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51.
The effects of temperature on the 13C NMR shifts of benzene, cyclohexane, pyridine, cyclohexene, neopentane, hexane, and heptane have been determined from +10 to +70°C. In addition, the temperature shift of 2D in D2O was found to be +10.4 × 10?3 ppm/°C. All shifts appear to be linear functions of temperature within experimental error. 相似文献
52.
53.
McLaughlin CK Lantero DR Manderville RA 《The journal of physical chemistry. A》2006,110(19):6224-6230
We have characterized the conformational properties of the C8-deoxyguanosine (C8-dG) nucleoside adduct, 8-(2"-hydroxyphenyl)-2'-dG (1), which is a potential biomarker for exposure to phenolic carcinogens. Adduct 1 possesses the unique ability to phototautomerize, through an excited-state intramolecular proton transfer (ESIPT) process, to generate its keto form. This tautomerization depends on the presence of an intramolecular hydrogen (H)-bond between the phenolic OH and the imine nitrogen (N7) and has permitted insight into the equilibrium ground states of adduct 1. The results of our studies demonstrate that adduct 1 undergoes an ESIPT despite preferring a nonplanar "twisted" conformation that is imposed by the deoxyribose (dR) sugar moiety. Interestingly, a planar conformation of adduct 1 is also formed in certain aprotic solvents due to the anchoring effect of the intramolecular H-bond. Our results provide a basis for future studies aimed at determining the conformations of adduct 1 within DNA that will aid in our understanding of phenol-mediated carcinogenesis. 相似文献
54.
55.
Thomas G. McLaughlin 《Mathematical Logic Quarterly》2010,56(3):323-330
Given a (nontrivial) Δ1 ultrapower ?/??, let ??U denote the set of all Π2‐correct substructures of ?/??; i.e., ??U is the collection of all those subsets of |?/??| that are closed under computable (in the sense of ?/??) functions. Defining in the obvious way the lattice ??(?/??)) with domain ??U, we obtain some preliminary results about lattice embeddings into – or realization as – an ??(?/??). The basis for these results, as far as we take the matter, consists of (1) the well‐known class of (non‐trivial) minimal ?/??'s, which function as atoms, and (2) the class of minimalfree ?/??'s, to whose nonemptiness a substantial section of the paper is devoted. It is shown that an infinite, convergent monotone sequence together with its limit point is embeddable in an ??(?/??), and that the initial segment lattices {0, 1,…, n } are not just embeddable in (as is trivial), but in fact realizable as, lattices ??(?/??). Finally, the diamond is (easily) embeddable; and if it is not realizable, then either the 1 ‐ 3 ‐ 1 lattice or the pentagon is at least embeddable (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
56.
Neutrinos are the principal messengers reaching us from the center of a supernova. Terrestrial neutrino telescopes can provide precious information about the processes in the core of the star. But the information that a neutrino detector can supply is restricted by the fact that little experimental data on the neutrino-nucleus cross sections exist and by the uncertainties in theoretical calculations. In this Letter, we propose a novel procedure that determines the response of a target nucleus in a supernova-neutrino detector, by using low-energy beta beams. We show that fitting "synthetic" spectra, constructed by taking linear combinations of beta-beam spectra, to the original supernova-neutrino spectra reproduces the folded differential cross sections very accurately. Comparing the response in a detector to these synthetic responses provides a direct way to determine the main parameters of the supernova-neutrino energy distribution. 相似文献
57.
Maeve H. S. McLaughlin Alexander C. Pakpour‐Tabrizi Richard B. Jackman 《Electroanalysis》2019,31(9):1775-1782
This work compares polished and unpolished boron doped diamond (BDD) electrodes decorated with two sizes of gold nanoparticles (AuNPs) for use as robust mercury sensors in aquatic environments. The size of the catalytically active AuNPs on the electrode surfaces was demonstrated to have a less significant effect on the sensitivity for mercury detection than the surface preparation of the BDD. The lowest limits of detection were achieved with the polished BDD electrodes, which both detected mercury at a concentration of 1 pM, six orders of magnitude greater sensitivity than the lowest detection limit of 5 μM achieved with an unpolished BDD electrode, and high in comparison with other reported electrode systems. 相似文献
58.
Double-stranded DNA sequences have been prepared in which single atoms (the O2-carbonyls of selected thymines) have been replaced by fluorine or methyl. To maintain normal Watson-Crick hydrogen bonding with the complementary purines, these analogue derivatives have been prepared as C-nucleosides. The O2-carbonyls of interest for this study are those involved in a bifurcated (or three-centered) hydrogen bond with the minor groove binding ligand 4',6-diamidino-2-phenylindole (DAPI). TM studies of the duplexes illustrate that the DNA duplexes are destabilized when fluorine or methyl replaces one or both of the minor groove O2-carbonyls, which can in part be explained by changes in minor groove hydration. In the presence of DAPI, most of the duplexes exhibit an increased TM due to the presence of DAPI bound in the minor groove. The extent of helix overstabilization negatively correlates with the presence of one or both methyl groups in the minor groove, suggesting that ligand binding is weakened in the presence of the non-carbonyl functional groups. The presence of single fluorine appears to promote helix stabilization, and native-like stabilization occurs when both fluorines are present. KD values quantitate binding effects between DAPI and the native and analogue sequences. Sequences with one or both methyl groups exhibit very poor binding with DAPI, while those containing a single fluorine behave essentially like native carbonyl-containing sequences. With both fluorines present, KD values were observed to increase by a moderate 3-fold at 100 mM NaCl and somewhat more at 200 mM NaCl. Binding affinities with both methyl groups present were 500-1000-fold weaker than native. The results suggest that organofluorines can function as hydrogen-bond acceptors, at least in the bifurcated interaction that contributes to minor groove binding by DAPI. 相似文献
59.
Gururaja TL Yung S Ding R Huang J Zhou X McLaughlin J Daniel-Issakani S Singh R Cooper RD Payan DG Masuda ES Kinoshita T 《Chemistry & biology》2007,14(10):1105-1118
Small-molecule library screening to find compounds that inhibit TNFalpha-induced, but not interleukin 1beta (IL-1beta)-induced, intercellular adhesion molecule 1 (ICAM-1) expression in lung epithelial cells identified a class of triazoloquinoxalines. These compounds not only inhibited the TNFalpha-induced nuclear factor kappaB (NFkappaB) survival pathway but also blocked death-pathway activation. Such dual activity makes them unique against other known NFkappaB-pathway inhibitors that inhibit only a subset of TNFalpha signals leading to increased TNFalpha-induced cytotoxicity. Interestingly, these compounds inhibited association of TNFalpha receptor (TNFalphaR) I with TNFalphaR-associated death domain protein (TRADD) and receptor interacting protein 1 (RIP1), the initial intracellular signaling event following TNFalpha stimulation. Further study showed that they blocked ligand-dependent internalization of the TNFalpha-TNFalphaR complex, thereby inhibiting most of the TNFalpha-induced cellular responses. Thus, compounds with a triazoloquinoxaline scaffold could be a valuable tool to investigate small molecule-based anti-TNFalpha therapies. 相似文献
60.
McLaughlin J Renzi D Parker K Wu Z 《The Journal of the Acoustical Society of America》2007,121(4):2438-2446
Two new experiments were created to characterize the elasticity of soft tissue using sonoelastography. In both experiments the spectral variance image displayed on a GE LOGIC 700 ultrasound machine shows a moving interference pattern that travels at a very small fraction of the shear wave speed. The goal of this paper is to devise and test algorithms to calculate the speed of the moving interference pattern using the arrival times of these same patterns. A geometric optics expansion is used to obtain Eikonal equations relating the moving interference pattern arrival times to the moving interference pattern speed and then to the shear wave speed. A cross-correlation procedure is employed to find the arrival times; and an inverse Eikonal solver called the level curve method computes the speed of the interference pattern. The algorithm is tested on data from a phantom experiment performed at the University of Rochester Center for Biomedical Ultrasound. 相似文献