Self-assembly of three new coordination complexes: Formation of 2-D square grid, 1-D chain and tape structures

Three distinct coordination complexes, viz., [Co(imi)(2)(tmb)(2)] (1) [where imi = imidazole], {[Ni(tmb)(2)(H2O)(3)]center dot 2H(2)O}(n) (2) and [Cu-2(mu-tmb)(4)(CH3OH)(2)] (3), have been synthesized hydrothermally by the reactions of metal acetates,2,4,6-trimethylbenzoic acid (Htmb) and with or without appropriate amine. The Ni analogue of 1 and the Co analogue of 2 have also been synthesized. X-ray single-crystal diffraction suggests that complex 1 represents discrete mononuclear species and complex 2 represents a 1D chain coordination polymer in which the Ni(H) ions are connected by the bridging water molecules. Complex 3 represents a neutral dinuclear complex. In 1, the central metal ions are associated by the carboxylate moiety and imidazole ligands, whereas the central metal atom is coordinated to the carboxylate moiety and the respective solvent molecules in 2 and 3. In 3, the four 2,4,6-trimethylbenzoate moieties act as a bridge connecting two copper (11) ions and the 0 atoms of methanol coord geometry, with the methanol molecule at the apical position. In all the three structures the central metal atom sits on a crystallographic inversion centre. In all the cases, the coordination entities are further organized via hydrogen bonding interactions to generate multifarious supramolecular networks. Complexes 1, 2 and 3 have also been characterized by spectroscopic (UV/Vis and IR) and thermal analysis (TGA). In addition, the complexes were found to exhibit antimicrobial activity. The magnetic susceptibility measurements, measured from 8 to 300 K, revealed antiferromagnetic interactions between the Co(II) ions in compound 1 and the Ni(II) ions in la, respectively.

A comparison of welfare outcomes for weaner and mature Bos indicus bulls surgically or tension band castrated with or without analgesia: 2. Responses related to stress, health and productivity

Tension banding castration of cattle is gaining favour because it is relatively simple to perform and is promoted by retailers of the banders as a humane castration method. Two experiments were conducted, under tropical conditions using Bos indicus bulls comparing tension banding (Band) and surgical (Surgical) castration of weaner (7–10 months old) and mature (22–25 months old) bulls with and without pain management (NSAID (ketoprofen) or saline injected intramuscularly immediately prior to castration). Welfare outcomes were assessed using a range of measures; this paper reports on some physiological, morbidity and productivity-related responses to augment the behavioural responses reported in an accompanying paper. Blood samples were taken on the day of castration (day 0) at the time of restraint (0 min) and 30 min (weaners) or 40 min (mature bulls), 2 h, and 7 h; and days 1, 2, 3, 7, 14, 21 and 28 post-castration. Plasmas from day 0 were assayed for cortisol, creatine kinase, total protein and packed cell volume. Plasmas from the other samples were assayed for cortisol and haptoglobin (plus the 0 min sample). Liveweights were recorded approximately weekly to 6 weeks and at 2 and 3 months post-castration. Castration sites were checked at these same times to 2 months post-castration to score the extent of healing and presence of sepsis. Cortisol concentrations (mean ± s.e. nmol/L) were significantly (P < 0.05) higher in the Band (67 ± 4.5) compared with Surgical weaners (42 ± 4.5) at 2 h post-castration, but at 24 h post-castration were greater in the Surgical (43 ± 3.2) compared with the Band weaners (30 ± 3.2). The main effect of ketoprofen was on the cortisol concentrations of the mature Surgical bulls; concentrations were significantly reduced at 40 min (47 ± 7.2 vs. 71 ± 7.2 nmol/L for saline) and 2 h post-castration (24 ± 7.2, vs. 87 ± 7.2 nmol/L for saline). Ketoprofen, however, had no effect on the Band mature bulls, with their cortisol concentrations averaging 54 ± 5.1 nmol/L at 40 min and 92 ± 5.1 nmol/L at 2 h. Cortisol concentrations were also significantly elevated in the Band (83 ± 3.0 nmol/L) compared with Surgical mature bulls (57 ± 3.0 nmol/L) at weeks 2–4 post-castration. The timing of this elevation coincided with significantly elevated haptoglobin concentrations (mg/mL) in the Band bulls (2.97 ± 0.102 for mature bulls and 1.71 ± 0.025 for weaners, vs. 2.10 ± 0.102 and 1.45 ± 0.025 respectively for the Surgical treatment) and evidence of slow wound healing and sepsis in both the weaner (0.81 ± 0.089 not healed at week 4 for Band, 0.13 ± 0.078 for Surgical) and mature bulls (0.81 ± 0.090 at week 4 for Band, 0.38 ± 0.104 for Surgical). Overall, liveweight gains of both age groups were not affected by castration method. The findings of acute pain, chronic inflammation and possibly chronic pain in the mature bulls at least, together with poor wound healing in the Band bulls support behavioural findings reported in the accompanying paper and demonstrate that tension banding produces inferior welfare outcomes for weaner and mature bulls compared with surgical castration.

Isotope shifts and hyperfine structure in the 555.8-nm S-1(0) -> P-3(1) line of Yb

We apply our technique of using a Rb-stabilized ring-cavity resonator to measure the frequencies of various spectral components in the 555.8-nm 1S0-->3P1 line of Yb. We determine the isotope shifts with 60 kHz precision, which is an order-of-magnitude improvement over the best previous measurement on this line. There are two overlapping transitions, 171Yb(1/2-->3/2) and 173Yb(5/2-->3/2), which we resolve by applying a magnetic field. We thus obtain the hyperfine constants in the 3P1 state of the odd isotopes with a significantly improved precision. Knowledge of isotope shifts and hyperfine structure should prove useful for high-precision calculations in Yb necessary to interpret ongoing experiments testing parity and time-reversal symmetry violation in the laws of physics.

The Feeding Practices and Structure Questionnaire (FPSQ-28): A parsimonious version validated for longitudinal use from 2-5 years

Prospective studies and intervention evaluations that examine change over time assume that measurement tools measure the same construct at each occasion. In the area of parent-child feeding practices, longitudinal measurement properties of the questionnaires used are rarely verified. To ascertain that measured change in feeding practices reflects true change rather than change in the assessment, structure, or conceptualisation of the constructs over time, this study examined longitudinal measurement invariance of the Feeding Practices and Structure Questionnaire (FPSQ) subscales (9 constructs; 40 items) across 3 time points. Mothers participating in the NOURISH trial reported their feeding practices when children were aged 2, 3.7, and 5 years (N = 404). Confirmatory Factor Analysis (CFA) within a structural equation modelling framework was used. Comparisons of initial cross-sectional models followed by longitudinal modelling of subscales, resulted in the removal of 12 items, including two redundant or poorly performing subscales. The resulting 28-item FPSQ-28 comprised 7 multi-item subscales: Reward for Behaviour, Reward for Eating, Persuasive Feeding, Overt Restriction, Covert Restriction, Structured Meal Setting and Structured Meal Timing. All subscales showed good fit over 3 time points and each displayed at least partial scalar (thresholds equal) longitudinal measurement invariance. We recommend the use of a separate single item indicator to assess the family meal setting. This is the first study to examine longitudinal measurement invariance in a feeding practices questionnaire. Invariance was established, indicating that the subscales of the shortened FPSQ-28 can be used with mothers to validly assess change in 7 feeding constructs in samples of children aged 2-5 years of age.

Child dietary and eating behaviour outcomes up to 3.5 years after an early feeding intervention: the NOURISH RCT

- Objective To evaluate dietary intake impact outcomes up to 3.5 years after the NOURISH early feeding intervention (concealed allocation, assessor masked RCT). - Methods 698 first-time mothers with healthy term infants were allocated to receive anticipatory guidance on protective feeding practices or usual care. Outcomes were assessed at 2, 3.7 and 5 years (3.5 years post-intervention). Dietary intake was assessed by 24-hour recall and Child Dietary Questionnaire. Mothers completed a food preference questionnaire and Children’s Eating Behaviour Questionnaire. Linear mixed models assessed group, time and time x group effects. - Results There were no group or time x group effects for fruit, vegetables, discretionary food and non-milk sweetened beverages intake. Intervention children showed a higher preference for fruits (74.6% vs 69.0% liked, P<.001), higher Child Dietary Questionnaire score for fruit and vegetables (15.3 vs 14.5, target>18, P=0.03), lower food responsiveness (2.3 vs 2.4, of maximum 5, P=.04) and higher satiety responsiveness (3.1 vs 3.0, of maximum 5, P=.04). - Conclusions Compared to usual care, an early feeding intervention providing anticipatory guidance regarding positive feeding practices led to small improvements in child dietary score, food preferences and eating behaviours up to 5 years of age, but not in dietary intake measured by 24-hour recall.

A comparative study of the early effects of phenobarbital and 3-methylcholanthrene on the synthesis and transport of ribonucleic acid in rat liver.

At 2-3 h after phenobaribtal administration, the drug has no effect on nucleoplasmic RNA synthesis and decreases nucleolar RNA synthesis. However, at this time there is an increase in the labelling of cytoplasmic poly(A)-containing RNA, even though there is decreased labelling of total polyribosomal RNA. The decrease in labelling of nucleolar and total polyribosomal RNA owing to phenobarbital is a transient phenomenon. Under similar conditions, 3-methylcholanthrene has no effect on nucleolar RNA synthesis, but leads to an increase in synthesis of nucleoplasmic and cytoplasmic poly(A)-containing RNA. Cytosol isolated from phenobarbital-treated, but not from 3-methyl-cholanthrene-treated, animals facilitates an enhanced transport of RNA from nuclei. At the time points investigated, 3-methylcholanthrene or its metabolite shows a 10-15-fold higher concentration in the chromatin than that of phenobarbital or its metabolite. It is suggested that the primary effect of phenobarbital is at the cytoplasmic level, promoting the transport of RNA from the nuclei, which can act as a trigger for enhanced transcription at later periods. 3-Methylcholanthrene or its metabolite directly binds to the chromatin and evokes a selective transcriptional response.

Purification and properties of protocatechuate-3,4-dioxygenase from Tecoma stans L

Protocatechuate-3,4-dioxygenase from the leaves of Tecoma stans was purified to near homogeneity and some of its properties studied. It was optimally active at pH 5.2 and at 40°C. Its molecular weight of approx. 150 000 was determined by gel filtration on a Sephadex G-150 column. The Km value for protocatechuate was found to be 330 μM and for ferrous sulfate, 40 μM. The enzyme was highly specific for protocatechuate and did not attack any of the substrate analogues. None of the substrate analogues tested inhibited the enzyme activity. Sulfhydryl reagents inhibited the enzyme activity which could be partially reversed by sulfhydryl compounds. The dioxygenase activity was not associated with polyphenol oxidase activity.

Interaction of substrate uridyl 3',5'-adenosine with ribonuclease A:a molecular dynamics study

A wealth of information available from x-ray crystallographic structures of enzyme-ligand complexes makes it possible to study interactions at the molecular level. However, further investigation is needed when i) the binding of the natural substrate must be characterized, because ligands in the stable enzyme-ligand complexes are generally inhibitors or the analogs of substrate and transition state, and when ii) ligand binding is in part poorly characterized. We have investigated these aspects i? the binding of substrate uridyl 3',5'-adenosine (UpA) to ribonuclease A (RNase A). Based on the systematically docked RNase A-UpA complex resulting from our previous study, we have undertaken a molecular dynamics simulation of the complex with solvent molecules. The molecular dynamics trajectories of this complex are analyzed to provide structural explanations for varied experimental observations on the ligand binding at the B2 subsite of ribonuclease A. The present study suggests that B2 subsite stabilization can be effected by different active site groups, depending on the substrate conformation. Thus when adenosine ribose pucker is O4'-endo, Gln69 and Glu111 form hydrogen-bonding contacts with adenine base, and when it is C2'-endo, Asn71 is the only amino acid residue in direct contact with this base. The latter observation is in support of previous mutagenesis and kinetics studies. Possible roles for the solvent molecules in the binding subsites are described. Furthermore, the substrate conformation is also examined along the simulation pathway to see if any conformer has the properties of a transition state. This study has also helped us to recognize that small but concerted changes in the conformation of the substrate can result in substrate geometry favorable for 2',3' cyclization. The identified geometry is suitable for intraligand proton transfer between 2'-hydroxyl and phosphate oxygen atom. The possibility of intraligand proton transfer as suggested previously and the mode of transfer before the formation of cyclic intermediate during transphosphorylation are discussed.

Anaerobic DNA cleavage activity in red light and photocytotoxicity of (pyridine-2-thiol)cobalt(III) complexes of phenanthroline bases

Cobalt(III) complexes [Co(pnt)(B)(2)](NO3)(2) (1-3) of pyridine-2-thiol (pnt) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyrido[3,2-d: 2',3'-f]quinoxaline (dpq in 2) and dipyrido[3,2-a:2',3'-c] phenazine (dppz in 3), have been prepared, characterized and their photo-induced anaerobic DNA cleavage activity studied. The crystal structure of 1a as mixed ClO4- and PF6- salt of 1 shows a (CoN5S)-N-III coordination geometry in which the pnt and phen showed N,S- and N,N-donor binding modes, respectively. The complexes exhibit Co(III)/Co(II) redox couple near -0.3 V (vs. SCE) in 20% DMF-Tris-HCl buffer having 0.1 M TBAP. The complexes show binding propensity to calf thymus DNA giving K-b values within 2.2 x 10(4)-7.3 x 10(5) M-1. Thermal melting and viscosity data suggest DNA surface and/or groove binding of the complexes. The complexes show significant anaerobic DNA cleavage activity in red light under argon atmosphere possibly involving sulfide anion radical or thiyl radical species. The DNA cleavage reaction under aerobic medium in red light is found to involve both singlet oxygen and hydroxyl radical pathways. The dppz complex 3 shows non-specific BSA and lysozyme protein cleavage activity in UV-A light of 365 nm via both hydroxyl and singlet oxygen pathways. The dppz complex 3 exhibits photocytotoxicity in HeLa cervical cancer cells giving IC50 values of 767 nM and 19.38 mu M in UV-A light of 365 nm and in the dark, respectively. A significant reduction of the dark toxicity of the dppz base (IC50 = 8.34 mu M in dark) is observed on binding to the cobalt(III) center.

Experimental studies on a two stage pulse tube cryocooler reaching 2.5K

A two stage Pulse Tube Cryocooler (PTC) is designed and fabricated which reaches a no-load temperature of 2.5K in the second stage and similar to 60 K in the first stage respectively. The system provides a cooling power of similar to 250 mW at 5K in the second stage. Stainless steel meshes (size 200) and lead (Pb) granules are used as the first stage regenerator materials and combination of Pb with Er3Ni / HoCu2 are used as the second stage regenerator materials. The system operates at 1.6 Hz using a 6 kW water cooled helium compressor. Studies conducted by varying the dimensions of Pulse Tubes and regenerators show that the dimensions of the Pulse Tubes are more critical to the performance of the Cryocooler than those of the regenerators. Experimental studies show that the optimum volume ratios of Er3Ni to Pb and HoCu2 to Pb in the second stage regenerator should be 3:2 and 2:3 respectively for the best performance. Further, systems with HoCu2 performed better than those with Er3Ni. The theoretical analysis of the system has been carried out using a simple isothermal model. The experimentally measured cooling powers are in good agreement with the theoretical predictions.

Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II)complexes(1-5)ofdi2pyridylketoneN(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Structural and spectral investigations on some new Ni(II) complexes of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone

Ni(II) complexes (1-5) of di-2-pyridyl ketone N(4)-phenylthiosemicarbazone (HL) have been synthesized and spectrochemically characterized. Elemental analyses revealed a NiL2 center dot 2H(2)O stoichiometry for compound 1. However, the single crystals isolated revealed a composition NiL, - 0.5(H,0)0.5(DMF). The compound crystallizes into a monoclinic lattice with the space group P-21/n. Complexes 2. 3 and 4 are observed to show a 1:1:1 ratio of metal: thioseicarbazone:gegenion, with the general formula NiLX center dot yH(2)O [X = NCS. Y = 2 for 2; X = Cl, Y = 3 for 3 and X = N-3, y = 4.5 for 4]. Compound 5 is a dimer with a metal:thiosemicarbazone:gegenion ratio of 2:2: 1. with the formula [Ni,L,(SO4)1 - 4H(2)O (c) 2007 Elsevier Ltd. All rights reserved.

Metal-ion-mediated tuning of duplex DNA binding by bis(2-(2-pyridyl)-1H-benzimidazole)

Studies of double-stranded-DNA binding have been performed with three isomeric bis)2-(n-pyridyl)-1H-benzimidazole)s (n = 2, 3, 4). Like the well-known Hoechst 33258, which is a bisbenzimidazole compound, these three isomers bind to the minor groove of duplex DNA. DNA binding by the three isomers was investigated in the presence of the divalent metal ions Mg2+, Co2+, Ni2+, Cu2+, and Zn2+. Ligand-DNA interactions were probed with fluorscence and circular dichroism spectroscopy. These studies revealed that the binding of the 2-pyridyl derivative to DNA is dramatically reduced in the presence of Co2+, Ni2+, and Cu2+ ions and is abolished completely at a ligand/metal-cation ratio of 1:1. Control experiments done with the isomeric 3- and 4-pyridyl derivatives showed that their binding to DNA is unaffected by the aforementioned transition-metal ions. The ability of 2-(2-pyridyl)benzimidazole changes of the ligand associated with ion chelation probably ledto such unusual binding results for the ortho isomer. The addition of ethylenediaminetetraacetic acid (EDTA) reversed the effects completely.

Exclusion of an Exotic Top Quark with -4/3 Electric Charge Using Soft Lepton Tagging

We present a measurement of the electric charge of the top quark using $\ppbar$ collisions corresponding to an integrated luminosity of 2.7~fb$^{-1}$ at the CDF II detector. We reconstruct $\ttbar$ events in the lepton+jets final state and use kinematic information to determine which $b$-jet is associated with the leptonically- or hadronically-decaying $t$-quark. Soft lepton taggers are used to determine the $b$-jet flavor. Along with the charge of the $W$ boson decay lepton, this information permits the reconstruction of the top quark's electric charge. Out of 45 reconstructed events with $2.4\pm0.8$ expected background events, 29 are reconstructed as $\ttbar$ with the standard model $+$2/3 charge, whereas 16 are reconstructed as $\ttbar$ with an exotic $-4/3$ charge. This is consistent with the standard model and excludes the exotic scenario at 95\% confidence level. This is the strongest exclusion of the exotic charge scenario and the first to use soft leptons for this purpose.

Indoleacetaldoxime hydro-lyase (4.2.1.29). III. Further studies on the nature and mode of action of the enzyme

Further purification of indoleacetaldoxime (IAOX) hydro-lyase from Gibberella fujikuroi by DEAE-cellulose chromatography is described. The purified enzyme was activated by dehydroascorbic acid (DHA), ascorbic acid (AA), and pyridoxal phosphate (PALP) and was inhibited by thiol compounds and thiol reagents including phenylthiocyanate. Ferrous ions but not ferric ions activated the purified enzyme. The enzyme was activated by dihydrofolic acid but inhibited by tetrahydrofolic acid. Phenylacetaldoxime, a competitive inhibitor, afforded partial protection of the enzyme from the action of N-ethylmaleimide suggesting the involvement of a thiol function at the active site or substrate-binding site. The inhibition of the enzyme by 2,3-dimercaptopropanol was reversed by DHA, PALP, or frozen storage. KCN inhibition of the enzyme was reversed by PALP. NaBH4 reduction of the purified enzyme in the presence of PALP gave an active enzyme which was further activated by PALP or DHA but not by ferrous ions. These results suggested a "structural" role for PALP in the activity of IAOX hydro-lyase. Dilute solutions of the purified enzyme, obtained during DEAE-cellulose chromatography and concentrated using sucrose, showed enhanced activity upon frozen storage and thawing. The increase in activity of the enzyme during certain culture conditions, the activation and inhibition of the enzyme by several unrelated compounds, and the effect of freezing indicate that IAOX hydro-lyase is probably a metabolically regulated enzyme with a structure composed of subunits.