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81.
Spectroscopic and Computational Study of a Nonheme Iron Nitrosyl Center in a Biosynthetic Model of Nitric Oxide Reductase 下载免费PDF全文
Dr. Saumen Chakraborty Julian Reed Matthew Ross Dr. Mark J. Nilges Igor D. Petrik Dr. Soumya Ghosh Prof. Dr. Sharon Hammes‐Schiffer Prof. Dr. J. Timothy Sage Prof. Dr. Yong Zhang Prof. Dr. Charles E. Schulz Prof. Dr. Yi Lu 《Angewandte Chemie (International ed. in English)》2014,53(9):2417-2421
A major barrier to understanding the mechanism of nitric oxide reductases (NORs) is the lack of a selective probe of NO binding to the nonheme FeB center. By replacing the heme in a biosynthetic model of NORs, which structurally and functionally mimics NORs, with isostructural ZnPP, the electronic structure and functional properties of the FeB nitrosyl complex was probed. This approach allowed observation of the first S=3/2 nonheme {FeNO}7 complex in a protein‐based model system of NOR. Detailed spectroscopic and computational studies show that the electronic state of the {FeNO}7 complex is best described as a high spin ferrous iron (S=2) antiferromagnetically coupled to an NO radical (S= 1/2) [Fe2+‐NO.]. The radical nature of the FeB‐bound NO would facilitate N? N bond formation by radical coupling with the heme‐bound NO. This finding, therefore, supports the proposed trans mechanism of NO reduction by NORs. 相似文献
82.
AbstractEffective extraction of phyto-biomolecules insures retaining maximum functionality along with higher recovery. In this study, ultrasound-solvent assisted extraction (USAE) was employed for optimal extraction of phyto-biomolecules from Sesamum indicum (sesame) leaves using the approach of Response Surface Methodology (RSM). The optimized condition of 200?W power, 59% methanol concentration with 1:14?g/mL solid–liquid ratio and 15?min of extraction time yielded 367.39?±?1.85?mg GAE/100?g of total phenolic content, 96.72?±?3.27% of free radical scavenging activity and 81.20?±?2.87% of iron chelating activity respectively. The extract consist of essential phytocomponents like gallic acid, chlorogenic acid, and quercetin with lipid peroxidation activities of >50% over incubation time of 48?h. Also, showed antimicrobial activity against various Gram’s negative and positive food borne pathogens. The results of this study implied the importance of USAE for effective and optimum recovery of phyto-biomolecules from Sesame leaves with retained functional properties. 相似文献
83.
Biswarup Chakraborty Shweta Kalra Rodrigo Beltrn‐Suito Chittaranjan Das Tim Hellmann Prashanth W. Menezes Matthias Driess 《化学:亚洲杂志》2020,15(6):852-859
In the urge of designing noble metal‐free and sustainable electrocatalysts for oxygen evolution reaction (OER), herein, a mineral Digenite Cu9S5 has been prepared from a molecular copper(I) precursor, [{(PyHS)2CuI(PyHS)}2](OTf)2 ( 1 ), and utilized as an anode material in electrocatalytic OER for the first time. A hot injection of 1 yielded a pure phase and highly crystalline Cu9S5, which was then electrophoretically deposited (EPD) on a highly conducting nickel foam (NF) substrate. When assessed as an electrode for OER, the Cu9S5/NF displayed an overpotential of merely 298±3 mV at a current density of 10 mA cm?2 in alkaline media. The overpotential recorded here supersedes the value obtained for the best reported Cu‐based as well as the benchmark precious‐metal‐based RuO2 and IrO2 electrocatalysts. In addition, the choronoamperometric OER indicated the superior stability of Cu9S5/NF, rendering its suitability as the sustainable anode material for practical feasibility. The excellent catalytic activity of Cu9S5 can be attributed to the formation of a crystalline CuO overlayer on the conductive Cu9S5 that behaves as active species to facilitate OER. This study delivers a distinct molecular precursor approach to produce highly active copper‐based catalysts that could be used as an efficient and durable OER electro(pre)catalysts relying on non‐precious metals. 相似文献
84.
85.
Soujan Ghosh Swati Chowdhury Subrata Kundu Sudipta Sasmal Dimitrios Z. Politis Stelios M. Potirakis Masashi Hayakawa Suman Chakraborty Sandip K. Chakrabarti 《Entropy (Basel, Switzerland)》2022,24(1)
We focus on the possible thermal channel of the well-known Lithosphere–Atmosphere–Ionosphere Coupling (LAIC) mechanism to identify the behavior of thermal anomalies during and prior to strong seismic events. For this, we investigate the variation of Surface Latent Heat Flux (SLHF) as resulting from satellite observables. We demonstrate a spatio-temporal variation in the SLHF before and after a set of strong seismic events occurred in Kathmandu, Nepal, and Kumamoto, Japan, having magnitudes of 7.8, 7.3, and 7.0, respectively. Before the studied earthquake cases, significant enhancements in the SLHF were identified near the epicenters. Additionally, in order to check whether critical dynamics, as the signature of a complex phenomenon such as earthquake preparation, are reflected in the SLHF data, we performed a criticality analysis using the natural time analysis method. The approach to criticality was detected within one week before each mainshock. 相似文献
86.
In this article, an assessment of surface structural heterogeneity in porous metal organic framework (MOF) structure has been demonstrated by employing the methane and carbon-dioxide adsorption isotherms data. The virgin MIL-101-(Cr) MOF was synthesized by the hydrothermal method and defects were induced in the MOF structure by doping with various alkali (K, Na, Li) cations. The synthesized MOFs were characterized by XRD, SEM, EDX and BET measurement techniques. In order to understand the defect induced surface heterogeneity by alkali cation dopants, the surface energy distributions for CH4 and CO2 adsorptions on MOFs were measured by Dubinin – Astakhov model equation. The surface heterogeneity is mainly controlled by the limiting uptakes of adsorbates, the polarizability of adsorbates and the adsorbate-adsorbent interaction energy. 相似文献
87.
This study was conducted in a continuous three-stage system of anaerobic (R1)-anoxic(R2)-aerobic (R3) reactors with synthetic
wastewater containing phenol (1000 mg/L), chemical oxygen demand (COD) (3000 mg/L), CN− (30 mg/L), SCN−(400 mg/L), and NH
4
+
-N (600 mg/L) as principal pollutants and well-acclimated heterogeneous microbial cultures. The final effluent was partially
returned to R2 with a recycle ratio of 1. Anaerobic stage served to detoxify the feed by removing up to 80% of cyanide. Complete
SCN− removal and denitrification could be achieved in the anoxic stage by utilizing phenol as an internal source of carbon. Nitrification
efficiency of 93% was obtained in the aerobic reactor. The results demonstrated that the three-stage system can give the desired
final treated effluent quality (0 mg/L of phenol, 0.2 mg/L of CN−, 210 mg/L of COD, and 20 mg/L of NH
4
+
-N) and that the NO
3
−
-N concentration can be lowered by a higher recycle ratio. 相似文献
88.
Chakraborty T Holm AI Hvelplund P Nielsen SB Poully JC Worm ES Williams ER 《Journal of the American Society for Mass Spectrometry》2006,17(12):1675-1680
Electron capture by both bare and microsolvated small peptide dications was investigated by colliding these ions with sodium vapor in an accelerator mass spectrometer to provide insight into processes that occur on the microsecond time frame. Survival of the intact peptide monocation after electron capture depends strongly on molecular size. For dipeptides, no intact reduced species were observed; the predominant ions correspond to loss of hydrogen and ammonia. In contrast, the intact reduced species was observed for larger peptides. Calculated structures indicate that the diprotonated dipeptide ions form largely extended structures with low probability of internal ionic hydrogen bonding (i.e., charge solvation) whereas internal ionic H-bonding occurs extensively for larger peptide dications. Solvation of the peptide ions with between one to seven methanol molecules reduces the total extent of H loss even for dipeptides where intact reduced species can survive more than a microsecond after electron capture. The yield of ions corresponding to cleavage of NCalpha bonds (c+ and z+* ions) does not depend strongly on peptide size but decreases with the extent of microsolvation for the dipeptide dications. H-bonding appears to play an important role for the survival of the intact reduced ions but less so for the formation of c+ and z+* ions. Our results indicate that electron capture predominantly occurs at the ammonium groups (at least 70 to 80%), and provides important new insights into the electron capture dissociation process. 相似文献
89.
Binita Ghosh Purushottam Chakraborty 《Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques》2010,4(3):518-524
Although electronics technologies have made great advances in device speed, optical devices can function in the time domain
inaccessible to electronics. In the time domain less than 1 ps, optical devices have no competition. Photonic or optical devices
are designed to switch and process light signals without converting them to electronic form. The major advantages that these
devices offer are speed and preservation of bandwidth. The switching is accomplished through changes in refractive index of
the material that are proportional to the light intensity. The third-order optical susceptibility, χ(3), known as the optical Kerr susceptibility which is related to the non-linear part of the total refractive index, is the nonlinearity
which provides this particular feature. Future opportunities in photonic switching and information processing will depend
critically on the development of improved photonic materials with enhanced Kerr susceptibilities, as these materials are still
in a relatively early stage of development. Different glass systems are now under investigation to increase their nonlinearity
by introducing a variety of modifiers into the glass-network. Ion implantation is an attractive method for inducing colloid
formation at a high local concentration unattainable by the melt-glass fabrication process and for confining the non-linearities
to specific patterned regions in a variety of host matrices. Recent works on metal-ion implanted colloid generation in bulk
fused silica glasses have shown that these nanocluster-glass composites under favourable circumstances have significant enhancement
of χ(3) with picosecond to femtosecond temporal responses. 相似文献
90.
Madhumala Ghosh Devkumar Das Chandan Chakraborty Ajoy K. Ray 《Micron (Oxford, England : 1993)》2010,41(7):840-846
This paper aims at introducing an automated approach to leukocyte recognition using fuzzy divergence and modified thresholding techniques. The recognition is done through the segmentation of nuclei where Gamma, Gaussian and Cauchy type of fuzzy membership functions are studied for the image pixels. It is in fact found that Cauchy leads better segmentation as compared to others. In addition, image thresholding is modified for better recognition. Results are studied and discussed. 相似文献