Influence of an Oriented External Electric Field on the Mechanism of Double Proton Transfer between Pyrazole and Guanidine: from an Asynchronous Plateau Transition State to a Synchronous or Stepwise Mechanism.

The double proton transfer (DPT) reaction between pyrazole and guanidine, a concerted reaction but strongly asynchronous and presenting a "plateau transition region", has been theoretically reinvestigated in the presence of an external uniform electric field. First, we computed the reaction path by DFT and proposed a very detailed description of the constitutive electronic events, based on the ELF topology and the bond evolution theory. Then, we studied the effect of an oriented external electric field (OEEF) on the reaction mechanism, for an OEEF oriented along the proton transfer axis. We observe that in one direction, the DPT reaction can be transformed into a stepwise reaction, going through a stabilized single proton transferred intermediate. Contrarily, the two proton transfers occur simultaneously when the electric field is applied in the opposite direction. In the latter case, the order in which the two protons are transferred in the same elementary step can even be reversed if the OEEF is intense enough. Finally, it has been shown that the evolution of the double proton transfer reaction in the presence of an electric field could be quantitatively anticipated by analyzing the ELF value at the bifurcation point between V(A, H) proton donor and V(B) proton acceptor of the double hydrogen bonded complex in the entrance channel.

Infrared Spectroscopy and Density Functional Theory Investigations of the Reactivity of Titanium Atoms with Carbon Monoxide and Water Isolated in Solid Argon: Sequential Evolution from Triplet to Singlet State.

Thermally evaporated titanium atoms reacted with carbon monoxide and water in solid argon at 12 K to produce the HTiOH-CO and HTiOH-(CO)2 molecules, which were characterized using infrared spectroscopy on the basis of CO, Ti, and water concentration variations and of isotopic substitutions. The insertion product, HTiOH, resulting from the reaction of a titanium atom with a water molecule reacts with CO spontaneously to give the HTiOH-CO molecule, which in turn reacts with a second CO molecule to give HTiOH-(CO)2 The density functional theory calculations were performed to elucidate the geometrical and electronic structures and support the spectral assignments. The topological analysis of the charge density within the experimentally observed molecules allowed us to rationalize the coordination sphere as well as the electron pairing on the titanium center.

Effects of hydrolyzed cottonseed protein supplementation on performance, blood metabolites, gastrointestinal development, and intestinal microbial colonization in neonatal calves.

The objective of this study was to investigate the effects of an enzymatically hydrolyzed cottonseed protein (HCSP) as a peptide source on performance, blood metabolites, gastrointestinal development, and intestinal microbes. Forty-eight newborn Holstein calves were randomly assigned to 1 of the 4 dietary treatments including 0, 2, 4, and 6% of HCSP (dry matter basis). All calves received the same amount of pasteurized whole milk, weaned on d 56 of the experiment, and the study was concluded on d 70. Data were analyzed using PROC MIXED in SAS (SAS Institute Inc., Cary, NC) as a randomized complete block design with linear and quadratic contrasts. Results showed that increased amount of HCSP linearly decreased the starter intake during the postweaning (d 57 to 70) and overall period (d 1 to 70). In addition, when dietary HCSP increased during the overall period, average daily gain tended to linearly decrease. All skeletal growth variables also linearly decreased as dietary HCSP increased at the end of the study, except for body length, which did not differ among the treatments. Serum cortisol concentration was higher in calves supplemented with 6% of HCSP at weaning and at the end of the study. This indicates that these calves may have experienced a stressful condition compared with calves in other treatments. Total antioxidant capacity was quadratically affected by HCSP supplementation; calves fed 2 and 4% of HCSP diets had the highest total antioxidant capacity, whereas calves fed 0 and 6% HCSP diets had lower total antioxidant capacity at weaning and at end of the study. Calves supplemented with 6% HCSP had lower empty reticulo-rumen and omasum weights and rumen wall thickness compared with calves in other treatments at the end of the study. In conclusion, supplementation of HCSP at the rate of 2% of starter diet enhanced antioxidant status without any detrimental effects on the performance and metabolic status of calves, whereas greater inclusion rates impaired starter intake and growth of calves, and exposed them to a stressful status.

Infrared Spectroscopy and Density Functional Theory Investigations of PdTi Heterodimer Reactivity with Carbon Monoxide Isolated in Solid Argon.

The reactivity of diatomic palladium-titanium toward carbon monoxide has been studied in solid argon by infrared spectroscopy (Fourier transform infrared) in the carbonyl stretching frequency region. Our technique of sublimation of Ti and Pd atoms from two filaments heated separately allowed the identification of five new molecules. Small polynuclear carbonyl clusters, PdTi(CO) n ( n = 1-3), have been characterized on the basis of isotopic substitutions, metal atom and CO concentration variations, and irradiation effects. Selective irradiation in the visible region leads to conversion between two isomers distinguished by the stretching frequency of the diatomic CO: PdTiCO Ti-eo (νCO = 1908.4 cm-1) and PdTiCO Pd-eo (νCO = 2009.3 cm-1). The density functional theory calculations have been carried out to elucidate the geometrical and electronic structures and support the spectral assignments. The nature of the metal-carbon bonding has been discussed using the topology of the Laplacian of the electron density.

Adjusting for 30-hour undigested neutral detergent fiber in substitution of wheat straw and beet pulp for alfalfa hay and corn silage in the diet of high-producing cows.

This study examined the feeding effects of wheat straw (WS) and beet pulp (BP) substituted for corn silage (CS) and alfalfa hay (AH) based on forage 30-h undigested neutral detergent fiber (uNDF30) on lactation performance in high-producing dairy cows. Twelve multiparous (body weight = 611 ± 31 kg, days in milk = 97 ± 13; 51 ± 3 kg/d of milk; mean ± standard error) Holstein cows were used in a replicated 3 × 3 Latin square design with 28-d periods. Three treatments were established by substituting WS for CS and AH such that the concentration of forage uNDF30 in all diets was the same. The treatments were (1) 0% forage uNDF30 from WS (WS0; control), (2) 50% forage uNDF30 from WS (WS50), and (3) 100% forage uNDF30 from WS (WS100). Beet pulp was added in the straw diets to achieve similar dietary neutral detergent fiber digestibility after 30-h incubation (NDFD30). The 3 diets were similar in forage uNDF30 (14% of dry matter), total uNDF30 (∼18.5% of dry matter), and NDFD30 (approximately 42% of neutral detergent fiber). The substitution of WS and BP for AH and CS decreased the proportion of forage (40, 31, and 22.3% of dry matter) and forage neutral detergent fiber (21.2, 19.7, and 18.3% of dry matter) for WS0, WS50, and WS100, respectively, in the diet. However, the substitution linearly increased mean rumen pH (5.90, 6.09, and 6.28 for WS0, WS50, and WS100, respectively), digestibility of nutrients, and selection for long particles of diets without affecting dry matter intake. The substitution also linearly increased cholesterol and blood urea nitrogen concentration in the blood. Milk fat percentage, fat production, fat:protein ratio, and milk urea nitrogen increased linearly when treatments changed from WS0 to WS100, whereas the production of energy-corrected milk (ECM) was not affected by the treatments. Milk yield and milk protein yield were affected in a curvilinear manner and were lower in WS100 than other treatments. The efficiency of ECM production linearly increased in the diet with higher inclusion of WS and BP substitution in the diet (1.66, 1.70, and 1.72 for WS0, WS50, and WS100, respectively), but body weight, body weight change, and backfat thickness of cows were not different among treatments. In conclusion, the substitution of WS and BP for CS and AH with fixed uNDF30 improved feed efficiency and rumen pH, decreased milk and protein yield, and did not affect ECM yield.

Performance of dairy cows fed diets with similar proportions of undigested neutral detergent fiber with wheat straw substituted for alfalfa hay, corn silage, or both.

This study evaluated the effects of feeding diets that were formulated to contain similar proportions of undigested neutral detergent fiber (uNDF) from forage, with wheat straw (WS) substituted for corn silage (CS), alfalfa hay (AH), or both. The diets were fed to lactating dairy cows and intake, digestibility, blood metabolites, and milk production were examined. Thirty-two multiparous Holstein cows (body weight = 642 ± 50 kg; days in milk = 78 ± 11 d; milk production = 56 ± 6 kg/d; mean ± standard deviation) were used in a randomized block design with 6-wk periods after a 10-d covariate period. Each period consisted of 14 d of adaptation followed by 28 d of data collection. The control diet contained CS and AH as forage sources (CSAH) with 17% of dietary dry matter as uNDF after 30 h of incubation (uNDF30). Wheat straw was substituted for AH (WSCS), CS (WSAH), or both (WSCSAH) on an uNDF30 basis, and beet pulp was used to obtain similar concentrations of NDF digestibility after 30 h of incubation (NDFD30 = 44.5% of NDF) across all diets. The 4 diets also contained similar concentrations of net energy for lactation and metabolizable protein. Dry matter intake was greatest for WSCS (27.8 kg/d), followed by CSAH (25.7 kg/d), WSCSAH (25.2 kg/d), and WSAH (24.2 kg/d). However, yields of milk, 3.5% fat-corrected milk (FCM), and energy-corrected milk did not differ, resulting in higher FCM efficiency (kg of FCM yield/kg of dry matter intake) for WSAH (1.83) and WSCSAH (1.79), followed by CSAH (1.69) and WSCS (1.64). Milk protein percentage was greater for CSAH (2.84%) and WSCS (2.83%) than for WSAH (2.78%), and WSCSAH (2.81%) was intermediate. The opposite trend was observed for milk urea nitrogen, which was lower for CSAH (15.8 mg/dL), WSCS (15.8 mg/dL), and WSCSAH (17.0 mg/dL) than for WSAH (20 mg/dL). Total-tract NDF digestibility and ruminal pH were greater for diets containing WS than the diet without WS (CSAH), but digestibility of other nutrients was not affected by dietary treatments. Cows fed WSAH had less body reserves (body weight change = -13.5 kg/period) than the cows fed the other diets, whereas energy balance was greatest for those fed WSCS. The results showed that feeding high-producing dairy cows diets containing different forage sources but formulated to supply similar concentrations of uNDF30 while maintaining NDFD30, net energy for lactation, and metabolizable protein constant did not influence milk production. However, a combination of WS and CS (WSCS diet) compared with a diet with CS and AH improved feed intake, ruminal pH, total-tract NDF digestibility, and energy balance of dairy cows.

Supplementation effects of pomegranate by-products on oxidative status, metabolic profile, and performance in transition dairy cows.

Recent studies demonstrated a high antioxidant capacity for pomegranate components due to their rich bioactive compounds, such as conjugated fatty acids and phenolics. The objective of the present study was, therefore, to assess whether pomegranate seed or pomegranate seed pulp (peel + seed) supplementation could be effective to improve antioxidant status, and hence metabolic profile and performance in periparturient dairy cows. After a 1-wk pretreatment period, Holstein cows (primiparous n = 12, multiparous n = 18) were assigned to 3 dietary treatments from 25 d before expected calving through 25 d postcalving. The dietary treatments included (1) control (CON); (2) diet supplemented with pomegranate seeds (PS; 400 g/cow per day); and (3) diet supplemented with pomegranate seed pulp (PSP; 400 g of seeds/cow per day + 1200 g of peels/cow per day). Compared with CON, supplementation with either PS or PSP had no effects on dry matter intake, rumen fermentation, and plasma concentrations of cholesterol, total protein, globulin, and aspartate amino transferase, but enhanced plasma total antioxidant activity, and lowered triacylglycerol, free fatty acids (FFA), and ß-hydroxybutyrate at both pre- and postpartum periods. Plasma concentration of glucose, albumin, malondialdehyde (MDA) and blood superoxide dismutase (SOD) activity were not affected by dietary treatments at prepartum, whereas SOD activity increased and glucose, albumin, MDA, and FFA-to-albumin ratio decreased by feeding both by-products at postpartum period. In contrast to PS, supplementing PSP resulted in a greater decrease in plasma glucose and triacylglycerol concentration and higher increase in SOD activity. Energy- and fat-corrected milk yields were higher in cows fed PSP diet compared with those fed CON or PS diets, but content of milk fat, protein, and lactose were similar across the dietary treatments. These findings indicated that dietary pomegranate by-products supplementation, in particular PSP, could improve antioxidant status, which was associated with a decline in lipid oxidation (FFA and ß-hydroxybutyrate) and peroxidation (MDA) and an enhancement in glucose utilization as well as fat-corrected milk yield.

Evaluation of Apoptotic Markers and Tissue Histology Indicate a Slight Advantage of Slow Freezing Method over Vitrification for Sheep Ovarian Tissues.

BACKGROUND: An efficient cryopreservation method is very important for preserving the fertility of sheep ovarian tissues. OBJECTIVE: To compare the slow freezing method and vitrification for cryopreservation of sheep ovarian tissues. METHODS: Dissected cortex fragments from ten sheep ovaries were used for the comparative study. Cryopreserved and control tissues were cultured for 24h and then evaluated according to follicular morphology and apoptotic assessment. RESULTS: In both slow freezing and vitrification methods, normal follicles were reduced when compared to the non-frozen control group. There were significantly more abnormal follicles with vitrification than with slow freezing method (P < 0.05). However, there were no significant differences with regard to apoptotic gene expression or the percentage of Caspase3 positive follicles among cryopreserved and control groups. CONCLUSION: A slight advantage of the slow freezing method was observed over vitrification for cryopreservation of sheep ovarian tissue fragments.

Linear, Trinuclear Cobalt Complexes with o-Phenylene-bis-Silylamido Ligands.

Transamination of [Co{N(SiMe3 )2 }2 ]2 with C6 H4 (NHSiiPr3 )2 gave the centrosymmetric trinuclear [{Coter N(SiMe3 )2 (µ-η-[o-C6 H4 (κNSiiPr3 )2 ])}2 Coint ] (1) (Coter , Coint =terminal, internal Co, respectively), with 3-coordinate Coter , and Coint "sandwiched" between the o-phenylenes of the two ligands; experimental and computational data support CoII centres and ditopic o-amido-imino-cyclohexen-allyl ligands; magnetic studies reveal intermetallic ferromagnetic interactions and single-molecule magnet (SMM) character. One-electron reduction of 1 yielded the salt [K(18-crown-6)(THF)2 ][{Coter N(SiMe3 )2 (µ-η-[o-C6 H4 (κNSiiPr3 )2 ])}2 Coint ] (4) with the anion isostructural to 1. The centrosymmetric Fe complex [{Feter N(SiMe3 )2 (µ-η-[o-C6 H4 (κNSiiPr3 )2 ])}2 Feint ] (5), analogous to 1, was also obtained.

Conformational Landscape of the 1/1 Diacetyl/Water Complex Investigated by Infrared Spectroscopy and ab Initio Calculations.

The complexes of diacetyl with water have been studied experimentally by Fourier transform infrared (FTIR) spectroscopy coupled to solid neon matrix and supersonic jet, and anharmonic ab initio calculations. The vibrational analysis of neon matrix spectra over the 100-7500 cm-1 infrared range confirms the existence of two nearly isoenergetic one-to-one (1/1) diacetyl-water S1 and S2 isomers already evidenced in a previous argon matrix study. A third form (S3) predicted slightly less stable ( J. Mol. Mod. 2015 , 21 , 214 ) is not observed. The correct agreement obtained between neon matrix and anharmonic calculated vibrational frequencies is exploited in several cases to derive band assignments for the vibrational modes of a specific isomer. Thereafter, theoretical xij anharmonic coupling constants are used for the attribution of combination bands and overtones relative to the 1/1 dimer. Finally, the most stable isomer of the one-to-two (1/2) diacetyl-water complex is identified in the OH stretching region of water on the grounds of comparison of experimental and calculated vibrational shifts between water dimer and the three most stable 1/2 isomers.

Response of lactating dairy cows to degree of steam-flaked barley grain in low-forage diets.

This study was conducted to investigate the effects of processing method (grinding vs. steam flaking) and increasing densities of steam-flaked barley grain on dry matter intake (DMI), rumen pH and fermentation characteristics, digestibility of dry matter in the total digestive tract (DDTT), and milk production of dairy cows. Eight multiparous mid-lactation Holstein cows averaging 103 ± 24 DIM, 44.5 ± 4.7 kg milk/day and weighing 611 ± 43 kg at the start of the experiment were used in a replicated 4 × 4 Latin square design with 21-day periods. Cows were fed diets consisting of (DM basis) 23.8% corn silage, 13.5% chopped alfalfa hay and 62.7% concentrate. The dietary treatments were either ground barley (GB) using a hammer mill or steam-flaked barley (SFB) - varying density at 390, 340 or 290 g/l. Processing method (GB vs. SFB) did not affect DMI (23.6 kg/day on average), DDTT (71.0% on average), milk yield (43.4 kg/day on average), milk components, rumen pH and molar proportions of acetate, propionate, butyrate and sorting activity. Ruminal isovalerate concentration tended (p = 0.06) to be higher for cows fed GB than those fed SFB-based diets. Decreasing the density of SFB from 390, 340 to 290 g/l tended to linearly increase DMI (p = 0.09), decrease total solids percentage of milk (p = 0.10) and linearly decreased milk urea nitrogen (12.8, 12.4 and 12.1 mg/dl; p = 0.04); also, the sorting index (SI) of the particles retained on the 19.0-mm sieve without affecting the SI of the particles retained on 8.0-mm, 1.18-mm or passed through 1.18-mm sieve (p = 0.05). These results indicated the limited effects of processing method (grinding vs. steam flaking) and densities of SFB (390, 290 or 290 g/l) on cows' performance and feed utilization for dairy cows fed low-forage diets. Therefore, both processing methods could be recommended under current feeding conditions of dairy cows.

Towards Magnetic Carbo-meric Molecular Materials.

Numerous studies have underlined the putative diradical character of π-conjugated molecules that can be described by closed-shell Lewis structures, for instance, p-dimethylene p-n phenylenes, or long polyacenes. In the latter compounds, the only way to save the aromaticity of the six-membered rings is to give up the Lewis electron pairing in the singlet biradical ground state. The present work considers the possibility of doing the same by using the basic C2 units of carbo-meric architectures. A series of acyclic and cyclic carbo-meric architectures is studied by using UB3LYP DFT broken-symmetry calculations, including spin decontaminations and subsequent geometry optimization of the singlet diradical. The C2 units are shown to stabilize the singlet biradical by spin delocalization, two of them playing approximately the same role as one radical-insulating 1,4 phenylene moiety. The results are generalized to the investigation of open-shell polyradical singlet states of rigid hydrocarbon structures, the symmetry and rigidity of which can assist cooperativity and self spin polarization effect. Several synthesis targets with challenging magnetic/spin properties are suggested in the carbo-mer series.

Synthesis, High-Resolution Infrared Spectroscopy, and Vibrational Structure of Cubane, C8H8.

Carbon-cage molecules have generated a considerable interest from both experimental and theoretical points of view. We recently performed a high-resolution study of adamantane (C10H16), the smallest hydrocarbon cage belonging to the diamandoid family ( Pirali , O. ; et al. J. Chem. Phys. 2012 , 136 , 024310 ). There exist another family of hydrocarbon cages with additional interesting chemical properties: the so-called platonic hydrocarbons that comprise dodecahedrane (C20H20) and cubane (C8H8). Both possess C-C bond angles that deviate from the tetrahedral angle (109.8°) of the sp(3) hybridized form of carbon. This generates a considerable strain in the molecule. We report a new wide-range high-resolution study of the infrared spectrum of cubane. The sample was synthesized in Bari upon decarboxylation of 1,4-cubanedicarboxylic acid thanks to the improved synthesis of literature. Several spectra have been recorded at the AILES beamline of the SOLEIL synchrotron facility. They cover the 600-3200 cm(-1) region. Besides the three infrared-active fundamentals (ν10, ν11, and ν12), we could record many combination bands, all of them displaying a well-resolved octahedral rotational structure. We present here a preliminary analysis of some of the recorded bands, performed thanks the SPVIEW and XTDS software, based on the tensorial formalism developed in the Dijon group. A comparison with ab initio calculations, allowing to identify some combination bands, is also presented.

A comparison of the effect of soybeans roasted at different temperatures versus calcium salts of fatty acids on performance and milk fatty acid composition of mid-lactation Holstein cows.

To evaluate the effect of soybeans roasted at different temperatures on milk yield and milk fatty acid composition, 8 (4 multiparous and 4 primiparous) mid-lactation Holstein cows (42.9±3 kg/d of milk) were assigned to a replicated 4×4 Latin square design. The control diet (CON) contained lignosulfonate-treated soybean meal (as a source of rumen-undegradable protein) and calcium salts of fatty acids (Ca-FA, as a source of energy). Diets 2, 3, and 4 contained ground soybeans roasted at 115, 130, or 145°C, respectively (as the source of protein and energy). Dry matter intake (DMI) tended to be greater for CON compared with the roasted soybean diets (24.6 vs. 23.3 kg/d). Apparent total-tract digestibilities of dry matter, organic matter, and crude protein were not different among the treatments. Actual and 3.5% fat-corrected milk yield were greater for CON than for the roasted soybean diets. Milk fat was higher for soybeans roasted at 130°C than for those roasted at either 115 or 145°C. No differences were observed between the CON and the roasted soybean diets, or among roasting temperatures, on feed efficiency and nitrogen concentrations in rumen, milk, and plasma. Milk from cows fed roasted soybeans had more long-chain fatty acids and fewer medium-chain fatty acids than milk from cows fed Ca-FA. Compared with milk from cows fed the CON diet, total milk fat contents of conjugated linoleic acid, cis-9,trans-11 conjugated linoleic acid, cis-C18:2, cis-C18:3, and C22:0 were higher for cows fed the roasted soybean diets. Polyunsaturated fatty acids and total unsaturated fatty acids were greater in milk from cows fed roasted soybean diets than in milk from cows fed CON. Concentrations of C16:0 and saturated fatty acids in milk fat were greater for CON than for the roasted soybean diets. Cows fed roasted soybean diets had lower atherogenic and thrombogenic indices than cows fed CON. Milk fatty acid composition did not differ among different roasting temperatures. In summary, results showed that cows fed CON had higher DMI and milk yield than cows fed roasted soybean diets. Among different roasting temperatures (115, 130, and 145°C), soybeans roasted at 115°C led to higher milk production and lower DMI. Cows fed roasted soybeans, regardless of the roasting temperature, had more unsaturated fatty acids in milk. Using roasted soybeans in dairy cow rations could, therefore, improve the health indices of milk for human nutrition.

Effects of partial replacement of barley grain with beet pulp on performance, ruminal fermentation and plasma concentration of metabolites in transition dairy cows.

The objective of this study was to determine the effect of partial replacement of barley grain with beet pulp (BP) on dry matter intake (DMI), ruminal fermentation, plasma concentration of metabolites and milk yield of transition dairy cows. Twenty-four multiparous Holstein cows [735 ± 26 kg of body weights and 3.5 ± 0.05 of body condition score (BCS)] were used in a randomized complete block design. Cows were assigned randomly on day 28 relative to expected parturition date to one of three treatments containing (i) 0% BP, (ii) 25% BP or (iii) 50% BP substituted for barley grain on a DM basis. During the pre-partum period, DMI and energy intake were greater (P < 0.01) in cows fed the BP diet compared with cows fed the barley grain diet. During the post-partum period, substituting BP for barley grain caused a response in DMI and energy intake, with the highest amount for the 25% BP diet and lowest for the 50% BP diet (P < 0.01). Milk yield was lowest (P < 0.01) for 50% BP diet than the other treatments. During the post-partum period, cows fed the 50% BP diets had greater rumen pH, molar proportion of butyrate and acetate: propionate ratio (P < 0.01) in the rumen compared with cows fed the 0% BP diets. In addition, cows fed the BP diets had greater (P < 0.01) plasma ß-hydroxybutyrate and lower plasma glucose (P < 0.05) and blood urinary nitrogen (BUN) (P < 0.01) concentrations than cows fed the barley grain diets. Results showed that substituting BP for barley grain was effective in increasing DMI, but it did not have a significant effect on net energy balance during the post-partum period. However, replacing BP for barley grain at 50% had adverse effects on DMI, milk yield and metabolic status, as indicated by key blood metabolite concentrations.

The missing entry in the agostic-anagostic series: Rh(I)-η(1)-C interactions in P(CH)P pincer complexes.

The missing entry, namely, the "C-anagostic" or η(1)-C interaction, closing the agostic-anagostic series of metal-CH(aryl) interactions is found in a bis(amidiniophosphine) P(CH)P pincer rhodium complex. The three entries, namely, agostic η(2)-(C,H), anagostic (related to hydrogen bonding, thus recoined here as "H-anagostic"), and C-anagostic interactions, are unambiguously characterized by electron localization function (ELF) topological analysis. Other theoretical tools such as noncovalent interaction (NCI) analysis and multicenter electron delocalization indices (MCIs) support the ELF characterization. A η(2)-(C,H) agostic interaction is evidenced by a disynaptic V(C,H) or trisynaptic V(M,C,H) ELF basin with a significant quantum topological atoms in molecules (QTAIM) atomic contribution of the metal M and a large covariance (in absolute value) with the metal core basin C(M). The C-anagostic η(1)-C interaction is characterized by a disynaptic V(M,C) basin, a weak covariance (in absolute value) of V(C,H) and C(M) populations, and a negligible QTAIM atomic contribution of M to V(C,H). The relevance of these ELF signatures is evidenced in a selected series of related rhodium and osmium complexes.

Activation of C-H and B-H bonds through agostic bonding: an ELF/QTAIM insight.

Agostic bonding is of paramount importance in C-H bond activation processes. The reactivity of the σ C-H bond thus activated will depend on the nature of the metallic center, the nature of the ligand involved in the interaction and co-ligands, as well as on geometric parameters. Because of their importance in organometallic chemistry, a qualitative classification of agostic bonding could be very much helpful. Herein we propose descriptors of the agostic character of bonding based on the electron localization function (ELF) and Quantum Theory of Atoms in Molecules (QTAIM) topological analysis. A set of 31 metallic complexes taken, or derived, from the literature was chosen to illustrate our methodology. First, some criteria should prove that an interaction between a metallic center and a σ X-H bond can indeed be described as "agostic" bonding. Then, the contribution of the metallic center in the protonated agostic basin, in the ELF topological description, may be used to evaluate the agostic character of bonding. A σ X-H bond is in agostic interaction with a metal center when the protonated X-H basin is a trisynaptic basin with a metal contribution strictly larger than the numerical uncertainty, i.e. 0.01 e. In addition, it was shown that the weakening of the electron density at the X-Hagostic bond critical point with respect to that of X-Hfree well correlates with the lengthening of the agostic X-H bond distance as well as with the shift of the vibrational frequency associated with the νX-H stretching mode. Furthermore, the use of a normalized parameter that takes into account the total population of the protonated basin, allows the comparison of the agostic character of bonding involved in different complexes.

Saturation of the biological response to orthodontic forces and its effect on the rate of tooth movement.

OBJECTIVES: Investigate the expression and activity of inflammatory markers in response to different magnitudes of orthodontic forces and correlate this response with other molecular and cellular events during orthodontic tooth movement. SETTING AND SAMPLE POPULATION: CTOR Laboratory; 245 Sprague Dawley male rats. METHODS AND MATERIALS: Control, sham, and 5 different experimental groups received different magnitudes of force on the right maxillary first molar using a coil spring. In the sham group, the spring was not activated. Control group did not receive any appliance. At days 1, 3, 7, 14, and 28, the maxillae were collected for RNA and protein analysis, immunohistochemistry, and micro-CT. RESULTS: There was a linear relation between the force and the level of cytokine expression at lower magnitudes of force. Higher magnitudes of force did not increase the expression of cytokines. Activity of CCL2, CCL5, IL-1, TNF-α, RANKL, and number of osteoclasts reached a saturation point in response to higher magnitudes of force, with unchanged rate of tooth movement. CONCLUSION: After a certain magnitude of force, there is a saturation in the biological response, and higher forces do not increase inflammatory markers, osteoclasts, nor the amount of tooth movement. Therefore, higher forces to accelerate the rate of tooth movement are not justified.

Effect of prepartal and postpartal dietary fat level on performance and plasma concentration of metabolites in transition dairy cows.

The objective of this study was to determine the effects of 2 levels of dietary fat (low and high) offered during the prepartal and postpartal periods on dry matter intake (DMI), plasma concentration of metabolites, and milk yield and composition. Twenty-four Holstein dry cows were assigned on d 21 relative to expected parturition date to 1 of 4 treatments in a 2×2 factorial arrangement of 2 levels of fat fed during the prepartal period and 2 levels of fat fed during the postpartal period: prepartal low fat and postpartal low fat (LF-LF), prepartal low fat and postpartal high fat (LF-HF), prepartal high fat and postpartal low fat (HF-LF), or prepartal high fat and postpartal high fat (HF-HF). Prepartal and postpartal LF diets contained no fat supplement. Prepartal HF diets contained 1.60% calcium salts of soybean oil. The proportion of calcium salts of soybean oil was increased to 1.70% of DM for the first 21 d of lactation and to 2.27% of DM from d 21 to 56 of lactation in the HF diet. Diets were fed for ad libitum intake from d 21 before calving until d 56 of gestation. Prepartal DMI was lower for cows fed the HF diet compared with those fed the LF diet (12.6 vs. 16.2kg/d). Postpartum, cows fed the HF-HF and HF-LF diets had, respectively, the lowest and highest DMI, although no significant differences existed between HF-LF and LF-LF. Net energy intake was higher for cows fed the postpartal HF diets compared with those fed the LF diets. Prepartal fat level had no effect on net energy intake. Cows offered the prepartal HF diet had higher milk yield when offered the postpartal LF diet compared with those offered the postpartal HF diet and no effect of the postpartal fat level was detected when cows were fed the prepartal LF diet. Milk composition was similar among treatments. Plasma cholesterol concentration postpartum was higher for cows fed the prepartal LF diet than for those fed the prepartal HF diet (5.16 vs. 3.74mmol/L) and postpartal fat level had no effect. Prepartal diet had no significant effect on postpartal plasma triglyceride concentration but the postpartal HF diet increased triglyceride and low-density lipoprotein concentrations compared with the postpartal LF diet. In conclusion, switching from a high to a low fat proportion in the postpartal diet may alleviate the negative effects of a high proportion of fat in the prepartal diet as shown by increased feed intake and milk production during the first 56 d of lactation.

Frequency of bacteria causing urinary tract infections and their antimicrobial resistance patterns among pediatric patients in Western Iran from 2007-2009.

Urinary Tract infections ( UTIs) are among the most common infections in infants and neonates. The aim of the current study was to evaluate the frequency of bacteria causing UTI and their relevant drug resistance patterns among infants and neonates hospitalized in Ilam province, Western Iran during 2007-2009. A total of 220 cases of UTI were enrolled in this cross-sectional retrospective study. A standard checklist was used for demographic and clinical data to be collected from their health records. Data was then analyzed using SPSS version 16.0. More than two-thirds (64.8%) of the cases were female. E. coli (44.5%), Klebsiella spp., (18.6%), Enterobacter spp., (15%) and Staphylococcus spp. (12.7%) were the most common microorganisms isolated from UTIs, respectively. High rates of resistance to tetracycline, ampicillin, and nalidixic acid were observed among these isolates. Similar to other studies, E. coli was the most common bacteria causing UTI and showed a high rate of resistance against most of the antimicrobial agents. Determining the antimicrobial sensitivity can be helpful for physicians in choosing an appropriate treatment for patients suffering from UTI, and also to reduce the complications related to serious UTI.