Improving functional properties of ZnO nanostructures by transition-metal doping: role of aspect ratio

Localized surface plasmon resonance (LSPR) of gold nanoparticles (AuNPs) has been used for biosensing and chemical sensing applications because the LSPR peak wavelength depends on the dispersion state and local refractive index of the surrounding medium. In this study, AuNP-loaded silica gels were prepared as sensing chips with high transparency and solution holding capability. The silica gels were prepared at various sintering temperatures from 500 to 900 °C, and the AuNPs precipitated in the gels by using a subsequent thermal reduction process. At sintering temperatures of 700, 800, and 900 °C, transparent and crack-free AuNP-loaded silica gels were obtained. Transmission electron microscopy observation revealed the AuNP size to be approximately 20 nm, and they were highly dispersed in all the silica gel samples. However, the sintering temperature of the silica gels strongly affected the LSPR property of the AuNPs and the porous property of the silica gel. The samples sintered at higher temperature exhibited a lower LSPR sensing ability against the refractive index of immersing solvents. The low sensing ability was considered as a result of a decrease in the contact area between the AuNPs and immersing solvent caused by an increase in the silica gel density with sintering temperature.     

From toluene to triquinanes: formal total syntheses of the sesquiterpenoid natural products (−)-hypnophilin and (−)-coriolin

The enantiomerically pure cis-1,2-dihydrocatechol 6, which is readily obtained via the whole-cell biotransformation of toluene, has been converted into the linear triquinane 3 using a reaction sequence involving Diels–Alder cycloaddition and oxa-di-π-methane rearrangement reactions as key steps. Compound 3 is an advanced intermediate associated with several previously reported total syntheses of the sesquiterpenoid natural products (?)-hypnophilin (1) and (?)-coriolin (2). Related chemistry has provided the tetracyclic compound 5, another established precursor to (?)-coriolin (2).     

New Surfactants with Sugar-Based Polar Heads Derived from Bile Acids: The N-Ursocholyl-d-glucosamine and N-Dehydrocholyl-d-glucosamine

Abstract

A simple route to new surfactants with a sugar-based polar head group coupled to a steroidal hydrophobic group is described. These compounds, N-ursocholyl-d-glucosamine and N-dehydrocholyl-d-glucosamine, were obtained in a three stage process by acylation of d-glucosamine with N-acylthiazolidine-2-thiones derived from ursocholic and dehydrocholic acids.     

Halocyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">de</Emphasis>]isoquinoline-1,3(2<Emphasis Type="Italic">H</Emphasis>)-dione

Cyclization of 2-(2-{4-[allylamino(thioxo)methyl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione by the action of iodine, bromine, or sulfuryl chloride gave 2-(2-{4-[4,5-dihydro-5-(halomethyl)-thiazol-2-yl]piperazin-1-yl}ethyl)-1H-benzo[de]isoquinoline-1,3(2H)-dione hydrohalides which were converted into 2-{2-[4-(5-methylthiazol-2-yl)piperazin-1-yl]ethyl}-1H-benzo[de]isoquinoline-1,3(2H)-dione.     

Clusterin protects H9c2 cardiomyocytes from oxidative stress-induced apoptosis via Akt/GSK-3β signaling pathway

Clusterin is a secretory glycoprotein, which is highly up-regulated in a variety of normal and injury tissues undergoing apoptosis including infarct region of the myocardium. Here, we report that clusterin protects H9c2 cardiomyocytes from H2O2-induced apoptosis by triggering the activation of Akt and GSK-3β. Treatment with H2O2 induces apoptosis of H9c2 cells by promoting caspase cleavage and cytochrome c release from mitochondria. However, co-treatment with clusterin reverses the induction of apoptotic signaling by H2O2, thereby recovers cell viability. The protective effect of clusterin on H2O2-induced apoptosis is impaired by PI3K inhibitor LY294002, which effectively suppresses clusterin-induced activation of Akt and GSK-3β. In addition, the protective effect of clusterin is independent on its receptor megalin, because inhibition of megalin has no effect on clusterin-mediated Akt/GSK-3β phosphoylation and H9c2 cell viability. Collectively, these results suggest that clusterin has a role protecting cardiomyocytes from oxidative stress and the Akt/GSK-3β signaling mediates anti-apoptotic effect of clusterin.     

Cellulase Production by <Emphasis Type="Italic">Streptomyces viridobrunneus</Emphasis> SCPE-09 Using Lignocellulosic Biomass as Inducer Substrate

An actinomycete strain, isolated from a soil sample under a sugar cane plantation in Brazil and identified as Streptomyces viridobrunneus SCPE-09, was selected as a promising cellulolytic strain, and tested for its ability to produce cellulases from agro-industrial residues. Sugar cane bagasse or wheat bran was tested as carbon source, and corn steep liquor tested as nitrogen source. Different concentrations of carbon and nitrogen were tested using factorial design to identify optimal cellulose production. The results showed that media containing wheat bran 2.0% (w/v) and corn steep liquid 0.19% (w/v) lead to the highest production, 2.0 U mL⁻¹ of CMCase, obtained on the fifth day of fermentation. The pH and temperature profile showed optimal activity at pH 4.9 and 50°C. As for thermostability, endoglucanases were most tolerant at 50°C, retaining more than 80% of maximal activity even after 2 h of incubation. Zymogram analyses using supernatant from growth under optimized conditions revealed the presence of two CMCase bands with apparent molecular masses of 37 and 119 kDa. The combination of pH tolerance and CMCase production from agro-industrial residues by S. viridobrunneus SCPE-09 offers promise for future bioethanol biotechnologies.     

Integrable Mott insulators driven by a finite electric field

We develop a method for extracting the steady nonequilibrium current from studies of driven isolated systems, applying it to the model of a one-dimensional Mott insulator at high temperatures. While in the nonintegrable model the nonequilibrium conditions can be accounted for by internal heating, the integrability leads to a strongly nonlinear dc response with a vanishingly small dc conductivity in the linear-response regime. The finding is consistent with equilibrium results for the dc limit of the optical conductivity determined in the presence of a weak and decreasing perturbation.     

Multiscale-tailored bioelectrode surfaces for optimized catalytic conversion efficiency

We describe the elaboration of a multiscale-tailored bioelectrocatalytic system. The combination of two enzymes, D-sorbitol dehydrogenase and diaphorase, is studied with respect to the oxidation of D-sorbitol as a model system. The biomolecules are immobilized in an electrodeposited paint (EDP) layer. Reproducible and efficient catalysis of D-sorbitol oxidation is recorded when this system is immobilized on a gold electrode modified by a self-assembled monolayer of 4-carboxy-(2,5,7-trinitro-9-fluorenylidene)malonitrile used as a mediator. The insertion of mediator-modified gold nanoparticles into the EDP film increases significantly the active surface area for the catalytic reaction, which can be further enhanced when the whole system is immobilized in macroporous gold electrodes. This multiscale architecture finally leads to a catalytic device with optimized efficiency for potential use in biosensors, bioelectrosynthesis, and biofuel cells.     

Thermodynamic analysis of the interaction of partially hydrophobic cationic polyelectrolytes with sodium halide salts in water

Isothermal titration calorimetry was used to determine the temperature and concentration dependence of the enthalpy of mixing of 3,3- and 6,6-ionene fluorides, bromides, and iodides with low molecular weight salts (NaF, NaCl, NaBr, and NaI) in water. The magnitudes of the enthalpies, measured in the temperature range from 273 to 318 K, depended on the number of methylene groups on the ionene polyion (hydrophobicity), and on the anion of the added salt (ion-specificity). All enthalpies of mixing of 3,3- and 6,6-ionene fluorides with low molecular weight salts (NaCl, NaBr, and NaI) were negative, which is in contrast to the predictions of standard theories of polyelectrolyte solutions. This fact was interpreted in the light of the ion–water short-range interactions that are not accounted for in those theories. In contrast, the enthalpies of mixing of 3,3- and 6,6-ionene bromides and iodides with NaF were positive, being in accord with theory. Using the calorimetric data, we performed a model thermodynamic analysis of the polyelectrolyte–salt mixing process to obtain changes in the apparent standard Gibbs free energy, enthalpy, entropy, and heat capacity relative to the pure ionene fluorides in water. The results prove that halide ions replace fluoride counterions with a strength increasing in the order chloride < bromide < iodide. The process is enthalpy governed, accompanied by a positive change in the heat capacity.     

Synthesis and structure of anhydrous complexes of magnesium(II) with β-ketoesters of higher alcohols

Methods for the synthesis of anhydrous complexes of magnesium(II) with β-ketoesters of higher alcohols have been developed. A number of novel magnesium complexes of the general formula MgL₂ (where HL is hexyl-, dodecyl-, tert-butyl-, cyclohexyl-, bornyl- and 1-adamantyl acetoacetate), which are readily soluble in organic media, have been synthesized. It has been found by X-ray crystallography that bis(1-adamantyl acetoacetato)magnesium(II) has a trimeric structure. The structure of the complexes in solutions is discussed.