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排序方式: 共有408条查询结果,搜索用时 15 毫秒
91.
Murray Hodgson 《Applied Acoustics》2003,64(11):1033-1048
To evaluate the accuracy of empirical models for predicting steady-state noise levels and reverberation times in typical industrial workshops, predictions by these models were compared with predictions by a ray-tracing model, nominally using the same input data. Comparisons were made for three workshops—‘long’, ‘flat’ and ‘quasi-cubic’ in shape—with reflective and absorbent ceilings, when empty and with four densities of fittings. In the case of the ‘long’ room, noise levels were predicted along both the long and short major horizontal axes. In ‘long’ and ‘flat’ workshops, steady-state prediction by the empirical models often agreed with ray-tracing prediction within 2 dB. This result suggests that the empirical models are fundamentally valid. However, agreement was worse at large source/receiver distances, and at 500 Hz. Empirical reverberation-time prediction generally agreed less well with ray tracing, possibly indicating that the empirical reverberation-time prediction models are less valid. Strong disagreement occurred between the models in the case of steady-state prediction in the ‘quasi-cubic’ workshop, indicating that the empirical steady-state models are invalid in this case. Agreement for reverberation time was good with a non-absorbent ceiling, but poor with an absorbent ceiling. 相似文献
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95.
M. R. Banks J. I. G. Cadogan I. M. Dawson I. Gosney K. J. Grant S. Gaur P. K. G. Hodgson D. E. Stevenson 《Chromatographia》1992,34(1-2):48-50
Summary Chromatographic separation of racemic amines, carboxylic acids and alcohols can be achieved with excellent resolution as measured in terms of the chromatographic separation factor by derivatization with a homochiral oxazolidin-2-one easily prepared in three steps fromendo-borneol. The resolved materials can be isolated in excellent yields by cleavage of the resultant diastereomers using conventional methods, which also allow recovery of the chiral resolving agent for re-use. 相似文献
96.
Steven T. G. Street Yunxiang He Xu-Hui Jin Lorna Hodgson Paul Verkade Ian Manners 《Chemical science》2020,11(32):8394
Polymer-based nanoparticles show substantial promise in the treatment and diagnosis of cancer and other diseases. Herein we report an exploration of the cellular uptake of tailored, low dispersity segmented 1D nanoparticles which were prepared from an amphiphilic block copolymer, poly(dihexylfluorene)-b-poly(ethyleneglycol) (PDHF13-b-PEG227), with a crystallizable PDHF core-forming block and a ‘stealth’ PEG corona-forming block with different end-group functionalities. Segmented C–B–A–B–C pentablock 1D nanofibers with varied spatially-defined coronal chemistries and a selected length (95 nm) were prepared using the living crystallization-driven self-assembly (CDSA) seeded-growth method. As the blue fluorescence of PDHF is often subject to environment-related quenching, a far-red BODIPY (BD) fluorophore was attached to the PEG end-group of the coronal B segments to provide additional tracking capability. Folic acid (FA) was also incorporated as a targeting group in the terminal C segments. These dual-emissive pentablock nanofibers exhibited uptake into >97% of folate receptor positive HeLa cells by flow cytometry. In the absence of FA, no significant uptake was detected and nanofibers with either FA or BD coronal groups showed no significant toxicity. Correlative light and electron microscopy (CLEM) studies revealed receptor-mediated endocytosis as an uptake pathway, with subsequent localization to the perinuclear region. A significant proportion of the nanofibers also appeared to interact with the cell membrane in an end-on fashion, which was coupled with fluorescence quenching of the PDHF core. These results provide new insights into the cellular uptake of polymer-based nanofibers and suggest their potential use in targeted therapies and diagnostics.The cellular uptake of tailored, modular, and segmented low dispersity nanofibers with a crystalline π-conjugated core has been studied. 相似文献
97.
Cherng-Chyi Tzeng Urszula Rychlewska Derek J. Hodgson Raymond P. Panzica 《Journal of heterocyclic chemistry》1986,23(1):33-42
The first examples of the unknown pyrazino[2,3-e]-as-triazine ring system, that is, the 6,7-dihydroxy-5,6,7,8-tetrahydropyrazino[2,3-e]-as-triazines, have been prepared by ring closure of selected 5,6-diamino-as-triazines with 40% aqueous glyoxal. These 4-azapteridines experience a novel exchange process with alcohols at the C(7)-position. When dissolved in alcohol and stirred at room temperature, the 7-alkoxy, 6-hydroxy analogues are formed and isolated. In fact, during ring closure, if alcohols are used as the solvent, only the latter compounds are obtained. Initially, cyclization of the ortho-diamino-as-triazines with glyoxal proceeds in a stereoselective manner giving rise to both the cis and trans adducts. A single-crystal X-ray diffraction study has determined the predominant and most stable adduct to be the trans (R,R or S,S) isomer. Spectroscopy (nmr) has verified the intermediacy of the cis adduct, but because of the aforementioned exchange process only the trans isomer is isolated. The site of exchange on these σ-adducts has been rigorously established as C(7). A plausible reaction mechanism by which this exchange process occurs is presented. 相似文献
98.
Zhang HH Filipponi A Di Cicco A Lee SC Scott MJ Holm RH Hedman B Hodgson KO 《Inorganic chemistry》1996,35(17):4819-4828
An X-ray absorption spectroscopy study has been carried out at the Fe and Cu K-edges for two bridged molecular assemblies, both of which contain an Fe-X-Cu (X = O(2)(-), OH(-)) bridge unit, some of whose features are relevant to the binuclear site of cytochrome c oxidase. The two complexes [(OEP)Fe-O-Cu(Me(6)tren)](1+) and [(OEP)Fe-(OH)-Cu(Me(5)tren)(OClO(3))](1+) have similar structural fragments around the metal centers except that they differ significantly in the bridge structure (the former contains a linear oxo bridge while the latter has a bent hydroxo bridge). We report a comparative study of these complexes using multiple-scattering (MS) EXAFS analysis and the program package GNXAS. It is found that there is a dramatic increase in the amplitude of the Fe-X-Cu MS pathway as the bridge unit approaches linearity. Full EXAFS MS analysis enables accurate quantitation of bridge metrical details and geometry for both complexes. These studies were done with an expanded version of GNXAS, which allows for simultaneous multiple-edge fitting. Such multiple-edge analysis (using both Fe and Cu edge data) allows common pathways (in this case involving the Fe-X-Cu bridge) to be constrained to be the same, thus improving the observation/variable ratio and enhancing sensitivity for determination of the bridge structure. The accuracy of the structural determination for the bridge units is evaluated by a statistical analysis methodology in which correlations among fitting parameters are identified and contour plots are used to determine random error. The overall error in the EXAFS structural determination is found by establishing the variance with the crystallographically determined values: for the EXAFS-determined parameters at distances below 4 ?, distances and angles deviated on average from crystallographic values by 0.014 ? and 1.5 degrees, respectively. It is also established that structural features in the Fe absorption preedge are diagnostic of oxo vs hydroxo ligation. The relevance of this study to the structural definition of binuclear bridged sites in cytochrome c oxidase and other metalloenzymes is considered. 相似文献
99.
Frank P Benfatto M Szilagyi RK D'Angelo P Della Longa S Hodgson KO 《Inorganic chemistry》2005,44(6):1922-1933
The structure of [Cu(aq)]2+ has been investigated by using full multiple-scattering theoretical (MXAN) analysis of the copper K-edge X-ray absorption (XAS) spectrum and density functional theory (DFT) to test both ideal Td and square-planar four-coordinate, five-coordinate square-pyramidal, and six-coordinate octahedral [Cu(aq)]2+ models. The best fit was an elongated five-coordinate square pyramid with four Cu-O(eq) bonds (2 x 1.98 +/- 0.03 A and 2 x 1.95 +/- 0.03 A) and a long Cu-O(ax) bond (2.35 +/- 0.05 A). The four equatorial ligands were D2d-distorted from the mean equatorial plane by +/-(17 +/- 4) degrees, so that the overall symmetry of [Cu(H2O)5]2+ is C2v. The four-coordinate MXAN fit was nearly as good, but the water ligands (4 x 1.96 +/- 0.02 A) migrated +/-(13 +/- 4) degrees from the mean equatorial plane, making the [Cu(H2O)4]2+ model again D2d-distorted. Spectroscopically calibrated DFT calculations were carried out on the C2v elongate square-pyramidal and D2d-distorted four-coordinate MXAN copper models, providing comparative electronic structures of the experimentally observed geometries. These calculations showed 0.85e spin on Cu(II) and 0.03e electron spin on each of the four equatorial water oxygens. All covalent bonding was restricted to the equatorial plane. In the square-pyramidal model, the electrostatic Cu-O(ax) bond was worth only 96.8 kJ mol(-1), compared to 304.6 kJ mol(-1) for each Cu-O(eq) bond. Both MXAN and DFT showed the potential well of the axial bond to be broad and flat, allowing large low-energy excursions. The irregular geometry and D2d-distorted equatorial ligand set sustained by unconstrained [Cu(H2O)5]2+ warrants caution in drawing conclusions regarding structural preferences from small molecule crystal structures and raises questions about the site-structural basis of the rack-induced bonding hypothesis of blue copper proteins. Further, previously neglected protein folding thermodynamic consequences of the rack-bonding hypothesis indicate an experimental disconfirmation. 相似文献
100.
Hodgson RJ 《Journal of colloid and interface science》2001,240(2):412-418
The application of genetic algorithms to the inversion of static light-scattering (SLS) measurements is investigated. The approach is illustrated using simulated data on samples with unimodal, bimodal, and trimodal distributions of spherical particles. Particles having diameters in the range from 100 to 4000 nm are treated. Results are compared with other inversion procedures. It is found that genetic algorithms yield very good results in this situation. 相似文献