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921.
Peter George Gordon Glenn P. A. Yap Seán Thomas Barry 《Journal of chemical crystallography》2011,41(3):375-378
Abstract
A crystal structure of dimerized 1,3-diisopropyl carbodiimide (CDI) has been obtained and its synthesis through a reaction of CDI with aluminum chloride (AlCl3) has been studied. It possesses space group P21/c, with a = 9.352(5), b = 7.956(4), c = 11.405(6) ? and β = 112.465(5)°. It has been observed that this reaction is catalytic with respect to AlCl3. Kinetic studies of the dimer show that its decomposition into CDI is first order with respect to the dimer. The reactivity of the dimer with metals has been investigated through reactions with methyl lithium and alane. The thermal stability of the dimer has been investigated by thermal gravimetric analysis and differential scanning calorimetry. 相似文献922.
Tracey M. McLean Deidre Cleland Keith C. Gordon Shane G. Telfer Mark R. Waterland 《Journal of Raman spectroscopy : JRS》2011,42(12):2154-2164
Detailed studies of the mechanism of surface‐enhanced (resonance) Raman spectroscopy (SE(R)RS), and its applications, place a number of demands on the properties of SERS scatterers. With large Raman cross‐sections, versatile synthetic chemistry and complete lack of fluorescence, free dipyrrins meet these demands but the Raman and SE(R)RS spectroscopy of free dipyrrins is largely unknown. The first study of the Raman spectroscopy of free dipyrrins is therefore presented in this work. The nonresonant Raman, resonant Raman and surface‐enhanced Raman spectra of a typical meso aryl‐substituted‐dipyrrin are reported. Absolute differential cross‐sections are obtained for excitation wavelengths in the near infrared and visible region, in solution phase and for dipyrrin adsorbed on the surface of silver nanoparticles. Raman enhancement factors for SERRS and resonance Raman are calculated from the observed differential cross‐sections. The magnitudes of the resonantly enhanced cross‐sections are similar to those recently reported for strong SERS dyes such as Rhodamine 6G and Crystal Violet. Free dipyrrins offer the advantages of existing SERS dyes but without the drawback of strong fluorescence. Free dipyrrins should therefore find applications in all areas of Raman spectroscopy including fundamental studies of the mechanisms of SERS and bioanalytical and environmental applications. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
923.
Harkewicz R Belov ME Anderson GA Pasa-Tolić L Masselon CD Prior DC Udseth HR Smith RD 《Journal of the American Society for Mass Spectrometry》2002,13(2):144-154
Data-dependent external m/z selection and accumulation of ions is demonstrated in use with ESI-FTICR instrumentation, with two different methods for ion selection being explored. One method uses RF/DC quadrupole filtering and is described in use with an 11.5 tesla (T) FTICR instrument, while the second method employs RF-only resonance dipolar excitation selection and is described in use with a 3.5 T FTICR instrument. In both methods ions are data-dependently selected on the fly in a linear quadrupole ion guide, then accumulated in a second linear RF-only quadrupole trap that immediately follows. A major benefit of ion preselection prior to external accumulation is the enhancement of ion populations for low-level species. This development is expected to expand the dynamic range and sensitivity of FTICR for applications including analysis of complex polypeptide mixtures (e.g., proteomics). 相似文献
924.
The kinetic method was used to determine the proton affinities of methyl esters of several saturated fatty acids. Decompositions of the proton-bound dimers of the methyl esters, AHB+, were observed under different conditions with two instruments. The proton affinities (PAs) of the methyl esters increase continually with increasing carbon number in the acid. Equilibrium and initial rate experiments were performed with a Fourier transform ion cyclotron resonance mass spectrometer on the methyl ester of the C22 saturated acid (methyl behenate). These experiments give values for PA (methyl behenate) that are perhaps slightly lower than those obtained with the kinetic method. The PAs of the methyl esters of the fatty acids could be correlated with the equation: PA (ester) = (40.0 ± 2.5)*log(n) + (784.7 ± 3.9) kJ/mol or PA (ester) = (864 ± 2) − (479 ± 41)/n, wheren = number of atoms in the molecule. Proton affinities of smaller sets of 1-alkylamines and 1-alkanols can be fit to similar equations. 相似文献
925.
Rockwood AL Kushnir MM Nelson GJ 《Journal of the American Society for Mass Spectrometry》2003,14(4):311-322
Traditional practice in tandem mass spectrometry is to select the mono-isotopic ion for dissociation. However, high molecular weight compounds often have weak mono-isotopic peaks, which limit that approach. Furthermore, the traditional approach does not take advantage of the very rich store of information available in the isotopic patterns from the dissociation of individual non-mono-isotopic peaks. Interpretation of these isotopic patterns requires a theory capable of predicting the patterns. However, a general theory for the prediction of these patterns has been lacking. This paper shows that the patterns can be obtained from a certain vector product, the outer product, of the full isotopic distribution of the product ion with the full isotopic distribution of the complementary product. Unlike previous approaches, the method is applicable to systems of arbitrary isotopic complexity. The patterns are potentially useful for elucidation of dissociation pathways, elemental composition, and chemical structure. The paper presents several applications of the theory. 相似文献
926.
Systems that are operated near their resonance frequencies experience vibrations that can lead to impaired performance, overstressing, fatigue fracture and adverse human reactions. Frequency response (FR) analysis can be invoked to mitigate the effects. When components of a system are described by random variables, modal frequencies and modal shapes, or, amplitudes and phases, are also random variables and the frequency response (FR) design of the system becomes more complex since it requires the solution of a frequency-variant probability problem. This paper presents a methodology to provide the frequency response design of uncertain systems using a transfer function approach. The methodology is found to be robust, expandable and flexible and can be applied to multi-disciplinary systems with n-dof and multiple design constraints. The novelty of the approach is the creation of a frequency-invariant probability problem through: (a) the discretization of the frequency band of interest into multiple contiguous point frequencies, (b) the introduction of new performance indices that measure the probability of success over the entire frequency band, and (c) the introduction of explicit meta-models to provide sufficiently fast probability evaluations through Monte Carlo simulation. The key to the performance indices are limit-state functions formed at all discrete, contiguous, frequencies. Each limit-state function establishes a conformance region in terms of the random design variables. The probabilities of the conformance regions are correctly combined to provide a single series-system index to be maximized by adjusting distribution parameters. The simple explicit meta-model is based on Kriging and performance measures at arbitrary design sets are efficiently calculated. Error analysis suggests ways to predict and control the errors with regards to meta-model fitting and probability calculations and so the method appears sufficiently accurate for engineering applications. The proposed methodology has applications in numerous areas such as electrical filters and structural mechanics – all with n-dof and multiple responses. The Performance indices can be evaluated at any frequency over any number of frequency ranges. A case study of a vibration absorber mechanism shows how the new methodology provides an improved and timely design with controllable accuracy when compared with previous proposals that employed modal frequencies. 相似文献
927.
The IR spectra of [Co(pz)2X2]n (pz = pyrazine; X = C1, Br, I), [Cu(pz)X2]n (X = C1, Br), [Cu(pz)2](C104)2 and [Cu(py)4] (C104)2 (py = pyridine) derived from deuterated pz and py, and their unlabelled analogues are discussed. Assignments of the metal-ligand vibrations are based on the effects of the isotopic substitutions. 相似文献
928.
Edward P. Mitchell Elodie Boller Elspeth J. Gordon Gordon A. Leonard Stéphanie Monaco 《Synchrotron Radiation News》2013,26(6):18-23
The challenge of harnessing the power of third-generation synchrotron sources for industrial R&D has been taken up by the ESRF ever since the first users arrived in 1994. However, working with industry has its own special requirements, and often mismatches and clashes between a traditional scientific “ivory tower” culture and the needs of the market-driven commercial world. After more than 15 years of industrial research at the ESRF, during which strong industrial programs in protein crystallography and microtomography have been established, we continue to build bridges between the two worlds. 相似文献
929.
In this paper, we describe a complete computer classification of the hemisystems in the two known flock generalized quadrangles of order (52, 5) and give numerous further examples of hemisystems in all the known flock generalized quadrangles of order (s 2, s) for s ≤ 11. By analysing the computational data, we identify two possible new infinite families of hemisystems in the classical generalized quadrangle H(3, s 2). 相似文献
930.
Sue Gordon Jackie Nicholas 《International Journal of Mathematical Education in Science & Technology》2013,44(7):1081-1091
We report on the survey responses of 51 students attending mathematics bridging courses at a major Australian university, investigating what mathematics, if any, these students had studied in the senior years of schooling and what factors affected their decisions about the level of mathematics chosen. Quantitative findings are augmented by qualitative responses to open-ended questions in the survey as well as excerpts from follow-up emails. The findings show that the major reasons for students taking lower levels of mathematics in senior year(s), or dropping mathematics, include finding enough time for non-mathematics subjects, confidence in mathematical capability, advice and maximizing potential ranking for university admission. 相似文献