Tight β-turns in peptides. DFT-based study of infrared absorption and vibrational circular dichroism for various conformers including solvent effects

Vibrational circular dichroism (VCD) has had a large impact on configurational studies of organic molecules largely due to the theoretical advances made by Philip Stephens and co-workers. For peptides, the structural issue is not one of the configuration, but of conformation, and the flexibility of the oligomeric structure raises major computational challenges. Turns are a vital aspect of peptide and protein conformation that allow such structures to fold into a compact unit. However, unlike helices and sheets, they are not extended repeating structures, but each residue has a different local conformation. Also, when turns are part of larger peptides their termini are connected to completely different structural elements. We have done extended comparative density functional theory (DFT) computations to characterize the expected spectral contributions of selected turn structures to the amide IR and VCD spectra of peptides. The isolated vacuum results for tri-amide turns (Ac-X-Y-NH₂) of a few different sequences are compared with calculations involving correction for solvation effects. In particular, we looked at the sequence variation in spectra and structure between Ala-Ala, Aib-Gly and D-Pro-Gly for the turn-specific X–Y residues. The nature of some turn-associated, amide originating, spectral transitions are developed and tested.     

流体力学半径对估算胶体微球聚集速率常数的影响

胶体粒子聚集速率常数实验值远低于理论值一直是被普遍关注的问题.聚集速率常数的理论推导是基于粒子的几何半径来考虑的,但决定粒子扩散速率及聚集速率的应该是粒子的流体力学半径(大于几何半径),因而它是使聚集速率常数实验值低于理论值的因素之一.影响流体力学半径的因素很多,其中,带电粒子在溶液中因表面存在双电层,会明显增大流体力学半径,造成聚集速率减慢.而双电层的厚度又随溶液中离子强度的不同而改变.本工作在聚集速率的公式中引入了修正因子,即几何半径与其流体力学半径之比,以修正由于用几何半径代替流体力学半径带来的误差.其中几何半径和流体力学半径可以分别用扫描电镜(SEM)和动态光散射(DLS)来测定.以两种粒径的聚苯乙烯带电微球为例,考察了在不同离子强度下,该误差的大小.结果发现,对于半径为30 nm的微球,用流体力学半径计算的慢聚集速率常数比理论值偏低约8%.该误差随离子强度增加而减少.对于快聚集情况,流体力学半径对聚集速率基本没有影响.     

Electrical transport measurements in a quasi-onedimensional semiconductor ZrS3

We have used the technique of chemical vapour transport to prepare needle shaped single crystal of ZrS₃. Results of the measurements of d.c. resistivity. Hall coefficient and thermoelectric power of the temperature range 100–500 K are reported. All the samples exhibited semiconducting behaviour with a room temperature resistivity of about 15 Ω-cm and an activation energy of 0.20±0.02 eV. Room temperature thermoelectric power is -850 μVK^?1 and the dominant carriers are electrons. The thermoelectric power varies as (1/T), a behaviour associated with a typical semiconductor. Mobility at low temperatures is limited by ionized impurity scattering and is given by μ₁ = 6.5 × 10^?2T^3/2 cm²V^7-1 sec^?1. At high temperatures, phonon scattering is dominant and the mobility is given by μ₂ = 1.35 × 10⁺⁵T^?32 cm²V^?1 sec^?1.     

X-ray Debye temperature of mechanically milled Ni0.5Zn0.5Fe2O4 spinel ferrite

The X-ray Debye temperatures, θ _M , of spinel ferrite composition Ni_0.5Zn_0.5Fe₂O₄, mechanically milled upto 9 hrs, were determined from integrated intensities of selected Bragg reflections. The θ _M was found to increase with milling time. The results are explained in the light of milling induced grain orientation and surface effect. The values of θ _M were found to be lower as compared to the Debye temperatures obtained from infrared spectral data analysis. The difference can be explained on the basis of increase in an excess free volume in the form of vacancies and vacancy clusters associated with grain boundaries.     

Modification of the magnetoconductance of a two-dimensional electron gas by altering the boundary conditions in the third dimension

Substrate bias can be used as a powerful diagnostic tool for studying the magneto-transport in an inversion layer. One can accurately determine the mobile carrier threshold by such a study. Marked changes in the mobility occur with increasing confinement to the surface; a decrease for high electrons densities and an increase for low electron densities. The former was expected while the latter was not.     

Microwave conductivity of K-TCNQ

Measurements of microwave conductivity of K-TCNQ in the temperature range 300–450 K are reported. K-TCNQ behaves as an extrinsic semiconductor with an activation energy of 0.26 eV below the spin-Peierls transition temperature of 396 K and 0.13 eV above the transition. A hystersis of about 1.5 K was observed. Carrier mobility appears to be reduced by a factor of 30 in the high temperature phase. A second type of crystal has been identified with room temperature conductivity two orders of magnitude higher than previously reported.