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PubMed1984

X-ray structure analysis of a membrane protein complex. Electron density map at 3 A resolution and a model of the chromophores of the photosynthetic reaction center from Rhodopseudomonas viridis.

X-ray analysis of three-dimensional crystals of the photosynthetic reaction center from the purple bacterium Rhodopseudomonas viridis led to an electron density distribution at 3 A resolution calculated with phases from multiple isomorphous replacement. The protein subunits of the complex were identified. An atomic model of the prosthetic groups of the reaction center complex (4 bacteriochlorophyll b, 2 bacteriopheophytin b. 1 non-heme iron, 1 menaquinone, 4 heme groups) was built. The arrangement of the ring systems of the bacteriochlorophyll b and bacteriopheophytin b molecules shows a local 2-fold rotation symmetry; two bacteriochlorophyll b form a closely associated, non-covalently linked dimer ("special pair"). A different local 2-fold symmetry axis is observed for the heme groups of the cytochrome part.

Bacterial Proteins↗

PubMed2004

Atomic absorption spectroscopic, conductometric and colorimetric methods for determination of fluoroquinolone antibiotics using ammonium reineckate ion-pair complex formation.

Three accurate, rapid and simple atomic absorption spectrometric, conductometric and colorimetric methods were developed for the determination of norfloxacin (NRF), ciprofloxacin (CIP), ofloxacin (OFL) and enrofloxacin (ENF). The proposed methods depend upon the reaction of ammonium reineckate with the studied drugs to form stable precipitate of ion-pair complexes, which was dissolved in acetone. The pink coloured complexes were determined either by AAS or colorimetrically at lambdmax 525 nm directly using the dissolved complex. Using conductometric titration, the studied drugs could be evaluated in 50% (v/v) acetone in the range 5.0-65, 4.0-48, 5.0-56 and 6.0-72 microg ml-1 of NRF, CPF, OFL and ENF, respectively. The optimizations of various experimental conditions were described. The results obtained showed good recoveries of 99.15 +/- 1.15, 99.30 +/- 1.40, 99.60 +/- 1.50, and 99.00 +/- 1.25% with relative standard deviations of 0.81, 1.06, 0.97, and 0.69% for NRF, CPF, OFL, and ENF, respectively. Applications of the proposed methods to representative pharmaceutical formulations are successfully presented.

Absorption↗

PubMed2001

Specific and non-specific interactions of integration host factor with DNA: thermodynamic evidence for disruption of multiple IHF surface salt-bridges coupled to DNA binding.

Site-specific DNA binding of architectural protein integration host factor (IHF) is involved in formation of functional multiprotein-DNA assemblies in Escherichia coli, while non-specific binding of IHF and other histone-like proteins serves to structure the nucleoid. Here, we report an isothermal titration calorimetry study of the thermodynamics of binding IHF to a 34 bp fragment composed entirely of the specific H' site from lambda-phage DNA. At low to moderate [K(+)] (60-100 mM), strong competition is observed between specific and non-specific binding as a result of a low specificity ratio (approximately 10(2)) and a very small non-specific site size. In this [K(+)] range, both specific and non-specific binding are enthalpy-driven, with large negative enthalpy, entropy and heat capacity changes and binding constants that are insensitive to [K(+)]. Above 100 mM K(+), only specific binding is observed, and both the binding constant and the magnitudes of enthalpy, entropy and heat capacity changes all decrease strongly with increasing [K(+)]. When interpreted in the context of the structure of the specific complex, the thermodynamics provide compelling evidence for a previously unrecognized design principle by which proteins that form extensive binding interfaces with nucleic acids control binding constants, binding site sizes and effects of temperature and ion concentrations on stability and specificity. We propose that up to 22 of the 23 IHF cationic side-chains that are located within 6 A of DNA phosphate oxygen atoms in the complex, are masked in the absence of DNA by pairing with anionic carboxylate groups in intramolecular salt-bridges (dehydrated ion-pairs). These salt-bridges increase in stability with increasing temperature and decreasing [K(+)]. To explain the unusual thermodynamics of IHF-DNA interactions, we propose that both specific and non-specific binding at low [K(+)] require disruption of salt-bridges (as many as 18 for specific binding) whereupon many of the unmasked charged groups hydrate and the cationic groups interact with DNA. From structural or thermodynamic parallels with IHF, we propose that large-scale coupling of disruption of protein salt-bridges to DNA binding is significant for other large-interface DNA wrapping proteins including the nucleosome, lac repressor core tetramer, RNA polymerase core protein, HU and SSB.

Bacterial Proteins↗

PubMed1997

Synthesis and Characterization of the Benzoylformato Ferrous Complexes with the Hindered Tris(pyrazolyl)borate Ligand as a Structural Model for Mononuclear Non-Heme Iron Enzymes.

By using a hindered tripodal ligand, hydrotris(3-tert-butyl-5-isopropylpyrazol-1-yl)borate HB(3-tBu-5-iPrpz)(3), a series of monomeric ferrous complexes having acetate, hydroxide, and benzoylformate ligands were synthesized. Reaction of KHB(3-tBu-5-iPrpz)(3) with anhydrous Fe(OAc)(2) yielded acetato complexes Fe(OAc)[HB(3-tBu-5-iPrpz)(3)] (1) and Fe(OAc)[HB(3-tBu-5-iPrpz)(3)](3-iPr-5-tBupzH) (2). A hydroxo complex Fe(OH)[HB(3-tBu-5-iPrpz)(3)] (3) was prepared by the treatment of 1 or 2 with aqueous NaOH. The geometry of Fe(II) in 3 is a slightly distorted tetrahedron as determined by X-ray crystallography. The hydroxo complex 3 reacted with benzoylformic acid to give the benzoylformato complex Fe(O(2)CC(O)Ph)[HB(3-tBu-5-iPrpz)(3)] (4), which showed thermochromism which depended on the coordination geometry of the benzoylformate ligand. The Fe(II) ion in the colorless form of 4 isolated at 4 degrees C is coordinated by a tetrahedral N(3)O(1) ligand donor set including the unidentate benzoylformato ligand. On the other hand, the bluish purple form of 4 isolated at -20 degrees C has a five-coordinate trigonal bipyramidal Fe(II) center. The benzoylformate ligand in this bluish purple form works as a chelate ligand through coordination of the unidentate carboxylate oxygen atom as well as the ketonic oxygen atom. A benzoylformato complex containing an additional pyrazole, Fe(O(2)CC(O)Ph)[HB(3-tBu-5-iPrpz)(3)](3-iPr-5-tBupzH) (5), was obtained by the reaction of 3 with benzoylformic acid in the presence of 3-tert-butyl-5-isopropylpyrazole. The iron atom in 5 is coordinated by an N(4)O(1) ligand donor set with trigonal bipyramidal geometry. A hydrogen-bonding interaction between the carboxylate oxygen atom and the additional pyrazole's NH proton in 5 is suggested from the short distance between O(carboxylate) and N(pyrazole) observed in the X-ray structure and the absence of the nuNH vibration in the IR spectrum.

Journal Article↗

PubMed2001

Polymeric bis[bis(2,2'-bipyridine)-nickel(II)] hexavanadate(V).

The structure of the title compound, mu-hexavanadato(V)-bis[bis(2,2'-bipyridine)nickel(II)], [(Ni(C(10)H(8)N(2))(2))(2)(V(6)O(17))], is composed of vanadium oxide layers intercalated by complex [Ni(bipy)(2)](2+) cations (bipy is 2,2'-bipyridine). The structure is isomorphous with that reported recently for [Zn(bipy)(2)](2)[V(6)O(17)] [Zhang, DeBord, O'Connor, Haushalter, Clearfield & Zubieta (1996). Angew. Chem. Int. Ed. Engl. 35, 989--991]. The vanadium oxide layers are built up solely from VO(4) tetrahedra by corner sharing and clearly exhibit a sinusoidal ruffling. Two O atoms from a single vanadium oxide layer are coordinated to each Ni atom of the complex cations in a cis fashion, with Ni--O distances of 2.027 (3) and 2.087 (3) A, thus maintaining the two-dimensional structure.

Journal Article↗

PubMed2006

A study of collective atomic fluctuations and cooperativity in the U1A-RNA complex based on molecular dynamics simulations.

Cooperative interactions play an important role in recognition and binding in macromolecular systems. In this study, we find that cross-correlated atomic fluctuations can be used to identify cooperative networks in a protein-RNA system. The dynamics of the RRM-containing protein U1A-stem loop 2 RNA complex have been calculated theoretically from a 10 ns molecular dynamics (MD) simulation. The simulation was analyzed by calculating the covariance matrix of all atomic fluctuations. These matrix elements are then presented in the form of a two-dimensional grid, which displays fluctuations on a per residue basis. The results indicate the presence of strong, selective cross-correlated fluctuations throughout the RRM in U1A-RNA. The atomic fluctuations correspond well with previous biophysical studies in which a multiplicity of cooperative networks have been reported and indicate that the various networks identified in separate individual experiments are fluctuationally correlated into a hyper-network encompassing most of the RRM. The calculated results also correspond well with independent results from a statistical covariance analysis of 330 aligned RRM sequences. This method has significant implications as a predictive tool regarding cooperativity in the protein-nucleic acid recognition process.

Amino Acid Sequence↗

PubMed2004

A family of dioxo-molybdenum(VI) complexes of N2X heteroscorpionate ligands of relevance to molybdoenzymes.

Four new Mo(VI)-dioxo complexes of a family of N2X heteroscorpionate ligands are reported which, together with data already available for (TpR)-, provide a unique example of a comprehensive set of isostructural, isoelectronic complexes differing only in one biologically relevant donor atom. A study of these complexes allows for a direct comparison of structural, spectroscopic, and oxygen atom transfer reactivity properties of the Mo(VI)-dioxo center (of relevance to various families of molybdoenzymes) as a function of donor atom identity.

Electrochemistry↗

PubMed2003

Use of analogues of methionine and methionyl adenylate to sample conformational changes during catalysis in Escherichia coli methionyl-tRNA synthetase.

Binding of methionine to methionyl-tRNA synthetase (MetRS) is known to promote conformational changes within the active site. However, the contribution of these rearrangements to enzyme catalysis is not fully understood. In this study, several methionine and methionyl adenylate analogues were diffused into crystals of the monomeric form of Escherichia coli methionyl-tRNA synthetase. The structures of the corresponding complexes were solved at resolutions below 1.9A and compared to those of the enzyme free or complexed with methionine. Residues Y15 and W253 play key roles in the strength of the binding of the amino acid and of its analogues. Indeed, full motions of these residues are required to recover the maximum in free energy of binding. Residue Y15 also controls the size of the hydrophobic pocket where the amino acid side-chain interacts. H301 appears to participate to the specific recognition of the sulphur atom of methionine. Complexes with methionyl adenylate analogues illustrate the shielding by MetRS of the region joining the methionine and adenosine moieties. Finally, the structure of MetRS complexed to a methionine analogue mimicking the tetrahedral carbon of the transition state in the aminoacylation reaction was solved. On the basis of this model, we propose that, in response to the binding of the 3'-end of tRNA, Y15 moves again in order to deshield the anhydride bond in the natural adenylate.

Adenosine Monophosphate↗

PubMed2001

Successful molecular dynamics simulation of two zinc complexes bridged by a hydroxide in phosphotriesterase using the cationic dummy atom method.

I report herein two 2.0 ns (1.0 fs time step) MD simulations of two zinc complexes bridged by a hydroxide in phosphotriesterase (PTE) employing the nonbonded method and the cationic dummy atom method that uses virtual atoms to impose orientational requirement for zinc ligands. The cationic dummy atom method was able to simulate the four-ligand coordination of the two zinc complexes in PTE. The distance (3.39 +/- 0.07A) between two nearby zinc ions in the time-average structure of PTE derived from the MD simulation using the cationic dummy atoms matched that in the X-ray structure (3.31 +/- 0.001A). Unequivocally, the time-average structure of PTE was able to fit into the experimentally determined difference electron density map of the corresponding X-ray structure. The results demonstrate the practicality of the cationic dummy atom method for MD simulations of zinc proteins bound with multiple zinc ions. In contrast, a 2.0 ns (1.0 fs time step) MD simulation using the nonbonded method revealed a striking difference in the active site between the X-ray structure and the time-average structure that was unable to fit into the density map of PTE. The results suggest that caution should be used in the MD simulations using the nonbonded method.

Algorithms↗

PubMed2005

Investigation on the complex of diperoxovanadate with 2-(2'-pyridyl)-imidazole.

A novel diperoxovanadate complex NH4[OV(O2)2{2-(2'-pyridyl)-imidazole}] x 4H2O was synthesized in aqueous solution under physiological conditions. The solution structure of the complex was characterized by multinuclear (1H, 13C, 14N, and 51V) as well as multi-dimensional (DOSY and C-H COSY) NMR techniques in the interaction system of NH4VO3/H2O2/2-(2'-pyridyl)-imidazole at room temperature. The crystal structure of the complex was determined at 173K by single-crystal X-ray diffraction method. It belongs to the monoclinic space group P21/c with a = 13.048(4), b = 6.984(2), c = 17.814(5) A, beta = 104.695(5), V = 1570.3(8) A3 and Z = 4. The crystal is composed of ammonium ions, {2-(2'-pyridyl)-imidazole}oxodiperoxovanadate(V) ions, and water molecules, which are held together by ionic and hydrogen bond forces. The metal atom in the complex is seven-coordinated with a distorted pentagonal bipyramidal geometry. It is the first mononuclear diperoxovanadate complex with a N, N'-chelating biheteroaromatic ligand and its 51V chemical shift is at the highest field among the known mononuclear diperoxovanadate(V) complexes.

Imidazoles↗

PubMed2005

Thermo-FTIR spectroscopic study of the siderophore ferrioxamine B: spectral analysis and stereochemical implications of iron chelation, pH, and temperature.

FTIR spectra of the microbial siderophore, ferrioxamine B, and its nonchelated form (iron free; desferrioxamine B) were studied to facilitate in-depth investigation on the undisrupted structure of the siderophore and its interactions with the environment. Effects of iron chelation as well as those of various levels of pH and temperature on the stereochemical structure of the free ligand and the ferric complex were examined. The presence of a number of functional groups in these compounds and the mutual interaction between them resulted in significant shifts and overlapping of their characteristic absorption bands. Thermal and pH treatments combined with a comprehensive use of curve-fitting analysis facilitated bands resolution. Absorption bands of all functional groups were identified. The results imply that the compact and rigid structure of the ferric complex (ferrioxamine B) is sustained by intense and specific intramolecular hydrogen bonds. Dehydration was the main process observed at low temperature (25-60 degrees C). At 105 degrees C the free ligand form (desferrioxamine B) had already begun to decompose, whereas ferrioxamine B exhibited stability. The thermal destruction became acute at the 170 degrees C treatment for both molecules. The secondary amide groups and the hydroxamate groups, which comprise the binding site for the Fe atom in the complex, were found to be the most sensitive to the thermal degradation. Significant pH effects were observed only for desferrioxamine B samples at pH 9, accompanied by partial decomposition, similar to that observed at 105 degrees C. Deprotonation of desferrioxamine B was found to begin with the deprotonation of the NH(3+) group. Characteristics of the rigid conformational structure of the ferric complex and the state of the NH(3+) group, both assumed to play an important role in the recognition and uptake of the siderophore by membranal receptors, were elaborated by means of FTIR and are discussed in detail.

Deferoxamine↗

PubMed2006

Novel oxygen chirality induced by asymmetric coordination of an ether oxygen atom to a metal center in a series of sugar-pendant dipicolylamine copperII complexes.

Six sugar-pendant 2,2'-dipicolylamine (DPA) ligands (L1-3 and L'1-3) have been prepared. OH-protected and unprotected D-glucose, D-mannose, and D-xylose were attached to a DPA moiety via an O-glycoside linkage. X-ray crystallography of the copper(II) complexes (1-5) with these ligands revealed that the anomeric oxygen atom is coordinated to the metal center in the solid state, generating a chiral center at the oxygen atom. The CD spectra of these copper complexes in methanol or aqueous solution exhibit Cotton effects in the d-d transition region, which indicates that the ether oxygen atoms remain coordinated to the metal center and the oxygen-atom chirality is preserved even in solution. For complexes 1 and 2, the inverted oxygen-atom chirality and chelate-ring conformation in the solid state are well correlated with the mirror-image CD spectra in methanol solution. The concomitant inversion of the asymmetric configuration around the copper center was also observed in a methanol solution of complex 3 and a pyridine solution of complex 2. The square-pyramidal/octahedral copper(II) centers also exhibited characteristic absorption and CD spectra.

Journal Article↗

PubMed1998

Circularization of mRNA by eukaryotic translation initiation factors.

Communication between the 5' cap structure and 3' poly(A) tail of eukaryotic mRNA results in the synergistic enhancement of translation. The cap and poly(A) tail binding proteins, eIF4E and Pab1p, mediate this effect in the yeast S. cerevisiae through their interactions with different parts of the translation factor eIF4G. Here, we demonstrate the reconstitution of an eIF4E/eIF4G/Pab1p complex with recombinant proteins, and show by atomic force microscopy that the complex can circularize capped, polyadenylated RNA. Our results suggest that formation of circular mRNA by translation factors could contribute to the control of mRNA expression in the eukaryotic cell.

Eukaryotic Initiation Factor-4E↗

PubMed2005

Solid- and solution-state studies of the novel mu-dicyanamide-bridged dinuclear spin-crossover system {[(Fe(bztpen)]2[mu-N(CN)2]}(PF6)3 x n H2O.

The mononuclear diamagnetic compound {Fe(bztpen)[N(CN)2]}(PF6)CH3OH (1) (bztpen = N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethylenediamine) has been synthesized and its crystal structure studied. Complex 1 can be considered to be the formal precursor of two new dinuclear, dicyanamide-bridged iron(II) complexes with the generic formula {[(Fe(bztpen)]2[mu-N(CN)2]}(PF6)3 x n H2O (n = 1 (2) or 0 (3)), which have been characterized in the solid state and in solution. In all three complexes, the iron atoms have a distorted [FeN6] octahedral coordination defined by a bztpen ligand and a terminal (1) or a bridging dicyanamide ligand (2 and 3). In the solid state, 2 and 3 can be considered to be molecular isomers that differ by the relative position of the phenyl ring of the two {Fe(bztpen)[N(CN)2]}+ halves (cis and trans, respectively). Depending on the texture of the sample, 2 exhibits paramagnetic behavior or displays a very incomplete spin transition at atmospheric pressure. Complex 3 undergoes a gradual two-step spin transition with no observed hysteresis in the solid state. Both steps are approximately 100 K wide, centered at approximately 200 K and approximately 350 K, with a plateau of approximately 80 K separating the transitions. The crystal structure of 3 has been determined in steps of approximately 50 K between 400 K and 90 K, which provides a fascinating insight into the structural behavior of the complex and the nature of the spin transition. Order-disorder transitions occur in the dicyanamide bridge and the PF6(-) ions simultaneously, with the spin-crossover behavior suggesting that these transitions may trigger the two-step character. In solution, 2 and 3 display very similar continuous spin conversions. Electrochemical studies of 2 and 3 show that the voltammograms are typical of dimeric systems with electronic coupling of the metals through the dicyanamide ligand.

Journal Article↗

PubMed2004

Strong protective action of Copper(II) N-substituted sulfonamide complexes against reactive oxygen species.

Copper(II) complexes of N-benzothiazolsulfonamides, [Cu(N-2-(5,6-dimethylbenzothiazole)toluenesulfonamidate)(2)(dmso)(2)] (1), [Cu(N-2-(6-chlorobenzothiazole)benzenesulfonamidate)(2)(dmso)(2)] (2) and [Cu(N-2-(6-chlorobenzothiazole)toluenesulfonamidate)(2)(dmso)(2)] (3) with interesting protective properties against superoxide radicals have been prepared. The compounds have been characterized by X-ray diffraction and their chemical properties have been studied by spectroscopic methods. The crystal structure of 1 shows that the copper(II) is surrounded by two benzothiazole N atoms from the sulfonamide ligands and two O atoms from the dimethylsulfoxide molecules in a square planar arrangement. The coordination polyhedron around copper(II) in 2 and 3 is distorted square pyramidal being the metal ion linked to benzothiazole N and sulfonamidate O atoms of the ligand and to two dimethylsulfoxide O atoms. The three complexes have a strong protective action over Delta sod1 mutant of Saccharomyces cerevisiae against reactive oxygen radicals derived from respiration and against those generated by hydrogen peroxide and menadione.

Journal Article↗

PubMedDate not supplied

[Investigation of protonation and complex formation processes of some new polyamino carboxylic acids].

The medicinal chemistry often needs chemical compound with special properties. The preparation of compounds with special properties generally needs 10-20 steps of preparation and the final product is available in small amount. The characterisation of this kinds of compounds needs special methods and procedures for investigation. This kind of method has been developed and used for characterisation of some new polyaminopolycarboxylic acid derivatives. Protolytic equilibrium of 2,2',2",2'"-[terpyridine-6,6"diyl)bis(methylenenitrilo)]tetrakisacetic acid and 3,5-bis[6'-bis (N,N-bis(carboxymethyl)aminomethyl]-2'-pyridyl)-1H,2, 4-triazole was investigated by pH-metric and spectrophotometric methods. The pK values of the aromatic nitrogen atoms were estimated. Complexation of Eu(III)ion with both ligands are studied by spectrophotometric method. Composition(ML2) and stability of complexes were determined.

Acetates↗

PubMed2005

Reaction systems related to dissimilatory nitrate reductase: nitrate reduction mediated by bis(dithiolene)tungsten complexes.

Kinetics of the oxygen atom transfer reactions [M(IV)(QC6H2-2,4,6-Pr(i)3)(S2C2Me2)2]1- + XO --> [M(VI)O(QC6H2-2,4,6-Pr(i)3)(S2C2Me2)2]1- + X in acetonitrile with substrates XO = NO3- and (CH2)4SO have been determined. The reactants are bis(dithiolene) complexes with M = Mo, W and sterically encumbered axial ligands with Q = O, S to stabilize mononuclear square pyramidal structures. The complex [MoIV(SC6H2-2,4,6-Pr(i)3)(S2C2Me2)2]1- is an analogue of the active site of dissimilatory nitrate reductase which in the reduced state contains a molybdenum atom bound by two pyranopterindithiolene ligands and a cysteinate residue. Nitrate reduction was studied with tungsten complexes because of unfavorable stability properties of the molybdenum complexes. Product nitrite was detected by a colorimetric method. All reactions with both substrates are second-order with associative transition states (deltaS approximately -20 eu). Variation of atoms M and Q, together with data from prior work, allows certain kinetics comparisons to be made. Among them, k2W/k2Mo = 25 for (CH2)4SO reduction (Q = S), an expression of the kinetic metal effect. Further, k2S/k2O = 28 and approximately 10(4) for nitrate and (CH2)4SO reduction, respectively, effects attributed to relatively more steric congestion in achieving the transition state with hindered phenolate vs thiolate ligands. The effect is more pronounced with the larger substrate. These results demonstrate the feasibility of tungsten-mediated nitrate reduction by direct atom transfer using molecules with both axial thiolate and phenolate ligands. Complexes of the type [M(IV)(OR)(S2C2Me2)2] are capable of reducing biological N-oxide, S-oxide, and nitrate substrates and thus constitute functional analogue reaction systems of enzymic transformations.

Binding Sites↗

PubMed2000

Low-temperature crystal structures of tetrakis-mu-3,5-diisopropylsalicylatobis-dimethylformamidodico pper(II) and tetrakis-mu-3,5-diisopropylsalicylatobis-diethyletheratodicopp er(II) and their role in modulating polymorphonuclear leukocyte activity in overcoming seizures.

Two binuclear copper(II) complexes of 3,5-diisopropylsalicylic acid were characterized by single crystal X-ray diffraction methods and examined for anti-inflammatory activity using activated polymorphonuclear leukocytes and for anticonvulsant activities using electroshock and metrazol models of seizures. These complexes were crystallized from dimethylformamide (DMF) or diethylether. Tetrakis-mu-3,5-diisopropylsalicylatobis-dimethylformamidodicop per(II) [Cu(II)2(3,5-DIPS)4(DMF)2] I is in space group P 1; a = 10.393 (2), b = 11.258 (2), c = 12.734 (2) A, alpha = 96.64 (2), beta = 92.95 (2), gamma = 94.90 (2) degrees; V = 1471.7 (4) A3; Z = 1. Tetrakis-mu-3,5-diisopropylsalicylatobis-etheratodicopper(II ) [Cu(II)2(3,5-DIPS)4(ether)2] II is in space group P 1; a = 10.409 (3), b = 11.901 (4), c = 12.687 (6) A, alpha = 91.12 (5), beta = 90.84 (5), gamma = 100.90 (4) degrees; V = 1542 (1) A3; Z = 1. The structure of I was determined at 140 K from 4361 unique reflections (I > 2sigma(1)) and refined on F2 to R1 = 0.04 and wR2 = 0.09. The structure of II was determined at 180 K from 4605 unique reflections (I > 2sigma(I)) and refined on F2 to R1 = 0.05 and wR2 = 0.13. Each compound is a crystallographically centrosymmetric binuclear complex with Cu atoms bridged by four 3,5-diisopropylsalicylate ligands related by a symmetry center [Cu-Cu(i): 2.6139 (9) A in I and 2.613 (1) in II]. The four nearest O atoms around each Cu atom form a nearly rectangular planar arrangement with the square pyramidal coordination completed by the dimethylformamide (or diethylether) oxygen atom occupying an apical position, at a distance of 2.129 (2) A in I and 2.230 (3) A in II. Each Cu atom is displaced towards the DMF (or diethylether) ligand, by 0.189 A in I and 0.184 A in II, from the plane of the four O atoms. The crystal structures of I and II are essentially similar to each other, except for the DMF or diethylether accommodation. Many disorder phenomena were found in the crystal structure of I. Copper(II)2(3,5-DIPS)4(DMF)2 inhibited polymorphonuclear leukocyte (PMNL) oxidative metabolism in vitro. This effect was concentration related and significant for concentrations higher than 10 microg or 0.68 nmol/ml. Copper(II)2(3,5-DIPS)4(DMF)2 was more active than the parent ligand, 3,5-DIPS, as has been demonstrated with copper complexes of other non-steroidal anti-inflammatory drugs. The DMF and diethylether ternary complexes of Cu(II)2(3,5-DIPS)4 were found to have anticonvulsant activity in the maximal electroshock model of grand mal epilepsy in doses ranging from 26 to 258 micromol/kg of body mass following intraperitoneal, subcutaneous, or oral treatment. The DMF ternary complex was also found to be effective in the subcutaneous injection of metrazol model of petit mal epilepsy. We conclude that both ternary copper complexes are lipophilic and bioavailable, capable of facilitating the inflammatory response to brain injury and causing the subsidence of this response in bringing about remission of these disease states.

Animals↗