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41.
The kinetics of base hydrolysis of (αβS) (salicylato) (tetraethylenepentamine) cobalt(III) have been investigated in aquo-organic solvent media at 15.0 < t, °C < 40.0, and I = 0.10 mol dm (ClO4?) using propane-2-ol (?70% v/v), t-butanol (?60% v/v), acetone (?70% v/v), acetonitrile (?50% v/v), and ethylene glycol (?70% v/v) as cosolvents. Both the spontaneous and base-catalyzed hydrolysis of the phenoxide species [(tetren)CoO2CC6H4O]+ were appreciably accelerated by the cosolvents PriOH, ButOH, Me2CO, and MeCN. On the contrary the base hydroylsis (k2) was retarded while spontaneous aquation (k1) was accelerated to a small extent with increased EG content. Variation of log k1 and log k (k = k2 at I = 0) with mole fraction (X0.S) or reciprocal of the relative permitivity (Ds?1) of the media were nonlinear. The transfer free energy of the transition state relative to that of the initial state of the substrate for transfer of species from water to mixed solvents also varied nonlinearly with X0.S, or Ds?1 indicating solvent specificity. The activation parameters, ΔH≠ and ΔS≠ varied nonlinearly with solvent composition exhibiting extrema. The preferential solvation and solvent structural effects mediated the kinetics and energetics of the reaction. © 1995 John Wiley & Sons, Inc. 相似文献
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Guru R. Valicherla Roshan A. Katekar Shailesh Dadge Mohammed Riyazuddin Anees A. Syed Sandeep K. Singh Athar Husain Muhammad Wahajuddin Jiaur R. Gayen 《Molecules (Basel, Switzerland)》2022,27(2)
PSTi8 is a pancreastatin inhibitory peptide that is effective in the treatment of diabetic models. This study investigates the pharmacokinetic (PK) properties of PSTi8 in Sprague Dawley rats, for the first time. In vitro and in vivo PK studies were performed to evaluate the solubility, stability in plasma and liver microsomes, plasma protein binding, blood–plasma partitioning, bioavailability, dose proportionality, and gender difference in PK. Samples were analyzed using the validated LC-MS/MS method. The solubility of PSTi8 was found to be 9.30 and 25.75 mg/mL in simulated gastric and intestinal fluids, respectively. The protein binding of PSTi8 was estimated as >69% in rat plasma. PSTi8 showed high stability in rat plasma and liver microsomes and the blood–plasma partitioning was >2. The bioavailability of PSTi8 after intraperitoneal and subcutaneous administration was found to be 95.00 ± 12.15 and 78.47 ± 17.72%, respectively, in rats. PSTi8 showed non-linear PK in dose proportionality studies, and has no gender difference in the PK behavior in rats. The high bioavailability of PSTi8 can be due to high water solubility and plasma protein binding, low clearance and volume of distribution. Our in vitro and in vivo findings support the development of PSTi8 as an antidiabetic agent. 相似文献
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Introduction of partially localized orbitals (PLOs) is shown to reduce the number of configurations needed to describe the bonding in transition metal clusters. Using this formalism, estimates are made of the molecular electron correlation energy that arises from including such terms as 3d → 3d′, 3p → 3p′ and 4s2 → 4p2 in the wavefunction. When this estimate of the additional correlation is added to the CAS SCF results of Walch, Bauschlicher, Roos and Nelin improved interaction potentials are obtained for the dimers V2 and Cr2. 相似文献
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[structure: see text] A novel cholaphane has been synthesized from a naturally occurring bile acid in just two steps. It has an ability to bind two fluoride ions selectively utilizing the glycolate motif in chloroform. This "inside-out" cyclodextrin analogue encapsulates fluoride through O-H...F(-) and C-H...F(-) interaction. 相似文献
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Weak interactions involving fluorine have been analyzed in the structure of 6-methoxy-1,2-diphenyl-1,2,3,4-tetrahydroisoquinoline with fluorine substitution at para-, meta- and ortho- positions, respectively, on the 1-phenyl ring. The packing modes in the crystalline lattice as determined by X-ray diffraction techniques generate motifs via F?F, C-H?F and C-F?π interactions. The three structures as compared to the parent compound depict conformational changes in the saturated tetrahydroisoquinoline moiety. The salient features of the four structures in terms of weak interactions involving fluorine suggest that organic fluorine does resemble the other halogens. 相似文献
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Let $h$ be a transcendental entire function of finite type such that all the coefficients in its Taylor series about the origin are non-negative, $h(x)\! >\!0 \hbox { for } x \!<~0,\,h(0)\ge 1$ and each finite singular value of $h$ is either real or is with unit modulus. For $J(z) = z + (1/z)\hbox { and } n \in \mathbb {N}$ , we define $f_{\lambda }(z)=\lambda J^n(h(z))$ . It is proved that there exists a $\lambda ^{*}$ such that the Julia set of $f_\lambda $ is a nowhere dense subset of $\widehat{\mathbb {C}}\hbox { for }0< \lambda \le \lambda ^*$ whereas it becomes equal to $\widehat{\mathbb {C}}$ for $\lambda >\lambda ^*$ . A detailed study of the Julia sets of Joukowski-exponential maps $\lambda J( e^z+1)$ is undertaken when it is not equal to the whole sphere. Such a Julia set consists of a non-singleton, unbounded and forward invariant component, infinitely many non-singleton bounded components and singleton components. A bounded component of the Julia set eventually not mapped into the unbounded Julia component is singleton if and only if it is not expanding. The Julia set contains two topologically as well as dynamically distinct completely invariant subsets. 相似文献