Transformation of highly ordered large pore silica mesophases (Fm3m, Im3m and p6mm) in a ternary triblock copolymer-butanol-water system

Exceptional control of the phase behavior of highly ordered large pore mesostructured silica (with the choice of Fm3m, Im3m or p6mm symmetry) is achieved using a triblock copolymer (EO(106)PO(70)EO(106)) and butanol at low acid concentrations.     

Cysteine carboxyl O-methylation of human placental 23 kDa protein

C-Terminal carboxyl methylation of a human placental 23 kDa protein catalyzed by membrane-associated methyltransferase has been investigated. The 23 kDa protein substrate methylated was partially purified by DEAE-Sephacel, hydroxyapatite and Sephadex G-100 gel filtration chromatographies. The substrate protein was eluted on Sephadex G-100 gel filtration chromatography as a protein of about 29 kDa. In the absence of Mg2+, the methylation was stimulated by guanine nucleotides (GTP, GDP and GTPgammaS), but in the presence of Mg2+, only GTPgammaS stimulated the methylation which was similar to the effect on the G25K/rhoGDI complex. AFC, an inhibitor of C-terminal carboxyl methylation, inhibited the methylation of human placental 23 kDa protein. These results suggests that the substrate is a small G protein different from the G25K and is methylated on C-terminal isoprenylated cysteine residue. This was also confirmed by vapor phase analysis. The methylated substrate protein was redistributed to membrane after in vitro methylation, suggesting that the methylation of this protein is important for the redistribution of the 23 kDa small G protein for its putative role in intracellular signaling.     

A novel and efficient approach to highly substituted indolizines via 5-endo-trig iodocyclization

A new approach to indolizines has been developed using a 5-endo-trig iodocyclization of allylic esters followed by isomerization and dehydroiodination facilitated by triethylamine at rt. This mild procedure enabled us to synthesize a number of highly substituted indolizines in good yields.     

Three-dimensional effects on the linear adiabatic molecular wavefunctions in the H + H2 system

The adiabatic molecular wavefunctions in the H + H₂ system are obtained in one dimension by solving the double-well potential problem. In three dimensions, the corresponding linear adiabatic molecular wavefunctions are obtained. A comparison between these wavefunctions clearly suggests that the probability of reaction is smaller in three dimensions.     

Heat shock protein 27 interacts with vimentin and prevents insolubilization of vimentin subunits induced by cadmium

Vimentin is an intermediate filament that regulates cell attachment and subcellular organization. In this study, vimentin filaments were morphologically altered, and its soluble subunits were rapidly reduced via cadmium chloride treatment. Cadmium chloride stimulated three major mitogen-activated protein kinases (MAPKs): extracellular signal-regulated kinase (ERK), c-Jun N-terminal kinase (JNK), and p38, and led apoptotic pathway via caspase-9 and caspase-3 activations. In order to determine whether MAPKs were involved in this cadmium-induced soluble vimentin disappearance, we applied MAPK-specific inhibitors (PD98059, SP600125, SB203580). These inhibitors did not abolish the cadmium-induced soluble vimentin disappearance. Caspase and proteosome degradation pathway were also not involved in soluble vimentin disappearance. When we observed vimentin levels in soluble and insoluble fractions, soluble vimentin subunits shifted to an insoluble fraction. As we discovered that heat-shock protein 27 (HSP27) was colocalized and physically associated with vimentin in unstressed cells, the roles of HSP27 with regard to vimentin were assessed. HSP27-overexpressing cells prevented morphological alterations of the vimentin filaments, as well as reductions of soluble vimentin, in the cadmium-treated cells. Moreover, HSP27 antisense oligonucleotide augmented these cadmium-induced changes in vimentin. These findings indicate that HSP27 prevents disruption of the vimentin intermediate filament networks and soluble vimentin disappearance, by virtue of its physical interaction with vimentin in cadmium-treated SK-N-SH cells.     

Electrorheological characterization of polyaniline-coated poly(methyl methacrylate) suspensions

Surface-conductive particles consisting of a poly(methyl methacrylate) (PMMA) core and a polyaniline (PA)-coated shell were synthesized and adopted as suspended particles for electrorheological (ER) fluids. The PA-PMMA composite particles synthesized were monodisperse and spherical in shape. The PA-PMMA suspensions in silicone oil showed typical ER characteristics under an applied electric field. The PA-PMMA composite particles possess a higher dielectric constant and conductivity than the pure PA particle, within an acceptable conductivity range for ER fluids, but the PA-based ER fluid showed larger shear-stress enhancement than the PA-PMMA-based systems. This phenomena can be explained by the interfacial polarizability of PA-based ER fluids, which is the difference between the ER fluid's dielectric constant and loss factor - this polarizability was higher than that of PA-PMMA-based ER fluids, as shown by the dielectric spectrum of each fluid. The insulating PMMA core suppressed the interfacial polarization in ER fluids, resulting in reduced interaction among particles under an imposed electric field.     

Circular Dichroism Study of the Inclusion-Dissociation Behavior of Complexes between a Molecular Nanotube and Azobenzene Substituted Linear Polymers

We have investigated the inclusion properties of molecular nanotubes composed ofcrosslinked -cyclodextrin. Induced circular dichroism was used to probe theformation and dissociation of complexes between the nanotubes and azobenzenemodified linear polymers. The polymer was poly(ethylene glycol) (PEG), either withor without a hydrophobic alkyl chain.It was found that the inclusion complex betweenthe nanotubes and polymers formed at room temperature, and that the polymers dissociated from the nanotubes with increasing temperature. Further, the polymer with hydrophobic alkyl chain was bound inside the nanotube more strongly and dissociated more abruptly with increasing temperature than its hydrophilic counterpart as expected theoretically.     

Bystander CD4+ T cells: crossroads between innate and adaptive immunity

T cells are the central mediators of both humoral and cellular adaptive immune responses. Highly specific receptor-mediated clonal selection and expansion of T cells assure antigen-specific immunity. In addition, encounters with cognate antigens generate immunological memory, the capacity for long-term, antigen-specific immunity against previously encountered pathogens. However, T-cell receptor (TCR)-independent activation, termed “bystander activation”, has also been found. Bystander-activated T cells can respond rapidly and secrete effector cytokines even in the absence of antigen stimulation. Recent studies have rehighlighted the importance of antigen-independent bystander activation of CD4⁺ T cells in infection clearance and autoimmune pathogenesis, suggesting the existence of a distinct innate-like immunological function performed by conventional T cells. In this review, we discuss the inflammatory mediators that activate bystander CD4⁺ T cells and the potential physiological roles of these cells during infection, autoimmunity, and cancer.Subject terms: T cells, CD4-positive T cells     

The predictive accuracy for estimating infinite dilution activity coefficients by γ∞-based UNIFAC

The predictive accuracy for estimating infinite dilution activity coefficients by a modification of the UNIFAC method wherein the group interaction parameters were based on only data (referred to as -based UNIFAC) has been studied. Estimates and measured values were compared for six prototypical solutes in a series of homologous n-alkanes, l-alcohols and alkanenitrile solvents. Despite the fact that the interaction parameters were derived using only data, this approach still gave serious errors due to several inherent problems in the original UNIFAC model. Its performance is sometimes even poorer than that of the original UNIFAC method. For example for nitromethane in alcohols and p-dioxane in nitriles values predicted by the -based UNIFAC are essentially zero. The large errors for these systems are most likely due to inaccurate interaction parameters in the -based UNIFAC method.     

Determination of estrone and 17 beta-estradiol in human hair by gas chromatography-mass spectrometry

An efficient procedure is described for the determination of estrone and 17 beta-estradiol in hair by gas chromatography-mass spectrometry (GC-MS). The method involves alkyloxycarbonylation with isobutyl chloroformate (isoBCF) of phenolic hydroxy groups after alkaline digestion of hair samples. The resulting isobutyloxycarbonyl derivatives of estrone and 17 beta-estradiol are extracted with hexane and subjected to chlorodifluoroacetyl derivatization in order to protect the remaining alcoholic hydroxy groups. When GC-MS with selected ion monitoring (SIM) was used, the quantitative ions were at m/z 270 and 384 in the electron ionization mass spectra for estrone and 17 beta-estradiol, respectively. The detection limits for SIM of the steroids were 1 and 2 pg, respectively, and the SIM responses were linear with correlation coefficients varying from 0.991 to 0.994 in the concentration range 0.2-4.0 ng g-1 for the estrogens studied. The detection of estrone and 17 beta-estradiol in hair samples was possible in the concentration range of 0.24-1.30 ng g-1. The concentrations of the two estrogens detected were different in male and female hair samples.