Oxovanadium(IV) and dioxouranium(VI) complexes with thiocarbohydrazones

Oxovanadium(IV) and dioxouranium(VI) complexes with thiocarbohydrazones have been prepared in an ethanolic medium and characterised by elemental analysis and molecular weight determination. They have 1:1 stoichiometry. The IR observations suggest that the ligands have coordinated through azomethine nitrogen atoms and reacted through hydroxy groups. The v(MN) and v(MO) vibrations have been assigned. The PMR spectral information supports the IR inference. The oxovanadium(IV) complexes show magnetic moments in the range of 1.74–1.94 B.M. The electronic spectra have been interpreted in the light of the BG model. Various NSH parameters have been calculated. The ESR spectra also render support for the spectral information. On the basis of this information it is suggested that oxovanadium(IV) complexes exhibit coordination number five and dioxouranium coordination number six.     

Synthesis of rhodium(III), iridium(III) and osmium(III) complexes with tris(2-aminoethanethiolato)cobalt(III)

Polynuclear sulfur bridged complexes where the neutral complex tris(2-aminoethanethiolato)cobalt(III) acts as a tridentate ligand to rhodium(III), iridium(III) and osmium(III) have been prepared. These complexes have been characterized by electronic spectroscopy, vibrational spectroscopy and nuclear magnetic resonance spectroscopy. Along with the previously prepared complexes of iron(III), ruthenium(III) and cobalt(III), these complexes form two series of complexes with the group 8 and group 9 elements from all three transition series.     

Chemistry and insulin-like properties of vanadium(IV) and vanadium(V) compounds

The chemistry of vanadium compounds that can be taken orally is very timely since a vanadium(IV) compound, KP-102, is currently in clinical trials in humans, and the fact that human studies with inorganic salts have recently been reported. VO(acac)2 and VO(Et-acac)2 (where acac is acetylacetonato and Et-acac is 3-ethyl-2,4-pentanedionato) have long-term in vivo insulin mimetic effects in streptozotocin induced diabetic Wistar rats. Structural characterization of VO(acac)2 and two derivatives, VO(Me-acac)2 and VO(Et-acac)2, in the solid state and solution have begun to delineate the size limits of the insulin-like active species. Oral ammonium dipicolinatooxovanadium(V) is a clinically useful hypoglycemic agent in cats with naturally occurring diabetes mellitus. This compound is particularly interesting since it represents the first time that a well-characterized organic vanadium compound with the vanadium in oxidation state five has been found to be an orally effective hypoglycemic agent in animals.     

Binding of tetrakis(pyrazoliumyl)porphyrin and its copper(II) and zinc(II) complexes to poly(dG-dC)2 and poly(dA-dT)2

Interactions of cationic porphyrins bearing five-membered rings at the meso position, meso-tetrakis(1,2-dimethylpyrazolium-4-yl)porphyrin (MPzP; M is H₂, Cu^II or Zn^II), with synthetic polynucleotides poly(dG-dC)₂ and poly(dA-dT)₂ have been characterized by viscometric, visible absorption, circular dichroisim and magnetic circular dichroism spectroscopic and melting temperature measurements. Both H₂PzP and CuPzP are intercalated into poly(dG-dC)₂ and are outside-bound to the major groove of poly(dA-dT)₂, while ZnPzP is outside-bound to the minor groove of poly(dA-dT)₂ and surprisingly is intercalated into poly(dG-dC)₂. The binding constants of the porphyrin and poly(dG-dC)₂ and poly(dA-dT)₂ are on the order of 10⁶ M⁻¹ and are comparable to those of other cationic porphyrins so far reported. The process of the binding of the porphyrin to poly(dG-dC)₂ and poly(dA-dT)₂ is exothermic and enthalpically driven for H₂PzP, whereas it is endothermic and entropically driven for CuPzP and ZnPzP. These results have revealed that the kind of the central metal ion of metalloporphyrins influences the characteristics of the binding of the porphyrins to DNA.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

Collagen-like triple helix formation of synthetic (Pro-Pro-Gly)10 analogues: (4(S)-hydroxyprolyl-4(R)-hydroxyprolyl-Gly)10, (4(R)-hydroxyprolyl-4(R)-hydroxyprolyl-Gly)10 and (4(S)-fluoroprolyl-4(R)-fluoroprolyl-Gly)10.

For the rational design of a stable collagen triple helix according to the conventional rule that the pyrrolidine puckerings of Pro, 4-hydroxyproline (Hyp) and 4-fluoroproline (fPro) should be down at the X-position and up at the Y-position in the X-Y-Gly repeated sequence for enhancing the triple helix propensities of collagen model peptides, a series of peptides were prepared in which X- and Y-positions were altogether occupied by Hyp(R), Hyp(S), fPro(R) or fPro(S). Contrary to our presumption that inducing the X-Y residues to adopt a down-up conformation would result in an increase in the thermal stability of peptides, the triple helices of (Hyp(S)-Hyp(R)-Gly)(10) and (fPro(S)-fPro(R)-Gly)(10) were less stable than those of (Pro-Hyp(R)-Gly)(10) and (Pro-fPro(R)-Gly)(10), respectively. As reported by B?chinger's and Zagari's groups, (Hyp(R)-Hyp(R)-Gly)(10) which could have an up-up conformation unfavorable for the triple helix, formed a triple helix that has a high thermal stability close to that of (Pro-Hyp(R)-Gly)(10). These results clearly show that the empirical rule based on the conformational preference of pyrrolidine ring at each of X and Y residues should not be regarded as still valid, at least for predicting the stability of collagen models in which both X and Y residues have electronegative groups at the 4-position.     

Iron and cobalt complexes with the ligand (2-aminoethyl)bis(2-pyridylmethyl)amine (uns-penp) and derivatives

A series of iron(II)/(III) and cobalt(II)/(III) complexes with the tetradendate tripodal ligands (2-aminoethyl)bis(2-pyridylmethyl)amine (uns-penp), its methylated derivatives Me₂-uns-penp and Me₄-uns-penp as well as the amide ligand N-acetyl-N,N-bis[(2-pyridyl)methyl]ethylenediamine (acetyl-uns-penp) were synthesized and structurally characterized. They have been investigated in regard to their reactivity towards dioxygen and/or hydrogen peroxide. Complexes of this type seem to have a high potential to be useful in the activation of dioxygen for selective oxidation reactions of organic substrates.     

Biphenyl derived oxovanadium(IV) and copper(II) salen-type complexes--structure and redox tuning

A series of vanadyl(IV) salen (N,N'-bis(salicylidene)ethylenediaminato)-type complexes (1-4) bearing phenyl or 2-hydroxyphenyl moieties have been prepared and characterized by means of mass spectrometry, infra-red, electron paramagnetic resonance (EPR), UV/Vis spectroscopy, cyclovoltammetry and X-ray crystallography. Their structures have been compared to their copper(II) analogs 5-8. Hydrogen intralinkages have been observed in the crystal structure of 5. The pendant hydroxy groups fine-tune the redox properties of the complexes. The catalytic activity in the oxygenation of ethyl phenyl sulfide to the corresponding sulfoxide was investigated. Results indicate that complex 1 bearing hydroxyphenyl subunits and a phenylene bridge is the most selective under these reaction conditions, with the smallest amount of the over-oxidized product, sulfone.     

The populations of Pseudophoxinus zeregi (Heckel) in Israel and Syria and the status of Pseudophoxinus (Pararhodeus) drusensis (Pellegrin) (Pisces:Cyprinidae)

Pseudophoxinus zeregi (Heckel) and P. (Pararhodeus) drusensis (Pellegrin) have been examined from populations near their respective type localities. It was found that there is no basis for the subgenus Pararhodeus and that the two forms are best regarded as subspecies of Pseudophoxinus zeregi.     

Zn(II)-113Cd(II) and Zn(II)-Mg(II) hybrids of alkaline phosphatase. 31P and 113Cd NMR

Methods have been developed for the addition of different metal ion species to the three distinct pairs of metal sites (A, B, and C) found in the dimer of apoalkaline phosphatase. This allows the preparation of hybrid alkaline phosphatases in which A and B sites of each monomer contain two different species of metal ion or the A and B sites of one monomer contain the same species of metal ion, while the adjacent monomer contains a second species. The following hybrids have been characterized in detail: (Zn(II)ACd(II)B)2 alkaline phosphatase, (Zn(II)AMg(II)B)2 alkaline phosphatase, (Cd(II)AZn(II)B)2 alkaline phosphatase, and (Zn(II)AZn(II]B)(Cd(II)ACd(II)B) alkaline phosphatase. 31P and, where appropriate, 113Cd NMR have been used to monitor the behavior of the covalent (E-P) and noncovalent (E X P) phosphointermediates and of the A and B metal ions. From the pH dependencies of the E-P in equilibrium E X P in equilibrium E + Pi equilibria, it is clear that A site metal is the dominant influence in dephosphorylation of E-P and may have a coordinated water molecule, which ionizes to ZnOH- at a low pH providing the nucleophile for dephosphorylation. A site metal also serves to coordinate phosphate in the E X P complex. B site metal has a much smaller effect on dephosphorylation rates, although it does dramatically alter the Pi dissociation rate, which is the rate-limiting step for the native enzyme at alkaline pH, and is probably important in neutralizing the charge on the phosphoseryl residue, thus potentiating the nucleophilic attack of the OH- bound at A site. Phosphate dissociation is slowed markedly by replacement of B site zinc by cadmium. There is clear evidence for long range effects of subunit-subunit interactions, since metal ion and phosphate binding at one active center alters the environments of A and B site metal ions and phosphoserine at the other active site.     

Salt-tolerant Acidihalobacter and Acidithiobacillus species from Vulcano (Italy) and Milos (Greece)

Extremophiles - Ferrous iron- and sulfur-oxidizing Acidihalobacter species and similar so far unclassified bacteria have been isolated from the islands of Vulcano (Italy) and Milos (Greece),...     

Mixed ligation to vanadium(III): Synthesis,spectra and structures of bis(acetylacetonato)(o-phenanthroline)vanadium(III) fluoroborate and bis(acetylacetonato)(o-phenanthroline)vanadium(III) perchlorate

Two mixed ligand vanadium(III) complexes bis(acetylacetonato)(phenanthroline)vanadium(III) fluoroborate (1) and bis(acetylacetonato)(phenanthroline)vanadium(III) perchorate (2) have been prepared and characterized by UV–Vis, IR, ¹H NMR spectroscopic techniques and single crystal X-ray diffraction. The electronic spectra are as expected for V(III) in an octahedral environment. The ¹H NMR spectra are typical of paramagnetic V(III) species. The complexes have crystallized with dichloromethane solvate and are isomorphous. The coordination sphere is composed of vanadium in a distorted octahedral environment, ligated to two bidentate chelating acetylacetonate ligands through the oxygen atoms and two phenanthroline nitrogens.     

(A)GGG(A), (A)CCC(A) and other potential 3' splice signals in primate nuclear pre-mRNA sequences

Several 3' splice signals in nuclear precursor mRNAs have already been known for some time: the AG doublet on the left-hand side of the splice and a run of pyrimidines just upstream of it. More recently it has been noted that the YNYTRAY sequence (where Y is a pyrimidine, R a purine and N any base) is a branching-sequence participating in formation of a lariat structure. Keller and Noon have shown the existence of several putative consensus sequences at this site. In this work, extensive computations of the distributions of 256 quartets in all primate nuclear pre-mRNA intron sequences present in GenBank have been carried out. Several putative signals upstream and downstream of the 3' splice have been detected. These have been compared with the results obtained in analogous computations carried out on all nuclear pre-mRNA introns present in a combined eukaryotic file containing mammal, non-mammalian vertebrate, invertebrate and plant sequences. The distributions of the more interesting oligomers are shown here. Of particular interest are the putative (A)GGG(A) signal 60 nucleotides upstream of the 3' splice site and (A)CCC(A) 3-40 nucleotides downstream of it. A possible splicing model explaining these data and involving formation of alternative hairpin loop structures is proposed.     

Conformational analysis of the tetranucleotides m6(2)A-m6(2)A-U-m6(2)A(m6(2)A = N6-dimethyladenosine) and U-m6(2)A-U-m6(2)A and of the hybrid dA-r(U-A). A one- and two-dimensional NMR study

A 1H-NMR investigation was carried out on the tetranucleotides U-m6(2)A-U-m6(2)A and m6(2)A-m6(2)A-U-m6(2)A (m6(2) = N6-dimethyladenosine) as well as on the hybrid trinucleotide dA-r(U-A). An extensive comparison with m6(2)A-U-m6(2)A and other relevant compounds is made. Previous proton NMR studies on trinucleotides have shown that purine-pyrimidine-purine sequences prefer to adopt a mixture of states which have as a common feature that the interior pyrimidine residue bulges out, whereas the flanking purine residues stack upon each other. A stacking interaction on the 3' side of the bulge is known to have no measurable effect on the bulge population. Chemical-shift data, ribose ring conformational analysis and information from NOE experiments now show unambiguously that the moderate U(1)-m6(2)A(2) stack in U-m6(2)A-U-m6(2)A diminishes the population of bulged-out structures in favour of a regular stack. This tendency towards conformational transmission in the downstream 5'----3' direction is fully confirmed by the fact that the strong m6(2)A(1)-m6(2)A(2) stack in the tetranucleotide m6(2)A-m6(2)A-U-m6(2)A virtually precludes the formation of bulged-out structures. The conformational characteristics of dA-r(U-A) appear comparable with those of m6(2)A-U-m6(2)A, which indicates that the presence of a 2'-hydroxyl group in the first purine residue is not a necessary prerequisite for the formation of a bulge.     

Dissimilatory Fe(III) and Mn(IV) reduction.

The oxidation of organic matter coupled to the reduction of Fe(III) or Mn(IV) is one of the most important biogeochemical reactions in aquatic sediments, soils, and groundwater. This process, which may have been the first globally significant mechanism for the oxidation of organic matter to carbon dioxide, plays an important role in the oxidation of natural and contaminant organic compounds in a variety of environments and contributes to other phenomena of widespread significance such as the release of metals and nutrients into water supplies, the magnetization of sediments, and the corrosion of metal. Until recently, much of the Fe(III) and Mn(IV) reduction in sedimentary environments was considered to be the result of nonenzymatic processes. However, microorganisms which can effectively couple the oxidation of organic compounds to the reduction of Fe(III) or Mn(IV) have recently been discovered. With Fe(III) or Mn(IV) as the sole electron acceptor, these organisms can completely oxidize fatty acids, hydrogen, or a variety of monoaromatic compounds. This metabolism provides energy to support growth. Sugars and amino acids can be completely oxidized by the cooperative activity of fermentative microorganisms and hydrogen- and fatty-acid-oxidizing Fe(III) and Mn(IV) reducers. This provides a microbial mechanism for the oxidation of the complex assemblage of sedimentary organic matter in Fe(III)- or Mn(IV)-reducing environments. The available evidence indicates that this enzymatic reduction of Fe(III) or Mn(IV) accounts for most of the oxidation of organic matter coupled to reduction of Fe(III) and Mn(IV) in sedimentary environments. Little is known about the diversity and ecology of the microorganisms responsible for Fe(III) and Mn(IV) reduction, and only preliminary studies have been conducted on the physiology and biochemistry of this process.     

Malate decarboxylases: evolution and roles of NAD(P)-ME isoforms in species performing C(4) and C(3) photosynthesis

In the C(4) pathway of photosynthesis two types of malate decarboxylases release CO(2) in bundle sheath cells, NADP- and NAD-dependent malic enzyme (NADP-ME and NAD-ME), located in the chloroplasts and the mitochondria of these cells, respectively. The C(4) decarboxylases involved in C(4) photosynthesis did not evolve de novo; they were recruited from existing housekeeping isoforms. NADP-ME housekeeping isoforms would function in the control of malate levels during hypoxia, pathogen defence responses, and microspore separation, while NAD-ME participates in the respiration of malate in the tricarboxylic acid cycle. Recently, the existence of three enzymatic NAD-ME entities in Arabidopsis, occurring by alternative association of two subunits, was described as a novel mechanism to regulate NAD-ME activity under changing metabolic environments. The C(4) NADP-ME is thought to have evolved from a C(3) chloroplastic ancestor, which in turn would have evolved from an ancient cytosolic enzyme. In this way, the C(4) NADP-ME would have emerged through gene duplication, acquisition of a new promoter, and neo-functionalization. In contrast, there would exist a unique NAD-ME in C(4) plants, which would have been adapted to perform a dual function through changes in the kinetic and regulatory properties of the C(3) ancestors. In addition to this, for the evolution of C(4) NAD-ME, insertion of promoters or enhancers into the single-copy genes of the C(3) ancestors would have changed the expression without gene duplication.     

Hydrodynamic perception in true seals (Phocidae) and eared seals (Otariidae)

Pinnipeds, that is true seals (Phocidae), eared seals (Otariidae), and walruses (Odobenidae), possess highly developed vibrissal systems for mechanoreception. They can use their vibrissae to detect and discriminate objects by direct touch. At least in Phocidae and Otariidae, the vibrissae can also be used to detect and analyse water movements. Here, we review what is known about this ability, known as hydrodynamic perception, in pinnipeds. Hydrodynamic perception in pinnipeds developed convergently to the hydrodynamic perception with the lateral line system in fish and the sensory hairs in crustaceans. So far two species of pinnipeds, the harbour seal (Phoca vitulina) representing the Phocidae and the California sea lion (Zalophus californianus) representing the Otariidae, have been studied for their ability to detect local water movements (dipole stimuli) and to follow hydrodynamic trails, that is the water movements left behind by objects that have passed by at an earlier point in time. Both species are highly sensitive to dipole stimuli and can follow hydrodynamic trails accurately. In the individuals tested, California sea lions were clearly more sensitive to dipole stimuli than harbour seals, and harbour seals showed a superior trail following ability as compared to California sea lions. Harbour seals have also been shown to derive additional information from hydrodynamic trails, such as motion direction, size and shape of the object that caused the trail (California sea lions have not yet been tested). The peculiar undulated shape of the harbour seals’ vibrissae appears to play a crucial role in trail following, as it suppresses self-generated noise while the animal is swimming.     

Facile entry to (-)-(R)- and (+)-(S)-mexiletine

The title compounds, 1a and 1b, have been synthesized in a three-step sequence starting from (-)-(S) and (+)-(R)-propylene oxide, respectively, in acceptable overall yields. The enantiomeric excess values for 1a and 1b were 96% and 93% respectively, as assessed by HPLC analysis on a chiral stationary phase of the corresponding N-acetyl derivatives. The synthetic route herein presented may represent a facile entry to highly enriched mexiletine enantiomers, alternative to those previously reported in the literature.     

Absorption and emission spectra of neodymium(III) and europium(III) complexes

The absorption and emission spectra of several complexes of neodymium(III) and europium(III) ions have been examined in order to obtain reliable information relating to coordination number, nature of bonding and symmetry around the lanthanide ion. It has been found that steric factors may force the polyhedron of coordination towards geometries less favourable by ligand–ligand repulsion. In general, no correlation has been found to exist between the low intensity of the hypersensitive transitions and high symmetry or low symmetry and high intensity. The results have pointed out the role of covalency in hypersensitivity.     

Synthesis, characterization, and antitumor activity of 1,2-bis(diphenylphosphino) ethane platinum(II) and palladium(II) complexes

A number of 1,2-bis(diphenylphosphino)ethane monomeric platinum(II) and palladium(II) complexes have been synthesized in light of their potential antitumor activity. The metal center is coordinated with a number of carboxylate anions in the cis-configuration. These complexes have been characterized by elemental analysis, conductivity measurement, and various spectroscopic techniques [IR and 195Pt NMR]. In vivo screening tests for activity of these complexes were performed against the L1210/0 murine leukemia cancer model, but none displayed a significant level of antitumor activity.     

Linkage between the loci for the Lp(a) lipoprotein (LP) and plasminogen (PLG)

Summary A locus, LP, that determines quantitative variation of Lp(a) lipoprotein phenotypes is linked to the plasminogen (PLG) locus (peak lod score =12.73). This linkage relationship assigns a locus with alleles that have an affect on risk for coronary artery disease to the long arm of chromosome 6.