Intrinsic chirality of multipartite graphs

We classify which complete multipartite graphs are intrinsically chiral.     

Distance rendering and perception of nearby virtual sound sources with a near-field filter model

Headphone rendering of nearby virtual sound sources represents to date an open issue in 3-D audio, due to a number of technical challenges and temporal requirements involved in the measurement of individual Head-Related Transfer Functions (HRTFs). In order to tackle this problem, we propose a filter model of near-field effects based on the Distance Variation Function (Kan et al., 2009). Thanks to its simple structure and low order, the model can be applied to any far-field virtual auditory display to yield a realistic and computationally efficient near-field compensation of spectral and binaural effects. The model is subjectively evaluated in two psychophysical experiments where the relative distance of pairs of virtually rendered sound sources is judged. Results show that even though sound intensity overshadows subtler near-field effects when it is available as a cue for distance, the model is capable of offering relative distance information of near lateral virtual sources when intensity cues are removed. Furthermore, performances of the model in relative distance rendering are compared to those of alternative near-field rendering methods available in the literature.     

Biodegradable PLGA-b-PEG polymeric nanoparticles: synthesis, properties, and nanomedical applications as drug delivery system

Liquid sodium containing titanium nanoparticles (LSnanop) of 10-nm diameter was prepared by dispersing titanium nanoparticles (2 at.% Ti) into liquid sodium with the addition of stirring and ultrasonic sound wave. The titanium nanoparticles themselves were prepared by the vapor deposition method. This new liquid metal, LSnanop, shows a remarkable stability due to the Brownian motion of nanoparticles in liquid sodium medium. In addition, the difference of measured heat of reaction to water between this LSnanop and liquid sodium indicates the existence of cohesive energy between the liquid sodium medium and dispersed titanium nanoparticles. The origin of the cohesive energy, which serves to stabilize this new liquid metal, was explained by the model of screened nanoparticles in liquid sodium. In this model, negatively charged nanoparticles with transferred electrons from liquid sodium are surrounded by the positively charged screening shell, which may inhibit the gathering of nanoparticles by the ??Coulombic repulsion coating.?? The atomic volume of LSnanop shows the shrinkage from the linear law, which also suggests the existence of cohesive energy. The viscosity of LSnanop is almost the same as that of liquid sodium. This behavior was explained by the Einstein equation. The surface tension of LSnanop is 17?% larger than that of liquid sodium. The cohesive energy and the negative adsorption may be responsible to this increase. Titanium nanoparticles in liquid sodium seem to be free from the Coulomb fission. This new liquid metal containing nanoparticles suggests the possibility to prepare various stable suspensions with new properties.     

Quantitative fingerprinting by headspace—Two-dimensional comprehensive gas chromatography–mass spectrometry of solid matrices: Some challenging aspects of the exhaustive assessment of food volatiles

The study proposes an investigation strategy that simultaneously provides detailed profiling and quantitative fingerprinting of food volatiles, through a “comprehensive” analytical platform that includes sample preparation by Headspace Solid Phase Microextraction (HS-SPME), separation by two-dimensional comprehensive gas chromatography coupled with mass spectrometry detection (GC × GC–MS) and data processing using advanced fingerprinting approaches.     

Disilicon Complexes with Two Hexacoordinate Si Atoms: Paddlewheel‐Shaped Isomers with (ClN4)Si?Si(S4Cl) and (ClN2S2)Si?Si(S2N2Cl) Skeletons

The reaction of 1‐methyl‐3‐trimethylsilylimidazoline‐2‐thione with hexachlorodisilane proceeds toward substitution of four of the disilane Cl atoms during the formation of disilicon complexes with two neighboring hexacoordinate Si atoms. The N,S‐bidentate methimazolide moieties adopt a buttressing role, thus forming paddlewheel‐shaped complexes of the type ClSi(μ‐mt)₄SiCl (mt=methimazolyl). Most interestingly, three isomers (i.e., with (ClN₄)Si? Si(S₄Cl), (ClN₃S)Si? Si(S₃NCl), and (ClN₂S₂)Si? Si(S₂N₂Cl) skeletons as so‐called (4,0), (3,1), and cis‐(2,2) paddlewheels) were detected in solution by using ²⁹Si NMR spectroscopic analysis. Two of these isomers could be isolated as crystalline solids, thus allowing their molecular structures to be analyzed by using X‐ray diffraction studies. In accord with time‐dependent NMR spectroscopy, computational analyses proved the cis‐(2,2) isomer with a (ClN₂S₂)Si? Si(S₂N₂Cl) skeleton to be the most stable. The compounds presented herein are the first examples of crystallographically evidenced disilicon complexes with two Si? Si‐bonded octahedrally coordinated Si atoms and representatives of the still scarcely explored class of Si coordination compounds with sulfur donor atoms.     

Synthesis of carboxyl cellulose sulfates with regioselective sulfation and regiospecific oxidation using cellulose trifluoroacetate as intermediates

Synthesis of cellulose sulfates (CSs) and carboxyl cellulose sulfates (COCSs) with regioselectively or regiospecifically distributed functional groups within anhydroglucose units was reported. CS with regioselectively distributed sulfate groups at 2,3-O- or 2,6-O-position were homogeneously synthesized and cellulose trifluoroacetate (CTFA) was used as intermediates. The trifluoroacetyl groups were detected primarily at 6-O-position and their distributions could be altered by changing the amount of trifluoroacetyl anhydride (TFAA). Various sulfating agents were used for further homogeneous sulfation of CTFA. The total degree of sulfation (DS_S) and the distribution of sulfate groups within the repeating units were affected by the amount of TFAA, the type and amount of sulfating agents. Subsequent homogenous 4-acetamide-TEMPO or TEMPO-mediated oxidation of CS led to COCS with carboxyl groups regiospecifically distributed at C6 position, which may be interesting structural mimics for natural occurring heparin.     

Simultaneous high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS-MS) analysis of cyanide and thiocyanate from swine plasma

An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na¹³C¹⁵N and NaS¹³C¹⁵N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted 1-cyano[f]benzoisoindole, while thiocyanate was chemically modified with monobromobimane to form an SCN-bimane product. The method produced dynamic ranges of 0.1–50 and 0.2–50 μM for cyanide and thiocyanate, respectively, with limits of detection of 10 nM for cyanide and 50 nM for thiocyanate. For quality control standards, the precision, as measured by percent relative standard deviation, was below 8 %, and the accuracy was within ±10 % of the nominal concentration. Following validation, the analytical procedure successfully detected cyanide and thiocyanate simultaneously from the plasma of cyanide-exposed swine.     

Controlling the early stages of pentacene growth by supersonic molecular beam deposition

The key role of the pentacene kinetic energy (Ek) in the early stages of growth on SiOx/Si is demonstrated: islands with smooth borders and increased coalescence differ remarkably from fractal-like thermal growth. Increasing Ek to 6.4 eV, the morphology evolves towards higher density of smaller islands. At higher coverage, coalescence grows with Ek up to a much more uniform, less defected monolayer. The growth, interpreted by the diffusion mediated model, shows the critical nucleus changing from 3 to 2 pentacene for Ek>5-6 eV. Optimal conditions to produce single crystalline films are envisaged.     

Network formation of tissue cells via preferential attraction to elongated structures

Vascular and nonvascular cells often form an interconnected network in vitro, similar to the early vascular bed of warm-blooded embryos. Our time-lapse recordings show that the network forms by extending sprouts, i.e., multicellular linear segments. To explain the emergence of such structures, we propose a simple model of preferential attraction to stretched cells. Numerical simulations reveal that the model evolves into a quasistationary pattern containing linear segments, which interconnect above the critical volume fraction of 0.2. In the quasistationary state, the generation of new branches offset the coarsening driven by surface tension. In agreement with empirical data, the characteristic size of the resulting polygonal pattern is density-independent within a wide range of volume fractions.     

Urea‐Induced Acid Amplification: A New Approach for Metal‐Free Insertion Chemistry

The enhanced catalytic activity of difluoroboronate ureas proved to be essential as an acidity amplifier to promote metal‐free O?H and S?H insertion reactions of α‐aryldiazoacetates in high yield. This methodology was found to be generally applicable to a broad substrate scope and presents a conceptually new approach for organocatalytic diazo insertion reactions. Mechanistic investigations suggest that the reaction pathway involves a urea‐induced protonation of the α‐aryldiazoester.