Fenchyl substituted 1,2-dioxetanes as an alternative to adamantyl derivatives for bioanalytical applications

The synthesis and study of the chemiluminescence parameters and thermal stability of 1,2-dioxetanes containing a spirofenchyl substituent are reported. Three fenchyl-substituted 1,2-dioxetanes were synthesized by photooxygenation of the corresponding alkenes, obtained by Barton-Kellogg olefination of the readily available (-)-fenchone. The fenchyl-substituted 1,2-dioxetanes showed thermal stabilities similar to those of the corresponding spiroadamantyl-substituted derivatives, although being slightly more labile with respect to unimolecular decomposition than the latter derivatives, which are widely utilized as labels in a great variety of chemiluminescent immunoassays. Fluoride induced decomposition of one triggerable fenchyl 1,2-dioxetane derivative showed kinetic parameters similar to those of the corresponding adamantyl-substituted derivative. The chemiluminescence quantum yields in the one percent range are also similar to that of other widely utilized chemiluminescence systems as the luminol reaction. These results indicate that fenchyl-substituted 1,2-dioxetanes can potentially be utilized as a cheaper alternative to substitute the corresponding spiroadamantyl derivatives in bioanalytical applications. (C) 2010 Elsevier B.V. All rights reserved.

Microwave-assisted solid-phase peptide synthesis at 60 degrees C: alternative conditions with low enantiomerization

Several conditions have been used in the coupling reaction of stepwise SPPS at elevated temperature (SPPS-ET), but we have elected the following as our first choice: 2.5-fold molar excess of 0.04-0.08 M Boc or Fmoc-amino acid derivative, equimolar amount of DIC/HOBt (1:1)or TBTU/DIPEA(1:3), 25% DMSO/toluene, 60 degrees C, conventional heating. In this study, aimed to further examine enantiomerization under such condition and study the applicability of our protocols to microwave-SPPS, peptides containing L-Ser, L-His, L-Cys and/or L-Met were manually synthesized traditionally, at 60 degrees C using conventional heating and at 60 degrees C using microwave heating. Detailed assessment of all crude peptides (in their intact and/or fully hydrolyzed forms) revealed that, except for the microwave-assisted coupling of L-Cys, all other reactions occurred with low levels of amino acid enantiomerization (<2%). Therefore, herein we (i) provide new evidences that our protocols for SPPS at 60 degrees C using conventional heating are suitable for routine use, (ii) demonstrate their appropriateness for microwave-assisted SPPS by Boc and Fmoc chemistries, (iii) disclose advantages and limitations of the three synthetic approaches employed. Thus, this study complements our past research on SPPS-ET and suggests alternative conditions for microwave-assisted SPPS. Copyright (C) 2009 European Peptide Society and John Wiley & Sons, Ltd.

External polyacrylate-coating as alternative material for preparation of photopolymerized sol-gel monolithic column

Photopolymerized sol-gel monolithic columns for use in capillary electrochromatography were prepared in 125 mu m i.d. polyacrylate-coated fused-silica capillaries. The polyacrylate-coating, unlike the polyimide one, is transparent to the radiation used (approximate to 370 nm), and thus, no coating removal is necessary. This is a very important particularity since intrinsic capillary column characteristics, such as flexibility and mechanical resistance, are unchanged. A mixture containing metacryloxypropyltrimethoxysilane (MPTMS) as the polymeric precursor, hydrochloric acid as the catalyst, toluene as the porogen and bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (Irgacure 819) as the photoinitiator was irradiated at 370 nm for 20 min inside the capillaries to prepare the columns through sol-gel approach. The versatility and viability of the use of polyacrilate as a new capillary external coating were shown through preparation of two columns under different conditions, which were tested in electrochromatography for separation of standard mixture containing thiourea (marker compound), propylbenzene, phenanthrene and pyrene. (C) 2008 Elsevier B.V. All rights reserved.

Triphenylmethane dyes, an alternative for mediated electronic transfer systems in glucose oxidase biofuel cells

The bioelectrochemical behavior of three triphenylmethane (TPM) dyes commonly used as pH indicators, and their application in mediated electron transfer systems for glucose oxidase bioanodes in biofuel cells was investigated. Bromophenol Blue, Bromothymol Blue, Bromocresol Green were compared bio-electrochemically against two widely used mediators, benzoquinone and ferrocene carboxy aldehyde. Biochemical studies were performed in terms of enzymatic oxidation, enzyme affinity, catalytic efficiency and co-factor regeneration. The different features of the TPM dyes as mediators are determined by the characteristics in the oxidation/reduction processes studied electrochemically. The reversibility of the oxidation/reduction processes was also established through the dependence of the voltammetric peaks with the sweep rates. All three dyes showed good performances compared to the FA and BQ when evaluated in a half enzymatic fuel cell. Potentiodynamic and power response experiments showed maxima power densities of 32.8 mu W cm(-2) for ferrocene carboxy aldehyde followed by similar values obtained for TPM dyes around 30 mu W cm(-2) using glucose and mediator concentrations of 10 mmol L(-1) and 1.0 mmol L(-1), respectively. Since no mediator consumption was observed during the bioelectrochemical process, and also good redox re-cycled processes were achieved, the use of triphenylmethane dyes is considered to be promising compared to other mediated systems used with glucose oxiclase bioanodes and/or biofuel cells. (C) 2011 Elsevier Inc. All rights reserved.

Alternative Identities and Foreign Language Learning

My D-essay has the working title “Alternative Identities and Foreign Language Learning”. I have chosen this area because I have noticed a certain reluctance among Swedish students to use the foreign language English in English classes. They often seem embarrassed to express themselves in a language which is not their mother tongue, but they seem less embarrassed when they are allowed to act somebody else. These two observations converge into a focus of discussion on the matter, which will be supported by a minor study of my own, by extracts from other people’s essays on the matter, and by an overview of current litterature on language, identity and drama.The aim of my essay is to compare Swedish students’ willingness to use the foreign language English when acting minor plays in school, as themselves and as a chosen character, and to investigate the possibility of improving students’ willingness to use a foreign language, when given the opportunity to do so through acting somebody else.

Inflation and debt indexation : the equivalence of two alternative schemes for the case of periodic payments

The presence of inflation has induced the financial institutions to implement procedures devised to protect the real values of theirs loans. Two of such procedurcs, the floaaing rale scheme and the monetary correction mechanism, tend to lead to very different streams of payments. However, whenever the floating rate scheme follows the rule of Strict adhercnce to lhe Fisher equation, lhe two procedures are financially equivalent.

After structuralism, a development alternative for Latin America

The paper, first, summarizes Latin American structuralism, and offers reasons why it was so influential and durable in the region, as it attended to real demands, and was part of 1950s’mainstream economics. Second, says why, with 1980s’Great Crisis, structuralism eventually ended itself into crisis, as it was unable to keep pace with historical new facts, particularly with the industrial revolution or takeoff, that made Latin American economies intermediary, still developing, but fully capitalist. Third, it lists the consensus that today exists on economic development. Forth, opposes “official orthodoxy” to “developmental populism”, the former deriving from neoclassical economics, the later from structuralism, and offers, in relation to six strategic issues, a progressive development alternative.

Integrability and the demand for monetary assets: an alternative approach to an old problem

This note provides necessary and su¢cient conditions for some speci…c multidimensional consumer’s surplus welfare measures to be well posed (path independent). We motivate the problem by investigating partial-equilibrium measures of the welfare costs of in‡ation. The results can also be used for checking path independence of alternative de…nitions of Divisia indexes of monetary services. Consumer theory classically approaches the integrability problem by considering compensated demands, homothetic preferences or quasi-linear utility functions. Here, instead, we consider demands of monetary assets generated from a shopping-time perspective. Paralleling the above mentioned procedure, of …nding special classes of utility functions that satisfy the integrability conditions, we try to infer what particular properties of the transacting technology could assure path independence of multidimensional welfare measures. We show that the integrability conditions are satis…ed if and only if the transacting technology is blockwise weakly separable. We use two examples to clarify the point.

On the cost of sympathy : a alternative model of insurance markets

The paper provides an alternative model for insurance market with three types of agents: households, providers of a service and insurance companies. Households have uncertainty about future leveIs of income. Providers, if hired by a household, perform a diagnoses and privately learn a signal. For each signal there is a procedure that maximizes the likelihood of the household obtaining the good state of nature. The paper assumes that providers care about their income and also about the likelihood households will obtain the good state of nature (sympathy assumption). This assumption is satisfied if, for example, they care about their reputation or if there are possible litigation costs in case they do not use the appropriate procedure. Finally, insurance companies offer contracts to both providers and households. The paper provides sufficient conditions for the existence of equilibrium and shows that the sympathy assumption 1eads to a 10ss of welfare for the households due to the need to incentive providers to choose the least expensive treatment.