Thiol–ene coupling reaction of fatty acid monomers

The reactivities and reaction rates of the thiol–ene coupling reaction of 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto acetate and 2‐ethyl‐(hydroxymethyl)‐1,3‐propanediol trimercapto propionate with two common unsaturated fatty acid methyl esters (methyl oleate and methyl linoleate) were evaluated. The reactions were monitored with real‐time IR and ¹H NMR, which both showed that the mercapto acetate was more reactive than the mercapto propionate. Both thiols were more prone to add to the monounsaturated methyl oleate than to methyl linoleate, which contained two unconjugated double bonds. According to bond energy calculations, the thiol hydrogen of mercapto acetate was somewhat more difficult to abstract than the hydrogen of mercapto propionate. Consequently, the formed S? C bond in the acetate case was stronger than in the propionate case, and so the equilibrium was more shifted toward the addition products. The real‐time IR measurements also showed that the cis unsaturation in methyl oleate isomerized much more quickly than that in methyl linoleate, and this also had an impact on the overall addition rate of the thiols because a trans unsaturation was more reactive than a cis unsaturation. The higher isomerization rates in the oleate systems, compared with those of the linoleate systems, was suggested to be due to a more restricted rotation along the C? C bond of the reacted unsaturation in linoleate. This study showed the importance of trans unsaturations in obtaining reasonable reaction rates in thiol–ene reactions with fatty acid derivatives. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 6346–6352, 2004     

An effective action for a variable electromagnetic field

This work consists essentially of two parts. The first part is an analysis of the one-loop effective action using the zeta-function approach. This gives a simple expression for the effective action in terms of the background field propagator. The next-of-kin to the zeta-function, the heat kernel, is given in terms of B. DeWitt's proper time expansion (also known as P. B. Gilkey's theorem). It is calculated in the second part for fermions interacting with an external electromagnetic field to first nonvanishing order in the variations of the gauge field.     

Microwave-enhanced and metal-catalyzed functionalizations of the 4-aryl-dihydropyrimidone template

Progress in organometallic catalysis and recent advancements in the development of carbonylative reaction protocols without direct use of carbon monoxide have been utilized for efficient functionalizations of 4-aryl-dihydropyrimidone structures. The use of modern microwave technology enabled both high reaction rates and convenient handling. Examples of palladium-catalyzed cross-couplings, Heck reactions, amino- and alkoxycarbonylations, and direct N-amidations of 4-(bromophenyl)-dihydropyrimidones were performed. Further, the first N3-arylations of the dihydropyrimidone ring system were successfully completed using the copper-catalyzed Goldberg reaction. Altogether, these protocols provide new tools for rapid generation of novel and diverse dihydropyrimidone derivatives.     

Coherent combining in an Yb-doped double-core fiber laser

Coherent combining is demonstrated in a clad-pumped Yb-doped double-core fiber laser. A slope efficiency of more than 70% is achieved with 96% of the total output power in the fundamental mode of one of the two cores. This high combining efficiency is obtained when both cores are coupled via a biconical fused taper in a Michelson interferometer configuration.     

A Comparison of Splittings and Integral Equation Solvers for a Nonseparable Elliptic Equation

Iterative numerical schemes for solving the electrostatic partial differential equation with variable conductivity, using fast and high-order accurate direct methods for preconditioning, are compared. Two integral method schemes of this type, based on previously suggested splittings of the equation, are proposed, analyzed, and implemented. The schemes are tested for large problems on a square. Particular emphasis is paid to convergence as a function of geometric complexity in the conductivity. Differences in performance of the schemes are predicted and observed in a striking manner. AMS subject classification (2000) 31A10, 35C15, 65R20.Received May 2004. Accepted September 2004. Communicated by Anders Szepessy.Johan Helsing: This work was supported by the Swedish Science Research Council under contract 621-2001-2799.     

The impact of metrological traceability on the validity of creatinine measurement as an index of renal function

When the calibration of a routine measurement procedure is traced back to metrological higher order, a significant discrepancy can occur between the analytical conditions of the routine measurement and the analytical conditions that were used in the clinical studies upon which the decision-making criteria are based. This can lead to serious interpretation errors with possible dramatic consequences for patients. The calibration of the creatinine Jaffé method is an excellent example of the importance of medical traceability. The compensated Jaffé method correlated accurately with the reference method and the compensated Jaffé creatinine clearance (CrCl), Cockroft and Gault and MDRD with the ⁵¹Cr EDTA clearance. The Schwartz estimate based upon the compensated Jaffé and enzymatic method overestimated, while uncompensated Jaffé slightly underestimated glomerular filtration rate (GFR). The situation in children is complex since serum creatinine concentrations are much lower in infants, rendering tubular secretion relatively more important. Low-molecular weight proteins have been suggested to replace serum creatinine as a marker for GFR. -trace protein, cystatin C, and ₂-microglobulin showed good correlation with GFR. However, care should be taken in patients presenting with some malignant tumors, since significant increases of cystatin C in patients with metastatic melanoma or colorectal cancer has been reported.Presented at the 9th Conference on Quality in the Spotlight, 18-19 March 2004, Antwerp, Belgium