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排序方式: 共有385条查询结果,搜索用时 15 毫秒
31.
In a previous DFT study a mechanism for the reductive half-reaction of pea seedling amine oxidase (PSAO) was suggested. In many of the suggested steps a lysine at the active site plays an important role. However, this lysine is not found in other amine oxidases. The primary aim of the present DFT study is therefore to investigate alternative mechanisms for those amine oxidases (CAO) where the lysine residue is not present. One of the most important roles suggested for the lysine in PSAO was to protonate the O2-site of TPQ before the critical Cbond;H bond cleavage of the substrate. In the absence of lysine the O2-site of TPQ is now suggested to be protonated by a water ligand on the copper metal complex, in line with experimental suggestions. In other steps the role of lysine is taken over by an asparagine. All results are compared with experimental observations and good agreement is generally found. 相似文献
32.
Polyaniline based nucleic acid sensor 总被引:1,自引:0,他引:1
Prabhakar N Arora K Singh H Malhotra BD 《The journal of physical chemistry. B》2008,112(15):4808-4816
Twenty-bases long NH2-modified DNA and PNA probes specific to a pathogen (Mycobacterium tuberculosis) were covalently immobilized onto a polyaniline (PANI)/Au electrode to detect nucleic acid hybridization with complementary, one-base mismatch and noncomplementary targets within 30 s using Methylene Blue. The PNA-PANI/Au electrode exhibits improved specificity (1000 times) and detection limit (0.125 x 10(-18) M) as compared to that of the DNA-PANI/Au electrode (2.5 x 10(-18) M). These PNA-PANI/Au electrodes can be utilized for detection of hybridization with the complementary sequence in 5 min sonicated M. tuberculosis genomic DNA within 1 min of hybridization time. These DNA-PANI/Au and PNA-PANI/Au electrodes can be used 6-7 and 13-15 times, respectively. 相似文献
33.
K.C. Devarayapalli S.V. Prabhakar Vattikuti T.V.M. Sreekanth Ki Soo Yoo P.C. Nagajyothi Jaesool Shim 《应用有机金属化学》2020,34(3):e5376
Herein, cobalt (Co)-based metal–organic zeolitic imidazole frameworks (ZIF-67) coupled with g-C3N4 nanosheets synthesized via a simple microwave irradiation method. SEM, TEM and HR-TEM results showed that ZIF-67 were uniformly dispersed on g-C3N4 surfaces and had a rhombic dodecahedron shape. The photocatalytic properties of g-C3N4/ZIF-67 nanocomposite were evaluated by photocatalytic dye degradation of crystal violet (CV), 4-chlorophenol (4-CP) and photocatalytic hydrogen (H2) production. In presence of visible light illumination, the photocatalytic dye results showed that 95% CV degradation and 53% 4-CP degradation within 80 min. The H2 production of the g-C3N4/ZIF-67 composite was 2084 μmol g−1, which is 3.84 folds greater than that of bare g-C3N4 (541 μmol g−1). 相似文献
34.
Lakshmi VV Murty MR Reddy TJ Ravikumar M Prabhakar S Vairamani M 《Rapid communications in mass spectrometry : RCM》2006,20(6):981-986
Off-site detection of the hydrolysed products of sulfur mustards in aqueous samples is an important task in the verification of Chemical Weapons Convention (CWC)-related chemicals. The hydrolysed products of sulfur mustards are studied under positive and negative electrospray ionisation (ESI) conditions using an additive with a view to detecting them at trace levels. In the presence of cations (Li(+), Na(+), K(+) and NH(4) (+)), the positive ion ESI mass spectra of all the compounds include the corresponding cationised species; however, only the [M+NH(4)](+) ions form [M+H](+) ions upon decomposition. The tandem mass (MS/MS) spectra of [M+H](+) ions from all the hydrolysed products of the sulfur mustard homologues were distinct and allowed these compounds to be characterised unambiguously. Similarly, the negative ion ESI mass spectra of all the compounds show prominent adducts with added anions (F(-), Cl(-), Br(-), and I(-)), but the [M-H](-) ion can only be generated by decomposition of an [M+F](-) ion. The MS/MS spectra of the [M-H](-) ions from all the compounds result in a common product ion at m/z 77. A precursor ion scan of m/z 77 is shown to be useful in the rapid screening of these compounds in aqueous samples at trace levels, even in the presence of complex masking agents, without the use of time-consuming sample preparation and chromatography steps. An MS/MS method developed to measure the detection limits of the hydrolysed products of sulfur mustards found these to be in the range of 10-500 ppb. 相似文献
35.
Over the last two decades many strategies have been planned to design specific drugs for rare diseases to target their action
at the DNA level. Advancements in our understanding of the interactions of small nonpeptide molecules with DNA have opened
the doors for “rational” drug design. Special methods have now been developed to give accurate account of the precise location
of ligand-DNA adducts on target DNA. We are now in a position to think of designing ligands that recognize particular sequences
of base pairs. This work will allow us to enter into a new era of gene therapy for diseases like Cystic fibrosis, Alzheimer’s
disease and many related disorders at genetic level. These ligands can also be employed in the treatment of various types
of cancers. They may also be useful as highly specific probes to locate particular sequences in the genomic DNA. 相似文献
36.
37.
An expedient procedure for the acylation of alcohols, phenols, and thiophenols using catalytic amount of Zn(OTf)2 is described. This procedure is highly suitable for industrial application due to use of less toxic metal as a part of catalyst, short reaction time at ambient temperature, without any racemization of chiral alcohols. 相似文献
38.
A DFT study of the mechanism of Ni superoxide dismutase (NiSOD): role of the active site cysteine-6 residue in the oxidative half-reaction 总被引:1,自引:0,他引:1
In the present DFT study, the catalytic mechanism of H2O2 formation in the oxidative half-reaction of NiSOD, E-Ni(II) + O2- + 2H+ --> E-Ni(III) + H2O2, has been investigated. The main objective of this study is to investigate the source of two protons required in this half-reaction. The proposed mechanism consists of two steps: superoxide coordination and H2O2 formation. The effect of protonation of Cys6 and the proton donating roles of side chains (S) and backbones (B) of His1, Asp3, Cys6, and Tyr9 residues in these two steps have been studied in detail. For protonated Cys6, superoxide binding generates a Ni(III)-O2H species in a process that is exothermic by 17.4 kcal/mol (in protein environment using the continuum model). From the Ni(III)-O2H species, H2O2 formation occurs through a proton donation by His1 via Tyr9, which relative to the resting position of the enzyme is exothermic by 4.9 kcal/mol. In this pathway, a proton donating role of His1 residue is proposed. However, for unprotonated Cys6, a Ni(II)-O2- species is generated in a process that is exothermic by 11.3 kcal/mol. From the Ni(II)-O2- species, the only feasible pathway for H2O2 formation is through donation of protons by the Tyr9(S)-Asp3(S) pair. The results discussed in this study elucidate the role of the active site residues in the catalytic cycle and provide intricate details of the complex functioning of this enzyme. 相似文献
39.
Cardoso AS Marques MM Srinivasan N Prabhakar S Lobo AM Rzepa HS 《Organic & biomolecular chemistry》2006,4(21):3966-3972
Rearrangement of N(a)-prenyl-N(b)-acetyltryptamine, induced by BF3.Et2O at low temperature, leads to a 2-prenyl derivative, and thence to the tricyclic tryptamine 7 and the indoline 8. Similarly, N(a)-prenyl-N(b)-phthaloyl-l-tryptophan methyl ester furnished the corresponding 2-prenyl derivative 16, a known advanced precursor of tryprostatin B. Density functional (B3LYP) calculations for the putative rearrangement transition state for N-prenylskatole show that prior coordination of BF3 to the indolic nitrogen changes the character of the subsequent sigmatropic pericyclic shifts from being entirely covalent to acquiring a significant degree of ionic character. The shifting prenyl group favours the endo over the exo mode of the transition state by 4.1 kcal mol(-1). 相似文献
40.
Jyoti Kannoujia Pavan Kumar Bangalore Srinivas Kantevari Prabhakar Sripadi 《Journal of mass spectrometry : JMS》2020,55(10)
The HPLC‐DAD and GC/MS methods were successfully used for the identification and characterization of the impurities in an agrochemical insecticide, bifenthrin technical. Three impurities ranging from 0.175%–0.541% were detected by the HPLC‐DAD method. The LC/MS technique with ESI or APCI source failed to detect the impurities detected by HPLC‐DAD, due to lack of ionization in ESI or APCI. The three impurities were enriched by prep‐HPLC, and then their structures were elucidated based on the GC/EIMS and CIMS data. The EI mass spectra of bifenthrin and its impurities displayed molecular ion and provided structure indicative fragment ions; the CIMS data further confirmed their molecular weight. The identity of the impurity 1 was further confirmed by the synthesis of the authentic sample followed by NMR and GC/MS data. 相似文献