Abstract：
:The glyoxalase system catalyzes the conversion of toxic methylglyoxal to nontoxic d-lactic acid using glutathione (GSH) as a coenzyme. Glyoxalase II (GlxII) is a binuclear Zn enzyme that catalyzes the second step of this conversion, namely the hydrolysis of S-d-lactoylglutathione, which is the product of the Glyoxalase I (GlxI) reaction. In this paper we use density functional theory method to investigate the reaction mechanism of GlxII. A model of the active site is constructed on the basis of the X-ray crystal structure of the native enzyme. Stationary points along the reaction pathway are optimized and the potential energy surface for the reaction is calculated. The calculations give strong support to the previously proposed mechanism. It is found that the bridging hydroxide is capable of performing nucleophilic attack at the substrate carbonyl to form a tetrahedral intermediate. This step is followed by a proton transfer from the bridging oxygen to Asp58 and finally C-S bond cleavage. The roles of the two zinc ions in the reaction mechanism are analyzed. Zn2 is found to stabilize the charge of tetrahedral intermediate thereby lowering the barrier for the nucleophilic attack, while Zn1 stabilizes the charge of the thiolate product, thereby facilitating the C-S bond cleavage. Finally, the energies involved in the product release and active-site regeneration are estimated and a new possible mechanism is suggested.
journal_name
J Inorg Biochemjournal_title
Journal of inorganic biochemistryauthors
Chen SL,Fang WH,Himo Fdoi
10.1016/j.jinorgbio.2008.10.016subject
Has Abstractpub_date
2009-02-01 00:00:00pages
274-81issue
2eissn
0162-0134issn
1873-3344pii
S0162-0134(08)00258-4journal_volume
103pub_type
杂志文章abstract：:The coordination structures of various species in the copper(II)-L-histidine (1:2) system in aqueous solution have been deduced by investigating the pH dependence of the electronic and circular dichroism spectra. The contribution to the spectra of the glycine-like and histamine-like binding modes of L-histidine has be...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(83)85036-3
更新日期：1983-02-01 00:00:00
abstract：:Oxyhemoglobin is oxidized to methemoglobin by copper(II) in a two-stage reaction that results in conversion of Fe(II) to Fe(III) in heme of the beta subunits, but not the alpha subunits. Glutathione and other thiols, which are slowly oxidized by Cu(II), protect oxyhemoglobin from Cu(II)-induced oxidation. In the prese...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(93)80038-b
更新日期：1993-11-15 00:00:00
abstract：:In this paper, Bi2S3 nanospheres with size of 212nm were prepared by a simple hydrothermal process. The selectively enhanced antibacterial effects of Bi2S3 nanospheres with three classes of ineffective antibiotics, β-lactam (cefuroxime, CXM; cefotaxime, CTX and piperacillin, PIP), quinolone (ciprofloxacin, CIP) and am...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2016.12.005
更新日期：2017-03-01 00:00:00
abstract：:The advantages of systems with Ag nanoparticles and their assemblies for surface-enhanced resonance Raman scattering (SERRS) spectral investigation, detection and determination of porphyrin species are demonstrated. SERRS spectral detection limits of the testing porphyrin species (including porphyrin aggregates) in th...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/s0162-0134(99)00172-5
更新日期：2000-04-01 00:00:00
abstract：:We have surveyed the chemical utility of the near-edge structure of molybdenum X-ray absorption edges from the hard X-ray K-edge at 20,000eV down to the soft X-ray M(4,5)-edges at approximately 230eV. We compared, for each edge, the spectra of two tetrahedral anions, MoO(4)(2-) and MoS(4)(2-). We used three criteria f...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2008.09.008
更新日期：2009-02-01 00:00:00
abstract：:New heteroditopic, bi- and multidentate imino- and aminophosphine ligands were synthesised and complexed to [AuCl(THT)] (THT=tetrahydrothiophene). X-ray crystallography confirmed Schiff base formation in three products, the successful reduction of the imino-group to the sp(3)-hybridised amine in several instances, and...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2015.01.014
更新日期：2015-04-01 00:00:00
abstract：:Antitumor antibiotic bleomycin can bind to and degrade DNA, both in vivo and in vitro. This DNA damaging property in vitro can be related to its ability to chelate ferrous ions under aerobic conditions leading to the formation of "active oxygens," which are thought to be directly responsible for the damage. At present...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/s0162-0134(00)80238-x
更新日期：1981-12-01 00:00:00
abstract：:Copper based nanoparticles (Cu-based NPs) of different compositions and sizes have been hydrothermally synthesized by varying the reaction time in the presence of the biocompatible surfactants polyoxyethylene (20) sorbitan laurate (Tween 20) and polyethylene glycol 8000 (PEG 8000). Effective control of the above synth...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2013.12.009
更新日期：2014-04-01 00:00:00
abstract：:Rats were fed 100 microM aluminum maltolate for one year in their drinking water. Brain aluminum contents have increased 4.2-fold in the aluminum-treated group, whereas no significant changes in the body weight, brain weight, and brain protein content were observed. Long-term aluminum feeding induced apoptosis as asse...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2005.06.032
更新日期：2005-10-01 00:00:00
abstract：:Cystine, selenocytsine, and several analogs were reduced by dithiothreitol (DTT), beta-mercaptoethanol (ME) and sodium borohydride (NaBH4). DTT was the most effective; DTT to cystine ratios from 10 to 80 were equally effective. With selenocysteine, however, absorption was considerably reduced at all ratios. Selenocyst...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/s0162-0134(00)80275-5
更新日期：1980-07-01 00:00:00
abstract：:Aggregation of amyloid β-proteins (Aβ) induced by Cu2+ is a crucial element in the pathogenesis of Alzheimer's disease (AD), and cerebral acidosis is a common complication of AD. Under mildly acidic conditions, Cu2+-Aβ species have higher tendency to generate neurotoxic aggregates. Hence it is of significance to devel...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2017.03.009
更新日期：2017-06-01 00:00:00
abstract：:The effect of inositol hexakisphosphate, 2,3-diphosphoglycerate, dextran sulphate, and heparin on the spectroscopic (absorbance, circular dichroism, EPR) properties of the nitric oxide derivative of ferrous dromedary (Camelus dromedarius) hemoglobin was investigated. The results obtained show that: (i) all polyanions ...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(88)85001-3
更新日期：1988-04-01 00:00:00
abstract：:This communication presents synthesis and spectral characterization of metalloporphyrin [Zn(X)TMPyP4] (TMPyP4 is 5,10,15,20-tetrakis (N-methylpyridinium-4-yl)porphyrin), and studies its binding onto anionic surface sites of synthetic double stranded polynucleotide Poly(A)-Poly(U). [Zn(X)TMPyP4] binding with Poly(A)-Po...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2016.05.004
更新日期：2016-08-01 00:00:00
abstract：:A one-pot strategy was first presented in this paper to synthesize gelatin/hydroxyapatite (HAP) composite microspheres in a water-in-oil (W/O) emulsion. Using gelatin droplets as microreactors and colloid protective medium, needle-like nano-HAP crystals (5 nm x 60-100 nm) in form of clusters were homogeneously and ord...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2006.11.018
更新日期：2007-04-01 00:00:00
abstract：:Polyamines are ubiquitous polycations that participate in cellular processes such as growth, differentiation and cell death. Among the different functions ascribed to these organic cations, the polyamine spermine is known to protect DNA from the damage produced by reactive oxygen species (ROS) generated by different a...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2005.07.005
更新日期：2005-10-01 00:00:00
abstract：:Ferredoxin:NADP(+) oxidoreductase (FNR) was treated with cadmium and after that its diaphorase reaction in the presence of dibromothymoquinone (DBMIB) or ferricyanide (FeCy, K(3)Fe(CN)(6)) was examined. CdSO(4) (5 mM) caused 50% inhibition after half hour incubation. At least two components were distinguishable in the...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2004.04.004
更新日期：2004-08-01 00:00:00
abstract：:The reactivities of copper(II) complexes with histidine-containing oligopeptides towards active oxygen species such as hydrogen peroxide (H2O2) and superoxide ion (O2-) were investigated by electron spin resonance (ESR)-spin trapping and thiobarbituric acid (TBA) methods. At physiological pH values, Cu(II) complexes w...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(94)85034-8
更新日期：1994-08-01 00:00:00
abstract：:Measurements of binding of certain divalent cations to yeast apoenolase were made using a pH-meter, chromatography, a divalent cation electrode, and ultrafiltration. The binding of the activating metal ions Mg2+ and Co2+ and the nonactivator Ca2+ were studied as functions of the presence or absence of substrate/produc...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(83)85030-2
更新日期：1983-11-01 00:00:00
abstract：:Twenty-seven sheep given either copper (Cu) and/or tetrathiomolybdate (TM) were used to study the subcellular distribution of Cu within the kidney and to monitor the location of lysosomes within the subcellular fractions using acid phosphatase (AP) as a marker enzyme. Copper dosing alone increased the Cu content in th...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(89)84003-6
更新日期：1989-01-01 00:00:00
abstract：:Fe(III)-salen (N,N-bis(salicylidene)-ethane-1,2-diimine) complexes of simple hydroxamic acids and the MMP (matrix metalloproteinase) inhibitor marimastat have been evaluated as hypoxia activated drug carriers. The aceto- (aha), propion- (pha), benzohydroxamato (bha), and marimastat complexes were prepared and characte...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2006.11.003
更新日期：2007-03-01 00:00:00
abstract：:This work describes the synthesis and characterization of six new dinuclear platinum complexes having N,N'-di-(2-aminoethyl)-1,3-diamino-2-propanol, aryl substituted N-benzyl-1,4-butanediamines and N-benzyl-1,6-hexanediamines as ligands. They were prepared by the reaction of cis-[PtCl(2)(DMSO)(2)] (DMSO=dimethyl sulfo...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/s0162-0134(03)00129-6
更新日期：2003-07-01 00:00:00
abstract：:Crystal structure analyses have helped to decipher the mode of binding of coenzyme B12 (AdoCbl) in the active site of AdoCbl-dependent enzymes. However, the question of how such enzymes perform their radical reactions is still incompletely answered. A pioneering study by Gruber and Kratky of AdoCbl-dependent glutamate...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2015.02.005
更新日期：2015-07-01 00:00:00
abstract：:The antineoplastic and antibiotic natural product mithramycin (MTM) is used against cancer-related hypercalcemia and, experimentally, against Ewing sarcoma and lung cancers. MTM exerts its cytotoxic effect by binding DNA as a divalent metal ion (Me(2+))-coordinated dimer and disrupting the function of transcription fa...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2015.12.011
更新日期：2016-03-01 00:00:00
abstract：:Vanadium compounds have arisen as potential therapeutic agent for the treatment of cancers over the past decades. A few studies suggested that vanadyl complexes may discriminate between the cancerous and the normal cells. Here, we reported the investigation on the pro-apoptotic effect and the underlying mechanism of b...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2018.08.005
更新日期：2018-11-01 00:00:00
abstract：:The reaction of zinc(II) chloride, cadmium(II) chloride and bromide with 3-thiophene aldehyde thiosemicarbazone leads to the formation of a series of new complexes. They have been characterized by spectroscopic studies: infrared, (1)H NMR, and electronic spectra. The crystal structures of the compound [ZnCl(2)(3TTSCH)...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2009.11.012
更新日期：2010-04-01 00:00:00
abstract：:Amino acid replacement is a useful strategy to assess the roles of axial heme ligands in the function of native heme proteins. THB1, the protein product of the Chlamydomonas reinhardtii THB1 gene, is a group 1 truncated hemoglobin that uses a lysine residue in the E helix (Lys53, at position E10 by reference to myoglo...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2019.110824
更新日期：2019-12-01 00:00:00
abstract：:Synthetic, structural and biochemical aspects of some organoboron complexes of sulphur containing ligands having ONS and SNNS donor systems have been described. The ligands were prepared by the condensation of 1-phenyl-1,3-butanedione, 2,4-pentanedione, diphenylethanedione, 2,3-butanedione, ethanedial and 1,4-benzened...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(90)84007-c
更新日期：1990-07-01 00:00:00
abstract：:Root border cells (RBCs) and their secreted mucilage are suggested to participate in the resistance against toxic metal cations, including aluminum (Al), in the rhizosphere. However, the mechanisms by which the individual cell populations respond to Al and their role in Al resistance still remain unclear. In this rese...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2011.04.004
更新日期：2011-07-01 00:00:00
abstract：:Ten new vanadocene complexes bearing N,N'-chelating ligands were prepared, characterized, and their cytotoxicity toward a panel of cancer cells was measured. Structures of four vanadocene compounds were determined by single crystal X-ray diffraction analysis. Complexes containing 1,2-bis(phenylimino)acenaphthene (bian...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/j.jinorgbio.2019.03.015
更新日期：2019-06-01 00:00:00
abstract：:Previous studies of the interaction of the haem undecapeptide (MP-11) with lipidated human serum albumin in aqueous solution have been extended to a range of MeOH/H2O solution compositions. It is demonstrated that the kinetic mechanism for the interaction does not change from a simple second- and first-order reversibl...
journal_title：Journal of inorganic biochemistry
pub_type： 杂志文章
doi：10.1016/0162-0134(93)80009-x
更新日期：1993-04-01 00:00:00
