• 제목/요약/키워드: Ts-effect

검색결과 334건 처리시간 0.023초

Effects of Processing of Starter Diets on Performance, Nutrient Digestibility, Rumen Biochemical Parameters and Body Measurements of Brown Swiss Dairy Calves

  • Nejad, J. Ghassemi;Torbatinejad, N.;Naserian, A.A.;Kumar, S.;Kim, J.D.;Song, Y.H.;Ra, C.S.;Sung, K.I.
    • Asian-Australasian Journal of Animal Sciences
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    • 제25권7호
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    • pp.980-987
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    • 2012
  • In order to investigate the effect of physical forms of starter diets on performance, weaning age, nutrient digestibility and rumen biochemical factors, 24 female of neonatal Brown Swiss calves (average body weight of $39.5{\pm}1.2kg$) were randomly assigned to three treatments. Dietary treatments were mashed (MS), pelleted (PS), and texturized (TS) starter using 8 calves from birth till 90 days of age in each treatment. Diets were formulated to be iso-nitrogenous with 21% crude protein. Based on the experimental results, calves that received PS and TS diets, had significant higher average daily gain (ADG) than those receiving MS (p<0.01). Dry matter intake in calves fed PS and TS was greater than calves fed MS (p<0.05), but there was no significant difference in feed efficiency. Treatments had no effect on initiation of rumination. Weaning age of calves in MS was longer than the other two treatments (p<0.05). Crude protein and organic matter digestibility in MS treated calves were lower than other treatments (p<0.05). No differences were observed in neutral detergent fiber (NDF) and ash digestibility among treatments (p>0.05). Ruminal pH was higher (p<0.01) in MS than the other groups, but ruminal ammonia (g/dl) concentration was not different among the treatments. Body measurements such as body length, pin width, hip width, pin to hip length, size of metacarpus and metatarsus bones, hip height, wither height, stomach size and heart girth were not significantly different among the treatments. Overall, it is concluded that starter diets in the form of pellet and texture can improve performance in neonatal Brown Swiss calves compared to the mashed form.

Atomic Layer Deposited ZrxAl1-xOy Film as High κ Gate Insulator for High Performance ZnSnO Thin Film Transistor

  • Li, Jun;Zhou, You-Hang;Zhong, De-Yao;Huang, Chuan-Xin;Huang, Jian;Zhang, Jian-Hua
    • Electronic Materials Letters
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    • 제14권6호
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    • pp.669-677
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    • 2018
  • In this work, the high ${\kappa}$ $Zr_xAl_{1-x}O_y$ films with a different Zr concentration have been deposited by atomic layer deposition, and the effect of Zr concentrations on the structure, chemical composition, surface morphology and dielectric properties of $Zr_xAl_{1-x}O_y$ films is analyzed by Atomic force microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and capacitance-frequency measurement. The effect of Zr concentrations of $Zr_xAl_{1-x}O_y$ gate insulator on the electrical property and stability under negative bias illumination stress (NBIS) or temperature stress (TS) of ZnSnO (ZTO) TFTs is firstly investigated. Under NBIS and TS, the much better stability of ZTO TFTs with $Zr_xAl_{1-x}O_y$ film as a gate insulator is due to the suppression of oxygen vacancy in ZTO channel layer and the decreased trap states originating from the Zr atom permeation at the $ZTO/Zr_xAl_{1-x}O_y$ interface. It provides a new strategy to fabricate the low consumption and high stability ZTO TFTs for application.

Nucleophilic Substitution Reactions of Phenyl Y-Substituted-Phenyl Carbonates with Butane-2,3-dione Monoximate and 4-Chlorophenoxide: Origin of the α-Effect

  • Kim, Min-Young;Min, Se-Won;Um, Ik-Hwan
    • Bulletin of the Korean Chemical Society
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    • 제34권1호
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    • pp.49-53
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    • 2013
  • Second-order rate constants have been measured spectrophotometrically for the reactions of phenyl Y-substituted-phenyl carbonates 7a-g with butane-2,3-dione monoximate ($Ox^-$) in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The ${\alpha}$-nucleophile $Ox^-$ is 53-95 times more reactive than the corresponding normal-nucleophile 4-$ClPhO^-$ toward 7a-g, indicating that the ${\alpha}$-effect is operative. The magnitude of the ${\alpha}$-effect (e.g., the $k_{Ox^-}/k_{4-ClPhO^-}$ ratio) is independent of the electronic nature of the substituent Y. The cause of the ${\alpha}$-effect for the reactions of 7a-g has been suggested to be ground-state (GS) effect rather than transition-state (TS) stabilization through a six-membered cyclic TS, in which $Ox^-$ behaves a general acid/base catalyst. This idea is further supported by the result that $OH^-$ exhibits negative deviation from the linear Br${\o}$nsted-type plot composed of a series of aryloxides, while $Ox^-$ deviates positively from the linearity. Differential solvation of the GS of $Ox^-$ and 4-$ClPhO^-$ has been suggested to be responsible for the ${\alpha}$-effect exerted by $Ox^-$.

Kinetics and Mechanism of the Anilinolysis of Diethyl Thiophosphinic Chloride in Acetonitrile

  • Hoque, Md. Ehtesham Ul;Lee, Hai-Whang
    • Bulletin of the Korean Chemical Society
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    • 제32권7호
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    • pp.2306-2310
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    • 2011
  • The nucleophilic substitution reactions of diethyl thiophosphinic chloride with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at 55.0 $^{\circ}C$. The values of deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) invariably increase from secondary inverse ($k_H/k_D$ < 1) to primary normal (kH/kD > 1) as the nucleophiles change from the strongly basic to weakly basic anilines. The secondary inverse with the strongly basic anilines and primary normal DKIEs with the weakly basic anilines are rationalized by the gradual transition state (TS) variation from a predominant backside attack, via invariably increasing the fraction of a frontside attack, to a predominant frontside attack, in which the reaction mechanism is a concerted $S_N2$ pathway. A frontside attack involving a hydrogen bonded, four-center-type TS is substantiated by the primary normal DKIEs.

Ab initio Studies on the Hetero Diels-Alder Cycloaddition

  • 이본수;김찬경;최정욱;이익준
    • Bulletin of the Korean Chemical Society
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    • 제17권9호
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    • pp.849-853
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    • 1996
  • Hetero Dieis-Alder reactions containing phosphorus atom at various positions of diene and dienophile as well as standard Dieis-Alder reaction between ethylene and cis-l,3-butadiene have been studied using ab initio method. Activation energy showed a good linear relationship with the FMO energy gap between diene and dienophile, which can be normally used to explain Dieis-Alder reactivity. Since π-bond cleavage and σ-bonds formation occur concertedly at the TS, geometrical distortion of diene and dienophile from the reactant to the transition state is the source of barrier. Based on the linear correlations between activation barrier and deformation energy, and between deformation energy and π-bond order change, it was concluded that the activation barrier arises mainly from the breakage of π-bonds in diene and dienophile. Stabilization due to favorable orbital interaction is relatively small. The geometrical distortions raise MO levels of the TS, which is the origin of the activation energy. The lower barrier for the reactions of phosphorus containing dienophile (reactions C, D, and E) can be explained by the electronegativity effect of the phosphorus atom.

Geometries and Energies of S$_N$2 Transition States$^\dag$

  • Lee, Ik-Choon;Kim, Chan-Kyung;Song, Chang-Hyun
    • Bulletin of the Korean Chemical Society
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    • 제7권5호
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    • pp.391-395
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    • 1986
  • MNDO calculations were carried out to determine reactant complexes and transition states of the $S_N2$ reactions of $CH_3X\;+\;Y^-\;{\to}\;CH_3Y\;+\;X^-$ where X = F, Cl, CN and Y = CN, OH, F, Cl. The leaving group ability was found to vary inversely with the activation barrier, which in turn was mainly ascribable to the deformation energies accompanied with bond stretching of C-X bond and inversion of $CH_3$ group. The nucleophilicity was shown to be in the order $Cl^->F^->OH^->CN^-$ but the effect on the activation barrier was relatively small compared with that of the leaving group. The bond breaking and bond formation indices and energy decomposition analysis showed that the TS for the reaction of $CH_3$Cl occurs in the early stage of the reaction coordinate relative to that of $CH_3$F. It has been shown that the potential energy surface (PES) diagrams approach can only accommodate thermodynamic effects but fails to correlate intrinsic kinetic effects on the TS structure.

Theoretical Studies on the Acyl Transfer Reactions Involving a Tetrahedral Intermediate$^\dag$

  • 이도영;김창곤;이본수;이익준
    • Bulletin of the Korean Chemical Society
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    • 제16권12호
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    • pp.1203-1208
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    • 1995
  • Theoretical studies of the effect of the nonleaving group (RY) on the breakdown mechanism of the tetrahedral anionic intermediate, T-, formed by the addition of a less basic phenoxide nucleophile (X) to phenyl benzoates with a more basic phenoxide leaving group (Z) have been carried out using the PM3 MO method. The identity acyl transfer reactions (X=Z) are facilitated by an electron-withdrawing RY whereas they are inhibited by an electron-donating RY group. The results of non-identity acyl transfer reactions indicate that a more electron-donating RY group leads to a greater lowering of the higher barrier, TS2, with a greater degree of bond cleavage, and a greater negative charge development on the phenoxide oxygen atom, whereas the opposite is true for a more electron-withdrawing RY group, i.e., leads to a greater lowering of the lower barrier, TS1. The results provide theoretical basis for the signs of ρXY(>0) and ρYZ(<0) observations.

The Effect of Solvent on Reactions of p-Nitrophenyl Acetate with Alicyclic Secondary Amines and with Anionic Nucleophiles in MeCN-H₂O Mixtures of Varying Compositions

  • 엄익환;신은희;권동숙
    • Bulletin of the Korean Chemical Society
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    • 제17권3호
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    • pp.234-238
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    • 1996
  • Second-order rate constants have been measured spectrophotometrically for the reaction of p-nitrophenyl acetate (PNPA) with morpholine, piperazine and piperidine in MeCN-H2O mixtures of varying compositions. The rate of the present aminolysis decreases upon additions of MeCN into H2O up to near 30-40 mole % MeCN and remains nearly constant upon further additions of MeCN. The reaction of PNPA with anionic nucleophiles, such as HO-, p-chlorophenoxide and butane-2,3-dione monoximate, has also exhibited two distinguishable reactivity zones. However, the reactivity trend for the anionic nucleophiles is quite different from the one obtained for the amine system, e.g. an initial rate decrease in the H2O-rich region followed by an increasing rate trend upon further additions of MeCN in the MeCN-rich region. The rate behaviors shown by the amine system in the MeCN-rich and by the anionic system in the H2O-rich region are unexpected based on the Hughes-Ingold rules. The present unusual rate trends have been attributed to changes in the solvent structure and pKa of the nucleophiles upon the addition of MeCN into H2O. The effect of solvent appears to be more significant for the TS than the GS, and the TS structure is considered to become tighter in the higher MeCN concentration.

금형의 국부적인 가열에 의한 사각통의 온간 디프로드로잉 성형성에 미치는 온도의 효과 (Temperature Effect On Warm Deep Drawability of Rectangular Cup Using Local Heating of Dies)

  • 김창호;박동환;강성수
    • 한국정밀공학회지
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    • 제13권5호
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    • pp.53-59
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    • 1996
  • Warm deep drawing of single-action dies using local heating has appeared to be an alternative attractive production method of multi-operation die sets generally used at room temperature in deep drawing of rectangular cup. Uniaxial tensile tests and deep drawing tests of various materials are carried out and the effect of temperature on tensile properties and drawability are examined at temperatures up to 200 .deg. C under three kinds of lubricants of teflon film, vinyl film and drawing oil. Good formability is achieved when punch and die temperature were differentiated intentionally in order to get large tensile strength(TS) at punch shoulder protion and small TS at die side. Throughout the experiments, it has been shown that the limiting drawing height of STS316L was increased with heating die and blank holder at 100 .deg. C, but that of STS430 wasn't. When vinyl or teflon film was attached on the plates, the drawability was increased considerably.

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