Equivalence of Ensembles,Condensation and Glassy Dynamics in the Bose–Hubbard Hamiltonian

Journal of Statistical Physics - We study mathematically the equilibrium properties of the Bose–Hubbard Hamiltonian in the limit of a vanishing hopping amplitude. This system conserves the...     

In Situ Generated Gold Nanoparticles on Active Carbon as Reusable Highly Efficient Catalysts for a C −C Stille Coupling

Gold nanoparticle catalysts are important in many industrial production processes. Nevertheless, for traditional C ?C cross‐coupling reactions they have been rarely used and Pd catalysts usually give a superior performance. Herein we report that in situ formed gold metal nanoparticles are highly active catalysts for the cross coupling of allylstannanes and activated alkylbromides to form C ?C bonds. Turnover numbers up to 29 000 could be achieved in the presence of active carbon as solid support, which allowed for convenient catalyst recovery and reuse. The present study is a rare case where a gold metal catalyst is superior to Pd catalysts in a cross‐coupling reaction of an organic halide and an organometallic reagent.     

Development and validation of a reversed‐phase HPLC method for CYP1A2 phenotyping by use of a caffeine metabolite ratio in saliva

CYP1A2 is important for metabolizing various clinically used drugs. Phenotyping of CYP1A2 may prove helpful for drug individualization therapy. Several HPLC methods have been developed for quantification of caffeine metabolites in plasma and urine. Aim of the present study was to develop a valid and simple HPLC method for evaluating CYP1A2 activity during exposure in xenobiotics by the use of human saliva. Caffeine and paraxanthine were isolated from saliva by liquid‐liquid extraction (chlorophorm/isopropanol 85/15v/v). Extracts were analyzed by reversed‐phase HPLC on a C₁₈ column with mobile phase 0.1% acetic acid/methanol/acetonitrile (80/20/2 v/v) and detected at 273nm. Caffeine and paraxanthine elution times were <13min with no interferences from impurities or caffeine metabolites. Detector response was linear (0.10–8.00µg/ml, R²>0.99), recovery was >93% and bias <4.47%. Intra‐ and inter‐day precision was <5.14% (n=6). The limit of quantitation was 0.10µg/ml and the limit of detection was 0.018±0.002µg/mL for paraxanthine and 0.032±0.002µg/ml for caffeine. Paraxanthine/caffeine ratio of 34 healthy volunteers was significantly higher in smokers (p<0.001). Saliva paraxanthine/caffeine ratios and urine metabolite ratios were highly correlated (r=0.85, p<0.001). The method can be used for the monitoring of CYP1A2 activity in clinical practice and in studies relevant to exposure to environmental and pharmacological xenobiotics. Copyright © 2015 John Wiley & Sons, Ltd.     

Visible-Light Augmented Lithium Storage Capacity in a Ruthenium(II) Photosensitizer Conjugated with a Dione-Catechol Redox Couple

Controlling redox activity of judiciously appended redox units on a photo-sensitive molecular core is an effective strategy for visible light energy harvesting and storage. The first example of a photosensitizer - electron donor coordination compound in which the photoinduced electron transfer step is used for light to electrical energy conversion and storage is reported. A photo-responsive Ru-diimine module conjugated with redox-active catechol groups in [Ru(II)(phenanthroline-5,6-diolate)₃]⁴⁻ photosensitizer can mediate photoinduced catechol to dione oxidation in the presence of a sacrificial electron acceptor or at the surface of an electrode. Under potentiostatic condition, visible light triggered current density enhancement confirmed the light harvesting ability of this photosensitizer. Upon implementation in galvanostatic charge-discharge of a Li battery configuration, the storage capacity was found to be increased by 100 %, under 470 nm illumination with output power of 4.0 mW/cm⁻². This proof-of-concept molecular system marks an important milestone towards a new generation of molecular photo-rechargeable materials.     

A Catalyst and Solvent Free Route for the Synthesis of N-Substituted Pyrrolidones from Levulinic Acid

An efficient, metal-free, catalyst-free and solvent-free methodology for the reductive amination of levulinic acid with different anilines has been developed using HBpin as the reducing reagent. This protocol offers an excellent method to avoid solvents and added catalysts on the synthesis of different kinds of N-substituted pyrrolidones under metal free conditions. It is also the first report for the synthesis of different pyrrolidones by solvent-free as well as catalyst-free methods. The proposed mechanism for the formation of pyrrolidone has been supported by DFT calculations and control experiments.     

Multiplex Detection of Enzymatic Activity with Responsive Lanthanide‐Based Luminescent Probes

Multiplex analyte detection in complex dynamic systems is desirable for the investigation of cellular communication networks as well as in medical diagnostics. A family of lanthanide‐based responsive luminescent probes for multiplex detection is reported. The high modularity of the probe design enabled the rapid assembly of both green and red emitters for a large variety of analytes by the simple exchange of the lanthanide or an analyte‐cleavable caging group, respectively. The real‐time three‐color detection of up to three analytes was demonstrated, thus setting the stage for the non‐invasive investigation of interconnected biological processes.     

Molden 2.0: quantum chemistry meets proteins

Since the first distribution of Molden in 1995 and the publication of the first article about this software in 2000 work on Molden has continued relentlessly. A few of the many improved or fully novel features such as improved and broadened support for quantum chemistry calculations, preparation of ligands for use in drug design related softwares, and working with proteins for the purpose of ligand docking.     

Biosynthesis,characterization, and antimicrobial effect of silver nanoparticles obtained using <Emphasis Type="Italic">Lavandula</Emphasis> × <Emphasis Type="Italic">intermedia</Emphasis>

The use..... of aqueous leaf extract of Lavandula × intermedia for biosynthesis of silver nanoparticles (AgNPs) is presented. The plant extract was obtained by boiling dried leaves and using the obtained filtrate for the synthesis of AgNPs. The study was conducted to investigate an ecofriendly approach to metal nanoparticle synthesis and to evaluate the antimicrobial potential of both the aqueous plant extract and resulting silver nanoparticles against different microbes using the disc diffusion method. The synthesis of silver nanoparticles was monitored using ultraviolet–visible (UV–v is) spectroscopy, which showed a localized surface plasmon resonance band at 411 nm and a shift of the band to higher wavenumber of 422 nm after 90 min of reaction. Powder X-ray diffraction analysis and transmission electron microscopy of the obtained AgNPs revealed their crystalline nature, with average size of 12.6 nm. Presence of elemental silver was further confirmed by energy-dispersive X-ray spectroscopy. Fourier-transform infrared spectroscopy confirmed presence of phytochemicals from Lavandula × intermedia leaf extract on the AgNPs. The AgNPs showed good antimicrobial activity with inhibition zone ranging from 10 to 23 mm; the largest inhibition zone (23 mm) occurred against Escherichia coli. Generally, the AgNPs displayed more antimicrobial activity against all investigated pathogens compared with Lavandula × intermedia leaf extract, and were also more active than streptomycin against Klebsiella oxytoca and E. coli at the same concentration. The silver nanoparticles showed prominent antimicrobial activity with a lowest minimum inhibitory concentration (MIC) value of 15 μg/mL against E. coli, K. oxytoca, and Candida albicans.     

Mechanically-induced dimensional extensibility of fibers towards tough fiber networks

The beneficial effect of materials with high aspect ratio as composite reinforcement has prompted continuous interest towards cellulosic fibers. Besides providing stiffness, fibers can potentially contribute to composite extensibility. While mechanical treatments are typically used to adjust the physical and surface properties of fibers, less is known about ensuing effects on their extensibility and that of associated networks. Fiber network dimensional extensibility of 16% was achieved by processing the precursor aqueous fiber dispersions following a simple mechanical treatment with a judicious combination of low (PFI refining) and high concentrations and temperatures (Wing defibrator). Consequently, deformation of fibers and increased inter-fiber bonding resulted in a three-fold increase in strength to rupture of the fiber network leading to the structures with unprecedented toughness.     

Reactivity of Aliphatic and Phenolic Hydroxyl Groups in Kraft Lignin towards 4,4′ MDI

Several efforts have been dedicated to the development of lignin-based polyurethanes (PU) in recent years. The low and heterogeneous reactivity of lignin hydroxyl groups towards diisocyanates, arising from their highly complex chemical structure, limits the application of this biopolymer in PU synthesis. Besides the well-known differences in the reactivity of aliphatic and aromatic hydroxyl groups, experimental work in which the reactivity of both types of hydroxyl, especially the aromatic ones present in syringyl (S-unit), guaiacyl (G-unit), and p-hydroxyphenyl (H-unit) building units are considered and compared, is still lacking in the literature. In this work, the hydroxyl reactivity of two kraft lignin grades towards 4,4′-diphenylmethane diisocyanate (MDI) was investigated. ³¹P NMR allowed the monitoring of the reactivity of each hydroxyl group in the lignin structure. FTIR spectra revealed the evolution of peaks related to hydroxyl consumption and urethane formation. These results might support new PU developments, including the use of unmodified lignin and the synthesis of MDI-functionalized biopolymers or prepolymers.