The action of bentonitic earth on natural product epoxides

The ring opening of the epoxide group in the epoxiguaianolides by commercially available bentonitic earth produces specifically the trans diol in good yield under mild conditions.     

Structure, dynamics, and electronic properties of lithium disilicate melt and glass

Ab initio molecular dynamics simulations within the framework of density functional theory have been performed to study the structural, dynamic, and electronic properties of lithium disilicate melt and the glass derived from quenching the melt. It is found that lithium ions have a much higher diffusion coefficient and show different diffusion mechanisms than the network forming silicon and oxygen ions in the melt. The simulated lithium disilicate glass structure has 100% four coordinated silicon, close to theoretical nonbridging oxygen to bridging oxygen ratio (2:3), and Q(n) distributions of 20.8%, 58.4%, and 20.8% for n=2,3,4, respectively. In the melt there are considerable amounts (10%-15%) of silicon coordination defects; however, the average silicon coordination number remains about 4, similar to that in the glass. The lithium ion coordination number increases from 3.7 in the glass to 4.4 in the melt mainly due to the increase of bridging oxygen in the first coordination shell. The bond length and bond angle distributions, vibrational density of states, and static structure factors of the simulated glass were determined where the latter was found to be in good agreement with experimental measurement. Atomic charges were obtained based on Bader and Hirshfeld population analyses [Atoms in Molecule: A Quantum Theory (Oxford University Press, Oxford, 1990); Theor. Chim. Acta 44, 129 (1977)]. The average Bader charges found in lithium disilicate glass were -1.729, 3.419, and 0.915 for oxygen, silicon, and lithium, respectively. The corresponding Hirshfeld charges were -0.307, 0.550, and 0.229. The electronic densities of states of the melt and glass were calculated and compared with those of crystalline lithium disilicate.     

Rhodium-Catalyzed C−H Methylation and Alkylation Reactions by Carbene-Transfer Reactions

In this combined computational and experimental study, the C−H functionalization of 2-phenyl pyridine with diazoalkanes was investigated. Initial evaluation by computational methods allowed the evaluation of different metal catalysts and diazoalkanes and their compatibility in this C−H functionalization reaction. With these findings, suitable reaction conditions for the C−H methylation reactions were quickly identified by using highly reactive TMS diazomethane and C−H alkylation reactions with donor/acceptor diazoalkanes, which is applied to a broad scope on alkylation reactions of 2-aryl pyridines with TMS diazomethane and donor/acceptor diazoalkane (51 examples, up to 98 % yield).     

Peptidomics: the integrated approach of MS, hyphenated techniques and bioinformatics for neuropeptide analysis

MS is currently one of the most important analytical techniques in biological and medical research. ESI and MALDI launched the field of MS into biology. The performance of mass spectrometers increased tremendously over the past decades. Other technological advances increased the analytical power of biological MS even more. First, the advent of the genome projects allowed an automated analysis of mass spectrometric data. Second, improved separation techniques, like nanoscale HPLC, are essential for MS analysis of biomolecules. The recent progress in bioinformatics is the third factor that accelerated the biochemical analysis of macromolecules. The first part of this review will introduce the basics of these techniques. The field that integrates all these techniques to identify endogenous peptides is called peptidomics and will be discussed in the last section. This integrated approach aims at identifying all the present peptides in a cell, organ or organism (the peptidome). Today, peptidomics is used by several fields of research. Special emphasis will be given to the identification of neuropeptides, a class of short proteins that fulfil several important intercellular signalling functions in every animal. MS imaging techniques and biomarker discovery will also be discussed briefly.     

Multi C−H Functionalization Reactions of Carbazole Heterocycles via Gold-Catalyzed Carbene Transfer Reactions

Herein we describe a multiple C−H functionalization reaction of carbazole heterocycles with diazoalkanes. We show that gold catalysts play a distinct role in enabling a multiple C−H functionalization reaction to introduce up to six carbene fragments onto molecules containing multiple carbazole units or to link multiple carbazole units into a single molecule. A one-pot stepwise approach enables the introduction of two different carbene fragments to allow orthogonal deprotection and straightforward derivatization.     

Stimuli responsive poly(1-[11-acryloylundecyl]-3-methyl-imidazolium bromide): dewetting and nanoparticle condensation phenomena

A stimuli-responsive homopolymer poly(ILBr) is fabricated via a "two-phase" atom transfer radical polymerization (ATRP) process, where ILBr stands for the reactive ionic liquid surfactant, 1-[11-acryloylundecyl]-3-methyl-imidazolium bromide. An extraordinarily wide molecular weight distribution (PDI = 6.0) was obtained by introducing the initiator (4-bromomethyl methyl benzoate) in a heterogeneous two-phase process. The molecular weight distribution of poly(ILBr) was characterized by size-exclusion chromatography (SEC). The resulting homopolymer was found to be surface active and stimuli responsive. Poly(ILBr) films coated on quartz exhibit stimuli-responsive dewetting after ion exchange of Br(-) by PF(6)(-). This dewetting phenomenon can be understood in chain segmental terms as a stimuli-induced structural relaxation and appears to be the first such reported stimuli-responsive polymeric dewetting. Titrating aqueous poly(ILBr) with aqueous bis(2-ethylhexyl)sulfosuccinate induces nanophase separation and results in the condensation of nanoparticles 30-60 nm in diameter.