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31.
Gray M Cuello AO Cooke G Rotello VM 《Journal of the American Chemical Society》2003,125(26):7882-7888
Two receptors, a diaminotriazine derivative (DAT) and diamidopyridine (DAP), are complementary to the electroactive naphthalimide (N) through three-point hydrogen bonding. The association constants of the two receptors were evaluated for both the fully oxidized and the radical anion forms of N. In the oxidized state, the two receptors displayed identical binding constants. Diamidopyridine, however, lowers the reduction potential of naphthalimide to a far greater extent than does diaminotriazine, indicating a greater affinity for diamidopyridine by naphthalimide in the radical anion form. This behavior was mirrored by EPR experiments that showed small deviations from the hyperfine coupling pattern of N(red) in the presence of DAT, with greater effects seen for the N(red).DAP complex. Computational simulations using the UB3LYP/6-311+G(d,p)//UHF/6-31G(d) hybrid gave theoretical hyperfine constants in good quantitative agreement with the experimental results. Using this correlation, we determined that electrostatics and hydrogen bond polarizability play key roles in controlling redox-modulated molecular recognition. 相似文献
32.
A range of mixed ether-esters of cellulose was prepared from partially substituted ethylcellulose and methylcellulose. The 13C-NMR analysis of ethylcellulose with a DS of 2.5 indicated that the hydroxyl groups at carbon six of anhydroglucose units were completely substituted. Acetylation of the ethylcellulose under different conditions yielded (acetyl) (ethyl) cellulose (AEC) samples with acetyl degree of substitution ranging from 0 to 0.5. Fully substituted (propionyl) (ethyl) cellulose (PEC) and (acetyl) (methyl) cellulose (AMC) were also prepared. Chiral nematic liquid crystals were formed in these mixed ester/ethers of cellulose in concentrated solutions of acidic solvents. The critical concentration for the phase separation of the cellulosic solutions depended on the nature of the substituent, the degree of substitution, and the solvent at a given temperature. Methylcellulose solutions in trifluoroacetic acid and dichloroacetic acid form chiral nematic liquid crystals with a left-handed helicoidal structure. The acetylated methyl cellulose samples did not show the reversal of handedness with increasing acetyl content that was previously observed for the corresponding ethylcellulose samples. © 1994 John Wiley & Sons, Inc. 相似文献
33.
Fulton R Jensen T Johnson DR Kagan H Kass R Morrow F Whitmore J Wilson P Bortoletto D Chen W Dominick J McIlwain RL Miller DH Ng CR Schaffner SF Shibata EI Shipsey IP Yao W Battle M Sparks K Thorndike EH Wang C Alam MS Kim IJ Li WC Romero V Sun CR Wang P Zoeller MM Goldberg M Haupt T Horwitz N Jain V Mestayer MD Moneti GC Rozen Y Rubin P Sharma V Skwarnicki T Thulasidas M Zhu G Csorna SE Letson T Alexander J Artuso M Bebek C Berkelman K Browder T Cassel DG Cheu E Coffman DM Crawford G DeWire JW 《Physical review D: Particles and fields》1991,43(3):651-663
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35.
Straub PB Jaffe DE Glass HD Adams MR Brown CN Charpak G Cooper WE Crittenden JA Finley DA Gray R Hemmi Y Hsiung YB Hubbard JR Jonckheere AM Jöstlein H Kaplan DM Lederman LM Luk KB Maki A Mangeot P McCarthy RL Miyake K Plaag RE Rutherfoord JP Sakai Y Santiard JC Sauli F Smith SR Yoshida T Young KK 《Physical review letters》1992,68(4):452-455
36.
Amber L. H. Gray Aleksandra Antevska Benjamin A. Link Bryan Bogin Susan J. Burke Samuel D. Dupuy J. Jason Collier Zachary A. Levine Michael D. Karlstad Thanh D. Do 《Chemical science》2021,12(16):5853
Despite being relatively benign and not an indicative signature of toxicity, fibril formation and fibrillar structures continue to be key factors in assessing the structure–function relationship in protein aggregation diseases. The inability to capture molecular cross-talk among key players at the tissue level before fibril formation greatly accounts for the missing link toward the development of an efficacious therapeutic intervention for Type II diabetes mellitus (T2DM). We show that human α-calcitonin gene-related peptide (α-CGRP) remodeled amylin fibrillization. Furthermore, while CGRP and/or amylin monomers reduce the secretion of both mouse Ins1 and Ins2 proteins, CGRP oligomers have a reverse effect on Ins1. Genetically reduced Ins2, the orthologous version of human insulin, has been shown to enhance insulin sensitivity and extend the life-span in old female mice. Beyond the mechanistic insights, our data suggest that CGRP regulates insulin secretion and lowers the risk of T2DM. Our result rationalizes how migraine might be protective against T2DM. We envision the new paradigm of CGRP : amylin interactions as a pivotal aspect for T2DM diagnostics and therapeutics. Maintaining a low level of amylin while increasing the level of CGRP could become a viable approach toward T2DM prevention and treatment.CGRP concentration is elevated in migraine conditions. The protective effect of migraine against type 2 diabetes is attributed to the ability of CGRP to remodel human amylin aggregation and to suppress the secretion of mouse insulin 2 (the orthologue of human insulin). 相似文献
37.
M. Bourquin R. M. Brown Y. Chatelus J. C. Chollet A. Degré D. Froidevaux A. R. Fyfe J. -M. Gaillard C. N. P. Gee W. M. Gibson R. J. Gray P. Igo-Kemenes P. W. Jeffreys B. Merkel R. Morand R. J. Ott H. Plothow J. -P. Repellin B. J. Saunders G. Sauvage B. Schiby H. W. Siebert V. J. Smith K. -P. Streit R. Strub J. J. Thresher 《Zeitschrift fur Physik C Particles and Fields》1982,12(4):307-321
The charged hyperon beam at the CERN Super Proton Synchrotron (SPS) has been used to collect data on semileptonic decays ofΣ ?,Ξ ? andΛ. A magnetic channel selects 100 GeV/c negatively charged particles produced in the forward direction by interaction of the 200 GeV/c SPS proton beam on a BeO target. TheΣ ? andΞ ? hyperons are concurrently identified in a DISC ?erenkov counter, and their decay products are analysed by a magnetic spectrometer. Electron-hadron discrimination is achieved by the combined use of lead-glass and lead/scintillator counters, transition radiation detectors, and a ?erenkov counter. In this article we report results on the \(\Sigma ^ - \to \Lambda e^ - \bar v\) decay mode. Measurements of the Λ polarization and of the centre-of-mass distributions (baryon kinetic energy, electron-neutrino correlation, and Dalitz plot distributions) yield the vector to axialvector form factor ratiof 1/g 1=+0.034±0.080, in agreement with the value expected from the conserved vector current hypothesis (f 1/g 1=0). TheΣ ?→Λe ? v→ branching ratio measurement gives a value of (5.41±0.30)×10?5. The effects of radiative corrections are not included in these results. They are discussed in the text. Results on the otherΞ ?,Σ ?, andΛ semileptonic decays are reported in separate articles. 相似文献
38.
Gray TG Rudzinski CM Meyer EE Holm RH Nocera DG 《Journal of the American Chemical Society》2003,125(16):4755-4770
The electronic, vibrational, and excited-state properties of hexanuclear rhenium(III) chalcogenide clusters based on the [Re(6)(mu(3)-Q)(8)](2+) (Q = S, Se) core have been investigated by spectroscopic and theoretical methods. Ultraviolet or visible excitation of [Re(6)Q(8)](2+) clusters produces luminescence with ranges in maxima of 12 500-15 100 cm(-)(1), emission quantum yields of 1-24%, and emission lifetimes of 2.6-22.4 microseconds. Nonradiative decay rate constants and the luminescence maxima follow the trend predicted by the energy gap law (EGL). Examination of 24 clusters in solution and 14 in the solid phase establish that exocluster ligands engender the observed EGL behavior; clusters with oxygen- or nitrogen-based apical ligands achieve maximal quantum yields and the longest lifetimes. The excited-state decay mechanism was investigated by applying nonradiative decay models to temperature-dependent emission experiments. Solid-state Raman spectra were recorded to identify vibrational contributions to excited-state deactivation; spectral assignments were enabled by normal coordinate analysis afforded from Hartree-Fock and DFT calculations. Excited-state decay is interpreted with a model where normal modes largely centered on the [Re(6)Q(8)](2+) core induce nonradiative relaxation. Hartree-Fock and DFT calculations of the electronic structure of the hexarhenium family of compounds support such a model. These experimental and theoretical studies of [Re(6)Q(8)](2+) luminescence provide a framework for elaborating a variety of luminescence-based applications of the largest series of isoelectronic clusters yet discovered. 相似文献
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40.
Michael P. Burrow George W. Gray David Lacey Kenneth J. Toyne 《Liquid crystals》2013,40(12):1643-1653
Abstract The synthesis is reported of fifteen three-ring 2,5-disubstituted pyridines and two pyridine-N-oxides where the pyridine rings carry a variety of alkyl, aryl, cyclohexyl, cyclohexylethyl and fluorinated-aryl substituents. The mesomorphic transition temperatures for these compounds have been measured; all the compounds show enantiotropic phases. The different substituent effects are discussed and comparisons are made with previous work on analogous systems where the hetero-function is replaced by C-F. 相似文献