 2 nanowires

We have studied the microstructure, surface states, valence fluctuations, magnetic properties, and exchange bias effect in MnO2 nanowires. High purity α-MnO 2 rectangular nanowires were synthesized by a facile hydrothermal method with microwave-assisted procedures. The microstructure analysis indicates that the nanowires grow in the [0 0 1] direction with the (2 1 0) plane as the surface. Mn3+ and Mn2+ ions are not found in the system by X-ray photoelectron spectroscopy. The effective magnetic moment of the manganese ions fits in with the theoretical and experimental values of Mn4+ very well. The uncoupled spins in 3d3 orbitals of the Mn 4+ ions in MnO 6 octahedra on the rough surface are responsible for the net magnetic moment. Spin glass behavior is observed through magnetic measurements. Furthermore, the exchange bias effect is observed for the first time in pure α-MnO2 phase due to the coupling of the surface spin glass with the antiferromagnetic α-MnO2 matrix. These α-MnO2 nanowires, with a spin-glass-like behavior and with an exchange bias effect excited by the uncoupled surface spins, should therefore inspire further study concerning the origin, theory, and applicability of surface structure induced magnetism in nanostructures.

Tailoring texture of γ-Y2Si2O7 by strong magnetic field alignment and two-step sintering

In this study, a well-dispersed γ-Y2Si2O 7 ethanol-based suspension with 30 vol% solid loading was prepared by adding 1 dwb% polyethylene imine dispersant, which allows feeble magnetic γ-Y2Si2O7 particles with anisotropic magnetic susceptibility to rotate in a 12 T strong magnetic field during slip casting, resulting in the development of a strong texture in green bodies. Pressureless sintering gives rise to more pronounced grain growth in the textured sample than in the untextured sample prepared without the magnetic field due to the rapid migration of the grain boundaries of the well-oriented grains, which was revealed by constant-heating-rate sintering kinetics. It was found that the use of two-step sintering is very efficient not only for inhibiting the grain growth but also for enhancing the texture. This implies that controlled grain growth is crucial for enhancing texture development in γ-Y2Si2O7.