排序方式: 共有41条查询结果,搜索用时 31 毫秒
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Kilpatrick JM Moore AJ Barton JS Jones JD Reeves M Buckberry C 《Optics letters》2000,25(15):1068-1070
We describe a high-speed digital speckle pattern interferometer incorporating a line-scan camera and a waveguide phase modulator for the measurement of complex deformation (vibration phase and amplitude) at audio acoustic frequencies. Experimental data show continuous phase-stepped recovery of out-of-plane surface deformation in one dimension, obtained at 100 kHz with 2pi/20-rad (0.02-mum) displacement resolution, for surface velocities of 3.2 mm s>(-1) . 相似文献
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Bush CE Goldston RJ Scott SD Fredrickson ED McGuire K Schivell J Taylor G Barnes CW Bell MG Boivin RL Bretz N Budny RV Cavallo A Efthimion PC Grek B Hawryluk R Hill K Hulse RA Janos A Johnson DW Kilpatrick S Manos DM Mansfield DK Meade DM Park H Ramsey AT Stratton B Synakowski EJ Towner HH Wieland RM Zarnstorff MC Zweben S 《Physical review letters》1990,65(4):424-427
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Rebekah L. N. Hailes Dr. Rebecca A. Musgrave Dr. Alexander F. R. Kilpatrick Dr. Andrew D. Russell Dr. George R. Whittell Prof. Dermot O'Hare Prof. Ian Manners 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(4):1044-1054
Polymetallocenes based on ferrocene, and to a lesser extent cobaltocene, have been well-studied, whereas analogous systems based on nickelocene are virtually unexplored. It has been previously shown that poly(nickelocenylpropylene) [Ni(η5-C5H4)2(CH2)3]n is formed as a mixture of cyclic ( 6 x ) and linear ( 7 ) components by the reversible ring-opening polymerisation (ROP) of tricarba[3]nickelocenophane [Ni(η5-C5H4)2(CH2)3] ( 5 ). Herein the generality of this approach to main-chain polynickelocenes is demonstrated and the ROP of tetracarba[4]nickelocenophane [Ni(η5-C5H4)2(CH2)4] ( 8 ), and disila[2]nickelocenophane [Ni(η5-C5H4)2(SiMe2)2] ( 12 ) is described, to yield predominantly insoluble homopolymers poly(nickelocenylbutylene) [Ni(η5-C5H4)2(CH2)4]n ( 13 ) and poly(tetramethyldisilylnickelocene) [Ni(η5-C5H4)2(SiMe2)2]n ( 14 ), respectively. The ROP of 8 and 12 was also found to be reversible at elevated temperature. To access soluble high molar mass materials, copolymerisations of 5 , 8 , and 12 were performed. Superconducting quantum interference device (SQUID) magnetometry measurements of 13 and 14 indicated that these homopolymers behave as simple paramagnets at temperatures greater than 50 K, with significant antiferromagnetic coupling that is notably larger in carbon-bridged 6 x /7 and 13 compared to the disilyl-bridged 14 . However, the behaviour of these polynickelocenes deviates substantially from the Curie–Weiss law at low temperatures due to considerable zero-field splitting. 相似文献
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Gawrys KL Blankenship GA Kilpatrick PK 《Langmuir : the ACS journal of surfaces and colloids》2006,22(10):4487-4497
While small-angle neutron scattering (SANS) has proven to be very useful for deducing the sizes and masses of asphaltenic aggregates in solution, care must be taken to account for solvation effects within the aggregates so as to not err in the characterization of these important systems. SANS measurements were performed on solutions of asphaltenes dispersed in deuterated solvents in which a broad spectrum of solute and solvent chemical compositions was represented. Fits to the scattering intensity curves were performed using the Guinier approximation, the Ornstein-Zernike (or Zimm) model, a mass-fractal model, and a polydisperse cylinder model. The mass-fractal model provided apparent fractal dimensions (2.2-3) for the aggregates that generally decreased with increasing aggregate size, indicating increased surface roughness for larger aggregates. The polydisperse cylinder model provided typical values of the particle thicknesses from 5 to 32 angstroms, the average particle radius from 25 to 125 angstroms, and approximately 30% radius polydispersity. Subsequent calculation of average aggregate molar masses suggested a range of solvent entrainment from 30 to 50% (v/v) within the aggregates that were consistent with previous viscosity measurements. Additional calculations were performed to estimate the proportion of microparticle to nanoparticle aggregates in the solutions. The results indicate that the inclusion of solvation effects is essential for the accurate determination of aggregate molecular weights and fractal dimensions. 相似文献
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S. Singh J. D. McLean P. K. Kilpatrick 《Journal of Dispersion Science and Technology》2013,34(1-2):279-293
The role of asphaltenes in stabilizing water-in-crude oil emulsions is extremely well established. The mechanism appears to be one in which planar, disk-like asphaltene molecules aggregate through lateral intermolecular forces to form primary aggregates or micelles which are interfacially active. These aggregates — upon adsorbing at the oil-water interface — crosslink through physical interactions to form a viscoelastic network, which has been characterized by some as a “skin” or a “plastic film”. The strength of this film, as gauged by shear and elastic moduli, seems to correlate well with water-in-oil emulsion stability. What is still relatively unknown is the role of chemistry in governing the strength of these lateral inter-asphaltene interactions. The candidate interactions include π-bonding between the delocalized electrons in the fused aromatic ring core, H-bonding between proton donors and acceptors imbedded in the asphaltenic cores, and metal-electron interactions between, for example, heavy metal ions such as vanadium or nickel and electron pairs in pyrrolic or porphyrin functional groups. We have probed these interactions indirectly by studying the destabilization of water-in-oil emulsions by a variety of aromatic solvents. In this paper, we review our previous results on both water-in-crude oil systems, as well as water-in-model oil (heptane-toluene-asphaltene mixtures) systems, in which the emulsions were progressively destabilized by addition of aromatic solvents. We also present new results with fused ring aromatic solvents, specifically methyl-naphthalene, phenanthrene, and phenanthridine. Our results suggest that fused ring aromatic solvents are considerably more effective at destabilizing asphaltene emulsions and proton-accepting fused ring aromatic solvents are most effective. These results indicate that both π-bonding and H-bonding play significant roles in mediating the aggregation of asphaltenes in oil-water interfacial films. 相似文献
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Sheikh KH Giordani C Kilpatrick JI Jarvis SP 《Langmuir : the ACS journal of surfaces and colloids》2011,27(7):3749-3753
Supported dipalmitoylphosphatidylcholine (DPPC) bilayers are widely used membrane systems in biophysical and biochemical studies. Previously, short-range positional and orientational order of lipid headgroups of supported DPPC bilayers was observed at room temperature using low deflection noise frequency modulation atomic force microscopy (FM-AFM). While this ordering was supported by X-ray diffraction studies, it conflicted with diffusion coefficient measurements of gel-phase bilayers determined from fluorescence photobleaching experiments. In this work, we have directly imaged mica-supported DPPC bilayers with submolecular resolution over scan ranges up to 146 nm using low deflection noise FM-AFM. Both orientational and positional molecular ordering were observed in the mesoscale, indicative of crystalline order. We discuss these results in relation to previous biophysical studies and propose that the mica support induces mesoscopic crystalline order of the DPPC bilayer at room temperature. This study also demonstrates the recent advance in the scan range of submolecular scale AFM imaging. 相似文献
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Neta P Pu QL Kilpatrick L Yang X Stein SE 《Journal of the American Society for Mass Spectrometry》2007,18(1):27-36
Some of the most prominent "neutral losses" in peptide ion fragmentation are the loss of ammonia and water from N-terminal glutamine. These processes are studied by electrospray ionization mass spectrometry in singly- and doubly-protonated peptide ions undergoing collision-induced dissociation in a triple quadrupole and in an ion trap instrument. For this study, four sets of peptides were synthesized: (1) QLLLPLLLK and similar peptides with K replaced by R, H, or L, and Q replaced by a number of amino acids, (2) QLnK (n = 0, 1, 3, 5, 7, 9, 11), (3) QLnR (n = 0, 1, 3, 5, 7, 9), and (4) QLn (n = 1, 2, 3, 4, 8). The results for QLLLPLLLK and QLLLPLLLR show that the singly protonated ions undergo loss of ammonia and to a smaller extent loss of water, whereas the doubly protonated ions undergo predominant loss of water. The fast fragmentation next to P (forming the y5 ion) occurs to a larger extent than the neutral losses from the singly protonated ions but much less than the water loss from the doubly protonated ions. The results from these and other peptides show that, in general, when N-terminal glutamine peptides have no "mobile protons", that is, the number of charges on the peptide is no greater than the number of basic amino acids (K, R, H), deamination is the predominant neutral loss fragmentation, but when mobile protons are present the predominant process is the loss of water. Both of these processes are faster than backbone fragmentation at the proline. These results are rationalized on the basis of resonance stabilization of the two types of five-membered ring products that would be formed in the neutral loss processes; the singly protonated ion yields the more stable neutral pyrrolidinone ring whereas the doubly protonated ion yields the protonated aminopyrroline ring (see Schemes). The generality of these trends is confirmed by analyzing an MS/MS spectra library of peptides derived from tryptic digests of yeast. In the absence of mobile protons, glutamine deamination is the most rapid neutral loss process. For peptides with mobile protons, dehydration from glutamine is far more rapid than from any other amino acid. Most strikingly, end terminal glutamine is by far the most labile source of neutral loss in excess-proton peptides, but not highly exceptional when mobile protons are not available. In addition, rates of deamination are faster in lysine versus arginine C-terminus peptides and 20 times faster in positively charged than negatively charged peptides, demonstrating that these formal neutral loss reactions are not "neutral reactions" but depend on charge state and stability. 相似文献
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Martin Kilpatrick Jr. und Mary L. Kilpatrick 《Fresenius' Journal of Analytical Chemistry》1927,71(1-2):52-53
Ohne Zusammenfassung 相似文献
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Yu LL Jarrett JM Davis WC Kilpatrick EL Oflaz R Turk GC Leber DD Valentin L Morel-Espinosa M Blount BC 《Analytical and bioanalytical chemistry》2012,404(6-7):1877-1886
Perchlorate, an inorganic anion, has recently been recognized as an environmental contaminant by the US Environmental Protection Agency. Urine is the preferred matrix for assessment of human exposure to perchlorate. Although the measurement technique for perchlorate in urine was developed in 2005, the calibration and quality assurance aspects of the metrology infrastructure for perchlorate are still lacking in that there is no certified reference material (CRM) traceable to the International System of Units. To meet the quality assurance needs in biomonitoring measurements of perchlorate and the related anions that affect thyroid health, the National Institute of Standards and Technology (NIST), in collaboration with the Centers for Disease Control and Prevention (CDC), developed Standard Reference Material (SRM) 3668 Mercury, Perchlorate, and Iodide in Frozen Human Urine. SRM 3668 consists of perchlorate, nitrate, thiocyanate, iodine, and mercury in urine at two levels that represent the 50th and 95th percentiles, respectively, of the concentrations (with some adjustments) in the US population. It is the first CRM being certified for perchlorate. Measurements leading to the certification of perchlorate were made collaboratively at NIST and CDC using three methods based on liquid or ion chromatography tandem mass spectrometry. Potential sources of bias were analyzed, and results were compared for the three methods. Perchlorate in SRM 3668 Level I urine was certified to be 2.70?±?0.21?μg?L(-1), and for SRM 3668 Level II urine, the certified value is 13.47?±?0.96?μg?L(-1). 相似文献