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31.
Higgins EM Sherwood JA Lindsay AG Armstrong J Massey RS Alder RW O'Donoghue AC 《Chemical communications (Cambridge, England)》2011,47(5):1559-1561
pK(a) values of 19.8-28.2 are reported for the conjugate acids of a large series of NHCs in water. The effects of ring size, N-substituent and C(4)-C(5) saturation on pK(a) are discussed. 相似文献
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34.
A Higgins 《The Journal of the Operational Research Society》1998,49(10):1026-1033
Before railway track maintenance crews can undertake any work, the allocation of activities to available time intervals in the train schedule as well as to crews must be undertaken. This paper puts forward a model aimed at determining the best allocation of maintenance activities and crews so as to mininise the disruption to and from scheduled trains and to reduce completion time. The model is subject to constraints such as available budget; maintenance activity precedence; track availability; and minimum travel time between track links. Solution to the model is found using the tabu search heuristic for which the neighbourhood is defined by swapping the order of jobs, maintenance crews, or both. Application to a 300?km track corridor with a four day planning horizon is discussed along with the impacts of modifying the number of maintenance crews. The optimal schedule achieved an 8% reduction in expected interference delay with the train schedule and a 7% reduction in average completion times, relative to the solution which was constructed manually. 相似文献
35.
A computer program is given for the identification of edible oils from their fatty acid ratios. The program was used with the Hewlett-Packard 3354 Laboratory Automation System in autocall mode to identify a number of vegetable oils from the fatty acid ratios determined by gas chromatography of the trans-esterified oil samples. 相似文献
36.
Peter M. Higgins 《Semigroup Forum》1988,37(1):31-36
Communicated by N. R. Reilly 相似文献
37.
The application of single-molecule spectroscopic methods in studies of individual nanoscale environments within sol-gel-derived silicate thin films is reviewed. Representative examples of the experiments performed and results obtained in several studies from the authors' laboratories are given. Included are investigations of the static and dynamic polarity properties of organically modified silicate (ORMOSIL) films. The results of these studies point to nonrandom variations in the film properties, providing strong evidence for the formation of phase-separated organic- and inorganic-rich domains. Studies of single-molecule diffusion through the same films yield important evidence for the formation of liquidlike silicate oligomers that facilitate probe molecule diffusion. Finally, single-molecule studies of the local pH within individual film environments are discussed. Valuable information on the contributions of local materials' acidity variations to overall sample heterogeneity is obtained. The results of immersion studies indicate that certain molecular environments are inaccessible to external solutions over periods as long as a few hours. The article concludes with a discussion of possible future challenges in this research that may be addressed by new and existing single-molecule methods. 相似文献
38.
Fu Y Ye F Sanders WG Collinson MM Higgins DA 《The journal of physical chemistry. B》2006,110(18):9164-9170
Single molecule spectroscopy is applied in studies of diffusion and surface adsorption in sol-gel-derived mesoporous silica thin films. Mesoporous films are obtained by spin casting surfactant-templated sols onto glass substrates. Small-angle X-ray diffraction results are consistent with hexagonally ordered mesophases in as-synthesized (i.e., surfactant-containing) films. Upon calcination, a 30% contraction and disordering of these structures occurs. Nile Red is used as a fluorescent probe of both the as-synthesized and calcined films. It is loaded into the samples at subnanomolar levels either prior to spin casting or after calcination. Fluorescence imaging and single-point fluorescence time transients show the dye molecules to be relatively mobile in the as-synthesized samples. In contrast, the molecules appear entrapped at fixed locations in dry calcined films. In calcined films rehydrated under high humidity conditions, the Nile Red molecules again become mobile. Time transients obtained from the as-synthesized and rehydrated samples provide clear evidence for frequent reversible adsorption of the dye to the silica surfaces. Autocorrelations of the time transients provide quantitative data on the mean diffusion coefficients (D = 2.4 x 10(-10) and 2.6 x 10(-10) cm2/s) and mean desorption times (1/k = 25 and 40 s) for the as-synthesized and rehydrated films, respectively. The results prove both water and surfactant play important roles in governing matrix interactions and mass transport. 相似文献
39.
In this paper, we present distribution-free tests to evaluate the effect of multiple treatments when there are a large number of repeated measurements from each subject nested in a treatment. We formulate new test statistics to account for heteroscedasticity and unbalanced designs. The asymptotic distributions for the test statistics are obtained when the repeated measurements from the same subject have long range dependence and weak dependence, respectively. The asymptotic results hold under the nonclassical setting in which the number of repeated measurements is large while the number of subjects per treatment may be small. A real application to compare cattle ear temperature profiles under different antibiotic treatments is given for illustration. Simulation studies are undertaken to compare the empirical performance of the proposed tests to commonly used methods. 相似文献
40.
Chuanli Wu Xiaohang Qiao Dr. Craig M. Robertson Prof. Simon J. Higgins Prof. Chenxin Cai Prof. Richard J. Nichols Dr. Andrea Vezzoli 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(29):12127-12132
Polyoxometalates have been proposed in the literature as nanoelectronic components, where they could offer key advantages with their structural versatility and rich electrochemistry. Apart from a few studies on their ensemble behaviour (as monolayers or thin films), this potential remains largely unexplored. We synthesised a pyridyl-capped Anderson–Evans polyoxometalate and used it to fabricate single-molecule junctions, using the organic termini to chemically “solder” a single cluster to two nanoelectrodes. Operating the device in an electrochemical environment allowed us to probe charge transport through different oxidation states of the polyoxometalate, and we report here an efficient three-state transistor behaviour. Conductance data fits a quantum tunnelling mechanism with different charge-transport probabilities through different charge states. Our results show the promise of polyoxometalates in nanoelectronics and give an insight on their single-entity electrochemical behaviour. 相似文献