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11.
Molecular Engineering of Push–Pull Porphyrin Dyes for Highly Efficient Dye‐Sensitized Solar Cells: The Role of Benzene Spacers 下载免费PDF全文
Shaik M. Zakeeruddin Shu‐Nung Chang Chi‐Hung Hsieh Chen‐Yu Yeh Michael Grätzel 《Angewandte Chemie (International ed. in English)》2014,53(11):2973-2977
Porphyrins have drawn much attention as sensitizers owing to the large absorption coefficients of their Soret and Q bands in the visible region. In a donor and acceptor zinc porphyrin we applied a new strategy of introducing 2,1,3‐benzothiadiazole (BTD) as a π‐conjugated linker between the anchoring group and the porphyrin chromophore to broaden the absorption spectra to fill the valley between the Soret and Q bands. With this novel approach, we observed 12.75 % power‐conversion efficiency under simulated one‐sun illumination (AM1.5G, 100 mW cm?2). In this study, we showed the importance of introducing the phenyl group as a spacer between the BTD and the zinc porphyrin in achieving high power‐conversion efficiencies. Time‐resolved fluorescence, transient‐photocurrent‐decay, and transient‐photovoltage‐decay measurements were employed to determine the electron‐injection dynamics and the lifetime of the photogenerated charge carriers. 相似文献
12.
Md. Aminul Haque Md. Rajibul Akanda Delwar Hossain M. Aminul Haque Ismail A. Buliyaminu Shaik Inayath Basha Munetaka Oyama Md. Abdul Aziz 《Electroanalysis》2020,32(3):528-535
In this study, the electrocatalytic characteristics of nitrogen‐doped carbon (NDC) prepared from Clerodendrum Infortunatum L leaves on a glassy carbon electrode (GCE) surface was evaluated with regards to its ability to detect the electroactive drug ketoconazole (KCZ). The NDC was prepared by carrying out a simple pyrolysis of dry powder of the leaves at 850 °C. The prepared NDC was characterized using field‐emission scanning electron microscopy, energy dispersive spectroscopy, transmission electron microscopy, X‐ray photoelectron spectroscopy and Brunauer‐Emmett‐Teller analysis, and was then used as an electrode material. The performance of the electrochemical KCZ sensor with the NDC‐modified glassy carbon electrode (NDC/GCE) was found to be optimal when using PBS buffer at pH 3 and a concentration of 0.1 mg/ml of NDC in the conjugate with Nafion polymer. Under these conditions, the NDC/GCE displayed a KCZ detection limit of 3 μM and a linear dependence of its response on KCZ concentration over a wide range of KCZ concentrations from 47 μM to 752 μM (R2=0.9742). These results confirmed the potential of NDC as an electrocatalyst. 相似文献
13.
Shaik A. Rao A. T. Venkatarao D. V. Rao S. V. M. Mohan Kishore P. V. V. N. 《Russian Journal of Organic Chemistry》2020,56(12):2179-2187
Russian Journal of Organic Chemistry - A series of novel 1,2,4-triazole nonsteroidal anti-inflammatory drugs (NSAIDs) derived from etodolac were designed and synthesized. The synthesized compounds... 相似文献
14.
Wang Y Hirao H Chen H Onaka H Nagano S Shaik S 《Journal of the American Chemical Society》2008,130(23):7170-7171
QM/MM calculations support experiment and show that StaP is a P450 that functions like a peroxidase: its active species is the one-electron-reduced Cpd II species with a radical on CPA, by analogy to cytochrome c peroxidase (CcP), and its reaction with the substrate proceeds by overall proton-coupled electron transfer (PCET), in analogy to the corresponding mechanism in horseradish peroxidase (HRP). The electron transfer is enabled by His250, the presence of carboxylate groups in CPA, and by the H-bonding network that tunes the energetic of the process. Theory supports experiment but reveals some novel aspects of this unusual P450. 相似文献
15.
A microtiter plate assay for quantitation of reduced (GSH) and oxidized (GSSG) glutathione in the rat liver tissue and bile
is described. The assay is based on the established enzymatic recycling method and a new thiol-masking reagent, 1-methyl-4-vinyl-pyridinium
trifluoromethane sulfonate (M4VP). Samples were first processed by homogenization with (liver) or addition of (bile) sulfosalicylic
acid. The total glutathione and GSSG were then determined before and after rapid (≤2 min) and efficient (100%) masking of
the GSH content of the samples with M4VP followed by the enzymatic recycling assay. The percentages of error and coefficient
of variation of the assay were within the accepted guidelines, indicating the accuracy and precision of the assay in the range
of 6.25–100 pmol GSH per microplate well and 2.17–140 pmol GSSG per well, with lower limit of quantitation of 6.25 and 2.17 pmol
per well for GSH and GSSG, respectively. Furthermore, the recoveries of added GSH or GSSG from the liver and bile samples
were accurate and precise. The assay was applied to measurement of GSH, GSSG, and GSH:GSSG ratio in the liver and serially
collected bile samples in sham-operated and ischemic rat livers, demonstrating a depletion of glutathione and a decrease in
the GSH:GSSG ratio as a result of ischemia. The developed assay is rapid, sensitive, accurate, and precise and is suitable
for studies of the redox status of liver under physiologic and pathophysiologic conditions. 相似文献
16.
Heme degradation by heme oxygenase (HO) enzymes is important in maintaining iron homeostasis and prevention of oxidative stress, etc. In response to mechanistic uncertainties, we performed quantum mechanical/molecular mechanical investigations of the heme hydroxylation by HO, in the native route and with the oxygen surrogate donor H2O2. It is demonstrated that H2O2 cannot be deprotonated to yield Fe(III)OOH, and hence the surrogate reaction starts from the FeHOOH complex. The calculations show that, when starting from either Fe(III)OOH or Fe(III)HOOH, the fully concerted mechanism involving O-O bond breakage and O-C(meso) bond formation is highly disfavored. The low-energy mechanism involves a nonsynchronous, effectively concerted pathway, in which the active species undergoes first O-O bond homolysis followed by a barrier-free (small with Fe(III)HOOH) hydroxyl radical attack on the meso position of the porphyrin. During the reaction of Fe(III)HOOH, formation of the Por+*FeIV=O species, compound I, competes with heme hydroxylation, thereby reducing the efficiency of the surrogate route. All these conclusions are in accord with experimental findings (Chu, G. C.; Katakura, K.; Zhang, X.; Yoshida, T.; Ikeda-Saito, M. J. Biol. Chem. 1999, 274, 21319). The study highlights the role of the water cluster in the distal pocket in creating "function" for the enzyme; this cluster affects the O-O cleavage and the O-Cmeso formation, but more so it is responsible for the orientation of the hydroxyl radical and for the observed alpha-meso regioselectivity of hydroxylation (Ortiz de Montellano, P. R. Acc. Chem. Res. 1998, 31, 543). Differences/similarities with P450 and HRP are discussed. 相似文献
17.
Chathuranga S. L. Rathnamalala Selena Hernandez Dr. Melissa Y. Lucero Chelsea B. Swartchick Dr. Abdul Kalam Shaik Prof. Dr. Nathan I. Hammer Amanda K. East Prof. Dr. Steven R. Gwaltney Prof. Dr. Jefferson Chan Prof. Dr. Colleen N. Scott 《Angewandte Chemie (International ed. in English)》2023,62(13):e202214855
Shortwave infrared (SWIR) dyes are characterized by their ability to absorb light from 900 to 1400 nm, which is ideal for deep tissue imaging owing to minimized light scattering and interference from endogenous pigments. An approach to access such molecules is to tune the photophysical properties of known near-infrared dyes. Herein, we report the development of a series of easily accessible (three steps) SWIR xanthene dyes based on a dibenzazepine donor conjugated to thiophene ( SCR-1 ), thienothiophene ( SCR-2 ), or bithiophene ( SCR-3 ). We leverage the fact that SCR-1 undergoes a bathochromic shift when aggregated for in vivo studies by developing a ratiometric nanoparticle for NO ( rNP-NO ), which we employed to successfully visualize pathological levels of nitric oxide in a drug-induced liver injury model via deep tissue SWIR photoacoustic (PA) imaging. Our work demonstrates how easily this dye series can be utilized as a component in nanosensor designs for imaging studies. 相似文献
18.
Bao‐Shiang Lee Sangeeth Krishnanchettiar Syed Salman Lateef Nabila Salman Lateef Shalini Gupta 《中国化学会会志》2006,53(3):745-750
Avidin functional affinity electrophoresis (AFAEP) is substituted for an avidin affinity column (AAC) to capture biotinylated peptides in the Isotope‐Coded Affinity Tagging (ICAT) technique which is a valuable tool in quantitative proteomics. In this new technique, the AFAEP‐captured ICAT‐labeled biotinylated peptides are extracted with the biotin tag intact from the polyacrylamide gel piece with aqueous 95% formamide (pH 8.2) at 65 °C for 20 min, and then detected by a matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometer. Bovine serum albumin (BSA) and the 12C‐ and 13C‐ICAT reagents are used to test this AFAEP‐ICAT technique. The results show that both AFAEP and AAC methods provide quantitative information of the relative amounts of 12C‐ and 13C‐ICAT‐labeled biotinylated tryptic peptides of BSA in a sample. Compared with AAC, the AFAEP is cheaper to perform, more stringent in capturing the biotinylated peptides, and capable of simultaneously processing multiple samples. 相似文献
19.
Song L Wu W Hiberty PC Shaik S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(28):7458-7466
The recently developed (L. Song, W. Wu, Q. Zhang, S. Shaik, J. Phys. Chem. A 2004, 108, 6017) valence bond method coupled with a polarized continuum model (VBPCM) has been applied to the identity SN2 reaction of halides in the gas phase and in aqueous solution. The barriers computed at the level of the breathing orbital VB method (P. C. Hiberty, J. P. Flament, E. Noizet, Chem. Phys. Lett. 1992, 189, 259), BOVB and VBPCM//BOVB, are comparable to CCSD(T) and CCSD(T)//PCM results and to experimentally derived barriers in solution (W. J. Albery, M. M. Kreevoy, Adv. Phys. Org. Chem. 1978, 16, 85). The reactivity parameters needed to apply the valence bond state correlation diagram (VBSCD) method (S. Shaik, J. Am. Chem. Soc. 1984, 106, 1227), were also determined by VB calculations. It has been shown that the reactivity parameters along with their semiempirical derivations provide a satisfactory qualitative and quantitative account of the barriers. 相似文献
20.
Calculations show that the transition structure for the synchronous oxygen transfer by Compound I is a second order saddle point. The process is unlikely. 相似文献