Irreversible temperature‐responsive formation of high‐strength hydrogel from an enantiomeric mixture of starburst triblock copolymers consisting of 8‐arm PEG and PLLA or PDLA

Starburst triblock copolymers consisting of 8‐arm poly(ethylene glycol) (8‐arm PEG) and biodegradable poly(L ‐lactide) (PLLA) or its enantiomer poly(D ‐lactide) (PDLA), 8‐arm PEG‐b‐PLLA‐b‐PEG ( Stri‐L ), and 8‐arm PEG‐b‐PDLA‐b‐PEG ( Stri‐D ) were synthesized. An aqueous solution of a 1:1 mixture ( Stri‐Mix ) of Stri‐L and Stri‐D assumed a sol state at room temperature, but instantaneously formed a physically crosslinked hydrogel in response to increasing temperature. The resulting hydrogel exhibited a high‐storage modulus (9.8 kPa) at 37 °C. Interestingly, once formed at the transition temperature, the hydrogel was stable even after cooling below the transition temperature. The hydrogel formation process was irreversible because of the formation of stable stereocomplexes. In aqueous solution, gradual hydrolytic erosion was observed because of degradation of the hydrogel. The combination of rapid temperature‐triggered irreversible hydrogel formation, high‐mechanical strength, and degradation behavior render this polymer mixture system suitable for use in injectable biomedical materials, for example, as a drug delivery system for bioactive reagents or a biodegradable scaffold for tissue engineering. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6317–6332, 2008     

Complexity of Body Movements during Sleep in Children with Autism Spectrum Disorder

Recently, measuring the complexity of body movements during sleep has been proven as an objective biomarker of various psychiatric disorders. Although sleep problems are common in children with autism spectrum disorder (ASD) and might exacerbate ASD symptoms, their objectivity as a biomarker remains to be established. Therefore, details of body movement complexity during sleep as estimated by actigraphy were investigated in typically developing (TD) children and in children with ASD. Several complexity analyses were applied to raw and thresholded data of actigraphy from 17 TD children and 17 children with ASD. Determinism, irregularity and unpredictability, and long-range temporal correlation were examined respectively using the false nearest neighbor (FNN) algorithm, information-theoretic analyses, and detrended fluctuation analysis (DFA). Although the FNN algorithm did not reveal determinism in body movements, surrogate analyses identified the influence of nonlinear processes on the irregularity and long-range temporal correlation of body movements. Additionally, the irregularity and unpredictability of body movements measured by expanded sample entropy were significantly lower in ASD than in TD children up to two hours after sleep onset and at approximately six hours after sleep onset. This difference was found especially for the high-irregularity period. Through this study, we characterized details of the complexity of body movements during sleep and demonstrated the group difference of body movement complexity across TD children and children with ASD. Complexity analyses of body movements during sleep have provided valuable insights into sleep profiles. Body movement complexity might be useful as a biomarker for ASD.     

Dependency of ligand free energy landscapes on charge parameters and solvent models

We performed replica-exchange molecular dynamics (REMD) simulations of six ligands to examine the dependency of their free energy landscapes on charge parameters and solvent models. Six different charge parameter sets for each ligand were first generated by RESP and AM1-BCC methods using three different conformations independently. RESP charges showed some conformational dependency. On the other hand, AM1-BCC charges did not show conformational dependency and well reproduced the overall trend of RESP charges. The free energy landscapes obtained from the REMD simulations of ligands in vacuum, Generalized-Born (GB), and TIP3P solutions were then analyzed. We found that even small charge differences can produce qualitatively different landscapes in vacuum condition, but the differences tend to be much smaller under GB and TIP3P conditions. The simulations in the GB model well reproduced the landscapes in the TIP3P model using only a fraction of the computational cost. The protein-bound ligand conformations were rarely the global minimum states, but similar conformations were found to exist in aqueous solution without proteins in regions close to the global minimum, local minimum or intermediate states.     

Experimental observation of rotational Doppler broadening in a molecular system

The first experimental evidence of rotational Doppler broadening in photoelectron spectra, reported here, show good agreement with recently described theoretical predictions. The dependence of the broadening on temperature and photoelectron kinetic energy is quantitatively predicted by the theory. The experiments verify that the rotational contributions to the linewidth are comparable to those from translational Doppler broadening and must be considered in the analysis of high-resolution photoelectron spectra. A classical model accounting for this newly observed effect is presented.     

Procyanidins are potent inhibitors of LOX-1: a new player in the French Paradox

Lectin-like oxidized LDL receptor-1 (LOX-1) is an endothelial receptor for oxidized LDL (oxLDL) and plays multiple roles in the development of cardiovascular diseases. We screened more than 400 foodstuff extracts for identifying materials that inhibit oxLDL binding to LOX-1. Results showed that 52 extracts inhibited LOX-1 by more than 70% in cell-free assays. Subsequent cell-based assays revealed that a variety of foodstuffs known to be rich in procyanidins such as grape seed extracts and apple polyphenols, potently inhibited oxLDL uptake in Chinese hamster ovary (CHO) cells expressing LOX-1. Indeed, purified procyanidins significantly inhibited oxLDL binding to LOX-1 while other ingredients of apple polyphenols did not. Moreover, chronic administration of oligomeric procyanidins suppressed lipid accumulation in vascular wall in hypertensive rats fed with high fat diet. These results suggest that procyanidins are LOX-1 inhibitors and LOX-1 inhibition might be a possible underlying mechanism of the well-known vascular protective effects of red wine, the French Paradox.     

Atmospheric pressure chemical vapour deposition of selenium and tellurium films by UV laser photolysis of diethyl selenium and diethyl tellurium

Excimer laser‐induced photolysis of gaseous diethyl selenium and diethyl tellurium (C₂H₅)₂M (M = Se, Te) is controlled by cleavage of both M? C bonds, it yields C₁–C₄ hydrocarbons (ethene as major product) and results in chemical vapour deposition of selenium films and nanosized tellurium powder. The selenium and tellurium properties were characterized by X‐ray photoelectron spectroscopy and Scanning electron Microscopy techniques. Copyright © 2001 John Wiley & Sons, Ltd.     

UV laser deposition of nanostructured Si/C/O/N/H from disilazane precursors and evolution to silicon oxycarbonitride

Megawatt ArF laser photolysis of gaseous methyldisilazanes [(CH₃)_nH_3?nSi]₂NH (n = 2, 3) in excess of Ar yields hydrocarbons (major volatile products), methylsilanes (minor volatile products) and allows chemical vapour deposition of solid amorphous Si/C/O/N/H powder containing Si? X (X? C, H, O, N) bonds. The incorporation of O is due to a high reactivity of the primarily formed products towards air moisture. The resulting solid materials possess nanometer‐sized texture and high specific area, contain Si‐centered radicals and anneal under argon to silicon oxycarbonitride, whose structure is described as a network of O‐ and N‐interconnected Si and C atoms. Copyright © 2006 John Wiley & Sons, Ltd.     

Effective photochemical synthesis of an air-stable anthracene-based organic semiconductor from its diketone precursor

A diketone precursor of air-stable bis-2-thienyl-2,6-anthracene was prepared and quantitatively converted to the target acene by photoirradiation of the n-π^∗ absorption both in solution and as a film, in air.