Slow visco-elastic flow past a cylinder in a rectangular channel

This paper is concerned with the flow of a visco-elastic liquid through a rectangular channel containing a cylindrical obstruction placed either in a symmetric or asymmetric position with respect to the centre of the channel. Numerical predictions of the flow are obtained using a well established finite element Galerkin mixed formulation. The influence of elasticity on the streamline pattern is found to be negligible, and one only observes changes due to different geometries, i.e. relative positions of cylinder and channel. However, both elasticity and a variable viscosity are found to have significant effects on the forces exerted on the cylinder.     

N=3 supersymmetry multiplets with vanishing trace anomaly: Building blocks of the N>3 supergravities

N?3 supergravity theories with vanishing one-loop trace anomaly may be constructed fron three basic N=3 multiplets, one of which contains an antisymmetric tensor gauge field. As an example we construct the N=4 theory and discuss its relationship to ten-dimensional supergravity.     

Microanalysis of serum triglycerides with or without separation by thin-layer chromatography

A manual colormetric procedure for the determination of tissue or serum triglyceride is described. This procedure utilizes very stable reagents and will allow for analysis of triglycerides after separation by TLC without prior extraction from the silica gel. Serum triglyceride analysis requires only 20 μl.     

Synthesis of Linear (Z)‐α,β‐Unsaturated Esters by Catalytic Cross‐Metathesis. The Influence of Acetonitrile

Kinetically controlled catalytic cross‐metathesis reactions that generate (Z)‐α,β‐unsaturated esters selectively are disclosed. A key finding is that the presence of acetonitrile obviates the need for using excess amounts of a more valuable terminal alkene substrates. On the basis of X‐ray structure and spectroscopic investigations a rationale for the positive impact of acetonitrile is provided. Transformations leading to various E,Z‐dienoates are highly Z‐selective as well. Utility is highlighted by application to stereoselective synthesis of the C1–C12 fragment of biologically active natural product (?)‐laulimalide.     

Five- and six-membered ring formation from the intramolecular reaction of a protonated oxirane and alkene

Computational studies of competing five- and six-membered cyclisation of alkenyloxiranes 1a-d show that intramolecular reaction of a protonated oxirane and alkene is a concerted, single-step, exothermic process. The reactions proceed via reactant-like transition states, but where the oxirane C-O bond is considerably stretched. Two factors are seen to affect the regiochemistry: (1) stabilisation of the transitory positive charge in the transition state favours cyclisation to the more highly substituted oxirane carbon; and (2) there is an inherent stereoelectronic preference for six-membered cyclisation over five-membered cyclisation. The inherent preference for six-membered cyclisation has a parallel in Baldwin's rules for six-membered ring closure of a carbocation with an alkene, rather than Baldwin's rule for intramolecular nucleophilic reaction of three-membered rings, suggesting that the protonated oxirane mimics a carbocation. The electronic and stereoelectronic effects for cyclisation are modified by steric interactions of axial methyl groups. These systems provide a model for the A-ring cyclisation of oxidosqualene.     

Observation of an acryloyl-thiamin diphosphate adduct in the first step of clavulanic acid biosynthesis

The first committed biosynthetic step toward clavulanic acid, the clinically important beta-lactamase inhibitor, is catalyzed by the thiamin diphosphate (ThDP)-dependent enzyme N2-(2-carboxyethyl)arginine synthase (CEAS). This protein carries out a unique reaction among ThDP-dependent processes in which a C-N bond is formed, and an electrophilic acryloyl-thiazolium intermediate of ThDP is proposed to be involved, unlike the nucleophilic enamine species typically generated by this class of enzymes. Here we present evidence for the existence of the putative acryloyl adduct and report the unexpected observation of a long-wavelength chromophore (lambda = 433 nm), which we attribute to this enzyme-bound species. Chemical models were synthesized that both confirm its expected absorption (lambda = 310-320 nm) and exclude self-condensation and intramolecular imine formation with the cofactor as its cause. Circular dichroism experiments and others discount charge transfer as a likely explanation for the approximately 120 nm red shift of the chromophore ( approximately 25 kcal). Examples are well-known of charged molecules that exhibit significantly red-shifted UV-visible spectra compared to their neutral forms as, for example, polyene cations and dyes such as indigo and the cyanines. Rhodopsin is the classic biochemical example where the protein (opsin)-bound protonated Schiff base of retinal displays a remarkable range of red-shifted absorptions modulated by the protein environment. Similar tuning of the chromophoric behavior of the enzyme-bound CEAS acryloyl.ThDP species may be occurring.     

Artificial Neural Networks for Noise Removal in Data-Sparse Charged Particle Imaging Experiments

We present the first demonstration of artificial neural networks (ANNs) for the removal of Poissonian noise in charged particle imaging measurements with very low overall counts. The approach is successfully applied to both simulated and real experimental image data relating to the detection of photoions/photoelectrons in unimolecular photochemical dynamics studies. Specific examples consider the multiphoton ionization of pyrrole and (S)-camphor. Our results reveal an extremely high level of performance, with the ANNs transforming images that are unusable for any form of quantitative analysis into statistically reliable data with an impressive similarity to benchmark references. Given the widespread use of charged particle imaging methods within the chemical dynamics community, we anticipate that the use of ANNs has significant potential impact – particularly, for example, when working in the limit of very low absorption/photoionization cross-sections, or when attempting to reliably extract subtle image features originating from phenomena such as photofragment vector correlations or photoelectron circular dichroism.     

Synthesis of cytotoxic cyanobactin,Wewakazole B

We report herein the synthesis of cytotoxic cyanobactin, Wewakazole B through an efficient solution-phase approach. The key steps of the synthesis are the macrocyclic lactamization of linear dodecapeptide and construction of two hexapeptides with three different substituted oxazole rings.     

Structure-based design of conformationally constrained cyclic peptidomimetics to target the MLL1-WDR5 protein–protein interaction as inhibitors of the MLL1 methyltransferase activity

We described herein structure-based design,synthesis and evaluation of conformationally constrained,cyclic peptidomimetics to block the MLL1-WDR5 protein–protein interaction as inhibitors of the MLL1 histone methyltransferase activity.Our study has yielded cyclic peptidomimetics with very high binding affinities to WDR5(Kivalues 1 nmol/L) and function as antagonists of the MLL1 histone methyltransferase activity.