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.

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.

Preparation and characterization of ordered intermetallic platinum phases for electrocatalytic applications

Ordered intermetallic phases of Pt with several transition metals have been prepared and their electrocatalytic properties studied. In light of these tests it is proposed that these catalysts could be used as electrodes in fuel cells, as they combine an excellent capacity to adsorb organic fuels at the Pt sites with low susceptibility to being poisoned by intermediates and reaction products at the transition-metal sites. An experimental procedure used to obtain the four intermetallic phases Pt-M (M = Mn, Pb, Sb and Sn) is described. The phases thus produced were characterized by X-ray diffraction, scanning electron microscopy with surface analysis by energy-dispersive X-ray spectrometry, scanning tunneling microscopy and X-ray photoelectron spectroscopy. The data thus obtained support the conclusion that the method described here is highly effective for the preparation of Pt-M phases featuring a range of structural and electronic modifications that will allow a useful relation to be established between their physicochemical properties and predicted electrocatalytic activity. (C) 2007 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.

Development of a new stir bar sorptive extraction coating and its application for the determination of six pesticides in sugarcane juice

In this article, a novel polydimethylsiloxane/activated carbon (PDMS-ACB) material is proposed as a new polymeric phase for stir bar sorptive extraction (SBSE). The PDMS-ACB stir bar, assembled using a simple Teflon (R)/glass capillary mold, demonstrated remarkable stability and resistance to organic solvents for more than 150 extractions. The SBSE bar has a diameter of 2.36 mm and a length of 2.2 cm and is prepared to contain 92 mu L of polymer coating. This new PDMS-ACB bar was evaluated for its ability to determine the quantity of pesticides in sugarcane juice samples by performing liquid desorption (LD) in 200 mu L of ethyl acetate and analyzing the solvent through gas chromatography coupled with mass spectrometry (GC-MS). A fractional factorial design was used to evaluate the main parameters involved in the extraction procedure. Then, a central composite design with a star configuration was used to optimize the significant extraction parameters. The method used demonstrated a limit of quantification (LOQ) of 0.5-40 mu g/L, depending on the analyte detected; the amount of recovery varied from 0.18 to 49.50%, and the intraday precision ranged from 0.072 to 8.40%. The method was used in the analysis of real sugarcane juice samples commercially available in local markets.

Identification of cause of impairment in spiral drawings, using non-stationary feature extraction approach

Parkinson’s disease is a clinical syndrome manifesting with slowness and instability. As it is a progressive disease with varying symptoms, repeated assessments are necessary to determine the outcome of treatment changes in the patient. In the recent past, a computer-based method was developed to rate impairment in spiral drawings. The downside of this method is that it cannot separate the bradykinetic and dyskinetic spiral drawings. This work intends to construct the computer method which can overcome this weakness by using the Hilbert-Huang Transform (HHT) of tangential velocity. The work is done under supervised learning, so a target class is used which is acquired from a neurologist using a web interface. After reducing the dimension of HHT features by using PCA, classification is performed. C4.5 classifier is used to perform the classification. Results of the classification are close to random guessing which shows that the computer method is unsuccessful in assessing the cause of drawing impairment in spirals when evaluated against human ratings. One promising reason is that there is no difference between the two classes of spiral drawings. Displaying patients self ratings along with the spirals in the web application is another possible reason for this, as the neurologist may have relied too much on this in his own ratings.

The latitude dependent irradiation distribution in Europe and its implication for the design of stationary concentrators

When a stationary solar concentrator is designed, the spatial distribution of the available irradiation is of vital interest. An irradiation distribution based only on solar geometry will look similar at different sites. The only difference is that the distribution of the incident irradiation is shifted to lower solar altitudes when latitude is increased. However, real irradiation distribution will show strong asymmetry at high latitude sites, since the winter irradiation is reduced by absorption and scattering in the atmosphere, and by seasonal changes in the climate. The reduced winter irradiation at high latitudes implies that the available annual radiation is concentrated to a narrower angular interval. This means that the degree of concentration that is possible increases with latitude.In the paper examples of irradiation distribution from different sites in Europe from latitude 38°N to 65°N are shown. The origin of the reduced winter irradiation with increased latitude is discussed, and numerical examples on the performance of different types of stationary concentrators for different latitudes are given.

EMISSIONS CHARACTERISTICS OF A RESIDENTIAL PELLET BOILER AND A STOVE

Gaseous and particulate emissions from a residential pellet boiler and a stove are measured at a realistic 6-day operation sequence and during steady state operation. The aim is to characterize the emissions during each phase in order to identify when the major part of the emissions occur to enable actions for emission reduction where the savings can be highest. The characterized emissions comprised carbon monoxide (CO), nitrogen oxide (NO), total organic carbon (TOC) and particulate matter (PM 2.5). In this study, emissions were characterised by mass concentration and emissions during start-up and stop phases were also presented in accumulated mass. The influence of start-up and stop phases on the emissions, average emission factors for the boiler and stove were analysed using the measured data from a six-days test. The share of start-up and stop emissions are significant for CO and TOC contributing 95% and 89% respectively at the 20kW boiler and 82% and 89% respectively at the 12 kW stove. NO and particles emissions are shown to dominate during stationary operation.

Robustness of stationary tests under long-memory alternatives

This paper investigates the presence of long memory in financiaI time series using four test statistics: V/S, KPSS, KS and modified R/S. There has been a large amount of study on the long memory behavior in economic and financiaI time series. However, there is still no consensus. We argue in this paper that spurious short-term memory may be found due to the incorrect use of data-dependent bandwidth to estimating the longrun variance. We propose a partially adaptive lag truncation procedure that is robust against the presence of long memory under the alternative hypothesis and revisit several economic and financiaI time series using the proposed bandwidth choice. Our results indicate the existence of spurious short memory in real exchange rates when Andrews' formula is employed, but long memory is detected when the proposed lag truncation procedure is used. Using stock market data, we also found short memory in returns and long memory in volatility.

Efeitos de ordenamento chiral em supercondutores e sistemas magnéticos desordenados

Este trabalho apresenta uma investigação experimental sobre as propriedades magnéticas e de transporte elétrico de sistemas caracterizados por desordem e frustração. Tais sistemas são amostras granulares do supercondutor de alta temperatura crítica YBa2Cu3O7-δ e amostras do tipo vidro-de-spin e reentrantes das ligas magnéticas diluídas AuMn 8at% e AuFe xat% (x = 8, 12, 15, 18 e 21). No supercondutor granular foram estudados os efeitos de flutuações termodinâmicas na magnetocondutividade nas proximidades da transição supercondutora e a linha de irreversibilidades magnéticas. A transição para o estado de resistência nula é um processo que ocorre em duas etapas. Inicialmente, a transição de pareamento estabiliza a supercondutividade no interior dos grãos. A transição de coerência ocorre em temperaturas inferiores e ativa ligações fracas entre os grãos através de um processo do tipo percolação. O regime que antecede a transição de coerência é caracterizado por flutuações na fase do parâmetro de ordem. A linha de irreversibilidades magnéticas, estudada a partir da magnetoresistência e magnetização DC, revela um comportamento do tipo Almeida-Thouless em baixos campos magnéticos aplicados, seguido de um crossover, em µ0H = 0.1 T, para um comportamento do tipo Gabay-Toulouse. A linha de irreversibilidades é interpretada como sendo uma manifestação experimental de uma transição de vidro chiral. As ligas magnéticas diluídas foram estudadas através do efeito Hall extraordinário. Os resultados mostram claramente que dois termos de sinais contrários contribuem para este efeito nestes sistemas. Em particular, é observada uma anomalia no coeficiente de Hall extraordinário em temperaturas próximas à temperatura de ordenamento dos vidros-de-spin e de “canting” dos reentrantes que não é prevista por nenhuma teoria convencional de efeito Hall. A interpretação dos resultados é feita em termos do modelo de vidro chiral, mostrando a importância de uma contribuição de origem puramente chiral. Esta é a primeira vez que a chiralidade, uma propriedade intrínseca de sistemas desordenados e frustrados, é observada experimentalmente de modo direto.

A contractive method for computing the stationary solution of the euler equation

A contractive method for computing stationary solutions of intertemporal equilibrium models is provide. The method is is implemented using a contraction mapping derived from the first-order conditions. The deterministic dynamic programming problem is used to illustrate the method. Some numerical examples are performed.