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211.
N,N′-Bis(6A-deoxy-β-cyclodextrin-6A-yl)urea behaves as a molecular reactor to bias competing reactions of indoxyl anion and isatin-5-sulfonate in water, to give indigo and indirubin-5′-sulfonate. It appears that the cyclodextrin dimer increases the relative reactivity of the isatin-5-sulfonate, by selectively complexing the reactive form. The molecular host also aligns the isatinsulfonate with indoxyl anion to favour production of indirubin-5′-sulfonate, with the result that the ratio of indigo and indirubin-5′-sulfonate produced is altered by a factor of at least 3500, without a substantial loss of yield. 相似文献
212.
Background: Amyloid plaques composed of the fibrillar form of the amyloid-β protein (Aβ) are the defining neuropathological feature of Alzheimer's disease (AD). A detailed understanding of the time course of amyloid formation could define steps in disease progression and provide targets for therapeutic intervention. Amyloid fibrils, indistinguishable from those derived from an AD brain, can be produced in vitro using a seeded polymerization mechanism. In its simplest form, this mechanism involves a cooperative transition from monomeric Aβ to the amyloid fibril without the buildup of intermediates. Recently, however, a transient species, the Aβ amyloid protofibril, has been identified. Here, we report studies of Aβ amyloid protofibril and its seeded transition into amyloid fibrils using atomic force microscopy.Results: Seeding of the protofibril-to-fibril transition was observed. Preformed fibrils, but not protofibrils, effectively seeded this transition. The assembly state of Aβ influenced the rate of seeded growth, indicating that protofibrils are fibril assembly precursors. The handedness of the helical surface morphology of fibrils depended on the chirality of Aβ. Finally, branched and partially wound fibrils were observed.Conclusions: The temporal evolution of morphologies suggests that the protofibril-to-fibril transition is nucleation-dependent and that protofibril winding is involved in that transition. Fibril unwinding and branching may be essential for the post-nucleation growth process. The protofibrillar assembly intermediate is a potential target for AD therapeutics aimed at inhibiting amyloid formation and AD diagnostics aimed at detecting presymptomatic disease. 相似文献
213.
J. F. Harper 《Applied Scientific Research》1982,38(1):343-352
This paper reviews recent progress in the theories of the surface boundary conditions of adsorbed solutes in liquids, and of the effects of those solutes on the steady motion of a bubble or drop in the liquid. Both singular perturbation theory and numerical solutions have useful roles in this problem, and their relationship is explored. In addition, analytical solutions are given to two problems concerning a spherical bubble rising steadily at low Reynolds number in a viscous fluid. One of these is displacement of the internal vortex centre from its position in the absence of surface activity when there is a small stagnant cap of surfactant at the rear. The results agree with experimental data in the direction of that displacement but give only about half its amount. The other problem is the velocity perturbation all round the surface caused by a very dilute solution of a weak surfactant at high Péclet number. This compares quite well with the numerical solution for a Péclet number of 60, having relative errors of order (60)–1/2 as would be expected. 相似文献
214.
Michael P. DiCicco Bridget Lang Thomas I. Harper 《Biomedical chromatography : BMC》2009,23(6):647-657
Medical devices sterilized by ethylene oxide (EtO) retain trace quantities of EtO residuals, which may irritate patients' tissue. Reliably quantifying trace level EtO residuals in small medical devices requires an extremely sensitive analytical method. In this research, a Doehlert uniform shell design was utilized in obtaining a response surface to optimize a novel headspace–solid‐phase microextraction–gas chromatographic (HS‐SPME‐GC) method developed for analyzing trace levels of EtO residuals in sterilized medical devices, by evaluating sterilized, polymer‐coated, drug‐eluting cardiovascular stents. The effects of four independent experimental variables (HS‐SPME desorption time, extraction temperature, GC inlet temperature and extraction time) on GC peak area response of EtO were investigated simultaneously and the most influential experimental variables determined were extraction temperature and GC inlet temperature, with the fitted model showing no evidence of lack‐of‐fit. The optimized HS‐SPME‐GC method demonstrated overall good linearity/linear range, accuracy, repeatability, reproducibility, absolute recovery and high sensitivity. This novel method was successfully applied to analysis of trace levels of EtO residuals in sterilized/aerated cardiovascular stents of various lengths and internal diameter, where, upon heating, trace EtO residuals fully volatilized into HS for extraction, thereby nullifying matrix effects. As an alternative, this novel HS‐SPME‐GC method can offer higher sensitivity compared with conventional headspace analyzer‐based sampling. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
215.
M M Hann A R Leach G Harper 《Journal of chemical information and computer sciences》2001,41(3):856-864
Using a simple model of ligand-receptor interactions, the interactions between ligands and receptors of varying complexities are studied and the probabilities of binding calculated. It is observed that as the systems become more complex the chance of observing a useful interaction for a randomly chosen ligand falls dramatically. The implications of this for the design of combinatorial libraries is explored. A large set of drug leads and optimized compounds is profiled using several different properties relevant to molecular recognition. The changes observed for these properties during the drug optimization phase support the hypothesis that less complex molecules are more common starting points for the discovery of drugs. An extreme example of the use of simple molecules for directed screening against thrombin is provided. 相似文献
216.
D Evenden P R Harper S C Brailsford V Harindra 《The Journal of the Operational Research Society》2006,57(12):1400-1412
Chlamydia is the most common sexually transmitted infection in the UK and constitutes a major public health problem. The UK Department of Health is phasing in a National Chlamydia Screening Programme (NCSP) but there is concern that blanket screening of the entire at risk population will simply add extra burden to the already overstretched health economy. This paper demonstrates that certain high-risk sub-groups within the general population are critical in the infection dynamics. Improved targeting of these high-risk populations achieves greater cost-effectiveness. Statistical risk-group clustering techniques have been used to identify indicators that are strong predictors in determining high-risk status while geomapping techniques visually display prevalence geographically across the region, thus identifying high prevalence postcode clusters and informing public health planners where to target intervention and screening strategies. A System Dynamics simulation model has been used to capture the infection dynamics and measure the cost-effectiveness of the intervention strategies. The model incorporates risk-group behaviour as identified by the above geomapping and statistical analysis components of the research. The combined use of computer simulation, statistical analysis and geomapping methodologies has provided a unique holistic view of the problem. 相似文献
217.
J M Moore D A Cooper I S Lurie T C Kram S Carr C Harper J Yeh 《Journal of chromatography. A》1987,410(2):297-318
A method has been developed that allows for the detection of the eleven stereoisomers of diphenylcyclobutanedicarboxylic acid in illicit cocaine samples, including alpha-, gamma-, and epsilon-truxillic acids and beta- and delta-truxinic acids. These, and other carboxylic acids, were also detected as ester moieties of alkaloidal impurities in illicit cocaine as well as in alkaloids of the South American coca leaf, e.g., alpha- and beta-truxilline. After lithium aluminum hydride reduction of the acidic and basic extracts of a prepared sample, the reduced species were derivatized with heptafluorobutyric anhydride in the presence of pyridine. The heptafluorobutyryl derivatives of the reduced diphenylcyclobutanedicarboxylic compounds were easily detected on-column at low picogram levels using a moderately polar fused-silica capillary column in the splitless mode and interfaced with a 63Ni electron-capture detector. 相似文献
218.
219.
Ainge GD Compton BJ Hayman CM Martin WJ Toms SM Larsen DS Harper JL Painter GF 《The Journal of organic chemistry》2011,76(12):4941-4951
Phosphatidylinositol mannosides (PIMs) isolated from mycobacteria have been identified as an important class of phosphoglycolipids with significant immune-modulating properties. We present here the synthesis of dipalmitoyl phosphatidylinositol hexamannoside (PIM(6)) 1 and the first reported functional biology of a synthetic PIM(6). Key steps in the synthetic protocol included the selective glycosylation of an inositol 2,6-diol with a suitably protected mannosyl donor and construction of the glycan core utilizing a [3 + 4] thio-glycosylation strategy. The target 1 was purified by reverse phase chromatography and characterized by standard spectroscopic methods, HPLC, and chemical modification by deacylation to dPIM(6). The (1)H NMR spectrum of synthetic dPIM(6) obtained from 1 matched that of dPIM(6) obtained from nature. PIM(6) (1) exhibited dendritic cell-dependent suppression of CD8(+) T cell expansion in a human mixed lymphocyte reaction consistent with the well established immunosuppressive activity of whole mycobacteria. 相似文献
220.
As is often the case in healthcare provision, public services may offer facilities at a hierarchy of levels in different locations, ranging from basic to specialised levels of care. In addition to efficiency objectives, with public services there is the concern of equity of provision when locating new facilities. We present, as a tool-kit for decision makers, a range of discrete hierarchical location models with bicriteria efficiency/equity objectives. These models are for use in location of facilities within hierarchical systems where a fair but efficient hierarchical service is sought. The hierarchical models have as efficiency criteria both p-median and maximal-covering types. These components are combined in a novel manner with appropriate equity objectives to give decision makers a range of choices of scenarios. We illustrate use of the models in a healthcare setting. 相似文献