Relationships between the plasma concentrations of insulin-like growth factor-I in dairy cows and their fertility and milk yield

The relationships between insulin-like growth factor-I (IGF-I) and the fertility and milk yield of Holstein-Friesian dairy cows were investigated. The concentration of IGF-I in blood was measured weekly from one week before to 12 weeks after calving in 177 multiparous cows and at four times during this period in 142 primiparous cows; the concentration of IGF-I in milk was measured in 50 of the multiparous cows. The plasma concentrations of IGF-I were higher in the primiparous than in the multiparous animals. in the primiparous cows, high concentrations of IGF-I before calving were associated with longer calving to conception intervals. Conversely, in the multiparous cows low concentrations of IGF-I before and after calving were associated with a failure to conceive, despite repeated services. Multiparous cows with IGF-I concentrations of greater than 25 ng/ml in the week after calving were 11 times more likely to conceive to first service than those with lower concentrations. Concentrations of IGF-I greater than 50 ng/ml at first service increased the likelihood of conception five-fold. Cows with higher peak milk yields had lower plasma concentrations of IGF-I and took longer to return to ovarian cyclicity. The negative relationship between milk yield and return to cyclicity was stronger in the multiparous cows (P<0(.)002) than in the primiparous cows (P<0(.)04). The concentrations of IGF-I in milk followed a different pattern and were not associated with the changes in plasma IGF-I or fertility.

Stabilisation of two Cu(I)-amino N bonds in presence of imino N's

Two structurally characterised examples of air stable Cu-1 (amino N)(2)(imino N)(2) chromophores having a Cu(II/I) potential of 0.01-0.19 V vs SCE in CH2Cl2 are provided using two tetradentate N-donor ligands.

Mixed ligand binuclear copper(I) complexes containing (Cu2N8)-N-I chromophores. Observation of emissions from MLCT excited states involving two different ligands

Using the 1:2 condensate (L) of diethylenetriamine and benzaldehyde as the main ligand, binuclear copper(l) complexes [Cu2L2(4,4'-bipyridine)](CIO4)(2).0.5H(2)O (1a) and [Cu2L2(1,2-bis(4-pyridyl)ethane)](CIO4)(2) (1b) are synthesised. The two metal ions in la are bridged by 4,4'-bipyridine and those in 1b by 1,2-bis(4-pyridyl)ethane, From the X-ray crystal structure of la, each metal ion is found to be bound to three N atoms of L and one of the two N atoms of the bridging ligand in a distorted tetrahedral fashion. The Cu(I)-N bond lengths in la lie in the range of 1.998(5)-2.229(6) Angstrom. Electrochemical studies in dichloromethane (DCM) show that the (Cu2N8)-N-I moieties in la and 1b are composed of two essentially non-interacting (CuN4)-N-I cores with Cu-II/I potential of 0.44 V vs. SCE. While la displays metal induced quenching of the inherent emission of 4,4'-bipyridine in DCM solution, 1b exhibits two weak emission bands in DCM solution at 425 and 477 nm (total quantum yield = 3.59 x 10(-5)) originating from MLCT excited states. With the help of Extended Huckel calculations it is established that the higher energy emission in 1b is from Cu(I) --> bridging-ligand charge transfer excited state and the lower energy one in 1b from Cu(I) --> L charge transfer excited state.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Divinyldisiloxane and divinylsilane complexes of rhodium(I)

Reaction of the tetrakis(cyclooctene)rhodium(I) complex [{Rh(C8H14-c)2(μ-Cl)}2] with the appropriate divinyldisiloxane molecules (ViSiR2)2O (R=Me or Ph) yields, by displacement of the cycloctene ligands, the complexes [{Rh(ViSiR2)2O(μ-Cl)}2] (R=Me (1) or Ph (2)). These react further with a tertiary phosphine PR3 to give cis-[Rh{(ViSiR2)2O}(PR′3)Cl] (R′=Ph or C6H4Me-p). The complex cis-[{Rh(Vi2SiMe2)(μ-Cl)}2] (7) was similarly prepared by the displacement of ethylene from [{Rh(C2H4)2(μ-Cl)}2] by the divinyldimethylsilane Vi2SiMe2. X-ray molecular structures of the crystalline complexes 1, 2 and 7 show a distorted square planar Rh(I) environment, the CH2CH groups being orthogonal to this plane; 1 and 2 have the Rh–(ViSiR2)2O metallacycle in the chair conformation, but differ in the nature of the central Rh(Cl)RhCl core, which is planar for 1 and puckered for 2, but each of 1 and 2 is the rac-diastereoisomer, whereas 7 has the meso-configuration. In solution 1 and 2 exist as a mixture of isomers, probably the rac- and meso-pairs as established by multinuclear NMR spectral studies. A series of saturation transfer NMR spectroscopic experiments showed that the divinyldisiloxane ligands in [{Rh(ViSiPh2)2O(μ-Cl)}2] underwent a dynamic process involving the dissociation, rotation and then reassociation of the vinyl groups.

A hydrogen-1 nuclear magnetic resonance, mass spectral and extended Hückel study of some olefin complexes of rhodium(I) and iridium(I) and the crystal and molecular structure of η4-2,4-dimethylpenta-1,4-diene(η5-formylcyclopentadienyl)rhodium(I)

A 1H NMR study of monosubstituted η-cyclopentadienyl-rhodium(I) complexes of type LLRh(C5H4X) and -iridium(I) complexes of type L2Ir(C5H4X) (L = ethene, LL = 1,3- or 1,5-diolefin; X = C(C6H5)3, CHO, or COOCH3) has been carried out. For complexes of both metals in which the neutral ligand is ethene or a non-conjugated diolefin the NMR spectra of the cyclopentadienyl protons are unusual in that H(2), H(5) resonate to high field either at room temperature or below. The corresponding NMR spectra for the cyclopentadienyl ring protons of complexes where the neutral ligand is a conjugated diene are, with one exception, normal. A single crystal X-ray structural analysis of (η4-2,4-dimethylpenta-1,4-diene)(η5-formylcyclopentadienyl)rhodium(I) (which exhibits an abnormal 1H NMR spectrum) reveals substantial localisation of electron density in the C(3)C(4) Cp ring bond (1.283(33) Å) which may be consistent with a contribution from an ‘allyl-ene’ rotamer to the ring—metal bonding scheme. An extended Hückel calculation with self consistent charge iteration was performed on this complex. The results predict a greater Mulliken overlap population for the C(3)C(4) bond in the cyclopentadienyl ring and show that the localisation is dependent on both the Cp ring substituent and the nature of the diolefin. The mass spectral fragmentation patterns of some representative diene complexes of iridium(I) and rhodium(I) are presented.

Mononuclear palladium and heterodinuclear palladium–ruthenium complexes of semicarbazone ligands: synthesis, characterization, and application in C–C cross-coupling reactions

Reaction of salicylaldehyde semicarbazone (L-1), 2-hydroxyacetophenone semicarbazone (L-2), and 2-hydroxynaphthaldehyde semicarbazone (L-3) with [Pd(PPh3)(2)Cl-2] in ethanol in the presence of a base (NEt3) affords a family of yellow complexes (1a, 1b and 1c, respectively). In these complexes the semicarbazone ligands are coordinated to palladium in a rather unusual tridentate ONN-mode, and a PPh3 also remains coordinated to the metal center. Crystal structures of the 1b and 1c complexes have been determined, and structure of 1a has been optimized by a DFT method. In these complexes two potential donor sites of the coordinated semicarbazone, viz. the hydrazinic nitrogen and carbonylic oxygen, remain unutilized. Further reaction of these palladium complexes (1a, 1b and 1c) with [Ru(PPh3)(2)(CO)(2)Cl-2] yields a family of orange complexes (2a, 2b and 2c, respectively). In these heterodinuclear (Pd-Ru) complexes, the hydrazinic nitrogen (via dissociation of the N-H proton) and the carbonylic oxygen from the palladium-containing fragment bind to the ruthenium center by displacing a chloride and a carbonyl. Crystal structures of 2a and 2c have been determined, and the structure of 2b has been optimized by a DFT method. All the complexes show characteristic H-1 NMR spectra and, intense absorptions in the visible and ultraviolet region. Cyclic voltammetry on all the complexes shows an irreversible oxidation of the coordinated semicarbazone within 0.86-0.93 V vs. SCE, and an irreversible reduction of the same ligand within -0.96 to -1.14 V vs. SCE. Both the mononuclear (1a, 1b and 1c) and heterodinuclear (2a, 2b and 2c) complexes are found to efficiently catalyze Suzuki, Heck and Sonogashira type C-C coupling reactions utilizing a variety of aryl bromides and aryl chlorides. The Pd-Ru complexes (2a, 2b and 2c) are found to be better catalysts than the Pd complexes (1a, 1b and 1c) for Suzuki and Heck coupling reactions.

Effect of an ancillary ligand on single helix-double helix interconversion in copper complexes. Copper(I)-water bond

Reaction of Cu(ClO(4))(2)center dot 6H(2)O with the 1:2 condensate of benzildihydrazone and 2-acetylpyridine, in methanol in equimolar ratio yields a green compound which upon recrystallisation from 1:1 CH(2)Cl(2)-C(6)H(6) mixture affords [CuL(H(2)O)](ClO(4))(2)center dot 1/2C(6)H(6). The complex crystallises in the space group P-1 with a = 8.028(11) angstrom, b = 12.316(17) angstrom, c = 18.14(3) angstrom, alpha = 97.191(10)degrees, beta = 94.657(10)degrees and gamma = 108.039(10)degrees. It is single helical with the metal having a distorted trigonal bipyramidal N(4)O coordination sphere. The acid dissociation constant of the Cu(I) complex in CH(3)CN is 3.34 +/- 0.19. The X band EPR spectrum of the compound is rhombic with g(1) = 2.43, g(2) = 2.10 g(3) = 2.02 and A(1) = 79.3 x 10(-4) cm(-1). The Cu(II/I) potential of the complex in CH(2)Cl(2) at a glassy carbon electrode is 0.43 V vs SCE. It is argued that the copper-water bond persists in the corresponding copper(I) species. Its implications on the single helix-double helix interconversion in copper helicates are discussed. DFT calculations at the B3LYP/6-311G** level shows that the binding energy of water in the single helicol live-coordinate copper(I) species [CuL(H(2)O)](+) is similar to 40 kJ mol(-1).

Structure and stability of two polymorphs of creatine and its monohydrate

An experimental search for crystalline forms of creatine including a variable temperature X-ray powder diffraction study has produced three polymorphs and a formic acid solvate. The crystal structures of creatine forms I and II were determined from X-ray powder diffraction data plus the creatine formic acid (1 : 1) solvate structure was obtained by single crystal X-ray diffraction methods. Evidence of a third polymorphic form of creatine obtained by rapid desolvation of creatine monohydrate is also presented. The results highlight the role of automated parallel crystallisation, slurry experiments and VT-XRPD as powerful techniques for effective physical form screening. They also highlight the importance of various complementary analytical techniques in structural characterisation and in achieving better understanding of the relationship between various solid-state forms. The structural relationships between various solid-state forms of creatine using the XPac method provided a rationale for the different relative stabilities of forms I and II of creatine with respect to the monohydrate form.

Spatial distribution of Diaphorina citri Kuwayama (Hemiptera: Psyllidae) in citrus orchards

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Orange juice improved lipid profile and blood lactate of overweight middle-aged women subjected to aerobic training

Objective This study investigated how consumption of orange juice associated with aerobic training affected serum lipids and physical characteristics of overweight middle-aged womenMethods The experimental group consisted of 13 women who consumed 500 mL/d of orange juice and did 1 h aerobic training 3 times a week for 3 months The control group consisted of another 13 women who did the same aerobic training program but did not consume orange juiceResults At the end of the experiment the control group lost an average of 15% of fat mass (P < 0 05) and 25% of weight (P < 0 05) whereas the experimental group lost 11% of fat mass and 1 2% of weight (P < 0 05) Consumption of orange juice by the experimental group was associated with Increased dietary intake of vitamin C and folate by 126% and 61% respectively Serum LDL-C decreased 15% (P < 0 05) and HDL-C increased 18% (P < 0 05) in the experimental group but no significant change was observed in the control group Both groups improved the anaerobic threshold by 20% (P < 0 05) but blood lactate concentration decreased 27% in the experimental group compared to the 17% control group suggesting that experimental group has less muscle fatigue and better response to trainingConclusions The consumption of 500 mL/d of orange juice associated with aerobic training in overweight women decreased cardiovascular disease risk by reducing LDL-C levels and increasing HDL-C levels This association also decreased blood lactate concentration and increased anaerobic threshold showing some improvement in the physical performance (C) 2010 Elsevier B.V. All rights reserved

The central repeat domain 1 of Kaposi's sarcoma-associated herpesvirus (KSHV) latency associated-nuclear antigen 1 (LANA1) prevents cis MHC class I peptide presentation

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Influence of physical and chemical factors during foraging and culture of the symbiont fungus in Atta sexdens rubropilosa (Hymenoptera : Formicidae)

The aim of this paper is to investigate the influence of physical and chemical factors on transport and use of substrate for Atta sexdens rubropilosa workers. Three types of rectangular fragments were used to study the physical influence factors: filter paper with paraffin, filter paper without paraffin and polyester film. To study the chemical factors, some fragments were impregnated with organic extract of orange albedo, others were soaked with soybean oil and for the remaining ones nothing was applied. The following parameters were evaluated: (i) attractiveness of substrate for transport and number of loading workers per treatment; (ii) foraged material incorporation; (iii) rejection by numbers of fragments deposited in the garbage or beside the fungus garden. All the polyester film fragments carried out to the fungus garden were subsequently rejected. We verified that chemical factors of the substrate were more quickly detected by the workers, whereas physical factors were used as a criterion in the decision-making to reject or accept the substrate collected.