Selective Reduction of CO2 with Silanes over Platinum Nanoparticles Immobilised on a Polymeric Monolithic Support under Ambient Conditions

Here, we demonstrate the use of Pt⁰ nanoparticles immobilised on a polymeric monolithic support as a ligand‐free heterogeneous catalytic system for the reduction of ¹³CO₂ at room temperature and atmospheric pressure. The described system effectively reduces ¹³CO₂ with dihydrosilanes as the hydrogen source to yield a mixture of silylformates, silylacetals and methoxysilanes, which upon further hydrolysis with D₂O, produces their respective C1‐type products, that is H¹³COOD, ¹³CH₂(OD)₂ and ¹³CH₃OD. If a monohydrosilane was used as the hydrogen source, a selective reduction of ¹³CO₂ to a product mixture of only silylformates was observed. Addition of diethylamine to this reaction mixture results in the formation of H¹³COOH and Et₂N¹³CHO. This robust catalytic system is not only maintenance‐free and simple to handle, as compared with organometallic and organocatalyst systems, but also shows 3‐ to 11‐fold better catalytic activity and exhibits higher turnover numbers (TONs) up to 21 900 (activity=6.22 kg g_Pt^?1 bar^?1).     

Electron beam triggered, free radical polymerization-derived monolithic capillary columns for high-performance liquid chromatography

Monolithic capillary columns were prepared via electron beam triggered free radical polymerization within the confines of 0.2 and 0.1mm I.D. capillary columns using ethyl methacrylate and trimethylolpropane triacrylate as monomers as well as 2-propanol, 1-dodecanol and toluene as porogenic system. The influence of column diameter on reproducibility and separation performance was investigated. For evaluation, a protein standard consisting of five proteins in the range of 5800-66,000 g mol(-1) was used. Reproducibility was checked by determining the relative standard deviations in retention times, peak widths at half height, asymmetry and resolution. Excellent run-to-run reproducibility was found for both 0.2 and 0.1mm I.D. columns; batch-to-batch reproducibility was good for both column types. In order to enhance the non-polar character of the monolithic columns, lauryl methacrylate-based capillary columns were prepared. These were successfully used for the separation of proteins and a cytochrome c digest.     

Monomial localizations and polymatroidal ideals

In this paper we consider monomial localizations of monomial ideals and conjecture that a monomial ideal is polymatroidal if and only if all its monomial localizations have a linear resolution. The conjecture is proved for squarefree monomial ideals where it is equivalent to a well-known characterization of matroids. We prove our conjecture in many other special cases. We also introduce the concept of componentwise polymatroidal ideals and extend several of the results known for polymatroidal ideals to this new class of ideals.     

Polymeric Monolithic Media: Synthesis,Pore Size Selective Functionalization and Applications

Summary: This contribution will briefly summarize the latest developments in ring-opening metathesis polymerization (ROMP) and electron beam-triggered free radical polymerization derived monolithic supports. Issues relevant to separation science and heterogeneous catalysis will be addressed.     

Design,Synthesis, and Anti-Proliferative Activity of Quinoxaline Linked 1,2,4-Oxadiazole Hybrids

Russian Journal of General Chemistry - Herein, synthesis of some new quinoxaline-1,2,4-oxadiazole derivatives is presented, and their in vitro anti-cancer activity against four human cancer cell...     

Sunitinib LC–MS/MS Assay in Mouse Plasma and Brain Tissue: Application in CNS Distribution Studies

Sunitinib malate is a multi-targeted tyrosine-kinase inhibitor, currently in clinical trials for glioma. Previously developed methods for preclinical studies in species such as mice have either employed high-performance liquid chromatography (HPLC) or did not describe a detailed analytical method, which could be employed by other preclinical laboratories. In this paper, we have developed and validated a simple, sensitive high-performance liquid chromatography tandem mass-spectrometric method (LC–MS/MS) for the determination of sunitinib concentration in mouse plasma and brain tissue homogenate using dasatinib-free base as the internal standard. A single step liquid–liquid extraction method was used for both the matrices. Since sunitinib exhibits light-induced E/Z isomerism, all sample preparation was done in light-protected conditions. Separation was performed on a ZORBAX Eclipse XDB C18 column 4.6 × 50 mm, 1.8 μm. The mobile phase consisted of 20 mM ammonium formate (with 0.1 % formic acid): acetonitrile (70:30, v/v) pumped isocratically at a flow rate of 0.25 mL min^?1 with a total run-time of 13 min. The retention times of sunitinib and dasatinib were 7.8 and 5.5 min, respectively. The calibration curve was linear over the range from 1.95 to 500 ng mL^?1 in both plasma and brain tissue homogenate with 1.95 ng mL^?1 as the lower limit of quantification (LLOQ) for both the matrices. Inter- and intra-day accuracy and precision was <15 % for low QC, med QC and high QC and <20 % for LLOQ. The method was applied to a pharmacokinetic study in FVB wild-type mice to determine the plasma and brain concentrations after a single oral sunitinib malate dose of 20 mg kg^?1.     

First stereoselective total synthesis of (+)-dodoneine

The first stereoselective total synthesis of the natural product (+)-dodoneine is described involving a Crimmins aldol reaction and a Horner-Wadsworth-Emmons olefination as the key steps.     

Energetic nitrogen-rich salts and ionic liquids

Energetic salts offer many advantages over conventional energetic molecular compounds. The use of nitrogen containing anions and cations contributes to high heats of formations and high densities. Their low carbon and hydrogen content gives rise to a good oxygen balance. The decomposition of these compounds is predominantly through the generation of dinitrogen which makes them very promising candidates for highly energetic materials for industrial or military applications.     

Stereoselective total synthesis of (+)-polyrhacitide A

A facile stereoselective total synthesis of secondary metabolite (+)-polyrhacitide A is described. Stereoselective aldol reaction, Horner-Wardsworth-Emmons reaction, Evans acetal intramolecular oxa-Michael reaction and diastereoselective syn reduction reaction are the key steps involved in the target synthesis.     

Chemical Synthesis and Immunological Evaluation of a Pentasaccharide Bearing Multiple Rare Sugars as a Potential Anti‐pertussis Vaccine

With the infection rate of Bordetella pertussis at a 60‐year high, there is an urgent need for new anti‐pertussis vaccines. The lipopolysaccharide (LPS) of B. pertussis is an attractive antigen for vaccine development. With the presence of multiple rare sugars and unusual glycosyl linkages, the B. pertussis LPS is a highly challenging synthetic target. In this work, aided by molecular dynamics simulation and modeling, a pertussis‐LPS‐like pentasaccharide was chemically synthesized for the first time. The pentasaccharide was conjugated with a powerful carrier, bacteriophage Qβ, as a vaccine candidate. Immunization of mice with the conjugate induced robust anti‐glycan IgG responses with IgG titers reaching several million enzyme‐linked immunosorbent assay (ELISA) units. The antibodies generated were long lasting and boostable and could recognize multiple clinical strains of B. pertussis, highlighting the potential of Qβ‐glycan as a new anti‐pertussis vaccine.