Room Temperature Ionic Liquid-Lithium Salt Mixtures: Optical Kerr Effect Dynamical Measurements

The addition of lithium salts to ionic liquids causes an increase in viscosity and a decrease in ionic mobility that hinders their possible application as an alternative solvent in lithium ion batteries. Optically heterodyne-detected optical Kerr effect spectroscopy was used to study the change in dynamics, principally orientational relaxation, caused by the addition of lithium bis(trifluoromethylsulfonyl)imide to the ionic liquid 1-buty1-3-methylimidazolium bis(trifluoromethylsulfonyl)imide. Over the time scales studied (1 ps-16 ns) for the pure ionic liquid, two temperature-independent power laws were observed: the intermediate power law (1 ps to similar to 1 ns), followed by the von Schweidler power law. The von Schweidler power law is followed by the final complete exponential relaxation, which is highly sensitive to temperature. The lithium salt concentration, however, was found to affect both power laws, and a discontinuity could be found in the trend observed for the intermediate power law when the concentration (mole fraction) of lithium salt is close to chi(LiTf(2)N) = 0.2. A mode coupling theory (MCT) schematic model was also used to fit the data for both the pure ionic liquid and the different salt concentration mixtures. It was found that dynamics in both types of liquids are described very well by MCT.

Unraveling Dynamical Heterogeneity in the Ionic Liquid 1-Butyl-3-methylimidazolium Chloride

Heterogeneous dynamics within a time range of nanoseconds was investigated by molecular dynamics (MD) simulations of 1 -butyl-3-methylimidazolium chloride ([bmim]Cl). After identifying groups of fast and slow ions, it was shown that the separation between the location of the center of mass and the center of charge of cations, d(CMCC), is a signature of such difference in ionic mobility. The distance d(CMCC) can be used as a signature because it relaxes in the time window of the dynamical heterogeneity. The relationship between the parameter dcmcc and conformations of the side alkyl chain in [bmim] is discussed. Since the relatively slow relaxation of dcmcc is a consequence of coexisting polar and nonpolar domains in the bulk, the MD simulations reveal a subtle interplay between structural and dynamical heterogeneity in ionic liquids.

Synthesis of new fluorous modular chiral ligand derivatives from amino alcohols and application in enantioselective carbon-carbon bond-forming alkylation reactions

N-Trifluoracyl beta-chalcogeno amides and N-perfluoracyl beta-thio amide ligands were prepared by a simple and efficient reaction sequence. These new ligands were evaluated in palladium-catalyzed alkylation of rac-(E)-1,3-diphenyl-2-propenyl acetate in the presence of dimethyl malonate and an enantioselectivity of up to 99% was obtained. After catalysis, the fluorous ligand can be easily recovered by liquid-liquid extraction and reused without loss in the activity. (C) 2010 Elsevier Ltd. All rights reserved.

First dynamic kinetic resolution of selenium-containing chiral amines catalyzed by palladium (Pd/BaSO(4)) and Candida antartica lipase (CAL-B)

An efficient method for chemoenzymatic dynamic kinetic resolution of selenium-containing chiral amines (organoselenium-1-phenylethanamines) has been developed, leading to the corresponding amides in excellent enantioselectivities and high isolated yields. This one-pot procedure employs two different types of catalysts: Pd on barium sulphate (Pd/BaSO(4)) as racemization catalyst and lipase (CAL-B) as the resolution catalyst. (C) 2009 Elsevier Ltd. All rights reserved.

Lipase-Catalyzed Highly Enantioselective Kinetic Resolution of Boron-Containing Chiral Alcohols

The first application of enzymes as catalysts to obtain optically pure boron compounds is described. The kinetic resolution of boron-containing chiral alcohols via enantioselective transesterification catalyzed by lipases was studied. Aromatic, allylic, and aliphatic secondary alcohols containing a boronate ester or boronic acid group were resolved by lipase from Candida antartica (CALB), and excellent E values (E > 200) and high enantiomeric excesses (up to >99%) of both remaining substrates and acetylated product were obtained.

Practical synthesis of chiral beta-telluro amines by ring-opening reaction of aziridines

A set of chiral beta-tellurium amines and their selenium and sulfur-containing derivatives have been efficiently synthesized in good to excellent yields via the ring-opening reaction of chiral aziridines by chalcogen nucleophilic species. (C) 2008 Elsevier B.V. All rights reserved.

Stereoselective Nucleophilic Addition of Potassium Alkyltrifluoroborates to Cyclic N-Acyliminium Ions: a Simple and Mild Approach to Chiral 5-Alkyl-pyrrolidin-2-ones

The stereoselective nucleophilic addition of potassium alkyltrifluoroborates to cyclic N-acyliminium ions derived from N-benzyl-3,4,5-triacetoxy-pyrrolidin-2-one, which affords 5-substituted-pyrrolidin-2-ones, is described. The products are obtained in moderate to good yields and are produced predominantly as the anti diastereomer.

Chemoselective screening for the reduction of a chiral functionalised (+/-)-2-(phenylthio)cyclohexanone by whole cells of Brazilian micro-organisms

The use of whole cells of micro-organisms to bring about the biotransformation of an organic compound offers a number of advantages, but problems caused by enzymatic Promiscuity may be encountered upon With Substrates hearing more than one functional group. A one-pot screening method, in which whole fungal cells were incubated with a Mixture of 4-rnethylcyclohexanone I and phenyl methyl Sulfide 2, has been employed to determine the chemoselectivity of various biocatalysts. The hyphomycetes, Aspergillus terreus CCT 3320 and A. terreus URM 3571, catalysed the oxidation of 2 accompanied by the reduction of I to 4-methylcyclohexanol 1a and, for strain A. terreus CCT 3320, the Baeyer-Villiger oxidation of 1. The Basidomycetes, Trametes versicolor CCB 202, Pycnoporus sanguineus CCB 501 and Trichaptum byssogenum CCB 203, catalysed the oxidation of 2 and the reduction 1, but no Baeyer-Villiger reaction products were detected. In contrast. Trametes rigida CCB 285 catalysed the biotransformation of 1 to 1a, exclusively, in the absence of any detectable Sulfide oxidation reactions. The chemoselective reduction Of (+/-)-2-(phenylthio)cyclohexanone 3 by T. rigida CCB 285 afforded exclusively the (+)-cis-(1R,2S) and (+)-trans-(1S,2S) diastereoisomers of 2-(phenylthio)cyclohexan-1-ol 3a in moderate yields (13% and 27%, respectively) and high enantiomeric excesses (>98%). Chemoselective screening for the reduction of a ketone and/or the oxidation Of a Sulfide group in one pot by whole cells of micro-organisms represents an attractive technique with applications in the development of synthesis of complex molecule hearing different functional groups. (C) 2008 Published by Elsevier Ltd.

New insights on surface-enhanced Raman scattering based on controlled aggregation and spectroscopic studies, DFT calculations and symmetry analysis for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine adsorbed onto citrate-stabilized gold nanoparticles

Asystematic study on the surface-enhanced Raman scattering (SERS) for 3,6-bi-2-pyridyl-1,2,4,5-tetrazine (bptz) adsorbed onto citrate-modified gold nanoparticles (cit-AuNps) was carried out based on electronic and vibrational spectroscopy and density functional methods. The citrate/bptz exchange was carefully controlled by the stepwise addition of bptz to the cit-AuNps, inducing flocculation and leading to the rise of a characteristic plasmon coupling band in the visible region. Such stepwise procedure led to a uniform decrease of the citrate SERS signals and to the rise of characteristic peaks of bptz, consistent with surface binding via the N heterocyclic atoms. In contrast, single addition of a large amount of bptz promoted complete aggregation of the nanoparticles, leading to a strong enhancement of the SERS signals. In this case, from the distinct Raman profiles involved, the formation of a new SERS environment became apparent, conjugating the influence of the local hot spots and charge-transfer (CT) effects. The most strongly enhanced vibrations belong to a(1) and b(2) representations, and were interpreted in terms of the electromagnetic and the CT mechanisms: the latter involving significant contribution of vibronic coupling in the system. Copyright (C) 2010 John Wiley & Sons, Ltd.

Mild and efficient one-pot synthesis of chiral beta-chalcogen amides via 2-oxazoline ring-opening reaction mediated by indium metal

A simple and efficient procedure for the synthesis of beta-seleno and beta-thio amides via the ring-opening reaction of chiral 2-oxazolines in the presence of indium metal has been developed. Features of this method include the following: (i) easily and accessible starting materials; (ii) indium metal is more stable and less expensive then its respective salts; (iii) useful to excellent yields of beta-chalcogen amides derivatives. (C) 2008 Elsevier B. V. All rights reserved.

Synthesis and application of chiral beta-amino disulfides as ligands for the enantioselective addition of diethylzinc to aldehydes

A new class of chiral beta-amino disulfides was synthesized from readily available and inexpensive starting materials by a straightforward method and their abilities as ligands were examined in the enantioselective addition of diethylzinc to aldehydes. Enantiomeric excesses of up to 99% have been obtained using 0.5 mol % of the chiral catalysts.

Stereoselective synthesis of azetidine-derived glutamate and aspartate analogues from chiral azetidin-3-ones

The stereoselective syntheses of cis conformationally constrained glutamate and aspartate analogues, containing an azetidine framework were accomplished from (S)-N-tosyl-2-phenylglycine in moderate overall yields. The key steps in these syntheses involved an efficient Wittig olefination of an azetidin-3-one, followed by a highly stereoselective rhodium catalyzed hydrogenation. The route could also be applied to the synthesis of a trans glutamate analogue, since epimerization of cis to trans isomer could be performed using DBU in toluene at reflux. (C) 2008 Elsevier Ltd. All rights reserved.

Kinetic resolution of iodophenylethanols by Candida antarctica lipase and their application for the synthesis of chiral biphenyl compounds

The kinetic resolution of (+/-)-iodophenylethanols was carried out using lipase from Candida antarctica and in some cases the enantiomeric excesses were high (up to >98%). Enantiomerically enriched (S)-iodophenylethanols produced by the enzymatic resolution process were used in the synthesis of chiral biphenyl compounds by the Suzuki reaction with good yields (63-65%). (C) 2010 Elsevier Ltd. All rights reserved.

Multimilligram enantioresolution of sulfoxide proton pump inhibitors by liquid chromatography on polysaccharide-based chiral stationary phase

The enantiomers of sulfoxide proton pump inhibitors - omeprazole, lansoprazole, rabeprazole and Ro 18-5364 - were enantiomerically separated by liquid chromatography at multimilligram scale on a poly saccharide-based chiral stationary phase using normal and polar organic conditions as mobile phase. The values of the recovery and production rate were significant for each enantiomer; better results were achieved using a solid-phase injection system. However, this system was applied just for the enantionteric separation of omeprazole to demonstrate the applicability of this injection mode at milligram scale. The chiroptical characterization of the compounds was performed using a polarimeter and a circular dichroism detector. The higher enantiomeric purity obtained for the isolated enantiomers suggests that the methods here described should be considered as a simple and rapid way to obtain enantiomeric pure standards for analytical purpose. (C) 2007 Elsevier B.V. All rights reserved.

Breaking the Conventions : Shakespeare, the Fair Young Man and the Dark Lady

The aim of this essay is to show how Shakespeare’s sonnets violated and reversed the conventional ideas in terms of beauty and idealisation. Furthermore, I will examine the way Shakespeare presented his beloved woman as an absolute opposite of the one created by Petrarch, and how he shifted all the divine metaphors from a woman to a fair young man, creating a new object of praise and admiration.