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91.
92.
McConnell H 《The Journal of chemical physics》2011,134(1):011102
Membrane composition fluctuations affect deuterium nuclear magnetic relaxation in lipid bilayers. The time dependence of the fluctuations depends on lipid diffusion. Near a miscibility critical point this diffusion involves an advective hydrodynamic coupling to the aqueous phase. The corresponding diffusion coefficient depends on both the critical length and the fluctuation wavelength. We calculate the effects of these dynamics on transverse deuterium nuclear relaxation in the 0.1(o)-10(o) range above the critical temperature. 相似文献
93.
Layre E Sweet L Hong S Madigan CA Desjardins D Young DC Cheng TY Annand JW Kim K Shamputa IC McConnell MJ Debono CA Behar SM Minnaard AJ Murray M Barry CE Matsunaga I Moody DB 《Chemistry & biology》2011,18(12):1537-1549
The lipidic envelope of Mycobacterium tuberculosis promotes virulence in many ways, so we developed a lipidomics platform for a broad survey of cell walls. Here we report two new databases (MycoMass, MycoMap), 30 lipid fine maps, and mass spectrometry datasets that comprise a static lipidome. Further, by rapidly regenerating lipidomic datasets during biological processes, comparative lipidomics provides statistically valid, organism-wide comparisons that broadly assess lipid changes during infection or among clinical strains of mycobacteria. Using stringent data filters, we tracked more than 5,000 molecular features in parallel with few or no false-positive molecular discoveries. The low error rates allowed chemotaxonomic analyses of mycobacteria, which describe the extent of chemical change in each strain and identified particular strain-specific molecules for use as biomarkers. 相似文献
94.
Anna J. McConnell Christopher J. Serpell Amber L. Thompson Dr. David R. Allan Dr. Paul D. Beer Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(4):1256-1264
The synthesis, structure and anion binding properties of the first calix[4]arene‐based [2]rotaxane anion host systems are described. Rotaxanes 9? Cl and 12? Cl, consisting of a calix[4]arene functionalised macrocycle wheel and different pyridinium axle components, are prepared via adaption of an anion templated synthetic strategy to investigate the effect of preorganisation of the interlocked host’s binding cavity on anion binding. Rotaxane 12? Cl contains a conformationally flexible pyridinium axle, whereas rotaxane 9? Cl incorporates a more preorganised pyridinium axle component. The X‐ray crystal structure of 9? Cl and solution phase 1H NMR spectroscopy demonstrate the successful interlocking of the calix[4]arene macrocycle and pyridinium axle components in the rotaxane structures. Following removal of the chloride anion template, anion binding studies on the resulting rotaxanes 9? PF6 and 12? PF6 reveal the importance of preorganisation of the host binding cavity on anion binding. The more preorganised rotaxane 9? PF6 is the superior anion host system. The interlocked host cavity is selective for chloride in 1:1 CDCl3/CD3OD and remains selective for chloride and bromide in 10 % aqueous media over the more basic oxoanions. Rotaxane 12? PF6 with a relatively conformationally flexible binding cavity is a less effective and discriminating anion host system although the rotaxane still binds halide anions in preference to oxoanions. 相似文献
95.
Brown S Cao J Musfeldt JL Conner MM McConnell AC Southerland HI Manson JL Schlueter JA Phillips MD Turnbull MM Landee CP 《Inorganic chemistry》2007,46(21):8577-8583
We report a systematic investigation of the temperature-dependent infrared vibrational spectra of a family of chemically related coordination polymer magnets based upon bridging bifluoride (HF(2)-) and terminal fluoride (F-) ligands in copper pyrazine complexes including Cu(HF(2))(pyz)(2)BF(4), Cu(HF(2))(pyz)(2)ClO(4), and CuF(2)(H(2)O)(2)(pyz). We compare our results with several one- and two-dimensional prototype materials including Cu(pyz)(NO(3))(2) and Cu(pyz)(2)(ClO(4))(2). Unusual low-temperature hydrogen bonding, local structural transitions associated with stronger low-temperature hydrogen bonding, and striking multiphonon effects that derive from coupling of an infrared-active fundamental with strong Raman-active modes of the pyrazine building-block molecule are observed. On the basis of the spectroscopic evidence, these interactions are ubiquitous to this family of coordination polymers and may work to stabilize long-range magnetic ordering at low temperature. Similar interactions are likely to be present in other molecule-based magnets. 相似文献
96.
Kenneth G. McConnell 《Experimental Mechanics》1994,34(3):181-193
The objective of a test program is to simulate a specified dynamic environment. The question is: How do I go from field-test data to a reasonable laboratory or finite-element simulation? This paper looks at a simple situation of a two degree-of-freedom vehicle that has a broadband excitation source and a two degree-of-freedom test item that can be attached to the vehicle. The paper shows that significantly different field data are obtained depending on field-test conditions, and vastly different simulation results are obtained when using these different field data as laboratory inputs. A relatively simple theoretical model is developed that explains how field data in this case can be modified in the frequency domain to obtain a more realistic laboratory test environment. This presentation shows that a general theory of vibration testing is needed, a theory that provides guidelines for this process of obtaining field data and developing realistic test specifications. 相似文献
97.
Dr. Gerald Platzer Dr. Moriz Mayer Andreas Beier Dr. Sven Brüschweiler Dr. Julian E. Fuchs Dr. Harald Engelhardt Dr. Leonhard Geist Dr. Gerd Bader Dr. Julia Schörghuber Dr. Roman Lichtenecker Bernhard Wolkerstorfer Dr. Dirk Kessler Dr. Darryl B. McConnell Prof. Dr. Robert Konrat 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(35):14971-14978
While CH–π interactions with target proteins are crucial determinants for the affinity of arguably every drug molecule, no method exists to directly measure the strength of individual CH–π interactions in drug–protein complexes. Herein, we present a fast and reliable methodology called PI (π interactions) by NMR, which can differentiate the strength of protein–ligand CH–π interactions in solution. By combining selective amino-acid side-chain labeling with 1H-13C NMR, we are able to identify specific protein protons of side-chains engaged in CH–π interactions with aromatic ring systems of a ligand, based solely on 1H chemical-shift values of the interacting protein aromatic ring protons. The information encoded in the chemical shifts induced by such interactions serves as a proxy for the strength of each individual CH–π interaction. PI by NMR changes the paradigm by which chemists can optimize the potency of drug candidates: direct determination of individual π interactions rather than averaged measures of all interactions. 相似文献
98.
Rapid method development for chiral separation in drug discovery using multi-column parallel screening and circular dichroism signal pooling 总被引:1,自引:0,他引:1
A novel strategy for rapid chiral method development has been developed using multi-column parallel screening and circular dichroism (CD) signal pooling. Described is the first use of a customized HPLC system that integrates an HPLC auto-sampler, one pump and five divided channels with five columns and five UV detectors to screen five chiral stationary phases (CSPs) simultaneously in parallel. A high-pressure semi-prep on-line pre-filter, a six-port manifold and five individually adjusted backpressure restrictors were installed in the system which allowed the sample and mobile phase to be evenly distributed over the five columns and UV detectors. The five CSPs, namely Chiralpak AD and AS, Chiralcel OJ and OD and Whelk-O1, were screened. The system guarantees a five-fold increase in speed for chiral column scouting compared with the widely used automated sequential column switching approach, and does not have the limitations of the coupled column screening approach for enantiomers whose elution order could be reversed on CSPs. Furthermore, the five channels after the UV detectors were recombined using a reversed flow splitter into a CD detector. The pooled CD signal from the five channels was recorded to track the elution order of the resolved enantiomers and to determine their sign, positive or negative. The signal pooling allows for the effective use of a single CD detector for multiple columns since unresolved racemate has little CD signal, and observing the sign of CD signal for one of the two enantiomer UV peaks is sufficient for tracking the enantiomeric elution order. 相似文献
99.
The first examples of the slippage formation of rotaxane‐like structures in the presence of an anion template are reported between a macrocycle, synthesised by exploiting Eglinton coupling, and stoppered pyridinium axle components. The role of the anion template in the slippage process has been explored by kinetic studies. 1H NMR spectroscopic investigations reveal the slippage species formed are not rotaxanes but pseudorotaxanes with some rotaxane character. The anion template significantly influences the amount of rotaxane character and the rate of slippage. Importantly, the fastest slippage rates, kon, are achieved with the non‐coordinating hexafluorophosphate anion, whereas the slowest slippage off rates, koff, are observed in the presence of coordinating anions, such as chloride. Since the koff rates are significantly smaller than the kon rates in the presence of coordinating anions, these anions act as templates favouring formation of the slippage species thermodynamically. Consequently, the resulting pseudorotaxanes with coordinating anions have greater rotaxane character. Two strategies for converting the slippage pseudorotaxanes into rotaxanes using hydrogenation or complexation with cobalt carbonyl are investigated. 相似文献
100.
We describe a method for measuring the lateral focal spot size of a multiphoton laser scanning microscope (LSM) with unprecedented accuracy. A specimen consisting of an aluminum film deposited on a glass coverslip was brought into focus in a LSM and the laser intensity was then increased enough to perform nanoablation of the metal film. This process leaves a permanent trace of the raster path usually taken by the beam during the acquisition of an optical image. A scanning electron microscope (SEM) was then used to determine the nanoablated line width to high accuracy, from which the lateral spot size and hence resolution of the LSM can be determined. To demonstrate our method, we performed analysis of a multiphoton LSM at various infrared wavelengths, and we report measurements of optical lateral spot size with an accuracy of 20 nm, limited only by the resolution of the SEM. 相似文献