Female-induced sexual arousal in male mice and rats: behavioral and testosterone response

Exposure of a male mouse to a female mouse separated from it by a holed partition induced specific behavior and an increase in blood testosterone in the male. The male made more approaches to the partition and spent more time at it. The time spent by the male mouse over the first 10 min at the partition, behind which an estrus female was placed, was increased sixfold compared to the time spent by a male mouse exposed to the vacant neighboring compartment; and 1.5-fold compared to that spent by a male mouse exposed to a nonreceptive female or a male. Increased blood testosterone level was detected at 20 min of exposure to a receptive female in winter and at 40 min in summer. No variation in blood testosterone levels in the male mouse exposed to a nonreceptive female or a male was observed. Similar response to a receptive female placed in the neighboring compartment was shown in a male rat. The time spent by the male rat at the partition was 12 times higher when there was an estrus female behind it than in control. Blood testosterone in the male rat increased in response to a female rat and did not change in response to a male rat indicating female-induced motivation. It was concluded that the partition time might serve as a quantitative measure of sexual motivation in the males and that the model of female-induced sexual arousal used was suitable for studying both motivational and hormonal components of sexual arousal in male mice and rats.     

Spectroscopic characterization of mononuclear, binuclear, and insoluble polynuclear oxovanadium(IV)-Schiff base complexes and their oxidation catalysis

The objective was to prepare mononuclear, binuclear, and insoluble polynuclear oxovanadium(IV)-Schiff base complexes and to use them for sulfoxidation and epoxidation of organic substrates. [VO(salen)] (complex 1) with tetradentate salen(salicylideneethylenediamine) being coordinated in the equatorial plane of oxovanadium(IV), [VO(salap)] (complex 2), and [(VO)₂(sal₂-dhdabp)] (complex 3) with tridentate salap(salicylideneorthoaminophenol) and sal₂-dhdabp(salicylidene-3,3^′-dihydroxy-4,4^′-diaminobiphenyl) being bound, respectively, in the equatorial plane, of which polynuclear complexes were constituted as monomer units, were prepared and spectroscopically characterized. A sulfide and olefins were oxidized by use of complexes 1 and 2 (mononuclear), complex 3 (binuclear), and the polynuclear complexes (poly-1 and poly-3) synthesized with 1 and 3, respectively. The reaction rates for poly-1 and -3 were a little lower than those of the corresponding 1 and 3. On oxidation of sulfides, poly-3 exhibited lowering of activity by about 15% in three cycles, while poly-1 showed significant lose of activity with each use. Poly-3 was efficient for the oxidation of the olefins only in the first cycle. It was suggested that the loss of activity depends not only on the coordination geometry of the oxovanadium complex, but also on the kind of the substrate.     

Oxo-transfer catalysis from t-BuOOH with C-H bond insertion using tridentate Schiff-base-chelate complexes of ruthenium(III)

Mixed-chelate complexes of ruthenium have been synthesized using tridentate Schiff-base ligands (TDLs) derived by condensation of aldehydes (salicyldehyde, 2-pyridinecarboxaldehyde) with 2-aminobenzoic acid, and bidentate ligands (2,2^′-bipyridine or picolinic acid). [Ru^III(cpsd)(bipy)(H₂O)]⁺ (1), [Ru^III(cpsd)(pic)(H₂O)] (2), [Ru^III(cppc)(bipy)(H₂O)]²⁺ (3) and [Ru^III(cppc)(pic)(H₂O)]⁺ (4) complexes (where, cpsd²⁻=(N-(2-carboxyphenyl)salicylaldiminato); cppc⁻=N-2-carboxyphenylpyridine-2-carboxaldiminato; bipy=2,2^′-bipyridine and pic⁻=picolinate) were characterized by analytical, spectral (IR and UV-Vis), conductance, magnetic moment and electrochemical studies. Catalysis of hydrocarbon oxidations for cyclohexene, cyclohexane, cyclohexanol, toluene, benzyl alcohol, and tetrahydrofuran have been studied using various O-atom transfer agents (t-BuOOH, H₂O₂, NaOCl, KHSO₅ and pyridinium-N-oxide). The influence of product yield as a function of solvent was evaluated for CH₂Cl₂, CH₃CN, and 1,4-dioxane. Coordinating solvents suppress the reactivity by inhibiting coordination of t-BuOOH, and compete for the Ru^VO group through their own intrinsic C-H reactivity. The main pathway transfers the oxo group from the [RuO(TDL)(XY)] intermediate, TDL=cpsd²⁻ and cppc²⁻; XY=bipy or pic⁻, with insertion of the oxo group into a C-H bond of all substrates tested (rather than olefin epoxidation for cyclohexene). A mechanism involving intermediacy of a high valent Ru(V)-oxo species is proposed for the catalytic oxidation processes.     

Reactions of seven coordinate complexes. Synthesis, structure, and copper complex of the novel ligand 3-methyltriazolo(1,5-a)6-acetylsemicarbazonepyridine

The reaction of aquachloro(2,6-diacetylpyridinedisemicarbazone)copper(II) with hydrazine hydrate gave the copper complex of 3-methyltriazolo(1,5-a)6-acetylsemicarbazonepyridine. The free ligand was isolated from the copper complex. The X-ray structures of both the copper complex and the free ligand are reported. The copper complex and the free ligand both crystallize in the triclinic space group with 2 molecules per cell. The Cu complex has cell dimensions of a=8.8574(4), b=10.1764(5), c=10.4434(5) Å, α=71.956(1), β=64.913(1), and γ=81.597(1)°. The Cu ion is in a square pyramidal arrangement, with the Cu, the ligand, and a Cl in the plane and a disordered Cl and H₂O in the apical position. The ligand has cell dimensions of a=7.2696(7), b=8.0516(7), c=9.9326(9) Å, α=110.534(2), β=96.730(2), and γ=100.089(2)°. The ligand is planar with a conformation determined by an internal N-H?H hydrogen bond. The role of the Cu ion in the formation of the triazolopyridine is discussed.     

Crystal structures and magnetic properties of tetranuclear copper(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine with a defective double-cubane core

Tetranuclear Cu(II) complexes of N-(2-hydroxymethylphenyl)salicylideneimine (H₂L1-H) and its homologues (5-CH₃: H₂L1-Me, 5-Cl: H₂L1-Cl), [Cu(L1-H)]₄ · 3H₂O (1), [Cu(L1-Me)]₄ · 2CH₂Cl₂ (2), and [Cu(L1-Cl)]₄ · 2CH₂Cl₂ (3), have been characterized by X-ray crystal structure analyses and magnetic measurements. The structure analyses revealed that the complexes 1-3 have a defective double-cubane tetra copper(II) core connected by μ₃-alkoxo bridges. The intramolecular Cu?Cu distances are in the range from 5.251(2)-5.256(3) Å for the longest to 3.0518(9)-3.092(2) Å for the shortest. Each Cu(II) ion has a square-pyramidal geometry and the dihedral angles between adjacent Cu(II) basal planes are almost right angles. Magnetic measurements of the present complexes indicate that weak antiferromagnetic interactions (J=−15 to −19 cm⁻¹) between neighboring copper(II) ions are dominant in these tetracopper cores.     

Synthesis, magnetic properties and MCD spectra of a four coordinate copper(II) complex with two chelated phenolate-substituted imino nitroxides

A reaction of Cu(II) nitrate and 4,4,5,5-tetramethyl-2-(2-hydroxophenyl)imidazolin-1-oxyl (IM2PhOH) with potassium methoxide in methanol gave a homoleptic bis(imino nitroxide) complex of [Cu(IM2PhO)₂] (1). The single-crystal X-ray analysis of 1 showed that the imino nitroxide anion, IM2PhO⁻, chelated to a Cu^II ion via an imino-N and a phenoxide-O atoms to form a six-membered chelate ring. The coordination geometry around the Cu(II) ion was a distorted square-planar polygon; the dihedral angle between the two coordination planes, each of which was defined by Cu and two ligating atoms of IM2PhO⁻, was 40.81°. The temperature dependences of the magnetic susceptibility and the EPR spectra of 1 indicate that the magnetic interaction between Cu(II) and the imino nitroxide is ferromagnetic, while there is a moderate antiferromagnetic interaction between two coordinated imino nitroxides. A balance between these opposite interactions attains the lowest molecular doublet spin-state in 1. The variable temperature magnetic circular dichroism (MCD) spectrum of the complex 1 also showed two negative components with a large C term, which may be due to the charge-transfer (CT) transition originated from the d orbital to the SOMO π^* orbital in the spin-coupled IM2PhO⁻ radicals; resulting in the largely split doublet excited states with the spin singlet and triplet d⁸ configurations.     

Synthesis and structural characterization of cadmium(II) complexes with 2-(2-pyridyl)imino-N-(2-thiazolin-2-yl)thiazolidine (PyTT)

We have carried out the synthesis of the cadmium coordination compounds [Cd(NO₃)₂(PyTT)(H₂O)] (1) and [CdCl₂{(μ-Cl)₂CdCl(μ-Cl)(μ-PyTT)Cd}₂]_n (2), together with their structural determination by means of X-ray diffraction. The compounds were also characterized through elemental analysis and infrared spectroscopy. The first complex presents a distorted pentagonal bipyramidal geometry with the axial positions occupied by one oxygen atom from a water molecule and a second one from a nitrate ion which acts as a monodentate ligand, whereas the equatorial plane contains three nitrogen atoms from the organic moiety and two oxygen atoms coming from the other nitrate group, which is bidentate. The structure of the second complex consists of parallel sheets linked by van der Waals forces, each one made up of structural units [CdCl₂{(μ-Cl)₂CdCl(μ-Cl)(μ-PyTT)Cd}₂], which possesses two PyTT ligands, 10 bridging chloro ligands and 5 cadmium(II) centres belonging to three environment types: octahedral CdN₂Cl₄, octahedral CdCl₆, on which a centre of symmetry is located, and tetrahedral CdNCl₃, present in a 2:1:2 ratio.     

On the stability of different experimental dimeric structures of the SL1 sequence from the genomic RNA of HIV-1 in solution: a molecular dynamics simulation and electrophoresis study

SL1 is a stem-loop RNA sequence from the genome of HIV-1 thought to be the initiation site for the dimerization of the retroviral genomic RNA. The aim of this study is to check the stability in solution of different experimental dimeric structures available in the literature. Two kinds of dimer have been evidenced: an extended duplex looking like a double helix with two internal bulges and a kissing complex in which the monomers with a stem/loop conformation are linked by intermolecular loop-loop interactions. Two divergent experimental structures of the kissing complex from the Lai isolate are reported in the literature, one obtained from NMR (Mujeeb et al., Nature Structural Biology, 1998, Vol. 5, pp. 432-436) and the other one from x-ray crystallography (Ennifar et al., Nature Structural Biology, 2001, Vol. 8, pp. 1064-1068). A crystallographic structure of the Mal isolate was also reported (Ennifar et al., Nature Structure Biology, 2001, Vol. 8, pp. 1064-1068). Concerning the extended duplex, a NMR structure is available for Lai (Girard et al., Journal of Biomolecular Structure and Dynamics, 1999, Vol. 16, pp. 1145-1157) and a crystallographic structure for Mal (Ennifar et al., Structure, 1999, Vol. 7, pp. 1439-1449). Using a molecular dynamics technique, all these experimental structures have been simulated in solution with explicit water and counterions. We show that both extended duplex structures are stable. On the contrary, the crystallographic structures of the Lai and Mal kissing complexes are rapidly destabilized in aqueous environment. Finally, the NMR structure of the Lai loop-loop kissing complex remains globally stable over a 20 ns MD simulation, although large rearrangements occur at the level of the stem/loop junctions that are flexible, as shown from free energy calculations. These results are compared to electrophoresis experiments on dimer formation.     

Balanced complex chromosomal rearrangements (BCCR) with at least three chromosomes and three or more breakpoints: report of three new cases

Balanced complex chromosomal rearrangements (BCCR) encompass a heterogeneous group of rare chromosomal aberrations. In this paper, we report three cases of BCCRs. In two the probands were referred for either genetic counseling or prenatal management. One case was ascertained after chromosome analysis performed because of psychiatric manifestations; this was an isolated finding. We also outline the molecular cytogenetic techniques, which were essential in confirming and precisely delineating the BCCRs identified in these patients. In addition the various aspects of genetic counseling for this type of chromosomal rearrangement, highlighting the details particular to each individual case are discussed. We discuss the classification for this type of chromosomal mutation.     

The reaction of indole with the aminoacrylate intermediate of Salmonella typhimurium tryptophan synthase: observation of a primary kinetic isotope effect with 3-[(2)H]indole

The bacterial tryptophan synthase alpha(2)beta(2) complex catalyzes the final reactions in the biosynthesis of L-tryptophan. Indole is produced at the active site of the alpha-subunit and is transferred through a 25-30 A tunnel to the beta-active site, where it reacts with an aminoacrylate intermediate. Lane and Kirschner proposed a two-step nucleophilic addition-tautomerization mechanism for the reaction of indole with the aminoacrylate intermediate, based on the absence of an observed kinetic isotope effect (KIE) when 3-[(2)H]indole reacts with the aminoacrylate intermediate. We have now observed a KIE of 1.4-2.0 in the reaction of 3-[(2)H]indole with the aminoacrylate intermediate in the presence of monovalent cations, but not when an alpha-subunit ligand, disodium alpha-glycerophosphate (Na(2)GP), is present. Rapid-scanning stopped flow kinetic studies were performed of the reaction of indole and 3-[(2)H]indole with tryptophan synthase preincubated with L-serine, following the decay of the aminoacrylate intermediate at 350 nm, the formation of the quinonoid intermediate at 476 nm, and the formation of the L-Trp external aldimine at 423 nm. The addition of Na(2)GP dramatically slows the rate of reaction of indole with the alpha-aminoacrylate intermediate. A primary KIE is not observed in the reaction of 3-[(2)H]indole with the aminoacrylate complex of tryptophan synthase in the presence of Na(2)GP, suggesting binding of indole with tryptophan synthase is rate limiting under these conditions. The reaction of 2-methylindole does not show a KIE, either in the presence of Na(+) or Na(2)GP. These results support the previously proposed mechanism for the beta-reaction of tryptophan synthase, but suggest that the rate limiting step in quinonoid intermediate formation from indole and the aminoacrylate intermediate is deprotonation.