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241.
242.
Stoyanovsky DA Tyurina YY Tyurin VA Anand D Mandavia DN Gius D Ivanova J Pitt B Billiar TR Kagan VE 《Journal of the American Chemical Society》2005,127(45):15815-15823
The nitrosation of cellular thiols has attracted much interest as a regulatory mechanism that mediates some of the pathophysiological effects of nitric oxide (NO). In cells, virtually all enzymes contain cysteine residues that can be subjected to S-nitrosation, whereby this process often acts as an activity switch. Nitrosation of biological thiols is believed to be mediated by N2O3, metal-nitrosyl complexes, and peroxynitrite. To date, however, enzymatic pathways for S-denitrosation of proteins have not been identified. Herein, we present experimental evidence that two ubiquitous cellular dithiols, thioredoxin and dihydrolipoic acid, catalyze the denitrosation of S-nitrosoglutathione, S-nitrosocaspase 3, S-nitrosoalbumin, and S-nitrosometallothionenin to their reduced state with concomitant generation of nitroxyl (HNO), the one-electron reduction product of NO. In these reactions, formation of NO and HNO was assessed by ESR spectrometry, potentiometric measurements, and quantification of hydroxylamine and sodium nitrite as end reaction products. Nitrosation and denitrosation of caspase 3 was correlated with its proteolytic activity. We also report that thioredoxin-deficient HeLa cells with mutated thioredoxin reductase denitrosate S-nitrosothiols less efficiently. We conclude that both thioredoxin and dihydrolipoic acid may be involved in the regulation of cellular S-nitrosothiols. 相似文献
243.
Sangita Dhara Nand Lal MisraKhush Dev Singh Mudher Suresh Kumar Aggarwal 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
A study to assess the applicability of Total Reflection X-ray Fluorescence (TXRF) spectrometry as a microanalytical technique for the determination of uranium and thorium as major elements in presence of each other has been made. Effect of dilution of the sample on the analytical results has been investigated. It has been found that dilution of the sample does not affect the analytical results significantly. Also the analytical results of uranium and thorium are similar with different internal standards e.g. cobalt, gallium and yttrium. With a sample size of 10 μL and the concentrations of the analytes in the range of 1–50 μg/mL and total matrix concentration less than 200 μg/mL, the precision and accuracy of the method were found to be better than 3% (1 s) and 4%, respectively. For higher concentration ranges of the analyte (up to about 700 μg/mL), the precision and accuracy values were better than 6% (1 s) and 5%, respectively. The TXRF method has an advantage of using small sample volume of about 10 μL, produces very small radioactive waste and is nondestructive but requires dissolution of the sample. 相似文献
244.
A family of oxorhenium(V) complexes of newly designed pyridylthioazophenolate ligands has been synthesized and isolated in
pure form. The solid state structure of an organic compound (HL1) has been established by X-ray crystallography. The molecular
structure observed in the solid state is that the two molecules of the ligand (HL1) in the asymmetric unit have similar geometries,
except for the orientation of the pyridine ring. This series of organic moieties acts as tetradentate monobasic NSNO donor
chelators in oxorhenium(V) complexes which has been characterized by elemental analyses, IR, 1H-NMR, UV–Vis. The complexes are 1:1 electrolytes in nature in MeOH solution, the counter anion being ClO
4
−
. The electrochemical studies of the [ReVO(L)Cl]ClO4 complexes in MeCN using TBAP as supporting electrolyte exhibit quasi-reversible voltammogram showing one-electron couple
for [ReVIO(L)Cl]2+−[ReVO(L)Cl]+ in the 1.11–1.29 V vs SCE range. 相似文献
245.
Chandrasekhar V Azhakar R Senapati T Thilagar P Ghosh S Verma S Boomishankar R Steiner A Kögerler P 《Dalton transactions (Cambridge, England : 2003)》2008,(9):1150-1160
The reaction of cyclohexylphosphonic acid (C(6)H(11)PO(3)H(2)), anhydrous CuCl(2) and 2,2'-bipyridine (bpy) in the presence of triethylamine followed by a metathesis reaction with KNO(3) afforded [Cu(4)(mu-Cl)(2)(mu(3)-C(6)H(11)PO(3))(2)(bpy)(4)](NO(3))(2) (1). In an analogous reaction involving Cu(OAc)(2).H(2)O, the complex [Cu(4)(mu-CH(3)COO)(2)(mu(3)-C(6)H(11)PO(3))(2)(2,2'-bpy)(4)](CH(3)COO)(2) (2) has been isolated. The three-component reaction involving Cu(NO(3))(2).3H(2)O, cyclohexylphosphonic acid and 2,2'-bipyridine in the presence of triethylamine afforded the tetranuclear assembly [Cu(4)(mu-OH)(mu(3)-C(6)H(11)PO(3))(2)(2,2'-bpy)(4) (H(2)O)(2)](NO(3))(3) (3). Replacing 2,2'-bipyridine with 1,10-phenanthroline (phen) in the above reaction resulted in [Cu(4)(mu-OH)(mu(3)-C(6)H(11)PO(3))(2)(phen)(4)(H(2)O)(2)](NO(3))(3) (4). In all the copper(II) phosphonates (1-4) the two phosphonate ions bridge the four copper(II) ions in a capping coordination action. Each phosphonate ion bridges four copper(II) ions in a mu(4), eta(3) coordination mode or 4.211 of the Harris notation. Variable-temperature magnetic studies on reveal that all four complexes exhibit moderately strong intramolecular antiferromagnetic coupling. The DNA cleavage activity of complexes 1-4 is also described. Compounds 1 and 3 were able to completely convert the supercoiled pBR322 DNA form I to nick form II without any co-oxidant. In contrast, 50% conversion occurred with and 40% with 4. In the presence of magnesium monoperoxyphthalate all four compounds achieved rapid conversion of form I to form II. 相似文献
246.
We report the experimental high electric field phase diagram of a nematic
liquid crystal which exhibits a large negative dielectric
anisotropy. We measure simultaneously
the birefringence (Δn) and the dielectric constant
(epsilon⊥) at various applied fields as
functions of the
local temperature of an aligned sample. We also measure the higher harmonics of
the electrical response of the
medium. The following experimental results are noted: (i) enhancement
of orientational order parameter
S in the nematic phase due to both
the Kerr effect and quenching of director fluctuations; (ii) enhancement in the paranematic to
nematic transition temperature (TPN) with field; (iii) divergence of the order parameter
susceptibility beyond the tricritical point as measured
by third harmonic electrical signal; (iv) a small second harmonic
electrical signal which also diverges
near TPN, indicating the presence of
polarised domains. Our measurements show that ΔTPN(= TPN(E)-TNI(0))
varies linearly with |E|
whereas the Landau de Gennes theory predicts a dependence on E2. It is argued that the quenching of director fluctuations by the field makes the dominant contribution to all the observations,
including the thermodynamics of the transition. 相似文献
247.
248.
The reaction of Cu2(O2CMe)(4).2H2O with tert-butylphosphonic acid and 3,5-di-tert-butylpyrazole in the presence of triethylamine leads to a high-yield synthesis of the tetranuclear compound [Cu2(3,5-t-Bu2PzH)2(t-BuPO3)2]2 (1). The latter has a distorted cubic cage structure and its core resembles the D4R (double-four-ring) motif found in zeolites. The phosphonate, [t-BuPO3]2-, functions as a dianionic tridentate ligand, while the pyrazole ligands are neutral and are monodentate. The coordination geometry at each copper atom is distorted square planar with a 3O,1N coordination environment. Magnetic measurements on 1 reveal that the chiT product continuously decreases to reach a value very close to zero at 1.8 K, indicating dominant antiferromagnetic interactions between Cu(II) ions that leads to an S=0 ground state. The tetranuclear cage 1 functions as a very effective artificial nuclease in the presence of an external oxidant, magnesium monoperoxyphthalate. 相似文献
249.
Iman Shackery Umarkant Patil Min‐Jung Song Ji Soo Sohn Sachin Kulkarni Surajit Some Su Chan Lee Min Sik Nam Wooyoung Lee Seong Chan Jun 《Electroanalysis》2015,27(10):2363-2370
A nickel hydroxide (Ni(OH)2)/3D‐graphene composite is used as monolithic free‐standing electrode for enzymeless electrochemical detection of glucose. Ni(OH)2 nanoflakes are synthesized by using a simple solution growth procedure on 3D‐graphene foam which was grown by chemical vapor deposition (CVD). The pore structure of 3D‐graphene allows easy access to glucose with high surface area, which leads to glucose detection with an ultrahigh sensitivity of 3.49 mA mM?1 cm?2 and a significant lower detection limit up to 24 nM. Cyclic voltammetry (CV) and potentionstatic mode is used for non‐enzymatic glucose sensing. The impedance and effective surface area have been studied well. The high sensitivity, low detection limit and simple configuration of Ni(OH)2/three dimensional (3D)‐graphene composite electrodes can evoke its industrial application in glucose sensing devices. 相似文献
250.
Dr. Debashis Dhara Dr. Laurence A. Mulard 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(18):5694-5711
Shigella sonnei surface polysaccharides are well-established protective antigens against this major cause of diarrhoeal disease. They also qualify as unique zwitterionic polysaccharides (ZPSs) featuring a disaccharide repeating unit made of two 1,2-trans linked rare aminodeoxy sugars, a 2-acetamido-2-deoxy-l -altruronic acid (l -AltpNAcA) and a 2-acetamido-4-amino-2,4,6-trideoxy-d -galactopyranose (AAT). Herein, the stereoselective synthesis of S. sonnei oligosaccharides comprising two, three and four repeating units is reported for the first time. Several sets of up to seven protecting groups were explored, shedding light on the singular conformational behavior of protected altrosamine and altruronic residues. A disaccharide building block equipped with three distinct N-protecting groups and featuring the uronate moiety already in place was designed to accomplish the iterative high yielding glycosylation at the axial 4-OH of the altruronate component and achieve the challenging full deprotection step. Key to the successful route was the use of a diacetyl strategy whereby the N-acetamido group of the l -AltpNAcA is masked in the form of an imide. 相似文献