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Journal articles on the topic 'Kinetic solvent isotope effect'

Author: Grafiati

Published: 5 June 2025

Last updated: 1 August 2025

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1

Away, Kenneth Charles West, and Zhu-Gen Lai. "Solvent effects on SN2 transition state structure. II: The effect of ion pairing on the solvent effect on transition state structure." Canadian Journal of Chemistry 67, no. 2 (1989): 345–49. http://dx.doi.org/10.1139/v89-056.

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Identical secondary α-deuterium kinetic isotope effects (transition state structures) in the SN2 reaction between n-butyl chloride and a free thiophenoxide ion in aprotic and protic solvents confirm the validity of the Solvation Rule for SN2 Reactions. These isotope effects also suggest that hydrogen bonding from the solvent to the developing chloride ion in the SN2 transition state does not have a marked effect on the magnitude of the chlorine (leaving group) kinetic isotope effects. Unlike the free ion reactions, the secondary α-deuterium kinetic isotope effect (transition state structure) f

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2

Karolczak, Stefan, Hugh A. Gillis, Gerald B. Porter, and David C. Walker. "Solvent-dependent rate constants of muonium atom reactions." Canadian Journal of Chemistry 81, no. 2 (2003): 175–78. http://dx.doi.org/10.1139/v03-009.

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The rates of reaction of muonium atoms with solutes, ionic and organic, were studied in solvents of wildly differing polarities (water, methanol, and hexane) and their rate constants were compared, where possible. In these reactions which are those of a highly reactive atom, an isotope of hydrogen it transpires that the reaction rates are higher in solvents in which the solute is more soluble and muonium diffuses faster. This study leads to various kinetic-solvent-effect ratios and to the observation of the reaction of muonium with free radicals being among the fastest reactions recorded s

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3

Westaway, Kenneth Charles, and Zhu-Gen Lai. "Isotope effects in nucleophilic substitution reactions. VI. The effect of ion pairing on the transition state structure of SN2 reactions." Canadian Journal of Chemistry 66, no. 5 (1988): 1263–71. http://dx.doi.org/10.1139/v88-205.

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Spectroscopic and conductivity studies of sodium thiophenoxide solutions in four different solvents and the secondary α-deuterium kinetic isotope effects found in the presence of 15-crown-5 ether demonstrate that the secondary α-deuterium kinetic isotope effect and transition state structure for the SN2 reaction between sodium thiophenoxide and n-butyl chloride are significantly different, depending on whether the ionic reactant is a solvent-separated ion-pair complex or a free ion. In all three solvents in which the form of the ionic reactant changes, a smaller isotope effect and tighter tran

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4

Pałka, Katarzyna, Katarzyna Podsadni, Jolanta Szymańska-Majchrzak, and Elżbieta Winnicka. "Deuterium isotope effects in mechanistic studies of biotransformations of l-tyrosine and p-hydroxyphenylpyruvic acid catalyzed by the enzyme l-phenylalanine dehydrogenase." Nukleonika 70, no. 2 (2025): 51–56. https://doi.org/10.2478/nuka-2025-0006.

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Abstract The mechanisms of the reversible oxidative deamination of l-tyrosine to p-hydroxyphenylpyruvic acid and reductive amination of phenylpyruvic acid to l-phenylalanine, both catalyzed by the enzyme l-phenylalanine dehydrogenase (PheDH, EC 1.4.1.20), were investigated using the kinetic isotope effect (KIE) and solvent isotope effect (SIE) methods. The values of deuterium kinetic effects in the 2-position of l-tyrosine and KIE in the (3S)-position of phenylpyruvic acid and solvent isotope effects for both reactions were determined using the non-competitive spectrophotometric method. Some m

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5

Inaniyan, Yashasvi, Pooja Tak, Pramila Naga, and Priyanka Purohit. "Correlation analysis of reactivity in the oxidation of some vicinal and non-vicinal diols by Tributylammonium chlorochromate: A kinetic and mechanistic approach." Research Journal of Chemistry and Environment 26, no. 9 (2022): 26–32. http://dx.doi.org/10.25303/2609rjce026032.

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The kinetics of oxidation of four vicinal, four non-vicinal diols by tributylammonium chlorochromate (TBACC) has been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order each in TBACC. Michaelies-Menten type of kinetics is observed with respect to the diols. The reaction is catalysed by hydrogen ions. The hydrogen ion dependence is taking the form: kobs = a + b[H+]. The oxidation of [1,1,2,2-2H4] ethanediol exhibits a substantial primary kinetic isotope effect (kH/kD = 5.81 at 298 K). The reaction has be

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6

Uspenskaya, Elena V., Tatyana V. Pleteneva, Anton V. Syroeshkin, Ilaha V. Kazimova, Tatyana E. Elizarova, and Artem I. Odnovorov. "Role of stable hydrogen isotope variations in water for drug dissolution managing." Current Issues in Pharmacy and Medical Sciences 33, no. 2 (2020): 94–101. http://dx.doi.org/10.2478/cipms-2020-0017.

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AbstractIn the present work, we provide the results of defining by utilizing Laser diffraction spectroscopy, the kinetic isotopic effect of solvent and constant of dissolution rate κ, s−1 of аn active pharmaceutical ingredient (API) in water with a different content of a stable _2^1{\rm{H}} isotope on the basis of the laws of first-order kinetics. This approach is based on the analysis of the light scattering profile that occurs when the particles of the dispersion phase in the aquatic environment are covered with a collimated laser beam. For the first time, the dependence of the rate of disso

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7

HUANG, Ter-Mei, Hui-Chih HUNG, Tsu-Chung CHANG, and Gu-Gang CHANG. "Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles." Biochemical Journal 330, no. 1 (1998): 267–75. http://dx.doi.org/10.1042/bj3300267.

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Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2,4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a pla

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8

Seema, Kothari, K. Sharma Pradeep, and K. Banerji Kalyan. "Down the polyhalide path." Journal of Indian Chemical Society Vol. 80, May 2003 (2003): 431–39. https://doi.org/10.5281/zenodo.5839269.

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E-mail : banerjikk@rediffmail.com     Fax: 91-291-2742977 <em>Manuscript received 10 October 2002</em> Kinetic and mechanistic studies of oxidation by several quaternary ammonium salts of poly halides, reported from this laboratory, are reviewed. Various kinetic and activation parameters have been reported. The effects of solvent composition, isotopic labeling and isotope composition of solvent have been discussed. Correlation analysis of the reactivity has been emphasized. Suitable mechanisms have been proposed.

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9

S., Sheik Mansoor, and Syed Shafi S. "Oxidation of formic and oxalic acids by imidazolium fluorochromate in non-aqueous media - A kinetic and mechanistic study." Journal of Indian Chemical Society Vol. 89, Jan 2012 (2012): 69–76. https://doi.org/10.5281/zenodo.5751585.

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Post Graduate and Research Department of Chemistry, C. Abdul Hakeem College, Melvisharam-632 509, Tamil Nadu, India <em>E-mail</em> : smansoors2000@yahoo.co.in Post Graduate and Research Department of Chemistry, Islamiah College, Vaniyambadi-635 752, Tamil Nadu, India <em>Manuscript received 26 August 2010, accepted 10 May 2011</em> Kinetics and mechanism of oxidation of formic and oxalic acids by imidazolium fluorochromate (IFC) have been studied in dimethyl sulphoxide (DMSO). The main product of oxidation is carbon dioxide. The reaction is first order with respect to IFC and organic acids. T

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10

Armesto, X. L., M. Canle L., V. García, and J. A. Santaballa. "Solvent isotope effects in the oxidation of dipeptides by aqueous chlorine." Canadian Journal of Chemistry 77, no. 5-6 (1999): 997–1004. http://dx.doi.org/10.1139/v99-105.

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A kinetic study of the mechanism of oxidation of Ala-Gly and Pro-Gly by aqueous chlorine has been carried out. Among other experimental facts, the deuterium solvent isotope effects were used to clarify the mechanisms involved. In a first stage, N-chlorination takes place, and then the (N-Cl)-dipeptide decomposes through two possible mechanisms, depending on the acidity of the medium. The initial chlorination step shows a small isotope effect. In alkaline medium, two consecutive processes take place: first, the general base-catalyzed formation of an azomethine (β ca. 0.27), which has an inverse

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11

Pająk, Małgorzata. "Kinetic and solvent isotope effects in oxidation of halogen derivatives of tyramine catalyzed by monoamine oxidase A." Journal of Biochemistry 167, no. 1 (2019): 49–54. http://dx.doi.org/10.1093/jb/mvz089.

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Abstract The isotope effects approach was used to elucidate the mechanism of oxidative deamination of 3′-halotyramines, catalyzed by monoamine oxidase A (EC 1.4.3.4). The numerical values of kinetic isotope effect (KIE) and solvent isotope effect (SIE) were established using a non-competitive spectrophotometric technique. Based upon KIE and SIE values, some of the mechanistic details of investigated reaction were discussed.

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12

Fernandez, Patrick L., and Andrew S. Murkin. "Inverse Solvent Isotope Effects in Enzyme-Catalyzed Reactions." Molecules 25, no. 8 (2020): 1933. http://dx.doi.org/10.3390/molecules25081933.

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Solvent isotope effects have long been used as a mechanistic tool for determining enzyme mechanisms. Most commonly, macroscopic rate constants such as kcat and kcat/Km are found to decrease when the reaction is performed in D2O for a variety of reasons including the transfer of protons. Under certain circumstances, these constants are found to increase, in what is termed an inverse solvent kinetic isotope effect (SKIE), which can be a diagnostic mechanistic feature. Generally, these phenomena can be attributed to an inverse solvent equilibrium isotope effect on a rapid equilibrium preceding th

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13

BORMAN, STU. "Studies elucidate solvent kinetic isotope effects." Chemical & Engineering News 72, no. 16 (1994): 25–26. http://dx.doi.org/10.1021/cen-v072n016.p025.

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14

Fang, Yao-Ren, and Kenneth Charles Westaway. "Isotope effects in nucleophilic substitution reactions. VIII. The effect of the form of the reacting nucleophile on the transition state structure of an SN2 reaction." Canadian Journal of Chemistry 69, no. 6 (1991): 1017–21. http://dx.doi.org/10.1139/v91-149.

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A spectroscopic investigation indicated that lithium thiophenoxide exists as a contact ion pair complex in dry diglyme whereas the other alkali metal thiophenoxides exist as a solvent-separated ion pair complex in diglyme. The addition of small amounts of water converts the lithium thiophenoxide contact ion pair complex into a solvent-separated ion pair complex. A smaller secondary α-deuterium kinetic isotope effect and a larger Hammett p value are observed when the nucleophile is the contact ion pair complex in the SN2 reaction between n-butyl chloride and thiophenoxide ion in diglyme. This i

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15

Malani, Neha, Manju Baghmar, Preeti Swami та Pradeep Kumar Sharma. "Kinetics and Mechanism of the Oxidation of Some α-Hydroxyacids by Morpholinium Chlorochromate". Progress in Reaction Kinetics and Mechanism 33, № 4 (2008): 393–405. http://dx.doi.org/10.3184/146867808x379300.

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The oxidation of glycollic, lactic, malic and a few substituted mandelic acids by morpholinium chlorochromate (MCC) in dimethylsulfoxide (DMSO) leads to the corresponding oxoacids. The reaction is first order each in MCC and hydroxyacid. The reaction failed to induce the polymerisation of acrylonitrile. The oxidation of α–deuteriomandelic acid shows a primary kinetic isotope effect ( kH/ kD = 5.63 at 298 K) but does not exhibit a solvent isotope effect. The reaction is catalysed by hydrogen ions according to: kobs = a + b[H+]. The oxidation of p-methyl mandelic acid has been studied in 19 diff

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16

Vasudha, Ranga, Soni Umashankar, Rao Ammilal, Purohit Priyanka, and K. Sharma Pradeep. "Oxidation studies of formic and oxalic acids by morpholinium fluorochromate : Kinetic and mechanistic study." Journal of Indian Chemical Society Vol. 93, Dec 2016 (2016): 1377–82. https://doi.org/10.5281/zenodo.5598849.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail </em>: drpkvs27@yahoo.com <em>Manuscript received 21 July 2016, accepted 27 July 2016</em> Kinetics and mechanism of oxidation of formic and oxalic acids by morpholinium fluorochromate (MFC) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first order with respect to MFC. Michaelis-Menten type of kinetics were observed with respect to the reductants. The reaction is acid-catalysed and the acid dependence has the form : <em>k</em><sub>obs</sub> = <e

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17

Pham, T. V., and K. C. Westaway. "Solvent effects on nucleophilic substitution reactions. III. The effect of adding an inert salt on the structure of the SN2 transition state." Canadian Journal of Chemistry 74, no. 12 (1996): 2528–30. http://dx.doi.org/10.1139/v96-283.

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The nitrogen and secondary α-hydrogen–deuterium kinetic isotope effects found for the SN2 reaction between thiophenoxide ion and benzyldimethylphenylammonium ion at different ionic strengths in DMF at 0 °C indicate that the structure of the transition state changes markedly with the ionic strength of the reaction mixture. In fact, a more reactant-like, more ionic, transition state is found at the higher ionic strength. This presumably occurs because a more ionic transition state is more stable in the more ionic solvent. Key words: transition state, ionic strength, secondary α deuterium kinetic

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18

Casey, Charles P., and Jeffrey B. Johnson. "Kinetic isotope effect evidence for the concerted transfer of hydride and proton from hydroxycyclopentadienyl ruthenium hydride in solvents of different polarities and hydrogen bonding ability." Canadian Journal of Chemistry 83, no. 9 (2005): 1339–46. http://dx.doi.org/10.1139/v05-140.

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The tolyl analogue of Shvo's hydroxycyclopentadienyl ruthenium hydride (4) efficiently transfers a hydride and proton to benzaldehyde or acetophenone to produce an alcohol. This reduction can be performed in toluene, methylene chloride, and THF. Reduction of benzaldehyde in toluene and methylene chloride occurs approximately 300 times faster than in THF at 0 °C. Reduction of acetophenone occurs between 75 and 150 times slower than benzaldehyde at 0 °C in each respective solvent. Despite the differences in rate, mechanistic studies have provided evidence for a similar concerted transfer of acid

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19

Shilpa, Pohani, Purohit Priyanka, Vyas Shweta, and K. Sharma Pradeep. "Kinetics and mechanism of the oxidation of oxalic and formic acids by tetraethylammonium chlorochromate." Journal of Indian Chemical Society Vol. 89, Mar 2012 (2012): 363–69. https://doi.org/10.5281/zenodo.5760265.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail </em>: drpkvs27@yahoo.com <em>Manuscript received 14 June 2010, revised 05 May 2011, accepted 12 July 2011</em> Kinetics and mechanism of oxidation of formic and oxalic acids by tetraethylammonium chlorochromate (<strong>TEACC</strong>) have been studied in dimethylsulphoxide. The main product of oxidation is carbon dioxide. The reaction is first order with respect to <strong>TEACC</strong> and the organic acids. The reaction is acid-catalysed and the acid dependence has the form : <em><strong>k<sub>obs<

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20

Panday, Dinesh, Teena Kachawa та Seema Kothari. "Kinetics and Correlation Analysis of Reactivity in the Oxidation of Some α-Hydroxy Acids by Benzimidazolium Dichromate". Progress in Reaction Kinetics and Mechanism 43, № 3-4 (2018): 300–314. http://dx.doi.org/10.3184/146867818x15319903829236.

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Kinetic and mechanistic studies of the oxidation of mandelic acid and nine monosubstituted mandelic acids by benzimidazolium dichromate (BIDC) in dimethyl sulfoxide are discussed with an emphasis on correlation of structure and reactivity. The reactions were of first order with respect to BIDC. However, Michaelis-Menten type kinetics were observed with respect to hydroxy acids. The reactions are catalysed by protons. The deuterium isotope effect for the oxidation of mandelic acid ( kH/ kD = 5.91 at 298 K) indicated an α-C-H bond cleavage in the rate-determining step. An analysis of the solvent

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21

Huang, Xicai, and Andrew J. Bennet. "Kinetic evidence for the importance of solvent-separated ion pairs during the solvolyses of adamantylideneadamantyl derivatives." Canadian Journal of Chemistry 82, no. 9 (2004): 1336–40. http://dx.doi.org/10.1139/v04-101.

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The aqueous ethanolysis reactions of adamantylideneadamantyl tosylate, -bromide, and -iodide (1-OTs, 1-Br and 1-I) were monitored as a function of ionic strength. Special salt effects are observed during the solvolyses of both homoallylic halides, but not in the case of the tosylate 1-OTs. The measured α-secondary deuterium kinetic isotope effects for the solvolysis of 1-Br in 80:20 and 60:40 v/v ethanolwater mixtures at 25 °C are 1.110 ± 0.018 and 1.146 ± 0.009, respectively. The above results are consistent with the homoallylic halides reacting via a virtual transition state in which both f

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22

Pradeep, K. Sharma. "Kinetics and mechanism of the oxidation of formic and oxalic acids by benzyltrimethylammonium chlorobromate." Journal of Indian Chemical Society Vol. 81, Apr 2004 (2004): 291–94. https://doi.org/10.5281/zenodo.5830729.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, India <em>Manuscript received 24 June 2003, accepted 1 September 2003</em> Kinetics and mechanism of oxidation of formic and oxalic acids by benzyltrimethylammonium chlorobromate (BTMACB) have been studied in acetic acid-water (1 : 1) solutions. The main product of oxidation is carbon dioxide. The reaction is first order with respect to BTMACB. Michaelis-Menten type of kinetics were observed with respect to the reductants. The oxidation of α-deuterioformic acid (DFA) exhibits a substantial primary kinetic isotope effect (k<su

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23

El Seoud, Omar A., Reinaldo C. Bazito, and Paulo T. Sumodjo. "Kinetic Solvent Isotope Effect: A Simple, Multipurpose Physical Chemistry Experiment." Journal of Chemical Education 74, no. 5 (1997): 562. http://dx.doi.org/10.1021/ed074p562.

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Virtanen, Noora, Lauri Polari, Maria Välilä, and Satu Mikkola. "Kinetic solvent deuterium isotope effect in transesterification of RNA models." Journal of Physical Organic Chemistry 18, no. 5 (2005): 385–97. http://dx.doi.org/10.1002/poc.883.

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25

Jarczewski, Arnold, Grzegorz Schroeder, and Kenneth T. Leffek. "The proton transfer reaction between bis(2,4-dinitrophenyl)methane and nitrogen bases in dimethyl sulfoxide and toluene solvents." Canadian Journal of Chemistry 69, no. 3 (1991): 468–73. http://dx.doi.org/10.1139/v91-070.

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Rate constants have been measured for the proton and deuteron transfer reactions of bis(2,4-dinitrophenyl)methane (1) with 1,1,3,3-tetramethylguanidine (TMG) and 1,5-diazabicyclo[5.4.0]undec-7-ene (DBU) in dimethyl sulfoxide (DMSO) and toluene solvents. Equilibrium constants, primary deuterium kinetic isotope effects, and activation parameters are reported. The reaction of 1 with DBU is faster than that with TMG by factors of 5 and 50 in toluene and DMSO respectively. The primary deuterium kinetic isotope effects, kH/kD = 7–9, which are independent of the polarity of the solvent, indicate an u

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26

A., K. Meena, Daiya A., Sharma A., Banerji J., Kotai L., and Sharma Vinita. "Oxidation of some vicinal and non-vicinal diols by tetrakis(pyridine)silver dichromate : A kinetic and mechanistic study." Journal of Indian Chemical Society Vol. 88, Dec 2011 (2011): 1887–93. https://doi.org/10.5281/zenodo.5791827.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail</em> : drvsharma29@gmail.com Department of Chemistry, RGP Mahavidyalaya, Kolar Road, Bhopal-462 042, Madhya Pradesh, India institute of Material & Environmental Chemistry, CRC, HAS, Budapest, H - 1025, Hungary <em>Manuscript received 12 October 2011, accepted 17 October 2011</em> The kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by tctrakis(pyridinc)silver dichromate (TPSD) have been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the

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27

Rupal, Kumbhat, Sharma Vinita, and K. Banerji Kalyan. "Kinetics and mechanism of the oxidation of formic and oxalic acids by quinolinium bromochromate." Journal of Indian Chemical Society Vol. 80, Sep 2003 (2003): 815–19. https://doi.org/10.5281/zenodo.5837471.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, India <em>E-mail : </em>banerjikk@rediffmail.com                               <em>Fax : </em>91-0291-2742977 <em>Manuscript received </em>6 <em>September 2002, revised 25 February 2003, accepted 16 April 2003</em> Kinetics and mechanism of oxidation of formic and oxalic acids by quinolinium bromochromate (QBC) have been studied in DMSO. The main product of oxidation is carbon dioxide

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S., Barthora, Baghmar M., Agarwal S., and Sharma Vinita. "Oxidation of some vicinal and non-vicinal diols by morpholinium chlorochrmnate : A kinetic and mechanistic study." Journal of Indian Chemical Society Vol. 88, May 2011 (2011): 677–83. https://doi.org/10.5281/zenodo.5769061.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail</em> : drpkvs27@yahoo.com Department of Chemistry, Govt. J. D. B. Girls College, Kota-324 008, Rajasthan, India <em>Manuscript received 01 April 2010, revised 15 September 2010, accepted 16 September 2010</em> The kinetics of oxidation of four vicinal, four non-vicinal diols and two of their monoethers by morpholinium chlorochromate (MCC) have been studied in dimethylsulphoxide (DMSO). The main product of oxidation is the corresponding hydroxycarbonyl compound. The reaction is first order in MCC and the

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Jangir, Rakesh, Ketul Kumawat, Pramila Bishnoi, and Om Prakash. "Structure-reactivity relation in the oxidation of some aliphatic aldehydes by Tripropylammonium chlorochromate." Research Journal of Chemistry and Environment 27, no. 3 (2023): 74–80. http://dx.doi.org/10.25303/2703rjce074080.

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The oxidation of six aliphatic aldehydes by tripropylammonium chlorochromate (TPACC) in dimethyl sulfoxide (DMSO) leads to the formation of corresponding carboxylic acids. The reaction is of first order each in TPACC. A Michaelis-Menten type of kinetics is observed with respect to the aldehydes. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a + b[H+]. The oxidation of deuteriated acetaldehyde MeCDO exhibited a substantial primary kinetic isotope effect (kH/kD = 5.75 at 298 K). The oxidation of acetaldehyde has been studied in nineteen different or

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Zhang, Shuming, Hong Gu, Haoyuan Chen, et al. "Isotope effect analyses provide evidence for an altered transition state for RNA 2′-O-transphosphorylation catalyzed by Zn2+." Chemical Communications 52, no. 24 (2016): 4462–65. http://dx.doi.org/10.1039/c5cc10212j.

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Solvent D<sub>2</sub>O and<sup>18</sup>O kinetic isotope effects on RNA 2′-O-transphosphorylation catalyzed by Zn<sup>2+</sup>demonstrate an altered transition state relative to specific base catalysis.

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KALLOL, K. GHOSH, and GHOSH SHARMISTHA. "Kinetics of the Alkaline Hydrolysis of N-Phenylbenzohydroxamic Acid." Journal of Indian Chemical Society Vol. 72, Sep 1995 (1995): 603–7. https://doi.org/10.5281/zenodo.5909452.

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School of Studies in Chemistry, Pt Ravishankar Shukla University, Raipur-492 010 <em>Manuscript received 23 September 1993, revised 4 January 1994, accepted 1 March 1994</em> Kinetics of the alkaline hydrolysis of <em>N</em>-phenylbenzohydroxamic acid have been investigated spectrophotometrically in sodium hydroxide in 10% (v/v) dioxan at several temperatures. The enthalpies and entropies of activation have been evaluated, as also the salt, solvent isotope and solvent (dioxan) effects for the substrate. The effects of substitution have been assessed by means of the Hammett equation. A suitable

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32

Wong, Kenny K., Maria A. Vanoni, and John S. Blanchard. "Glutathione reductase: solvent equilibrium and kinetic isotope effects." Biochemistry 27, no. 18 (1988): 7091–96. http://dx.doi.org/10.1021/bi00418a063.

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Ram, Ganpat, Varsha Bishnoi, and Om Prakash. "Correlation analysis of reactivity in oxidation of some aliphatic aldehydes by 2-picolinium chlorochromate: A kinetic study." Research Journal of Chemistry and Environment 25, no. 11 (2021): 64–70. http://dx.doi.org/10.25303/2511rjce6470.

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The oxidation of six aliphatic aldehydes by 2- picolinium chlorochromate (PICC) in dimethyl sulfoxide (DMSO) leads to the formation of corresponding carboxylic acids. The reaction is of first order each in PICC. A Michaelis-Menten type of kinetics is observed with respect to the aldehydes. The reaction is catalysed by hydrogen ions. The hydrogen-ion dependence has the form: kobs = a + b[H+]. The oxidation of deuteriated acetaldehyde MeCDO exhibited a substantial primary kinetic isotope effect (kH/kD = 5.69 at 298 K). The oxidation of acetaldehyde has been studied in nineteen different organic

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34

Lai, Zhu-Gen, and Kenneth Charles Westaway. "Isotope effects in nucleophilic substitution reactions. VII. The effect of ion pairing on the substituent effects on SN2 transition state structure." Canadian Journal of Chemistry 67, no. 1 (1989): 21–26. http://dx.doi.org/10.1139/v89-004.

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The secondary α-deuterium kinetic isotope effects and substituent effect found in the SN2 reactions between a series of para-substituted sodium thiophenoxides and benzyldimethylphenylammonium ion are significantly larger when the reacting nucleophile is a free ion than when it is a solvent-separated ion pair complex. Tighter transition states are found when a poorer nucleophile is used in both the free ion and ion pair reactions. Also, the transition states for all but one substituent are tighter for the reactions with the solvent-separated ion pair complex than with the free ion. Hammett ρ va

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Uspenskaya, Elena V., Tatiana V. Pleteneva, Ilaha V. Kazimova, and Anton V. Syroeshkin. "Evaluation of Poorly Soluble Drugs’ Dissolution Rate by Laser Scattering in Different Water Isotopologues." Molecules 26, no. 3 (2021): 601. http://dx.doi.org/10.3390/molecules26030601.

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The most important task in the design of dosage forms is to modify the pharmaceutical substances structure in order to increase solubilization, targeted delivery, controlled rate of drug administration, and its bioavailability. Screening—laboratory (in vitro) or computer (in silico)—as a procedure for selecting a prototype for the design of a drug molecule, involves several years of research and significant costs. Among a large number of solvents and diluents (alcohol, ether, oils, glycerol, Vaseline) used in the pharmaceutical industry for the manufacture of drugs water finds the greatest app

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Liu, Min, Eleni Girma, Marcie A. Glicksman, and Ross L. Stein. "Kinetic Mechanistic Studies of Cdk5/p25-Catalyzed H1P Phosphorylation: Metal Effect and Solvent Kinetic Isotope Effect." Biochemistry 49, no. 23 (2010): 4921–29. http://dx.doi.org/10.1021/bi100244j.

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Hille, Russ. "Electron transfer within xanthine oxidase: a solvent kinetic isotope effect study." Biochemistry 30, no. 35 (1991): 8522–29. http://dx.doi.org/10.1021/bi00099a004.

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Ghosh, Kallos K., and Shiv G. Tandon. "Kinetic solvent isotope effect on acid-catalyzed hydrolysis of hydroxamic acids." Reaction Kinetics & Catalysis Letters 45, no. 1 (1991): 79–84. http://dx.doi.org/10.1007/bf02078612.

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Koo, In Sun, Ikchoon Lee, Jieun Oh, Kiyull Yang, and T. W. Bentley. "Substituent effects on the kinetic solvent isotope effect in solvolyses of arenesulphonyl chlorides." Journal of Physical Organic Chemistry 6, no. 4 (1993): 223–27. http://dx.doi.org/10.1002/poc.610060405.

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Dinesh, Panday, and Kothari Seema. "Kinetics and mechanism of the oxidation of formic and oxalic acids by benzimidazolium dichromate." Journal of Indian Chemical Society Vol. 89, Sep 2012 (2012): 1183–89. https://doi.org/10.5281/zenodo.5769139.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail</em> : seemakothari23@gmail.com, profskothari@gmail.com <em>Manuscript received 25 May 2011, accepted 16 December 2011</em> The oxidation of formic and oxalic acids by benzimidazolium dichromate (BIDC), in dimethyl sulfoxide, leads to the formation of carbon dioxide. The reaction is first order with respect to BIDC. Michaelis-Menten type kinetics were observed with respect to the organic acids. The values of the formation constants of the organic acid-BIDC complexes and the rates of their decomposition h

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M., Gehlot, Gilla M., Mishra P., and Sharma Vinita. "Kinetics and mechanism of the oxidation of aliphatic primary alcohols by imidazolium fluorochromate." Journal of Indian Chemical Society Vol. 88, May 2011 (2011): 685–92. https://doi.org/10.5281/zenodo.5769067.

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Chemical Kinetics Laboratory, Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail </em>: drpkvs27@yahoo.com <em>Manuscript received 06 April 2010, revised 15 September 2010, accepted 16 September 2010</em> The oxidation of nine aliphatic primary alcohols by imidazolium fluorochromate (IFC) in dimethylsulphoxide leads to the formation of corresponding aldehydes. The reaction is first order with respect to IFC. A Michaelis-Menten type kinetics is observed with respect to alcohols. The reaction is promoted by hydrogen ions; the hydrogen-ion dependence has th

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M., Gilla, K. Meena A., Swami P., Baghmar M., and Sharma Vinita. "Kinetics and mechanism of the oxidation of lower oxyacids of phosphorus by imidazolium fluorochromate." Journal of Indian Chemical Society Vol. 88, May 2011 (2011): 699–705. https://doi.org/10.5281/zenodo.5769081.

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Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India <em>E-mail</em> : drpkvs27@yahoo.com <em>Manuscript received 12 July 2010, revised 15 September 2010, accepted 16 September 2009</em> Oxidation of lower oxyacids of phosphorus by imidazolium nuorochromate (IFC) in dimethylsulphoxide (DMSO) leads to the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibits 1 : 1 stoichiometry. The reaction is first order with respect to IFC. A Michaelis-Menten type of kinetics was observed with respect to the reductants. The reaction

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Singadiya, Ambika, Rakesh Jangir, Pramila Bishnoi, and Om Prakash. "OXIDATION KINETICS AND INFLUENCE OF MEDIA ON SOME -HYDROXY ACIDS BY 2-PICOLINIUM CHLOROCHROMATE." RASAYAN Journal of Chemistry 15, no. 04 (2022): 2512–19. http://dx.doi.org/10.31788/rjc.2022.1547088.

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A few substituted mandelic acids are oxidized by one of the halochromates 2-picolinium chlorochromate (PiCC) under the influence of dimethyl-sulphoxide (DMSO) as a solvent medium, leading to the form of some oxo-acids. It was observed that this reaction is found to be of unit order with oxidant and less than unity with the reactant. It was also observed that the reaction is not proceeding through the free radical mechanism. A considerable kinetic isotope effect was observed in the oxidation of the deuteriated form of mandalic acid (DMA). The solvent isotope effect was also absent in this react

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Pruszynski, Przemyslaw, and Kenneth T. Leffek. "Phenyltetramethylguanidines: substituent effect on rates and isotope effects in their reaction with bis(4-nitrophenyl)cyanomethane in acetonitrile." Canadian Journal of Chemistry 69, no. 2 (1991): 205–10. http://dx.doi.org/10.1139/v91-033.

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A series of 22 phenyl substituted derivatives of 2-phenyl-1,1′,3,3′-tetramethylguanidine were used as bases in the proton transfer reaction from bis(4-nitrophenyl)cyanomethane in acetonitrile solvent. Brønsted and Hammett type relationships are examined for this family of closely related substrates. The Brønsted relationship constructed from the pKa values determined in acetonitrile shows β = 0.55 ± 0.03. The best fit of the Hammett relationship, with special values for p-NO2 and p-CN groups, gives the reaction constant ρ = −1.39 ± 0.1. The kinetic isotope effect, kH/kD, increases from 9.6 to

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Dragulska, Sylwia, and Marianna Kańska. "Enzymatic oxidation of substituted tryptamines catalysed by monoamine oxidase." Nukleonika 59, no. 3 (2014): 91–95. http://dx.doi.org/10.2478/nuka-2014-0015.

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Abstract The enzymatic deamination of 5-fl uorotryptamine and 5-hydroxytryptamine, 5-HT, catalysed by enzyme monoamine oxidase A (MAO-A, EC 1.4.3.4) was investigated using the kinetic (KIE) and solvent (SIE) isotope effects methods. The numerical values of deuterium isotope effects in the (1R) positions of 5-F-tryptamine were determined using non-competitive spectrophotomeric method. Isotopologue 5-F-[(1R)- -2H]-tryptamine, needed for kinetic studies was obtained by enzymatic decarboxylation of 5´-fl uoro-L-tryptophan, 5´-F-L-Trp, in fully deuteriated medium.

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Leffek, Kenneth T., and Przemyslaw Pruszynski. "Proton transfer reactions between ortho-methyl substituted derivatives of 4-nitrophenylphenylcyanomethane and nitrogen bases in acetonitrile solvent." Canadian Journal of Chemistry 66, no. 6 (1988): 1454–58. http://dx.doi.org/10.1139/v88-234.

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Equilibrium constants, rate constants, primary deuterium isotope effects, and activation parameters have been measured for the proton transfer reactions in acetonitrile solvent of 4-nitrophenylphenylcyanomethane and 2-methyl-4-nitrophenylphenyl-cyanomethane with tetramethylguanidine base and for the reactions of 2-methyl-4-nitrophenylphenylcyanomethane and 2,6-di-methyl-4-nitrophenylphenylcyanomethane with 1,5-diazabicyclo[5.4.0]undec-7-ene base. Introduction of the ortho-methyl groups in the substrate molecule caused significant reductions in the equilibrium and rate constants. The expected r

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Martin, Bruce L., and Donald J. Graves. "Isotope effects on the mechanism of calcineurin catalysis: kinetic solvent isotope and isotope exchange studies." Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology 1206, no. 1 (1994): 136–42. http://dx.doi.org/10.1016/0167-4838(94)90082-5.

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Lee, Ikchoon, Won Heui Lee, and Hai Whang Lee. "Kinetic solvent isotope effect studies on the methanolysis of 1-phenylethyl chlorides." Journal of Physical Organic Chemistry 6, no. 6 (1993): 361–66. http://dx.doi.org/10.1002/poc.610060608.

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Elsing, C., A. Hirlinger, E. L. Renner, B. H. Lauterburg, P. J. Meier, and J. Reichen. "Solvent isotope effect on bile formation in the rat." Biochemical Journal 307, no. 1 (1995): 175–81. http://dx.doi.org/10.1042/bj3070175.

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2H2O affects many membrane transport processes by solvent and kinetic isotope effects. Since bile formation is a process of osmotic filtration where such effects could be important, we investigated the effects of 2H2O on bile formation in the in situ perfused rat liver. Dose finding experiments showed that at high concentrations, 2H2O increased vascular resistance and induced cholestasis; at 60% 2H2O however, a clear dissociation between the vascular and biliary effects was observed. Therefore, further experiments were carried out at this concentration. The main finding was a reduction in bile

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A., Choudhary, Yajurvedi D., Soni S., Agarwal S., and Sharma Vinita. "Oxidation of aliphatic primary alcohols by morpholinium chlorochromate : A kinetic and mechanistic approach." Journal of Indian Chemical Society Vol. 87, Sep 2010 (2010): 1061–66. https://doi.org/10.5281/zenodo.5802043.

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Chemical Kinetics Laboratory, Department of Chemistry, J. N. V. University, Jodhpur-342 005, Rajasthan, India Department of Chemistry, Govt. JDB Girls College, Kota, Rajasthan, India <em>E-mail :</em> drpkvs27@yahoo.com <em>Manuscript received 5 March 2009, revised 19 February 2010, accepted 4 March 2010</em> The oxidation of nine aliphatic primary alcohols by morpholinium chlorochromate (MCC) in dimethyisulf-oxide leads to the transformation or alcohols to the corresponding aldehydes &. The reaction is first order with respect to both MCC and the alcohol both. The reaction is ca

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