The excess energy dissipation process of photoexcited S 1 trans-stilbene in solution has been studied with picosecond time-resolved Raman spectroscopy. The peak position of the 1570-cm -1 band (CdC stretch) is shown to be useful as an indicator of picosecond temperature changes; a picosecond time-resolved Raman spectrometer can be regarded as a "picosecond Raman thermometer". The cooling rates of S 1 trans-stilbene thus observed in 10 different solvents show a strong correlation with the thermal diffusivities of the bulk solvents. Based on this observation, a simple numerical model is proposed for the solute-solvent energy dissipation process in solution. The observed cooling kinetics are analyzed with this macroscopic model. It is concluded that the excess energy is first shared among the solute and the nearest solvent molecules in a few picoseconds or faster. The further heat conduction to outer-sphere solvent molecules determines the whole dissipation rate, which explains the observed correlation between the vibrational cooling rate and the thermal diffusivity of the solvent.

We show several pieces of Raman spectroscopic evidence that are indicative of local structure formation in imidazolium-based ionic liquids. Low-frequency Raman spectra of C n mimX, where C n mim stands for 1-alkyl(C n H 2 n+1 )-3-methylimidazolium cation and X represents the anion, exhibit broad bands assignable to collective modes of local structures. Spatial distributions of coherent anti-Stokes Raman scattering (CARS) signals from C n mim[PF 6] are consistent with local structures whose size increases with increasing n. Picosecond Raman spectra of S 1 trans-stilbene as a "picosecond Raman thermometer" show microscopic thermal inhomogeneity ascribable to local structure formation in C 2mimTf 2N and C 4mimTf 2N. We also describe two novel phenomena that we believe are relevant to extraordinary nanoenvironments generated by local structures in a magnetic ionic liquid C 4mim[FeCl 4].

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SEMSs were associated with a longer patency than PSs in patients with unresectable hilar biliary stricture. SEMSs were also more advantageous in reducing the number of reintervention sessions and the overall treatment cost.

BackgroundAccumulating evidence suggests that dysregulation of the immune system is involved in the pathophysiology of autism spectrum disorders (ASD). The aim of the study was to explore immunological markers in peripheral plasma samples from non-medicated subjects with high-functioning ASD.Methodology/Principal FindingsA multiplex assay for cytokines and chemokines was applied to plasma samples from male subjects with high-functioning ASD (n = 28) and matched controls (n = 28). Among a total of 48 analytes examined, the plasma concentrations of IL-1β, IL-1RA, IL-5, IL-8, IL-12(p70), IL-13, IL-17 and GRO-α were significantly higher in subjects with ASD compared with the corresponding values of matched controls after correction for multiple comparisons.Conclusion/SignificanceThe results suggest that abnormal immune responses as assessed by multiplex analysis of cytokines may serve as one of the biological trait markers for ASD.

BackgroundAs regulators of gene expression, microRNAs (miRNAs) play a key role in the transcriptional networks of the developing human brain. Circulating miRNAs in the serum and plasma are remarkably stable and are suggested to have promise as noninvasive biomarkers for neurological and neurodevelopmental disorders. We examined the serum expression profiles of neurologically relevant miRNAs in autism spectrum disorder (ASD), a complex neurodevelopmental disorder characterized by multiple deficits in communication, social interaction and behavior.MethodsTotal RNA, including miRNA, was extracted from the serum samples of 55 individuals with ASD and 55 age- and sex-matched control subjects, and the mature miRNAs were selectively converted into cDNA. Initially, the expression of 125 mature miRNAs was compared between pooled control and ASD samples. The differential expression of 14 miRNAs was further validated by SYBR Green quantitative PCR of individual samples. Receiver-operating characteristic (ROC) analysis was used to evaluate the sensitivity and specificity of miRNAs. The target genes and pathways of miRNAs were predicted using DIANA mirPath software.ResultsThirteen miRNAs were differentially expressed in ASD individuals compared to the controls. MiR-151a-3p, miR-181b-5p, miR-320a, miR-328, miR-433, miR-489, miR-572, and miR-663a were downregulated, while miR-101-3p, miR-106b-5p, miR-130a-3p, miR-195-5p, and miR-19b-3p were upregulated. Five miRNAs showed good predictive power for distinguishing individuals with ASD. The target genes of these miRNAs were enriched in several crucial neurological pathways.ConclusionsThis is the first study of serum miRNAs in ASD individuals. The results suggest that a set of serum miRNAs might serve as a possible noninvasive biomarker for ASD.

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Six kinds of poly(silyleneethynylenephenyleneethynylene)s [−Si(R)H−C⋮C−C6H4−C⋮C−], wherein the phenylene group was the meta-, para- or ortho-form and R represents a phenyl, methyl, or hydrogen atom, were prepared, and the properties of the resulting polymers were investigated. The polymers, especially poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] (R = Ph), which were thermosetting, soluble in solvent, fusible, and moldable, showed high heat-resistant and burning-resistant properties. A cross-linking reaction mechanism concerning the Si−H and C⋮C bonds was proposed, and the correlation between the molecular structures and the thermal properties was discussed. Fiber-reinforced polymers prepared using glass, carbon, or SiC fibers showed sufficient mechanical strength even at 400 °C under air. A black, hard, and glassy material (C−SiC) was obtained when poly[(phenylsilylene)ethynylene-1,3-phenyleneethynylene] was heated above 1000 °C under argon.