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11.
The reduction of 1,10-phenanthroline-5,6-quinone(I), 5,8-quinolinequinone(II) and 6,7-dichloro-5,8-quinolinequinone(III) was investigated using cyclic voltammetry and coulometry at mercury electrodes and 50% dimethylsulfoxide+water solvent. Each compound is reduced to the corresponding hydroquinone in a diffusion-controlled, reversible two-electron process. The pH-dependence of the reversible potential indicated that the quinone forms were unprotonated, but the hydroquinones could be protonated at the heterocyclic nitrogen atom with pKa = 5.3 for I and 3.5 for III. Careful analysis of the cyclic voltammetric peak shape revealed that the difference between the standard potentials for the introduction of successive electrons, E20 ? E10, was 70 ±20, >100 and 80 ± 20 mV for I–III. Investigation of the pH-dependence of E10 and E20 showed that the pKa of the semiquinone of I was about 8. 相似文献
12.
Madeline J. Simpson Horacio Poblete May Griffith Emilio I. Alarcon Juan C. Scaiano 《Photochemistry and photobiology》2013,89(6):1433-1441
The role of recombinant Type‐I human collagen in the free form or forming AgNP@collagen on the photophysical and photochemical behavior of rose Bengal was analyzed. The formation of dye aggregates on the protein surface was experimentally observed and corroborated by docking calculations. The formation of such aggregates is believed to change the main oxidative mechanism from Type‐II (singlet oxygen) to Type‐I (free radical) photosensitization. Remarkably, the presence of AgNP in the form of AgNP@collagen altered the dynamics of dye triplet deactivation, effectively preventing the dye degradation and reducing the extent of protein crosslinked. Both crosslinked rHC and AgNP@collagen were able to support fibroblasts proliferation, but only the material containing silver was resistant to S. epidermidis infection. 相似文献
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14.
Dr. Andrew T. Krueger Dr. Carsten Kroll Edgar Sanchez Prof. Linda G. Griffith Prof. Barbara Imperiali 《Angewandte Chemie (International ed. in English)》2014,53(10):2662-2666
Described is the development and application of a versatile semisynthetic strategy, based on a combination of sortase‐mediated coupling and tetrazine ligation chemistry, which can be exploited for the efficient incorporation of tunable functionality into chimeric recombinant proteins. To demonstrate the scope of the method, the assembly of a set of bivalent ligands, which integrate members of the epidermal growth factor (EGF) ligand family, is described. By using a series of bivalent EGFs with variable intraligand spacing, the differences in structure were correlated with the ability to bias signaling in the ErbB receptor family in a cell motility assay. Biasing away from EGFR‐HER2 dimerization with a bivalent EGF was observed to reduce cell motility in an intraligand distance‐dependent fashion, thus demonstrating the utility of the approach for acutely perturbing receptor‐mediated cell signaling pathways. 相似文献
15.
Davies CJ Griffith JD Sederman AJ Gladden LF Johns ML 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2007,187(1):170-175
Analysis of diffusion measurements as a function of observation time (Delta), to calculate surface-to-volume ratios (S/V) and tortuosities (kappa), is a useful tool in the characterisation of porous media using NMR. However, using conventional pulsed field gradient (PFG) measurements, this requires long total experiment times (typically hours). Here, we show how the rapid diffusion measurement pulse sequence, Difftrain, can be used to provide the required experimental data much more rapidly (typically within minutes) with a consequential reduction in total experiment time of typically over an order of magnitude. Several novel modifications to the Difftrain pulse sequence are also presented to tailor it to this particular application; these include a variable delay between echoes (to ensure optimal echo position with respect to Delta) and a variable tip angle for the refocusing pulse (to ensure optimal use of available signal). Difftrain is applied to measure both S/V and kappa for a model glass bead pack; excellent agreement is found with both a conventional PFG measurement and with a bulk gravimetric measurement of S/V. 相似文献
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van den Brand JF Ent R Anthony PL Arnold RG Arrington J Beise EJ Belz JE Bosted PE Bulten H Chapman MS Coulter KP Dietrich FS Epstein M Filippone BW Gao H Gearhart RA Geesaman DF Hansen J Holt RJ Jackson HE Jones CE Keppel CE Kinney ER Kuhn S Lee K Lorenzon W Lung A Makins NC Margaziotis DJ McKeown RD Milner RG Mueller B Napolitano J Nelson J O'Neill TG Papavassiliou V Petratos GG Potterveld DH Rock SE Spengos M Szalata ZM Tao LH van Bibber K Wasson DA White JL Zeidman B 《Physical review D: Particles and fields》1995,52(9):4868-4871
18.
Purpose
The purpose was to study the effect of estrogen deficiency on contrast agent diffusion into intervertebral disc in a rat model.Materials and Methods
Seven-month-old female Sprague–Dawley rats were used. Fourteen rats had ovariectomy, and nine rats had sham surgery. Magnetic resonance imaging (MRI) of sagittal midsection of lumbar spine was performed with a 1.5-T magnet. Dynamic MRI was performed after a bolus injection of Gd-DOTA (0.3 mmol/kg) through tail vein. Eight hundred images were acquired at 0.6 s per acquisition. Regions of interests were drawn over three discs per rat. Maximum enhancement (Emax) and enhancement slope (Eslope) were evaluated. MRI was carried out at baseline and 8 weeks postsurgery.Result
All disc enhancements demonstrated an initial fast wash-in phase followed by a second slower wash-in phase. For initial wash-in phase, E1max and E1slope of all rats remained unchanged at the two time points. For second wash-in phase, E2max and E2slope of control rats remained unchanged, while with ovariectomized rats, E2max showed reduction at 8 weeks (4.5%±5.6%) compared to baseline (10.3%±6.3%, P=.037), and E2slope was lower at 8 weeks (0.015±0.017) than the baseline (0.029±0.022), although it was not statistically significant (P=.101).Conclusion
Ovariectomy induced detectable decrease in second wash-in phase of contrast agent into lumbar disc. 相似文献19.
Christopher P. Gordon Neal Dalton Nicholas Vandegraaff John Deadman David I. Rhodes Jonathan A. Coates Stephen G. Pyne Renate Griffith John B. Bremner Paul A. Keller 《Tetrahedron》2018,74(12):1253-1268
As of mid-2017, only one structure of the human immunodeficiency virus (HIV) integrase core domain co-crystallised with an active site inhibitor was reported. In this structure (1QS4), integrase is complexed with a diketo-acid based strand-transfer inhibitor (INSTI). This structure has been a preferred platform for the structure-based design of INSTIs despite concerns relating to structural irregularities arising from crystallographic packing effects. A survey of the current pool of 297 reported integrase catalytic core structures indicated that the anatomy of the active site in the complex structure 1QS4 exhibits subtle variations relative to all other structures examined. Consequently, the 1QS4 structure was employed for docking studies. From the docking of twenty-seven allyltyrosine analogues, a 3-point inhibitor binding motif required for activity was established and successfully utilised in the development of a tripeptide displaying an EC50 value of 10 ± 5 μM in HIV infected human T-cells. Additional docking of “in-house” compound libraries unearthed a methyl ester based nitrile derivative displaying an IC50 value of 0.5 μM in a combined 3′-processing and strand-transfer assay. 相似文献
20.
C. A. Burke G. B. Birrell G. H. Lesch O. H. Griffith 《Photochemistry and photobiology》1974,19(1):29-34
Abstract— The application of photoelectron microscopy as a general method of imaging organic and biological surfaces requires a knowledge of the photoelectric effect of very thin organic films. In this study, low magnification images of a 7 Å thick pattern of copper phthalocyanine were obtained, demonstrating that it is possible to visualize a monolayer of organic compound in photoelectron microscopy. Relative photoelectron currents were measured for a series of copper phthalocyanine films ranging in thickness up to 1900 Å. The relative photoelectron currents were independent of temperature (90–298°K), suggesting that electron-electron and not electron-phonon scattering is the dominant mechanism. The photoelectric properties measured are determined primarily by the large organic ring structure and not the central metal atom, as evidenced by the fact that substitution of metal-free phthalocyanine for copper phthalocyanine did not substantially alter the values of observed photoelectron currents. An analysis of the data indicates the depth resolution is 15 ű 5 Å, and equals the electron mean free path. This very good depth resolution is a result of the low kinetic energy associated with electrons released by irradiation near the photoemission threshold. 相似文献