Smooth Frame-Path Termination for Higher Order Sigma-Delta Quantization

We study the performance of finite frames for the encoding of vectors by applying standard higher-order sigma-delta quantization to the frame coefficients. Our results are valid for any quantizer with accuracy ε > 0 operating in the no-overload regime. The frames under consideration are obtained from regular sampling of a path in a Hilbert space. In order to achieve error bounds that are comparable to results on higher-order sigma-delta for the quantization of oversampled bandlimited functions, we construct frame paths that terminate smoothly in the zero vector, that is, with an appropriate number of vanishing derivatives at the endpoint.     

Pentopyranosyl Oligonucleotide Systems. 9th Communication

Pyranosyl‐RNA (‘p‐RNA’ ) is an oligonucleotide system isomeric to natural RNA and composed of the very same building blocks as RNA. Its generational, chemical, and informational properties are deemed to be those of an alternative nucleic acid system that could have been a candidate in Nature's evolutionary choice of the molecular basis of genetic function. We consider the study of the chemistry of p‐RNA as etiologically relevant in the sense that knowledge of its structural, chemical, and informational properties on the chemical level offers both a perspective and reference points for the recognition of specific structural assets of the RNA structure that made it the (supposedly) superior system among possible alternatives and, therefore, the system that became part of biology as we know it today. The paper describes the chemical synthesis of β‐d‐ (and L )‐ribopyranosyl‐(4′→2′)‐oligonucleotide sequences, presents a resume of their structural and chemical properties, and cautiously discusses what we may and may not have learned from the pyranosyl isomer of RNA with respect to the conundrum of RNA's origin.     

Influence of trans-cis photoisomerizations of solubilized compounds on transition temperatures in the system cetyltrimethylammonium bromide-water: Light-induced phase transitions

Transition temperatures (TN1) from the nematic lyotropic liquid-crystalline phase to the isotropic phase were measured for the system cetyltrimethylammonium bromide (CTAB) water in the presence of small amounts of 3-stilbene carboxylic acid (3SC), 4-stilbene carboxylic acid (4SC) and Δ2/2'-bi-(2H-l,4-benzothiazine) (BT). TNI, increases as a function of trans-3SC or trans-4SC concentration, ranging from 01 to 08 wt %, by up to 12°C. A further increase in TNI between 2 and 5°C can be achieved by photochemically converting the solubilized trans stilbene derivatives to the cis isomers. Irradiation of a trans-3SC containing sample at a temperature just above TNl leads to a light-induced phase transition to the lyotropic liquid-crystalline phase. Solubilization of trans-BT causes a slight decrease of TNI while photoisomerization to cis-BT increases T_NI by 1°C.     

Microbial Baeyer-Villiger Oxidation of Ketones by Cyclohexanone and Cyclopentanone Monooxygenase – A Computational Rational for Biocatalyst Performance

Summary. Recombinant Escherichia coli overexpressing Pseudomonas sp. NCIMB 9872 cyclopentanone monooxygenase (CPMO, EC 1.14.13.16) and Acinetobacter sp. NCIMB 9871 cyclohexanone monooxygenase (CHMO, EC 1.14.13.22) have been utilized in whole-cell Baeyer-Villiger biotransformations of prochiral bicycloketones. A significant difference in substrate acceptance and stereoselectivity was observed for bicyclo[3.3.0] and bicyclo[4.3.0] substrates. A plausible mechanism of these transformations was established by means of high level DFT/B3LYP calculations suggesting an essential difference in electronic requirements for a successful enzymatic conversion, which was similarly encountered in recombinant whole-cell mediated biooxidations. Some of the lactones produced in the biocatalytic Baeyer-Villiger oxidation represent key intermediates for the synthesis of indole alkaloids.     

3rd International Conference on Trace Element Speciation in Biomedical,Nutritional and Environmental Sciences

3rd International Conference on Trace Element Speciation in Biomedical, Nutritional and Environmental Sciences     

Crystallographic report: Crystal structure of 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide

For the unsymmetrical title compound, 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide, two independent molecules were found in the asymmetric unit. Copyright © 2003 John Wiley & Sons, Ltd.