First charge-transfer complexes between tetrathiafulvalene and 1,2,5-chalcogenadiazole derivatives: Design,synthesis, crystal structures,electronic and electrical properties

The first charge-transfer complexes of tetrathiafulvalene (1) with 1,2,5-chalcogenadiazole derivatives, i.e. with [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (2) and 3,4-dicyano-1,2,5-telluradiazole (3), were designed, prepared in the form of air and thermally stable single crystals and structurally defined by X-ray diffraction as 1·2 and 1·3₂, respectively. Starting compound 2 (effective electron acceptor with potentially broad application in the field) was synthesized by a new efficient one-pot method from 3,4-diamino-1,2,5-oxadiazole and disulfur dichloride. The electronic structure of complexes 1·2 and 1·3₂ and thermodynamics of their formation were studied by means of DFT and QTAIM calculations and UV–Vis spectroscopy. The electrical properties of single crystals of the complexes were investigated revealing semiconductor properties with an activation energy of 0.34 eV for 1·2 and 0.40 eV for 1·3₂. Polycrystalline films of the complexes displayed photoconductive effects with increased conductivity under white-light illumination.     

Practical quantum bit commitment protocol

A quantum protocol for bit commitment the security of which is based on technological limitations on non demolition measurements and long-term quantum memory is presented.     

Comparative Account of Bandwidth Efficiency in Optical Burst Switching and Optical Circuit Switching Networks

The performance of Optical Burst Switched (OBS) networks is compared to that of Optical Circuit Switched (OCS) networks in terms of bandwidth efficiency. Two traffic flow models are employed to investigate the effects of traffic grooming, packetization, buffering and burst assembly on bandwidth efficiency and utilization. Traffic is represented by fluid-flow continuous bit streams in the first model and by packet-based discrete flows in the second model. It is shown that the parameters of traffic characteristics and burst assembly have significant impact on the relative bandwidth savings of OBS. The bandwidth efficiency of OBS compared to OCS should not be taken for granted and has to be examined carefully on a case by case basis.     

Poly(N-vinylguanidine): Characterization, and catalytic and bactericidal properties

Poly(N-vinylguanidine) (PVG) is one of the simplest guanidine-bearing polyelectrolytes, but is virtually unknown in the scientific literature. An efficient synthetic route for poly(N-vinylguanidine) (PVG) is described that involves free-radical polymerization of N-vinylformamide (NVF) followed by basic hydrolysis of the PNVF and guanidinylation of the resulting polyvinylamine (PVAm). The molecular weights can be varied by altering the initial NVF/azo initiator ratio. Characterization of the PVG by ¹H and ¹³C NMR, FTIR and FT-Raman spectroscopy methods supports the PVG structure. The PVG possesses an average pK_a of 13.4 and is an active hydrolyzing species for diisopropyl fluorophosphate (DFP), an organophosphate mimic for combat nerve agents. The second-order rate constant of the DFP hydrolysis by PVG at pH 7.8 and 25 °C was measured to be 3.9 × 10⁻³ M⁻¹ s⁻¹, expressed per concentration of the catalytic amino or imino moieties in each PVG monomer. The hydrolysis occurs via the general S_N2 mechanism of base catalysis. The guanidinylation of PVAm affords PVG with 10- to 40-fold lower minimum inhibition concentration (MIC) when tested against four Gram-positive and four Gram-negative bacteria relative to the PVAm itself. Hence, the PVG is effective both as a hydrolyzing agent against toxic organophosphates and as a bactericide, thus exhibiting potential as a material for use in chemical and biological defense as well as a disinfectant in clinical and industrial applications.     

Pressure‐Responsive Hierarchical Chiral Photonic Aerogels

Pressure‐responsive chiral photonic aerogels are fabricated by combining liquid crystal self‐assembly and ice‐templating processes. The aerogels have a hierarchical structure in which the primary 2D chiral nematic structured walls of cellulose nanocrystals form ribbons that support a secondary 3D cellular network. Owing to the flexibility of the aerogels in solvent, the 3D structure of the aerogel can easily be transformed to a 2D structure by pressure‐induced rearrangement. The aerogels vary from white in color, which arises from light scattering, to a reflective photonic crystal displaying bright iridescent colors that depend on the immersed solvent. A solvent‐sensitive ink that shows quick color response to different solvents is designed using the pressure‐responsive photonic aerogel. This material demonstrates a new response mechanism for the design of smart and mechanoresponsive photonic materials.     

A Markov chain model to describe fluidization of particles with time-varying properties

A one-dimensional mathematical model of particulate solids thermal treatment in a fluidized bed based on the theory of Markov chains is proposed. A feature of the model takes into account the variation of particle properties that takes place during the fluidization. This variation occurs due to thermo-physical and chemical processes that take place during particulate solids treatment in the fluidized bed. These variations affect the particle settling velocity which is the main parameter that forms the bed expansion and local velocity of flow around the particles that strongly influences the thermo-physical and chemical processes in the bed. A generalized correlation for the drag force coefficient is proposed and tested for various materials. It was necessary to have more precise calculation of the particle settling velocity in the model. The model was developed to describe the drying process in the bed. A good correlation between computed and experimental data was achieved.     

Amino acid composition of protein termini are biased in different manners

An exhaustive statistical analysis of the amino acid sequencesat the carboxyl (C) and amino (N) termini of proteins and ofcoding nucleic acid sequences at the 5' side of the stop codonswas undertaken. At the N ends, Met and Ala residues are over-representedat the first (+1) position whereas at positions 2 and 5 Thris preferred. These peculiarities at N-termini are most probablyrelated to the mechanism of initiation of translation (for Met)and to the mechanisms governing the life-span of proteins viaregulation of their degradation (for Ala and Thr). We assumethat the C-terminal bias facilitates fixation of the C endson the protein globule by a preference for charged and Cys residues.The terminal biases, a novel feature of protein structure, haveto be taken into account when molecular evolution, three-dimensionalstructure, initiation and termination of translation, proteinfolding and life-span are concerned. In addition, the bias ofprotein termini composition is an important feature which shouldbe considered in protein engineering experiments.     

Dialkyldithiophosphate substituted on poly(vinylchloride): Synthesis and performance

Preparation of sodium salt of di(2-ethylhexyl)dithiophosphoric acid (DTPANa) by reaction of the corresponding DTPA with sodium hydride has been described. Nucleophilic substitution of chlorine on poly(vinylchloride) (PVC) by a di(2-ethylhexyl)dithiophosphate group resulting in modified polymer (MP) was characterized by the second order rate constant equal to 6.6 × 10^?5 M^?1 s^?1. Formation of homogeneous stable gelled phases composed of MP and DTPA, as well as MP, PVC, and DTPA, was demonstrated. The gelled material is capable of selective separation of metal ions under the conditions of extraction chromatography. © 1993 John Wiley & Sons, Inc.     

Vibration-induced auditory-cortex activation in a congenitally deaf adult

Considerable changes take place in the number of cerebral neurons, synapses and axons during development, mainly as a result of competition between different neural activities [1-4]. Studies using animals suggest that when input from one sensory modality is deprived early in development, the affected neural structures have the potential to mediate functions for the remaining modalities [5-8]. We now show that similar potential exists in the human auditory system: vibrotactile stimuli, applied on the palm and fingers of a congenitally deaf adult, activated his auditory cortices. The recorded magnetoencephalographic (MEG) signals also indicated that the auditory cortices were able to discriminate between the applied 180 Hz and 250 Hz vibration frequencies. Our findings suggest that human cortical areas, normally subserving hearing, may process vibrotactile information in the congenitally deaf.