Enantioselective approach to indolizidine and quinolizidine scaffolds. Application to the synthesis of peptide mimics

An enantioselective approach to substituted indolizidine and quinolizidine frameworks has been developed. Key steps of the synthesis are the enantioselective, palladium-catalyzed N-allylation of an imide, the nucleophilic allylation of an acyliminium ion and a ring closing metathesis. This general strategy has been applied to the synthesis of indolizidine peptide mimics, starting from a chiral imide derived from l-aspartic acid. It was observed that the preexisting stereogenic center of this substrate has a moderate influence on the stereoselectivity of the electrophilic allylation, which is mainly determined by the sense of chirality of the catalyst.     

The certification of SRM 1546 – Meat Homogenate, a new reference material for nutrients in a high protein, high fat matrix

In response to reference material needs expressed by the food industry and government regulators, the National Institute of Standards and Technology (NIST) has developed a new Standard Reference Material (SRM) consisting of a canned meat product with certified and reference values for a large number of constituents. SRM 1546 Meat Homogenate consists of a mixture of finely ground pork and chicken prepared and canned by a commercial process. NIST determined the concentration levels of cholesterol, sodium, calcium, iron, and seven fatty acids in this SRM using well defined methods and procedures. These analytes as well as 34 other constituents or properties were determined in an interlaboratory comparison exercise involving 21 laboratories, most of which are associated with the National Food Processors Association (NFPA) Food Industry Analytical Chemists Subcommittee (FIACS). From statistical analysis of the data, NIST assigned certified concentrations for the eleven analytes measured at NIST and reference concentrations for the proximates, six additional fatty acids, seven minerals, and seven water-soluble vitamins. Information values without uncertainties are provided for the concentrations of six additional constituents for which the uncertainties could not adequately be assessed. SRM 1546 will provide laboratories with a means to evaluate the accuracy of the methods they use to assign nutrient levels to processed meats and similar products. Received: 11 October 2000 / Revised: 15 December 2000 / Accepted: 21 December 2000     

Bacterial Photosensory Proteins and Their Role in Plant–pathogen Interactions

Light is an important environmental signal for almost all living organisms. The light perception is achieved by photoreceptor proteins. As can be observed from the great number of bacterial genomes sequenced, plant pathogenic bacteria encode for a large number of photoreceptor proteins. The physiological implications of these photoreceptors are still poorly characterized. However, recent studies revealed the participation of these photosensory proteins in the pathogenic process. Here, we summarize what is known about these proteins and their role during the virulence process, concluding that the light environment modulates the plant–pathogen interaction.     

Validation of Sun Exposure Reported Annually Against Interim Self‐report and Daily Sun Diaries

Data on personal sun exposure over a period exceeding the immediate past days or weeks are typically self‐reported in brief questionnaire items. The validity of such self‐reporting of longer term personal sun exposure, for example over a year, including detail on variation across seasons, has not previously been investigated. In a volunteer sample (n = 331) of Australian adults aged 18 years and over, we assessed the 12‐month reliability of sun exposure reported separately for each season, and its accuracy compared to a daily sun diary in the same season. Seasonal time outdoors displayed fair‐to‐good reliability between baseline and end of study (12 months), with responses showing higher agreement at lower levels of time outdoors. There was good agreement for ranking of individuals' time outdoors with the daily sun diary data, although the actual diary time outdoors was typically considerably lower than the self‐reported questionnaire data. Place of residence, education, being a smoker, day of the week (i.e. working day vs nonworking day) and working mainly outdoors were significant predictors of agreement. While participants overestimated their actual time outdoors, the self‐report questionnaire provided a valid ranking of long‐term sun exposure against others in the study that was reliable over time.     

Base promoted isomerization of aziridinyl ethers: a new access to alpha- and beta-amino acids

Aziridinyl ethers are selectively and easily converted to either amino vinyl ethers or alkoxy allylamines by treatment with mixed metal bases (superbases).     

Stable quantum resonances in atom optics

A theory for stabilization of quantum resonances by a mechanism similar to one leading to classical resonances in nonlinear systems is presented. It explains recent surprising experimental results, obtained for cold cesium atoms when driven in the presence of gravity, and leads to further predictions. The theory makes use of invariance properties of the system allowing for separation into independent kicked rotor problems. The analysis relies on a fictitious classical limit where the small parameter is not Planck's constant, but rather the detuning from the frequency that is resonant in the absence of gravity.     

A Shifted-Barrier Primal-Dual Algorithm Model for Linearly Constrained Optimization Problems

In this paper we describe a Newton-type algorithm model for solving smooth constrained optimization problems with nonlinear objective function, general linear constraints and bounded variables. The algorithm model is based on the definition of a continuously differentiable exact merit function that follows an exact penalty approach for the box constraints and an exact augmented Lagrangian approach for the general linear constraints. Under very mild assumptions and without requiring the strict complementarity assumption, the algorithm model produces a sequence of pairs converging quadratically to a pair where satisfies the first order necessary conditions and is a KKT multipliers vector associated to the linear constraints. As regards the behaviour of the sequence x ^k alone, it is guaranteed that it converges at least superlinearly. At each iteration, the algorithm requires only the solution of a linear system that can be performed by means of conjugate gradient methods. Numerical experiments and comparison are reported.     

A critical analysis of the hand and Othmer-Tobias correlations

Carniti, P., Cori, L. and Ragaini, V., 1978. A Critical Analysis of the Hand and Othmer-Tobias Correlations. Fluid Phase Equilibria, 2: 39–47.The Hand (H) and Othmer-Tobias (OT) correlations are extensively analyzed on 83 aqueous and 26 non-aqueous ternary systems. Twenty solutropic systems are also included. 65% and 58% of the systems give a linear correlation coefficient greater than 0.99 for H and OT respectively.An analysis of the sensitivity to systematic or random errors demonstrates the H correlation to be highly insensitive. A remarkable insensitivity, although not completly for some systematic errors, is also demonstrated for the OT correlation. However there is sufficient proof that they are both unsuitable as a check of experimental data, even though they are used for this purpose.The relation, not necessarily linear, derived from the H correlation, log(x₃₂/x₂₂) vs. log(x₃₁/x₁₁) is useful in locating the plait point.