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PubMed2002

Antimony speciation in alkaline sulfide solutions: role of zerovalent sulfur.

Antimony is subject to a lower drinking water standard than arsenic, its notorious group 15 cohort in the periodic table. Both elements often co-vary in nature and are fairly soluble under reducing, alkaline conditions. Of the two, much less is known about the environmental chemistry of Sb. Measurements of Sb solubility in sulfidic solutions equilibrated with stibnite (Sb2S3) and orthorhombic sulfur reveal the existence of two new complexes that may control Sb behavior in many reducing environments. Formation reactions and stability constants (23 +/- 2 degrees C) are HS- + S(s) + Sb2S3(s) <==> HSb2S5-, log K = -1.47 +/- 0.17; and HS- + 2S(s) + Sb2S3(s) <==> Sb2S6(2-) + H+, log K = -9.55 +/- 0.07. The first complex is a mixed-valence Sb(III,V) complex; the second is an Sb(V) complex. Their stability in sulfidic solutions may explain previously puzzling evidence of Sb(V) in natural anoxic environments. Owing to these complexes, zerovalent S can enhance stibnite solubility up to 3 orders of magnitude. In neutral-to-alkaline, reducing environments, less than 7 microM HS- will transform O-coordinated, electrically neutral Sb(OH)3o to predominantly anionic S-coordinated complexes. This transformation could diminish the adsorption of Sb to negatively charged mineral surfaces, lowering retardation factors in anoxic aquifers.

Adsorption↗

PubMed2005

Addition of water, methanol, and ammonia to Al3O3- clusters: reaction products, transition states, and electron detachment energies.

Products of reactions between the book and kite isomers of Al3O3- and three important molecules are studied with electronic structure calculations. Dissociative adsorption of H2O or CH3OH is highly exothermic and proton-transfer barriers between anion-molecule complexes and the products of these reactions are low. For NH3, the reaction energies are less exothermic and the corresponding barriers are higher. Depending on experimental conditions, Al3O3- (NH3) coordination complexes or products of dissociative adsorption may be prepared. Vertical electron detachment energies of stable anions are predicted with ab initio electron propagator calculations and are in close agreement with experiments on Al3O3- and its products with H2O and CH3OH. Changes in the localization properties of two Al-centered Dyson orbitals account for the differences between the photoelectron spectra of Al3O3- and those of the product anions.

Journal Article↗

PubMed2003

Poly[sodium(I)-micro(6)-hydrogen benzene-1,4-dicarboxylato].

Alkali metal salts of terephthalic acid are common reagents in the preparation of metal-ligand coordination complexes containing terephthalate anions. In the title compound, sodium hydrogen terephthalate, [Na(C(8)H(5)O(4))](n), the cations occupy crystallographic inversion centres, and each bridging anion coordinates to six octahedral cations and vice versa. As seen in the known potassium derivative [Kaduk (2000). Acta Cryst. B56, 474-485; Miyakubo, Takeda & Nakamura (1994). Bull. Chem. Soc. Jpn, 67, 2301-2303], sodium hydrogen terephthalate contains short O-H.O hydrogen bonds between anions [O.O = 2.4734 (17) A]. The structure is centrosymmetric and exhibits disorder of the H-atom position in the hydrogen bond and of the non-bridging ring C atoms in the terephthalate ion.

Journal Article↗

PubMedDate not supplied

[Activation of molecular oxygen by hemin complexes].

This paper considers main properties, structure of the active center and the mechanism of action of cytochromes P-450 of different origin. It compares the literature data on structural models of P-450. Three hemin complexes which are functional models of P-450 were synthesized. Hemin was covalently bonded via carboxyl or methine groups with amino groups of polymethyl methacrylate-based polymers or coordination bonded via iron with imidazole containing polymethyl methacrylate. The diimidazole coordination complex showed the highest specific activity. In H2O2-dependent reactions the complex displayed V M and K M similar to those of liver microsomal cytochrome P-450. In NADPH-dependent reactions the specific activity of the complex was only 1-3% that of cytochrome P-450. The above findings as well as the electronic and EPR-spectra suggest that the complex can be regarded as a functional but not as a structural model of cytochrome P-450.

Binding Sites↗

PubMed1986

DNA binding specificity of a series of cationic metalloporphyrin complexes.

The sequence specificities of a series of cationic metalloporphyrins toward a 139 base pair restriction fragment of pBR-322 DNA have been studied by DNase I footprinting methodology. Analysis using controlled digests and quantitative autoradiography/microdensitometry revealed that the 5- and 6-coordinate complexes of meso-tetrakis(N-methyl-4-pyridiniumyl)porphine, MT4MPyP, where M is Mn, Fe, Co, and Zn, were found to bind to AT regions of DNA. Footprinting analysis involving the radiolabel on the opposing strand of restriction fragment showed site skewing in the direction of the 3' end of the fragment, indicating that the porphyrins bind in the minor groove of DNA. The significant increase in DNase I catalyzed hydrolysis observed in various regions of the fragment appeared to be primarily due to a decrease in available substrate DNA upon porphyrin binding with possible contributions from structural changes in DNA caused by ligand binding. The complexes NiT4MPyP and CuT4MPyP were found to bind to both AT and GC regions of the fragment, producing different degrees of inhibition in the two regions. Since the outside-binding porphyrins can neither intercalate or effectively hydrogen bond to DNA, they appear to read sequence by responding to steric and/or electrostatic potential effects located in the minor groove of DNA.

Base Sequence↗

PubMed1993

New platinum antitumor complexes.

Over the past two decades, platinum-based drugs (cisplatin and, latterly, the less toxic analogue carboplatin) have conferred significant therapeutic benefit to a large number of cancer sufferers. However, there remains scope for substantial improvement in the clinical utility of metal coordination complexes through the discovery of additional platinum-based complexes (or possibly alternative metals). Future drug discovery strategies should focus on tumor resistance and its circumvention. To date, only one series of compounds, those containing a 1,2-diaminocyclohexane carrier ligand (e.g., oxaliplatin, tetraplatin), has entered clinical trial based on their circumvention of acquired cisplatin resistance in some (mainly murine) preclinical tumor models. At present these agents are in early clinical trial and thus their true clinical utility in cisplatin/carboplatin refractory disease is not yet determinable (and may not be due to dose-limiting neurotoxicity). Over the past few years, our understanding of mechanisms of resistance to cisplatin and its interaction with DNA has vastly increased. This new information will undoubtedly guide the development of new strategies aimed at the circumvention of intrinsic and acquired tumor resistance to cisplatin. Approaches to circumvent resistance will probably involve not only the rational development of a new generation of platinum-based drugs (e.g., compounds designed to overcome reduced cisplatin accumulation or enhanced removal of cisplatin-induced DNA adducts) but also non-platinum drugs which are capable of modulating resistance (e.g., modulators of signal transduction pathways, ras and myc oncogene expression and glutathione biosynthesis). One may look forward with a great deal of optimism that these promising new approaches will result in clinical benefit by the end of the century. Nevertheless, cisplatin and carboplatin remain the standard anticancer drugs to which novel platinum-based complexes must be compared.

Animals↗

PubMedDate not supplied

Construction of coordinatively saturated rhodium complexes containing appended peptides.

Phenanthrenequinone diimine (phi) complexes of rhodium(III) bearing appended peptides have been prepared using two complementary solid phase synthetic strategies. The first method involves the direct coupling of the coordinatively saturated rhodium complex containing a pendant carboxylate to the N-terminus of a resin-bound peptide, in a manner analogous to the chain-elongation step in solid phase peptide synthesis. The second involves coupling a bidentate chelator containing the pendant carboxylate to the resin-bound peptide, followed by coordination of [Rh(phi)2]3+ to the bidentate chelator attached to the peptide. Peptides of length 5-30 residues have been covalently attached to rhodium complexes in 5-18% yield using both methods. Despite the low overall yields, the regioselective modification of the peptide chain afforded by these strategies is a distinct advantage over solution phase methods. With coordination complexes which are stable to peptide deprotection and cleavage conditions from the resin, the solid phase synthetic strategies are convenient to apply. Amino acid analysis, electronic spectroscopy, and circular dichroism confirm the presence of the two components in the metal-peptide chimeras; the metal-peptide complexes exhibit the combined spectral properties of the parent metal complex and the appended peptide. Significantly, plasma desorption mass spectrometry reveals a novel pattern of peptide fragmentation for the metal-peptide chimeras that is not observed in the absence of the tethered metal complex; this fragmentation facilitates the sequence analysis of the appended peptide. Thus, metal-peptide chimeras may be conveniently prepared using solid phase methodologies, and features of coordination chemistry may be exploited for new peptide design and analysis.

Amino Acid Sequence↗

PubMed2005

Thermodynamic profiles for CO photodissociation from heme model compounds: effect of proximal ligands.

Here we present a comprehensive study of the thermodynamic parameters (enthalpy, entropy, and volume changes) associated with carbon monoxide photodissociation and rebinding to Fe(II) microperoxidase-11 (Fe(II)MP11) and Fe(ll) tetrakis(4-sulfonatophenyl)porphine complex (FeII4SP) with water and 2-methylimidazole as proximal ligands. CO photodissociation from FeII4SP complexes is accompanied by a positive volume change of approximately 17 mL mol(-1). A smaller volume change of approximately 12 mL mol(-1) was observed for CO dissociation from Fe(II)MP-11. We attribute the positive volume change to cleavage of the Fe-CO covalent bond and to solvent reorganization due to the low-spin to high-spin transition. CO binding is an exothermic reaction with an enthalpy change of -17 kcal mol(-1) for the CO-FeII4SP complexes and -13 kcal mol(-1) for the CO-Fe(II)MP11 complex. In all cases, the ligand recombination occurs as a single-exponential process indicating that CO dissociation is followed by direct CO rebinding to a high-spin five-coordinate complex without concomitant dissociation of the proximal base. In addition, observed negative activation entropies and volumes for ligand binding to (2-Melm)FeII4SP and MP-11, respectively, suggest that CO rebinding can be described by an associative mechanism with bond formation being the rate-limiting step.

Journal Article↗

PubMedDate not supplied

N,N-bis(2-mercaptoethyl)methylamine: a new coligand for Tc-99m labeling of hydrazinonicotinamide peptides.

Hydrazinonicotinamide (HYNIC) forms stable coordination complexes with Tc-99m when reacted with Tc(V)oxo species such as Tc-mannitol or other Tc-polyhydric complexes. However, radio-HPLC of [Tc-For-MLFK-HYNIC] labeled via Tc-polyhydric ligands demonstrated multiple radiochemical species each with unique biodistribution patterns. This is likely due to the fact that Tc can bind to the hydrazino moiety, as well as polyhydric ligands, in a variety of coordination geometries. Tridentate ligands, such as bis(mercaptoethyl)methylamine (NS2), may constrain the possible coordination geometries and improve overall stability. To investigate this, we synthesized NS2, converted the [Tc-mannitol-For-MLFK-HYNIC] to the corresponding NS2-containing complex [Tc-NS2-For-MLFK-HYNIC], and compared its infection imaging and biodistribution properties with [Tc-mannitol-For-MLFK-HYNIC]. Conversion to the NS2 complex was confirmed by HPLC which showed a single unique hydrophobic species with retention time greater than the [Tc-mannitol-For-MLFK-HYNIC] complex. Imaging experiments with both preparations were performed in rabbits with E. coli infections in the left thigh. Tissue radioactivity measurements demonstrated that compared to Tc-mannitol-peptide, accumulation of Tc-NS2-peptide was lower in blood, heart, and normal muscle and higher in spleen, infected muscle, and pus (p < 0.01). These results indicate that the Tc-NS2-peptide complex is chemically more homogeneous and exhibits improved infection localization and biodistribution properties. In an effort to model the interactions of the metal-HYNIC core with NS2 and related ligand types, the reactions of [ReCl3(NNC5H4NH)(NHNC5H4N)] and [99TcCl3(NNC5H4NH)(NHNC5H4N)], effective structural analogues for the [M(NNC5H4NH(x))2] core, with NS2, C5H3N-2,6-(CH2SH)2, O(CH2CH2SH)2, and S(CH2CH2SH)2 were investigated and the compounds [M[CH3N(CH2CH2S)2](NNC5H4N)(NHNC5H4N] (M = 99Tc (5a), Re (5b)), [Re[C5H3N-2,6-(CH2S)2](NNC5H4N)(NHNC5H4N)].CH2Cl2.0.5MeOH (7), [Re[SCH2CH2)2O] (NNC5H4N)(NHNC5H4N)] (8), and [Re[(SCH2CH2)2S](NNC5H4NH)(NHNC5H4N)]Cl (9) were isolated. Similarly, the reaction of [ReCl3(NNC5H4NH)(NHNC5H4N)] with the bidentate ligands pyridine-2-methanethiol and 3-(trimethlysilyl)pyridine-2-thiol led to the isolation of [ReCl(C5H4N-2-CH2S) (NNC5H4N)(NHNC5H4N)] (10) and [Re(2-SC5H3N-3-SiMe3)2 (NNC5H4N)(NHNC5H4N)] (11), respectively, while reaction with N-methylimidazole-2-thiol yielded the binuclear complex [Re(OH)Cl(SC3H2N2CH3)2(NNC5H4N)2 (NHNC5H4N)2] (12). The analogous metal-(HYNIC-OH) precursor, [ReCl3[NNC5H3NH(CO2R)] [NHNC5H3N(CO2R)]] (R = H, 13a; R = CH3, 13b) has been prepared and coupled to lysine to provide [RCl3[NNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)] [NHNC5H3NH(CONHCH2CH2CH2CH2CH(NH2)CO2H)]].2HCl (14.2HCl), while the reaction of the methyl ester 13b with 2-mercaptopyridine yields [Re(2-SC5H4N)2[NNC5H3N(CO2Me)][NHNC5H3N(CO2Me)]] (15). While the chemical studies confirm the robustness of the M-HYNIC core (M = Tc, Re) and its persistence in ligand substitution reactions at adjacent coordination sites of the metal, the isolation of oligomeric structures and the insolubility of the peptide conjugates of 13, 14, and 15 underscore the difficulty of characterizing these materials on the macroscopic scale, an observation relevant to the persistent concerns with reagent purity and identity on the tracer level.

Animals↗

PubMed1993

Thermodynamics of binding of the CO2-competitive inhibitor imidazole and related compounds to human carbonic anhydrase I: an isothermal titration calorimetry approach to studying weak binding by displacement with strong inhibitors.

The visible spectrum of Co(II)-substituted human carbonic anhydrase I (HCA I) complexed with the unique CO2-competitive inhibitor imidazole undergoes a marked alkaline intensification, with a midpoint near pH 8 [Bauer, R., Limkilde, P., & Johansen, J. T. (1977) Carlsberg Res. Commun. 42, 325-339]. This change was first attributed to the ionization of a nondisplaced water ligand of the active-site metal in a five-coordinate complex. Later proposals favored assigning it to the deprotonation of the bound imidazole itself to give a tetrahedrally coordinated imidazolate anion at high pH. We have determined by isothermal titration calorimetry the pH dependence of the enthalpy of binding of imidazole and its analogues to HCA I and Co(II)HCA I. We devised an indirect strategy whereby the enthalpy of binding of the strong sulfonamide inhibitor methazolamide was determined in the absence and presence of a constant high concentration of the competing imidazole or its analogues. The standard enthalpy of binding of deprotonated methazolamide to the "acid" form of HCA I and Co(II)HCA I was found to be pH independent over the pH range of 6.5-9.5, as expected. It was also identical for both the zinc (-13.5 +/- 1.1 kcal M-1) and the cobalt (-13.7 +/- 0.4 kcal M-1) forms. The standard enthalpy of binding of neutral imidazole (average value -6.1 +/- 0.8 kcal M-1) surprisingly did not show any marked pH dependence, varying by about 1.1 and 2.6 kcal M-1 for the zinc and cobalt enzymes, respectively.(ABSTRACT TRUNCATED AT 250 WORDS)

Binding, Competitive↗

PubMed2003

Visible-spectroscopy study of the adsorption of alizarinate by Al-montmorillonite in aqueous suspensions and in solid state.

The adsorption of the monovalent anionic dye alizarinate onto Na- and Al-montmorillonite was carried out by adding the dye into aqueous clay suspensions. Electronic spectra of aqueous suspensions and of air-dried dye-clay complexes were studied. Na-montmorillonite adsorbed only part of the added dye. With total amount of alizarinate up to 5 mmol dye per 100 g clay the adsorption of the dye takes place on the broken bonds, leading to peptization of the clay. Al-montmorillonite adsorbed alizarinate completely up to 10 mmol per 100 g clay. Above this loading there was a partition of the dye between the clay and the supernatant. The maximum adsorption for Na- and Al-clay was 4 and 25 mmol dye per 100 g clay, respectively. Absorption bands in the spectrum of Al-montmorillonite suspensions (488-504 nm) appear at longer wavelengths than in the spectrum of air-dried Al-montmorillonite (415-455 nm). Thermo-X-ray study of these clay-alizarinate complexes suggests that the organic compound was located in the interlayer space in Al-montmorillonite but was not located there in Na-montmorillonite. In Al-montmorillonite alizarinate formed a coordination complex with exchangeable Al(3+). In Na-montmorillonite it formed bonds with Al exposed on the broken-bonds sites.

Adsorption↗

PubMed2001

Synthesis of oligopyridines and their metal complexes as precursors to topological stereoisomers.

[structure: see text]. Palladium-based carbon-carbon coupling reactions in sequence with halogen-exchange chemistry on a series of heterocycles lead to an efficient synthetic strategy for oligopyridines that bind metal ions such as ruthenium to form coordination racks. The particular structures are designed to form terpyridine subunits for octahedral binding. Reaction of 4,6-diiodopyrimidine produces a "double-bay" terpyridine from which binuclear coordination complexes have been formed.

Journal Article↗

PubMed2004

Expression of the HXT1 low affinity glucose transporter requires the coordinated activities of the HOG and glucose signalling pathways.

Expression of the HXT1 gene, which encodes a low affinity glucose transporter in Saccharomyces cerevisiae, is regulated positively in response to glucose by the general glucose induction pathway, involving the Snf3/Rgt2 membrane glucose sensors, the SCF-Grr1 ubiquitination complex and the Rgt1 transcription factor. In this study we show that, in addition to the glucose signaling pathway, regulation of HXT1 expression also requires the HOG pathway. Deletion of components in the glucose signaling pathway or in the HOG pathway results in impaired HXT1 expression. Genetic analyses showed that, whereas the glucose signaling pathway regulates HXT1 through modulation of the Rgt1 transcription factor, the HOG pathway modulates HXT1 through regulation of the Sko1-Tup1-Ssn6 complex. Coordinated regulation of the two signaling pathways is required for expression of HXT1 by glucose and in response to osmostress.

Gene Deletion↗

PubMed1999

The active site of Serratia endonuclease contains a conserved magnesium-water cluster.

Serratia endonuclease is an important member of a class of magnesium dependent nucleases that are widely distributed in nature. Here, we describe the location and geometry of a magnesium-water cluster within the active site of this enzyme. The sole protein ligand of the magnesium atom is Asn119; this metal ion is also associated with five water molecules to complete an octahedral coordination complex. These water molecules are very well ordered and there is no evidence of rotational disorder or motion. Glu127 and His89 are located nearby and each is hydrogen bonded to water molecules in the coordination sphere. Asp86 is not chelated to the magnesium or its surrounding water molecules. Results of kinetics and site-specific mutagenesis experiments suggest that this metal-water cluster contains the catalytic metal ion of this enzyme. All residues which hydrogen bond to the water molecules that coordinate the magnesium atom are conserved in nucleases homologous to Serratia endonuclease, suggesting that the water cluster is a conserved feature of this family of enzymes. We offer a detailed structural comparison to one other nuclease, the homing endonuclease I-PpoI, that has recently been shown, in spite of a lack of sequence homology, to share a similar active site geometry to Serratia endonuclease. Evidence from both of these structures suggests that the magnesium of Serratia nuclease participates in catalysis via an inner sphere mechanism.

Amino Acid Sequence↗

PubMed2005

Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands.

The reaction of the unsymmetrical ligands 1-diphenylphosphino-1'-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1'-(phenylselenyl)ferrocene, Fc(EPh)PPh2(E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}](M = Au, X = Cl, C6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO4, [Au(C6F5)3{Fc(EPh)PPh2}], [Au2(C6F5)6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2}2]PF6(E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au...Cl or Au...Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands.

Crystallography, X-Ray↗

PubMed1998

Structure of the C-type lectin carbohydrate recognition domain of human tetranectin.

Tetranectin (TN) is a C-type lectin involved in fibrinolysis, being the only endogenous ligand known to bind specifically to the kringle 4 domain of plasminogen. TN was originally isolated from plasma, but shows a wide tissue distribution. Furthermore, TN has been found in the extracellular matrix of certain human carcinomas, whereas none or little is present in the corresponding normal tissue. The crystal structure of full-length trimeric TN (2.8 A resolution) has recently been published [Nielsen et al. (1997). FEBS Lett. 412, 388-396]. The crystal structure of the carbohydrate recognition domain (CRD) of human TN (TN3) has been determined separately at 2.0 A resolution in order to obtain detailed information on the two calcium binding sites. This information is essential for the elucidation of the specificity of TN towards oligosaccharides. TN3 crystallizes as a dimer, whereas it appears as a monomer in solution. The overall fold of TN3 is similar to other known CRDs. Each monomer is built of two distinct regions, one region consisting of six beta-strands and two alpha-helices, and the other region is composed of four loops harboring two calcium ions. The calcium ion at site 1 forms an eightfold coordinated complex and has Asp116, Glu120, Gly147, Glu150, Asn151, and one water molecule as ligands. The calcium ion at site 2, which is believed to be involved in recognition and binding of oligosaccharides, is sevenfold coordinated with ligands Gln143, Asp145, Glu150, Asp165, and two water molecules. One sulfate ion has been located at the surface of TN3, forming contacts to Glu120, Lys148, Asn106 of a symmetry-related molecule, and to an ethanol molecule.

Amino Acid Sequence↗

PubMed2004

Aggregation of [Cu(II)4] building blocks into [Cu(II)8] clusters or a [Cu(II)4]infinity chain through subtle chemical control.

Coordination complexes of the ligand H3L [1,3-bis(3-oxo-3-phenylpropionyl)-2-hydroxy-5-methylbenzene] with Cu(II) are reported. Clusters showing various nuclearities or modes of supramolecular organization have been prepared by slightly changing the reaction conditions and have been crystallographically characterized. The reaction of H3L with one equivalent of Cu(OAc)2 in DMF yields the dinuclear complex [Cu2(HL)2(dmf)2] (1). Reaction in MeOH of H3L with an increased amount of metal, in the form of Cu(NO3)2, and excess strong base (nBu4NOH) affords the cluster [Cu8(L)2(OMe)8(NO3)2] (2). Complex 2 is a dimer of two linear [Cu4] arrays bridged by methoxide ligands, where the polynucleating ligand is fully deprotonated. The [Cu4]2 clusters are linked to each other by NO3- bridges to form one-dimensional coordination polymers. The link between [Cu8] units and their relative spatial positioning can be modified by changing the anion of the Cu(II) salt, as demonstrated by the synthesis of the cluster polymers [Cu8(L)2(OMe)8Cl2] (3) and [Cu8(L)(OMe)7.86Br2.14] (4), where only NO3- has been replaced by Cl- or Br-, respectively. Similarly, when ClO4- is used, compound [Cu8(L)2(OMe)8(ClO4)2(MeOH)4] (5) can be isolated. It contains independent [Cu8] units. A slight change in the stoichiometry of the reaction leading to 2 affords the related complex catena-[Cu4(L)(OMe)3(NO3)2(H2O)0.36] (6). This polymer contains essentially the same [Cu4] moiety as 2, albeit organized in a completely different arrangement. Each [Cu4] unit in 6 is linked by OMe- ligands to two such equivalent groups to form an infinite chain. Magnetic susceptibility measurements reveal weak antiferromagnetic exchange between Cu(II) centers in 1 (J = -0.73 cm(-1)) and strong antiferromagnetic coupling within [Cu4] chains in 2, 5, and 6 (most negative J values of -113.8 and -177.3 cm(-1) for 2 and 6, respectively).

Benzene Derivatives↗

PubMed1983

Antidiabetic behavior of biguanides.

The existence of active electron pairs on some nitrogen atoms in phenformin hydrochloride is inferred from the presence of a hydrogen catalytic polarographic wave. This finding emphasizes the ability of biguanides to form hydrogen bridges with other molecular species such as amino acids and proteins, as well as to form coordination complexes with zinc and other metallic cations by means of these electron pairs. The antidiabetic action of phenformin and other related biguanides can be explained in terms of competition between these molecules and insulin to coordinate cationic oligoelements together with their ability to form hydrogen bonds between the biguanide moiety and insulin itself.

Biguanides↗