Role of thiol‐disulfide exchange in episulfide polymerization

Episulfide polymerization offers a number of features that are uncommon in other ring‐opening anionic mechanisms. Besides the negligible sensitivity to water, the most distinctive and novel one is likely to be the role of disulfides, which may act both at the levels of chain transfer and end‐capping, producing polymers that feature both terminal and internal disulfides. In this article, we have qualitatively studied the kinetics of chain transfer and measured the thiolate–disulfide exchange equilibrium constants. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 2233–2249, 2008     

Theoretical study of the performance for short channel carbon nanotube transistors with asymmetric contacts

We have simulated short channel carbon nanotube field-effect transistors with asymmetric source and drain contacts using a coupled mode space approach within the non-equilibrium Green's function framework. The simulated results show that the asymmetric conduction properties under positive and negative drain-to-source voltages are caused by the asymmetric Schottky barriers to carriers at the source and drain contacts. Under negative drain-to-source voltages, hole and electron conduction are dominated by thermionic emission and tunneling through the Schottky barrier, respectively, leading to the different subthreshold behaviors of the hole and electron conduction. With increasing channel length, short channel effects can be suppressed effectively and ON/OFF ratio can be improved.     

A solid-phase approach to the synthesis of N-1-alkyl analogues of cyclic inosine-diphosphate-ribose (cIDPR)

We report here an efficient solid-phase synthesis of N-1-alkyl-substituted analogues of cyclic inosine-diphosphate-ribose (cIDPR), a mimic of cyclic ADP-ribose (cADPR). Our synthetic strategy makes use of a polystyrene support to which inosine was bonded through a 2′,3′-acetal linkage. Insertion of a ω-hydroxy-polymethylene chain of variable length on N-1, followed by conversion into N-1-alkylinosine-bis-phosphate derivatives and cyclization, allowed to obtain analogues of cIDPR of various ring size. The cyclization step was carried out both in solid-phase and in solution by pyrophosphate bond formation. The effect of the N-1-polymethylene chain length on the cyclization yields as well as the reaction conditions, which led to the solid-phase pyrophosphate bond formation, were thoroughly investigated.     

Redetermination of the X-ray structure of nitroxylcobalamin: base-on nitroxylcobalamin exhibits a remarkably long Co-N(dimethylbenzimidazole) bond distance

The X-ray structures of three new crystals of nitroxylcobalamin (NOCbl) have been determined. Unlike our earlier reported structure in which NOCbl was partially oxidized (L. Hannibal, C. A. Smith, D. W. Jacobsen and N. E. Brasch, Angew. Chem., Int. Ed. 2007, 46, 5140), the O atom of the nitroxyl ligand is located in a single position with a N=O bond distance of 1.12-1.14 ?, consistent with a double bond. The Co-N-O angle is in the 118.9-120.3 ? range. The α-axial Co-N(dimethylbenzimidazole) (Co-NB3) bond distance is a remarkable 2.32-2.35 ? in length, ~0.1 ? longer than that reported for all other cobalamin structures. The change in the Gibbs free energy for the base-on/base-off equilibrium now correlates extremely well with the Co-NB3 bond distance, as observed for other cobalamins.     

Photochemistry in Photonic Crystal Fiber Nanoreactors

We report the use of a liquid‐filled hollow‐core photonic crystal fiber (PCF) as a highly controlled photochemical reactor. Hollow‐core PCFs have several major advantages over conventional sample cells: the sample volume per optical path length is very small (2.8 nL cm^?1 in the fiber used), long optical path lengths are possible as a result of very low intrinsic waveguide loss, and furthermore the light travels in a diffractionless single mode with a constant transverse intensity profile. As a proof of principle, the (very low) quantum yield of the photochemical conversion of vitamin B₁₂, cyanocobalamin (CNCbl) to hydroxocobalamin ([H₂OCbl]⁺) in aqueous solution was measured for several pH values from 2.5 to 7.5. The dynamics of the actively induced reaction were monitored in real‐time by broadband absorption spectroscopy. The PCF nanoreactor required ten thousand times less sample volume compared to conventional techniques. Furthermore, the enhanced sensitivity and optical pump intensity implied that even systems with very small quantum yields can be measured very quickly—in our experiments one thousand times faster than in a conventional cuvette.     

Role of disorder and anharmonicity in the thermal conductivity of silicon-germanium alloys: a first-principles study

The thermal conductivity of disordered silicon-germanium alloys is computed from density-functional perturbation theory and with relaxation times that include both harmonic and anharmonic scattering terms. We show that this approach yields an excellent agreement at all compositions with experimental results and provides clear design rules for the engineering of nanostructured thermoelectrics. For Si(x)Ge(1-x), more than 50% of the heat is carried at room temperature by phonons of mean free path greater than 1 μm, and an addition of as little as 12% Ge is sufficient to reduce the thermal conductivity to the minimum value achievable through alloying. Intriguingly, mass disorder is found to increase the anharmonic scattering of phonons through a modification of their vibration eigenmodes, resulting in an increase of 15% in thermal resistivity.     

Dysregulation of chemo-cytokine production in schizophrenic patients versus healthy controls

Background  

The exact cause of schizophrenia is not known, although several aetiological theories have been proposed for the disease, including developmental or neurodegenerative processes, neurotransmitter abnormalities, viral infection and immune dysfunction or autoimmune mechanisms. Growing evidence suggests that specific cytokines and chemokines play a role in signalling the brain to produce neurochemical, neuroendocrine, neuroimmune and behavioural changes. A relationship between inflammation and schizophrenia was supported by abnormal cytokines production, abnormal concentrations of cytokines and cytokine receptors in the blood and cerebrospinal fluid in schizophrenia. Since the neuropathology of schizophrenia has recently been reported to be closely associated with microglial activation we aimed to determined whether spontaneous or LPS-induced peripheral blood mononuclear cell chemokines and cytokines production is dysregulated in schizophrenic patients compared to healthy subjects. We enrolled 51 untreated first-episode schizophrenics (SC) and 40 healthy subjects (HC) and the levels of MCP-1, MIP-1α, IL-8, IL-18, IFN-γ and RANTES were determined by Elisa method in cell-free supernatants of PBMC cultures.     

Scalable InP integrated wavelength selector based on binary search

We present an InP monolithically integrated wavelength selector that implements a binary search for selecting one from N modulated wavelengths. The InP chip requires only log(2)N optical filters and log(2)N optical switches. Experimental results show nanosecond reconfiguration and error-free wavelength selection of four modulated wavelengths with 2 dB of power penalty.