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91.
Spectroscopic and Computational Study of a Nonheme Iron Nitrosyl Center in a Biosynthetic Model of Nitric Oxide Reductase
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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
92.
Dr. Victor Malgras Dr. Priyanka Jood Dr. Ziqi Sun Prof. Shi Xue Dou Prof. Yusuke Yamauchi Prof. Jung Ho Kim 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(33):10451-10455
Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation. 相似文献
93.
Priyanka Verma Shamshad Ahmad Khan Ajay Kumar Mathur Karuna Shanker Raj Kishori Lal 《Applied biochemistry and biotechnology》2014,173(3):663-672
Hydroxylase/acetyltransferase elicitors and cyclooxygenase inhibitor along with various precursors from primary shikimate and secoiridoid pools have been fortified to vincamine less hairy root clone of Vinca minor to determine the regulatory factors associated with vincamine biosynthesis. Growth kinetic studies revealed that acetyltransferase elicitor acetic anhydride and terpenoid precursor loganin significantly reduce the growth either supplemented alone or in combination (GI?=?140.6?±?18.5 to 246.7?±?24.3), while shikimate and tryptophan trigger biomass accumulation (GI?=?440.2?±?31.5 to 540.5?±?40.3). Loganin also downregulates total alkaloid biosynthesis. Maximum flux towards vincamine production (0.017?±?0.001 % dry wt.) was obtained when 20-day-old hairy roots were fortified with secologanin (10 mg/l) along with tryptophan (100 mg/l), naproxen (8.4 mg/l), hydrogen peroxide (20 μg/l), and acetic anhydride (32.4 mg/l). This was supported by RT PCR (qPCR) analysis where 2- and 3-fold increase in tryptophan decarboxylase (TDC; RQ?=?2.0?±?0.09) and strictosidine synthase (STR; RQ?=?3.3?±?0.36) activity, respectively, was recorded. The analysis of variance (ANOVA) for growth kinetics, total alkaloid content, and gene expression studies favored highly significant data (P?<?0.05–0.01). Above treated hairy roots were also up-scaled in a 5-l stirred-tank bioreactor where a 40-day cycle yielded 8-fold increase in fresh root mass. 相似文献
94.
Priyanka Sharma Rupesh Kumar Gaurav Bhargava 《Journal of heterocyclic chemistry》2020,57(12):4115-4135
Pyrrolin-4-ones/pyrrolin-3-ones and its derivatives are important heterocyclic systems which are observed in vast variety of natural products, pharmaceuticals, and biologically important compounds. Different researchers all across the world have developed different synthetic methodologies for the construction of functionalized pyrrolin-4-ones/pyrrolin-3-one scaffolds such as the transition-metal catalyzed/mediated cycloisomerizations of 1-aminoynones and dimerization of enaminones or α-diazo-β-oxoamides etc. The present review article summarizes various reports on the synthesis of various simple and functionalized pyrrolin-4-ones/pyrrolin-3-ones from 2000 onward. 相似文献
95.
Priyanka Michael Espen Hansen Johan Isaksson Jeanette H. Andersen 《Natural product research》2020,34(14):2059-2064
AbstractThe new guanidine alkaloid Dendrobeaniamine A (1) was isolated from the organic extract of the Arctic marine bryozoan Dendrobeania murrayana. The chemical structure of 1 was elucidated by spectroscopic experiments, including 1D and 2D NMR and HRESIMS analysis. Compound 1 is a lipoamino acid, consisting of a C12 fatty acid anchored to the amino acid arginine. The bioactivity of 1 was evaluated using cellular and biochemical assays, but the compound did not show cytotoxic, antimicrobial, anti-inflammatory or antioxidant activities 相似文献
96.
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
97.
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
98.
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
99.
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
100.
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