Heteropolynuclear complexes with the ligand Ph2PCH2SPh: theoretical evidence for metallophilic Au-M attractions

Addition of two equivalents of diphenylthiomethylphosphine (PPh2-CH2SPh) to the starting materials [Au(tht)2]A (tht = tetrahydrothiophene), AgCF3SO3, or [Cu(CH3CN)4]CF3SO3 produces the mononuclear derivatives [M(PPh2CH2SPh)2]A (M = Au, A = CF3SO3 (1a); M = Au, A = ClO4 (1b); M = Ag, A = CF3SO3 (4); M = Cu, A = CF3SO3 (5)) which are able to form the heterodinuclear complexes [AuM'(PPh2CH2SPh)2](CF3SO3)2 (M' = Ag (2), Cu (3)) with a P-Au-P environment. If the starting gold complex is [Au(C6F5)(tht)], reaction with the phosphine produces [Au(C6F5)-(PPh2CH2SPh)] (6) from which, by reaction with AgCF3SO3 or [Cu(CH3CN)4]CF3SO3, the "snake"-type linear complexes [Au2M(C6F5)2-(PPh2CH2SPh)2]CF3SO3 (M = Ag (7), Cu (8)) are obtained. If the silver starting complex is AgCF3CO2, reaction in a 1:1 ratio gives the tetranuclear complex [Au2Ag2(C6F5)2(PPh2CH2SPh)2-(CF3CO2)2] (9). When the molar ratio is 1:2 the trinuclear complex [AuAg2(C6F5) (CF3CO2)2(PPh2CH2SPh)] (10) is obtained. According to ab initio calculations, the presence of only one gold atom is enough to induce metallophilic attractions in the group congeners, and this effect can be modulated depending on the gold ligand.     

Development of a new UPLC‐MSMS method for the determination of temozolomide in mice: application to plasma pharmacokinetics and brain distribution study

A sensitive and accurate liquid chromatography method with mass spectrometry detection was developed and validated for the quantification of temozolomide in mouse plasma and brain. Theophyllin was used as the internal standard. A single‐step protein precipitation was used for plasma and brain sample preparation. The method was validated with respect to selectivity, extraction recovery, linearity, intra‐ and inter‐day precision and accuracy, limit of quantification and stability. The method has a limit of quantification of 50 ng/mL for temozolomide in plasma and 125 ng/g in brain. This method was used successfully to perform brain and plasma pharmacokinetic studies of temozolomide in mice after intraperitoneal administration. Copyright © 2013 John Wiley & Sons, Ltd.     

Carbon Nanomaterials for Targeted Cancer Therapy Drugs: A Critical Review

Cancer represents one of the main causes of human death in developed countries. Most current therapies, unfortunately, carry a number of side effects, such as toxicity and damage to healthy cells, as well as the risk of resistance and recurrence. Therefore, cancer research is trying to develop therapeutic procedures with minimal negative consequences. The use of nanomaterial‐based systems appears to be one of them. In recent years, great progress has been made in the field using nanomaterials with high potential in biomedical applications. Carbon nanomaterials, thanks to their unique physicochemical properties, are gaining more and more popularity in cancer therapy. They are valued especially for their ability to deliver drugs or small therapeutic molecules to these cells. Through surface functionalization, they can specifically target tumor tissues, increasing the therapeutic potential and significantly reducing the adverse effects of therapy. Their potential future use could, therefore, be as vehicles for drug delivery. This review presents the latest findings of research studies using carbon nanomaterials in the treatment of various types of cancer. To carry out this study, different databases such as Web of Science, PubMed, MEDLINE and Google Scholar were employed. The findings of research studies chosen from more than 2000 viewed scientific publications from the last 15 years were compared.     

Engineered biosynthesis of hybrid macrolide polyketides containing D-angolosamine and D-mycaminose moieties

The glycosylation of natural product scaffolds with highly modified deoxysugars is often essential for their biological activity, being responsible for specific contacts to molecular targets and significantly affecting their pharmacokinetic properties. In order to provide tools for the targeted alteration of natural product glycosylation patterns, significant strides have been made to understand the biosynthesis of activated deoxysugars and their transfer. We report here efforts towards the production of plasmid-borne biosynthetic gene cassettes capable of producing TDP-activated forms of D-mycaminose, D-angolosamine and D-desosamine. We additionally describe the transfer of these deoxysugars to macrolide aglycones using the glycosyl transferases EryCIII, TylMII and AngMII, which display usefully broad substrate tolerance.     

SOLVENT EFFECTS ON THE TAUTOMERIZATION OF 5'-DEOXYPYRIDOXAL. A PHOTOPHYSICAL STUDY

Abstract— Absorption and fluorescence spectra of 5'-deoxypyridoxal (DPL) in various pure solvents and mixtures were recorded both at room temperature and over the range10–65°C. The areas under the absorption bands were analyzed to obtain the mole fraction (f_N, f_z) of two tautomers (the zwitterionic, Z, and neutral, N, forms) in the ground state. The following spectral parameters were determined from the fluorescence spectra: Stokes shift (Δ v ), fluorescence quantum yield of the neutral form (Q_N), fluorescence ratio of the neutral to the zwitterionic form (ø_N/ø_Z) and the rate constant of tautomerization ( k ₁) from Z to N in the excited state. Some of these parameters (f_N, Δ v , Q_N, k ₁) were found to depend on the proton donor character of the solvent, whereas others (ø_N/ø_Z) depended on its dipole moment. Thus, the absorption and fluorescence spectra of DPL allow one to obtain information on the polarity and the concentration of –OH groups on its environment.     

Hierarchical ZSM‐5 Zeolites in Shape‐Selective Xylene Isomerization: Role of Mesoporosity and Acid Site Speciation

The isomerization of o‐xylene, a prototypical example of shape‐selective catalysis by zeolites, was investigated on hierarchical porous ZSM‐5. Extensive intracrystalline mesoporosity in ZSM‐5 was introduced by controlled silicon leaching with NaOH. In addition to the development of secondary porosity, the treatment also induced substantial aluminum redistribution, increasing the density of Lewis acid sites located at the external surface of the crystals. However, the strength of the remaining Brønsted sites was not changed. The mesoporous zeolite displayed a higher o‐xylene conversion than its parent, owing to the reduced diffusion limitations. However, the selectivity to p‐xylene decreased, and fast deactivation due to coking occurred. This is mainly due to the deleterious effect of acidity at the substantially increased external surface and near the pore mouths. A consecutive mild HCl washing of the hierarchical zeolite proved effective to increase the p‐xylene selectivity and reduce the deactivation rate. The HCl‐washed hierarchical ZSM‐5 displayed an approximately twofold increase in p‐xylene yield compared to the purely microporous zeolite. The reaction was followed by operando infrared spectroscopy to simultaneously monitor the catalytic performance and the buildup of carbonaceous deposits on the surface. Our results show that the interplay between activity, selectivity, and stability in modified zeolites can be optimized by relatively simple post‐synthesis treatments, such as base leaching (introduction of mesoporosity) and acid washing (surface acidity modification).