The synthesis and characterisation of two new iron thioantimonates: [Fe(en)(3)](2)Sb2S5 center dot 0.55H(2)O and [Fe(en)(3)](2)Sb4S8

Two new iron thioantimonates, [Fe(en)(3)](2)Sb2S5 (.) 0.55H(2)O (1) and [Fe(en)(3)](2)Sb4S8 (2). were synthesised under solvothermal conditions from the reactions of Sb2S3, FeCl2 and S in the presence of ethylenediamine at 413 and 438 K, respectively. The products were characterised by single-crystal X-ray diffraction, elemental analysis and SQUID magnetometry. Compound 1 is unusual in containing isolated Sb2S54- anions formed from two corner-sharing SbS33- trigonal pyramids. These units are arranged in rippled layers, 4 A apart, parallel to the bc-plane. Octahedrally coordinated [Fe(en)(3)](2+) cations lie in depressions within these anionic layers. In compound (2), repeated corner linking of SbS33- trigonal pyramids generates SbS2- chains, which may be considered as a polymerised form of the Sb2S54- anions in 1. The SbS2- chains are separated by [Fe(en)(3)](2+) cations. In both compounds, there is an extensive network of hydrogen bonds between the nitrogen atoms of the ethylenediamine ligands and the sulfur atoms of the anions and, in the case of 1, the uncoordinated water molecule. (c) 2005 Elsevier Ltd. All rights reserved.

Two new mu-(1,3-azido)-bridged polymers: alternating single and double bridges in a 1D nickel(II) complex and uniform bridge in a 2D copper(II) complex: Syntheses, single-crystal structures and magnetic studies

Two polymeric azido bridged complexes [Ni2L2(N-3)(3)](n)(ClO4). (1) and [Cu(bpdS)(2)(N-3)],(ClO4),(H2O)(2.5n) (2) [L = Schiff base, obtained from the condensation of pyridine-2-aldehyde with N,N,2,2-tetramethyl-1,3-propanediamine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and their crystal structures have been determined. Complex 1, C26H42ClN15Ni2O4, crystallizes in a triclinic system, space group P1 with a 8.089(13), b = 9.392(14), c = 12.267(18) angstrom, a = 107.28(l), b 95.95(1), gamma = 96.92(1)degrees and Z = 2; complex 2, C20H21ClCuN7O6.5S4, crystallizes in an orthorhombic system, space group Pnna with a = 10.839(14), b = 13.208(17), c = 19.75(2) angstrom and Z = 4. The crystal structure of I consists of 1D polymers of nickel(L) units, alternatively connected by single and double bridging mu-(1,3-N-3) ligand with isolated perchlorate anions. Variable temperature magnetic susceptibility data of the complex have been measured and the fitting,of magnetic data was carried out applying the Borris-Almenar formula for such types of alternating one-dimensional S = 1 systems, based on the Hamiltonian H = -J Sigma(S2iS2i-1 + aS(2i)S(2i+1)). The best-fit parameters obtained are J = -106.7 +/- 2 cm(-1); a = 0.82 +/- 0.02; g = 2.21 +/- 0.02. Complex 2 is a 2D network of 4,4 topology with the nodes occupied by the Cu-II ions, and the edges formed by single azide and double bpds connectors. The perchlorate anions are located between pairs of bpds. The magnetic data have been fitted considering the complex as a pseudo-one-dimensional system, with all copper((II)) atoms linked by [mu(1,3-azido) bridging ligands at axial positions (long Cu...N-3 distances) since the coupling through long bpds is almost nil. The best-fit parameters obtained with this model are J = -1.21 +/- 0.2 cm(-1), g 2.14 +/- 0.02. (c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

Anion-directed template synthesis and hydrolysis of mono-condensed Schiff base of 1,3-pentanediamine and o-hydroxyacetophenone in Ni-II and Cu-II complexes

Bis(o-hydroxyacetophenone)nickel(II) dihydrate, on reaction with 1,3-pentanediamine, yields a bis-chelate complex [NiL2]center dot 2H(2)O (1) of mono-condensed tridentate Schiff base ligand HL {2-[1-(3-aminopentylimino)ethyl]phenol}. The Schiff base has been freed from the complex by precipitating the Nil, as a dimethylglyoximato complex. HL reacts smoothly with Ni(SCN)(2)center dot 4H(2)O furnishing the complex [NiL(NCS)] (2) and with CuCl2 center dot 2H(2)O in the presence of NaN3 or NH4SCN producing [CuL(N-3)](2) (3) or [CuL(NCS)] (4). On the other hand, upon reaction with Cu(ClO4)(2)center dot 6H(2)O and Cu(NO3)(2)center dot 3H(2)O, the Schiff base undergoes hydrolysis to yield ternary complexes [Cu(hap)(pn)(H2O)]ClO4 (5) and [Cu(hap)(pn)(H2O)]NO3 (6), respectively (Hhap = o-hydroxyacetophenone and pn = 1,3-pentanediamine). The ligand HL undergoes hydrolysis also on reaction with Ni(ClO4)(2)center dot 6H(2)O or Ni(NO3)(2)center dot 6H(2)O to yield [Ni(hap)(2)] (7). The structures of the complexes 2, 3, 5, 6, and 7 have been confirmed by single-crystal X-ray analysis. In complex 2, Ni-II possesses square-planar geometry, being coordinated by the tridentate mono-negative Schiff base, L and the isothiocyanate group. The coordination environment around Cu-II in complex 3 is very similar to that in complex 2 but here two units are joined together by end-on, axial-equatorial azide bridges to result in a dimer in which the geometry around Cu-II is square pyramidal. In both 5 and 6, the Cu-II atoms display the square-pyramidal environment; the equatorial sites being coordinated by the two amine groups of 1,3-pentanediamine and two oxygen atoms of o-hydroxyacetophenone. The axial site is coordinated by a water molecule. Complex 7 is a square-planar complex with the Ni atom bonded to four oxygen atoms from two hap moieties. The mononuclear units of 2 and dinuclear units of 3 are linked by strong hydrogen bonds to form a one-dimensional network. The mononuclear units of 5 and 6 are joined together to form a dimer by very strong hydrogen bonds through the coordinated water molecule. These dimers are further involved in hydrogen bonding with the respective counteranions to form 2-D net-like open frameworks. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

(Ni-2), (Ni-3), and (Ni-2 + Ni-3): A Unique Example of Isolated and Cocrystallized Ni-2 and Ni-3 Complexes

Structural and magnetic characterization of compound {[Ni-2(L)(2)(OAC)(2)][Ni-3(L)(2) (OAc)(4)]) center dot 2CH(3)CN (3) (HL = the tridentate Schiff base ligand, 2-[(3-methylaminb-propylimino)-methyl]-phenol) shows that it is a rare example of a crystal incorporating a dinuclear Ni(II) compound, [Ni-2(L)(2)(OAc)(2)], and a trinuclear one, [Ni-3(L)(2)(OAC)(4)]. Even more unusual is the fact that both Ni (II) complexes, [Ni-2(L)(2)(OAc)(2)] (1) and [Ni-3(L)(2)(OAc)(4)(H2O)(2)] center dot CH2Cl2 center dot 2CH(3)OH (2), have also been isolated and structurally and magnetically characterized. The structural analysis reveals that the dimeric complexes [Ni-2(L)(2)(OAc)(2)] in cocrystal 3 and in compound 1 are almost identical-in both complexes, the Ni(II) ions possess a distorted octahedral geometry formed by the chelating tridentate ligand (L), a chelating acetate ion, and a bridging phenoxo group with very similar bond angles and distances. On the other hand, compound 2 and the trinuclear complex in the cocrystal 3 show a similar linear centrosymmetric structure with the tridentate ligand coordinated to the terminal Ni(II) and linked to the central Ni(II) by phenoxo and carboxylate bridges. The only difference is that a water molecule found in 2 is not present in the trinuclear unit of complex 3; instead, the coordination sphere is completed by an additional bridging oxygen atom from an acetate ligand. Variable-temperature (2-300 K) magnetic susceptibility measurements show that the dinuclear unit is antiferromagnetically coupled in both compounds (2J = -36.18 and -29.5 cm(-1) in 1 and 3, respectively), whereas the trinuclear unit shows a very weak ferromagnetic coupling in compound 3 (2J = 0.23 cm(-1)) and a weak antiferromagnetic coupling in 2 (2J = -8.7(2) cm(-1)) due to the minor changes in the coordination sphere.

Lanthanide complexes of 2-hydroxynicotinic acid: synthesis, luminescence properties and the crystal structures of [Ln(HnicO)(2)(mu-HnicO)(H2O)] center dot nH(2)O (Ln = Tb, Eu)

New lanthanide complexes of 2-hydroxynicotinic acid (H(2)nicO) [Ln(HnicO)(2)(mu-HnicO)(H2O)] (.) nH(2)O (Ln = Eu, Gd, Tb, Er, Tm) were prepared. The crystal structures of the [Tb(HnicO)(2)(g-HnicO)(H2O)] (.) 1.75H(2)O(1) and [Eu(HniCO)(2)(mu-HnicO)(H2O)] (.) 1.25H(2)O (2) complexes were determined by X-ray diffraction. The 2-hydroxynicotinate ligand coordinates through O,O-chelation to the lanthanide(III) ions as shown by X-ray diffraction and the infrared, Raman and NMR spectroscopy results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes. Lifetimes of 0.592 +/- 0.007 and 0.113 +/- 0.002 ms were determined for the Eu3+ and Tb3+ emitting states D-5(0) and D-5(4), respectively. A value around 30% was found for the D-5(0) quantum efficiency. The energy transfer mechanisms between the lanthanide ions and the ligands are discussed and compared with those observed in similar complexes involving the 3-hydroxypicolinate ligand based on the luminescence of the respective Gd3+-based complexes. (C) 2003 Published by Elsevier Ltd.

Synthesis and characterization of packed mesoporous tungsteno-silicates: application to the catalytic dehydrogenation of 2-propanol

The synthesis of highly ordered mesoporous tungsteno-silicas in which a high percentage of tungsten is introduced into a silica framework is reported hereafter. Powder XRD and TEM have been used to characterize the materials synthesized at room temperature. The materials are shown to be homogeneous as there is no evidence for any crystalline species other than the silica framework. The pore diameter and the surface area of the materials, evaluated from the nitrogen adsorption isotherms and unit cell parameter indicate a pore diameter of about 2 nm and a surface area of 1400 m(2) g(-1) for a content of 10% tungsten. Catalyzed dehydration of 2-propanol has been investigated and the activity of the materials synthesized is significant, even for low tungsten content W-MCM-41 materials. (C) 2003 Elsevier B.V. All rights reserved.

Low-lying excited states and primary photoproducts of [Os-3(CO)(10)-(s-cis-L)] (L = cyclohexa-1,3-diene, buta-1,3-diene)] clusters studied by picosecond time-resolved UV/Vis and IR spectroscopy and by density functional theory

Combined picosecond transient absorption and time-resolved infrared studies were performed, aimed at characterising low-lying excited states of the cluster [Os-3(CO)(10)(s-cis-L)] (L= cyclohexa-1,3-diene, 1) and monitoring the formation of its photoproducts. Theoretical (DFT and TD-DFT) calculations on the closely related cluster with L=buta-1,3-diene (2') have revealed that the low-lying electronic transitions of these [Os-3(CO)(10)(s-cis-1,3-diene)] clusters have a predominant sigma(core)pi*(CO) character. From the lowest sigmapi* excited state, cluster 1 undergoes fast Os-Os(1,3-diene) bond cleavage (tau=3.3 ps) resulting in the formation of a coordinatively unsaturated primary photoproduct (1a) with a single CO bridge. A new insight into the structure of the transient has been obtained by DFT calculations. The cleaved Os-Os(1,3-diene) bond is bridged by the donor 1,3-diene ligand, compensating for the electron deficiency at the neighbouring Os centre. Because of the unequal distribution of the electron density in transient la, a second CO bridge is formed in 20 ps in the photoproduct [Os-3(CO)(8)(mu-CO)(2)- (cyclohexa-1,3-diene)] (1b). The latter compound, absorbing strongly around 630 nm, mainly regenerates the parent cluster with a lifetime of about 100 ns in hexane. Its structure, as suggested by the DFT calculations, again contains the 1,3-diene ligand coordinated in a bridging fashion. Photoproduct 1b can therefore be assigned as a high-energy coordination isomer of the parent cluster with all Os-Os bonds bridged.

Marked influence of the bridging carbonyl ligands on the photo- and electrochemistry of the clusters [Ru-3(CO)(8)(mu-CO)(2)-(alpha-diimine)] (alpha-diimine = 2,2 '-bipyridine, 4,4 '-dimethyl-2,2 '-bipyridine and 2,2 '-bipyrimidine)

Bonding, photochemical and electrochemical properties of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] (alpha-diimine=2,2'-bipyridine (1), 4,4'-dimethyl-2,2'-bipyridine (2) and 2,2'-bipyrimidine (3)) are strongly influenced by the presence of bridging carbonyl ligands. Irradiation at 471 nm initially results in the population of a sigma(Ru-3)pi*(alpha-diimine) excited state. From this state, fast decay takes place to the optically hardly directly accessible pi(Ru/mu-CO) pi*(alpha-diimine) lowest excited state. These assignments agree with theoretical (TD-DFT) results, resonance Raman and picosecond time-resolved infrared spectra. The involvement of the bridging carbonyl ligands in the electron transfer increases the energetic barrier for the formation of open-structure photoproducts such as biradicals and zwitterions. Zwitterions were therefore only obtained in strongly coordinating media such as pyridine at 250 K. The bridging carbonyl ligands also stabilize the radical anions produced upon one-electron reduction of the clusters [Ru-3(CO)(8)(mu-CO)(2)(alpha-diimine)] and observed with cyclic voltammetry, EPR and IR spectroelectrochemistry (for alpha-diimine=2,2'-bipyrimidine). In contrast, open-triangle intermediates formed along the reduction path to [Ru(CO)(2)(alpha-diimine)](n) and [Ru-2(CO)(8)](2-) are more reactive than their triosmium analogues.

Synthesis and properties of tetra-μ-acetatodiruthenium(II,III) phenylphosphinate and phenylphosphonate complexes: X-ray crystal structures of [Ru2(μ-O2CCH3)4(HPhPO2)2]H and [Ru2(μ-O2CCH3)4(PhPO3H)2]H·H2O

Phenylphosphinic acid (HPhPO2H) and phenylphosphonic acid (PhPO3H2) react with a methanolic solution of [Ru2(μ-O2CCH3)4(O2CCH3)2]H·0.7H2O at room temperature to give [Ru2(μ-O2CCH3)4(HPhPO2)2H (1) and [Ru2(μ-O2CCH3)4 (PhPO3H)2]H·H2O (2), respectively. The X-ray crystal structures of 1 and 2 each show the RuRu core to be ligated by four bridging bidentate acetate ligands [RuRu distances: 1 = 2.272(1) Å; 2 = 2.267(2) Å] and two axial phenylphosphinate and phenylphosphonate ligands, respectively. In each complex the individual bimetallic molecules are linked together by a hydrogen ion which bridges the oxygen atoms of neighbouring axial ligands. In 2 the water molecule is also hydrogen-bonded to one of the axial phenylphosphonate groups. Spectroscopic, magnetic and cyclic voltammetric data for the complexes are given.

Synthesis of water-soluble and ether-soluble tetra-μ-acetatodiruthenium(II,III) complexes and X-ray crystal structure of [Ru2(μ-O2CC6H5)4(C2H5OH)2][Ru2(μ-O2CC6H5)4(HSO4)2]

[Ru2(μ-O2CCH3)4Cl] reacts readily with aqueous Ag2SO4 (2: 1 molar ratio) to give the sulphate salt [Ru2(μ-O2CCH3)4(H2O)2]2(SO4) (1). Addition of NaBPh4 to an aqueous solution of 1 produces the ether-soluble tetraphenylborate salt [Ru2(μ-O2CCH3)4(H2O)2][BPh4] (2). A methanolic solution of 1 reacts with Ba(C6H5CCCO2)2 · H2O to give the tetraacetatemonophenylpropynoate complex [Ru2(μ-O2CCH3)4(O2CCCC6H5)] · H2O (3). The reaction of an ethanolic suspension of [Ru2(μ-O2CC6H5)4Cl] with Ag2SO4 and H2SO4 (2 : 1 : 1 molar ratio) leads to the tetra-μ-benzoatodiruthenium(II,III) double complex salt [Ru2(μ-O2CC6H5)4(C2H5OH)2][Ru2(μ-O2CC6H5)4(HSO4)2] (4). Complex 4 is also obtained by reacting an ethanolic solution of 1 with an excess of benzoic acid in the presence of H2SO4. The X-ray crystal structure of 4 shows it to consist of [Ru2(μ-O2CC6H5)4(C2H5OH)2]+ and [Ru2(μ-O2CC6H5)4(HSO4)2]− ions, which are linked together by hydrogen bonds into an infinite polymeric chain. The RuRu distances in the cation and anion are very similar [2.265(2) and 2.272(2) Å, respectively]. Spectroscopic, magnetic, conductivity and cyclic voltammetry data are given for the complexes.

Stepwise construction of [Os6(CO)18(μ6-P)]-, a hexanuclear osmium cluster monoanion with trigonal-prismatic co-ordination for phosphorus: X-ray crystal structures of [Os6(μ-H)2(CO)20(MeCN)(μ3-PH)] and [PPh3Me][Os6(CO)18(μ6-P)]

Treatment of the labile cluster [Os3(CO)11(MeCN)] with PH3 affords the substituted product [Os3(CO)11(PH3)](1) in high yield. Subsequent reaction of (1) with Na2CO3 in MeOH, followed by acidification, gives the hydrido phosphido cluster [Os3(µ-H)(CO)10(µ-PH2)](2). When (2) is heated to 45–60 °C in the presence of [Os3(CO)11(MeCN)] a hexanuclear complex with the formulation [Os6(µ-H)2(CO)21(µ3-PH)](3) is obtained. If this reaction is repeated using [Os3(CO)10(MeCN)2] instead of [Os3(CO)11(MeCN)], an acetonitrile-containing product, [Os6(µ-H)2(CO)20(MeCN)(µ3-PH)](4), is obtained. An X-ray analysis of (4) shows that two Os3 triangular units are linked by a µ3-phosphinidene ligand, which symmetrically bridges an Os–Os edge of one triangle and is terminally co-ordinated to one Os atom of the second triangle. When (3) is treated with a weak base, such as [N(PPh3)2]Cl or [PPh3Me] Br, deprotonation to the corresponding cluster monoanion [Os6(µ-H)(CO)21(µ3-PH)]–(5) occurs. Treatment of (5) with a weak acid regenerates (3) in quantitative yield. Thermolysis of (3) leads to a closing up of the metal framework, affording the cluster [Os6(µ-H)(CO)18(µ6-P)], which readily deprotonates to give the anion [Os6(CO)18(µ6-P)]–(7) in the presence of [N(PPh3)2] Cl or [PPh3Me]Br. The same anion (7) may also be obtained by direct thermolysis of (5). An X-ray analysis of the [PPh3Me]+ salt of (7) confirms that the phosphorus occupies an interstitial site in a trigonal-prismatic hexaosmium framework, and co-ordinates to all six metal atoms with an average Os–P distance of 2.31 (1)Å. Proton and 31P n.m.r. data on all the new clusters are presented, and the position of the phosphorus resonance in the 31P n.m.r. spectrum is related to the changes in the environment of the phosphorus atom.

Homoleptic copper(II) and copper(I) complexes of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline. Six-coordinate copper(I) in solution

Reaction of 5,6-dihydro-5,6-epoxy-1,10-phenanthroline (L) with Cu(ClO(4))(2)center dot 6H(2)O in methanol in 3:1 M ratio at room temperature yields light green [CuL(3)](ClO(4))(2)center dot H(2)O (1). The X-ray crystal structure of the hemi acetonitrile solvate [CuL(3)](ClO(4))(2)center dot 0.5CH(3)CN has been determined which shows Jahn-Teller distortion in the CuN(6) core present in the cation [CuL(3)](2+). Complex 1 gives an axial EPR spectrum in acetonitrile-toluene glass with g(parallel to) = 2.262 (A(parallel to) = 169 x 10 (4) cm (1)) and g(perpendicular to) = 2.069. The Cu(II/I) potential in 1 in CH(2)Cl(2) at a glassy carbon electrode is 0.32 V versus NHE. This potential does not change with the addition of extra L in the medium implicating generation of a six-coordinate copper(I) species [CuL(3)](+) in solution. B3LYP/LanL2DZ calculations show that the six Cu-N bond distances in [CuL(3)](+) are 2.33, 2.25, 2.32, 2.25, 2.28 and 2.25 angstrom while the ideal Cu(I)-N bond length in a symmetric Cu(I)N(6) moiety is estimated as 2.25 angstrom. Reaction of L with Cu(CH(3)CN)(4)ClO(4) in dehydrated methanol at room temperature even in 4:1 M proportion yields [CuL(2)]ClO(4) (2). Its (1)H NMR spectrum indicates that the metal in [CuL(2)](+) is tetrahedral. The Cu(II/I) potential in 2 is found to be 0.68 V versus NHE in CH(2)Cl(2) at a glassy carbon electrode. In presence of excess L, 2 yields the cyclic voltammogram of 1. From (1)H NMR titration, the free energy of binding of L to [CuL(2)](+) to produce [CuL(3)](+) in CD(2)Cl(2) at 298 K is estimated as -11.7 (+/-0.2) kJ mol (1).

DE-2 observations of filamentary currents at ionospheric altitudes

Conjunctive measurements made by the Dynamics Explorer 1 and 2 spacecraft on October 22, 1981, under conditions of southward IMF, suggest the existence of a cusp ion injection from a region at the magnetopause with a scale size of ∼ 1/2 to 1 R E . Current signatures observed by the LAPI and MAGB instruments on board DE-2 indicate the existence of a rotation in the magnetic field that is consistent with a filamentary current system. The observed current structure can be interpreted as the ionospheric signature of a flux transfer event (FTE). In addition to this large-scale current structure there exist three small-scale filamentary current pairs. These current pairs close locally and thus, if our interpretation of this event as an FTE is correct, represent the first reported observations of FTE interior structure at low-altitudes.

Direct observation by time-resolved infrared spectroscopy of the bright and the dark excited states of the [Ru(phen)2(dppz)]2+ light-switch compound in solution and when bound to DNA

The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.

Role of glutaredoxin 2 and cytosolic thioredoxins in cysteinyl-based redox modification of the 20S proteasome

The yeast 20S proteasome is subject to sulfhydryl redox alterations, such as the oxidation of cysteine residues (Cys-SH) into cysteine sulfenic acid (Cys-SOH), followed by S-glutathionylation (Cys-S-SG). Proteasome S-glutathionylation promotes partial loss of chymotrypsin-like activity and post-acidic cleavage without alteration of the trypsin-like proteasomal activity. Here we show that the 20S proteasome purified from stationary-phase cells was natively S-glutathionylated. Moreover, recombinant glutaredoxin 2 removes glutathione from natively or in vitro S-glutathionylated 20S proteasome, allowing the recovery of chymotrypsin-like activity and post-acidic cleavage. Glutaredoxin 2 deglutathionylase activity was dependent on its entry into the core particle, as demonstrated by stimulating S-glutathionylated proteasome opening. Under these conditions, deglutathionylation of the 20S proteasome and glutaredoxin 2 degradation were increased when compared to non-stimulated samples. Glutaredoxin 2 fragmentation by the 20S proteasome was evaluated by SDS-PAGE and mass spectrometry, and S-glutathionylation was evaluated by either western blot analyses with anti-glutathione IgG or by spectrophotometry with the thiol reactant 7-chloro-4-nitrobenzo-2-oxa-1,3-diazole. It was also observed in vivo that glutaredoxin 2 was ubiquitinated in cellular extracts of yeast cells grown in glucose-containing medium. Other cytoplasmic oxido-reductases, namely thioredoxins 1 and 2, were also active in 20S proteasome deglutathionylation by a similar mechanism. These results indicate for the first time that 20S proteasome cysteinyl redox modification is a regulated mechanism coupled to enzymatic deglutathionylase activity.