The reaction of [(eta(6)-p-cymene)Ru(ATSC)Cl]PF(6) (ATSC = 9-anthraldehyde thiosemicarbazone) with human serum albumin was investigated at different temperatures using fluorescence and infrared spectrophotometry. The binding constant, K, for the reaction was determined using a number of different methods. Using a modified Stern-Volmer equation, K was determined to be 9.09 x 10(4), 12.1 x 10(4), and 13.1 x 10(4) M(-1) at 293 K, 298 K, and 308 K, respectively. A thermodynamic analysis showed that the reaction is spontaneous with DeltaG being negative. The enthalpy of reaction DeltaH = 16.5kJ mol(-1) and the entropy of reaction DeltaS = 152 Jmol(-1)K(-1). The values of DeltaH and DeltaS suggest that hydrophobic forces are dominant in the mode of interaction and that the process is mostly entropy driven.
采用荧光和红外分光光度法研究了[(eta(6)-对伞花素)Ru(ATSC)Cl]PF(6) (ATSC = 9-蒽醛硫代氨基脲)与人血清白蛋白在不同温度下的反应。反应的结合常数K是用许多不同的方法测定的。使用改进的Stern-Volmer方程，在293 K, 298 K和308 K下，K分别为9.09 x 10(4)， 12.1 x 10(4)和13.1 x 10(4) M(-1)。热力学分析表明，该反应为自发反应，DeltaG为负。反应焓δ δ = 16.5kJ mol(-1)，熵δ δ = 152 Jmol(-1)K(-1)。δ δ和δ δ的值表明疏水力在相互作用模式中占主导地位，并且该过程主要是熵驱动的。
{"title":"Reaction of the Anticancer Organometallic Ruthenium Compound, [(eta-p-Cymene)Ru(ATSC)Cl]PF(6) with Human Serum Albumin.","authors":"Floyd A Beckford","doi":"10.1155/2010/975756","DOIUrl":"https://doi.org/10.1155/2010/975756","url":null,"abstract":"<p><p>The reaction of [(eta(6)-p-cymene)Ru(ATSC)Cl]PF(6) (ATSC = 9-anthraldehyde thiosemicarbazone) with human serum albumin was investigated at different temperatures using fluorescence and infrared spectrophotometry. The binding constant, K, for the reaction was determined using a number of different methods. Using a modified Stern-Volmer equation, K was determined to be 9.09 x 10(4), 12.1 x 10(4), and 13.1 x 10(4) M(-1) at 293 K, 298 K, and 308 K, respectively. A thermodynamic analysis showed that the reaction is spontaneous with DeltaG being negative. The enthalpy of reaction DeltaH = 16.5kJ mol(-1) and the entropy of reaction DeltaS = 152 Jmol(-1)K(-1). The values of DeltaH and DeltaS suggest that hydrophobic forces are dominant in the mode of interaction and that the process is mostly entropy driven.</p>","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2010-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1155/2010/975756","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"29158990","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Monomeric five coordinated adducts of bis(O-ethyldithiocarbonato)copper(II) of general formula [Cu(C2H5OCS2)2(L)], [L = 2-, 3-, 4-methylpyridines and 2-, 3-, 4-ethylpyridines] have been synthesized and characterized by elemental analysis, i.r. and electronic spectroscopy, magnetic and conductivity measurements. Analytical results show that the adducts have 1 : 1 stoichiometry. The adducts were found to be paramagnetic and their magnetic moments at room temperature lie within the 1.81–1.94 B.M. range and this indicates the presence of one unpaired electron. All the adducts have distorted square pyramidal geometry.
{"title":"Synthesis and Characterization of the Adducts of Bis(O-ethyldithiocarbonato)copper(II) with Substituted Pyridines","authors":"G. Kour, Inderjeet Kour, R. Sachar","doi":"10.1155/2013/502856","DOIUrl":"https://doi.org/10.1155/2013/502856","url":null,"abstract":"Monomeric five coordinated adducts of bis(O-ethyldithiocarbonato)copper(II) of general formula [Cu(C2H5OCS2)2(L)], [L = 2-, 3-, 4-methylpyridines and 2-, 3-, 4-ethylpyridines] have been synthesized and characterized by elemental analysis, i.r. and electronic spectroscopy, magnetic and conductivity measurements. Analytical results show that the adducts have 1 : 1 stoichiometry. The adducts were found to be paramagnetic and their magnetic moments at room temperature lie within the 1.81–1.94 B.M. range and this indicates the presence of one unpaired electron. All the adducts have distorted square pyramidal geometry.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2009-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87936053","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
S. Vitushkina, D. V. Ziolkovskiy, V. Starodub, I. Presniakov, A. Sobolev, M. Kaj, A. Feher
The splitting of the quasidegenerate electronic states in dinuclear bis[(1,3-dithiole-2-thione-4,5-dithiolato)-di-(carbonyl) -cyclopentadienyliron (II)] complex with the bridging, S–S coupled, dimerized sulfur-rich dithiolate ligands, [Fe(C5H5)(CO)2(C3S5-C3S5)Fe(C5H5)(CO)2] (I) was found by the means of Mossbauer spectroscopy and by the measurement of the temperature dependence of magnetic susceptibility in a wide temperature range from 2?K to 300?K. The experimental results were confirmed by the calculations of the singlet and triplet states of the complex, as well as of the distribution of spin density within the bounds of the DFT method in the B3LYP/6-31(dp)G basis. In the more stable triplet state, the spin density is significantly delocalized, which is a characteristic of olefindithiolate complexes.
{"title":"Exchange Interaction in Complex Bis((1,3-Dithiole-2-Thione- 4,5-Dithiolato)-di-(Carbonyl)-Cyclopentadienyl Iron(II))","authors":"S. Vitushkina, D. V. Ziolkovskiy, V. Starodub, I. Presniakov, A. Sobolev, M. Kaj, A. Feher","doi":"10.1155/2009/243296","DOIUrl":"https://doi.org/10.1155/2009/243296","url":null,"abstract":"The splitting of the quasidegenerate electronic states in dinuclear bis[(1,3-dithiole-2-thione-4,5-dithiolato)-di-(carbonyl) -cyclopentadienyliron (II)] complex with the bridging, S–S coupled, dimerized sulfur-rich dithiolate ligands, [Fe(C5H5)(CO)2(C3S5-C3S5)Fe(C5H5)(CO)2] (I) was found by the means of Mossbauer spectroscopy and by the measurement of the temperature dependence of magnetic susceptibility in a wide temperature range from 2?K to 300?K. The experimental results were confirmed by the calculations of the singlet and triplet states of the complex, as well as of the distribution of spin density within the bounds of the DFT method in the B3LYP/6-31(dp)G basis. In the more stable triplet state, the spin density is significantly delocalized, which is a characteristic of olefindithiolate complexes.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2009-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73842028","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A new series of macrocyclic complexes of type [M(TML)X]X2; where M = Cr(III), Mn(III), or Fe(III); TML is tetradentate macrocyclic ligand and X = Cl−1, NO3−1, CH3COO−1 for Cr(III), Fe(III), and X = CH3COO−1 for Mn(III) has been synthesized by template condensation of succinyldihydrazide and glyoxal. The complexes have been formulated as [M(TML)X]X2 due to 1:2 electrolytic natures of these complexes as shown by conductivity measurements. The complexes have been characterized with the help of elemental analyses, molar conductance, electronic, infrared, far infrared spectral studies and magnetic susceptibilities. On the basis of these studies, a five-coordinate distorted square-pyramidal geometry, in which two nitrogens and two carbonyl oxygen atoms are suitably placed for coordination toward the metal ion, has been proposed for all the complexes. The complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activities against some selected bacterial strains. The minimum inhibitory concentration shown by these complexes was compared with minimum inhibitory concentration shown by some standard antibiotics like linezolid and cefaclor.
{"title":"Synthesis and Characterization of Biologically Active 10-Membered Tetraazamacrocyclic Complexes of Cr(III), Mn(III), and Fe(III)","authors":"D. Singh, V. Malik, Ramesh Kumar","doi":"10.1155/2009/824561","DOIUrl":"https://doi.org/10.1155/2009/824561","url":null,"abstract":"A new series of macrocyclic complexes of type [M(TML)X]X2; where M = Cr(III), Mn(III), or Fe(III); TML is tetradentate macrocyclic ligand and X = Cl−1, NO3−1, CH3COO−1 for Cr(III), Fe(III), and X = CH3COO−1 for Mn(III) has been synthesized by template condensation of succinyldihydrazide and glyoxal. The complexes have been formulated as [M(TML)X]X2 due to 1:2 electrolytic natures of these complexes as shown by conductivity measurements. The complexes have been characterized with the help of elemental analyses, molar conductance, electronic, infrared, far infrared spectral studies and magnetic susceptibilities. On the basis of these studies, a five-coordinate distorted square-pyramidal geometry, in which two nitrogens and two carbonyl oxygen atoms are suitably placed for coordination toward the metal ion, has been proposed for all the complexes. The complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activities against some selected bacterial strains. The minimum inhibitory concentration shown by these complexes was compared with minimum inhibitory concentration shown by some standard antibiotics like linezolid and cefaclor.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2009-04-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85908480","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The reaction has been studied spectrophotometrically; the reaction shows two steps, both of which are dependent on ligand concentration and show a limiting nature. An associative interchange mechanism is proposed. Kinetic and activation parameters (k1∼10−3s−1 and k2∼10−5s−1) and (ΔH≠1=13.8±1.3kJmol−1, ΔS≠1=−250±4JK−1mol−1, ΔH≠2=55.53±1.5kJmol−1, and ΔS≠2=−143±5JK−1mol−1) have been calculated. From the temperature dependence of the outer sphere association equilibrium constant, thermodynamic parameters (ΔH∘1=16.6±2.3kJmol−1 and ΔS∘1=95±7JK−1mol−1; ΔH∘2=29.4±3.2kJmol−1 and ΔS∘2=128±10JK−1mol−1) have also been calculated.
{"title":"Kinetic and Mechanistic Studies on the Reaction of DL-Methionine with [(H2O)(tap)2RuORu(tap)2(H2O)]2","authors":"Tandra Das, A. Datta, A. Ghosh","doi":"10.1155/2009/314672","DOIUrl":"https://doi.org/10.1155/2009/314672","url":null,"abstract":"The reaction has been studied spectrophotometrically; the reaction shows two steps, both of which are dependent on ligand concentration and show a limiting nature. An associative interchange mechanism is proposed. Kinetic and activation parameters (k1∼10−3s−1 and k2∼10−5s−1) and (ΔH≠1=13.8±1.3kJmol−1, ΔS≠1=−250±4JK−1mol−1, ΔH≠2=55.53±1.5kJmol−1, and ΔS≠2=−143±5JK−1mol−1) have been calculated. From the temperature dependence of the outer sphere association equilibrium constant, thermodynamic parameters (ΔH∘1=16.6±2.3kJmol−1 and ΔS∘1=95±7JK−1mol−1; ΔH∘2=29.4±3.2kJmol−1 and ΔS∘2=128±10JK−1mol−1) have also been calculated.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2009-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91525766","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The kinetics and mechanism of the reduction of chromium(VI) by lactic acid (Lac) in aqueous acidic medium was studied with spectrophotometry in a temperature range of 298.15 K~313.15 K. Under the conditions of the pseudo-first order ([Lac]0≫[Cr(VI)]0), the observed rate constant (𝑘obs) increased with the increase in [Lac] and [H
{"title":"Kinetic and Mechanistic Study of the Reduction of Chromium(VI) by Lactic Acid","authors":"J. Shan, F. Wang, C. Song, He Wang","doi":"10.1155/2008/314045","DOIUrl":"https://doi.org/10.1155/2008/314045","url":null,"abstract":"The kinetics and mechanism of the reduction of chromium(VI) by lactic acid (Lac) in aqueous acidic medium was studied with spectrophotometry in a temperature range of 298.15 K~313.15 K. Under the conditions of the pseudo-first order ([Lac]0≫[Cr(VI)]0), the observed rate constant (𝑘obs) increased with the increase in [Lac] and [H","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2008-12-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84736270","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Reaction of M(CO)6; M = Mo or W with isatin in the presence of triphenylphosphine in THF under reduced pressure gave the tricarbonyl derivatives complexes [M(CO)3(isatH)(PPh3)]. The two complexes were characterized by elemental analysis, infrared, mass and 1H NMR spectroscopy. The spectroscopic studies show that the two complexes exist in fac- and mer-isomers in solutions through exchange the CO group and PPh3. The Uv-Vis spectra of the complexes in different solvents were studied.
{"title":"Molybdenum and Tungsten Tricarbonyl Complexes of Isatin with Triphenylphosphine","authors":"M. Khalil, F. A. Al-Seif, S. Arabia","doi":"10.1155/2008/746058","DOIUrl":"https://doi.org/10.1155/2008/746058","url":null,"abstract":"Reaction of M(CO)6; M = Mo or W with isatin in the presence of triphenylphosphine in THF under reduced pressure gave the tricarbonyl derivatives complexes [M(CO)3(isatH)(PPh3)]. The two complexes were characterized by elemental analysis, infrared, mass and 1H NMR spectroscopy. The spectroscopic studies show that the two complexes exist in fac- and mer-isomers in solutions through exchange the CO group and PPh3. The Uv-Vis spectra of the complexes in different solvents were studied.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2008-11-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73016014","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Kinetics and mechanism of oxidation of leucine and alanine by Ag(III) complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III) complex and amino acids (leucine, alanine). The second-order rate constant, 𝑘−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.
{"title":"Kinetics and Mechanism of Oxidation of Leucine and Alanine by Ag(III) Complex in Alkaline Medium","authors":"C. Song, Lei Chen, J. Shan","doi":"10.1155/2008/786857","DOIUrl":"https://doi.org/10.1155/2008/786857","url":null,"abstract":"Kinetics and mechanism of oxidation of leucine and alanine by Ag(III) complex were studied spectrophotometrically in alkaline medium at constant ion strength. The reaction was in first order with respect to Ag(III) complex and amino acids (leucine, alanine). The second-order rate constant, 𝑘−, decreased with the increasing in [OH−] and [IO4−]. A plausible mechanism was proposed from the kinetics study, and the rate equations derived from mechanism can explain all experimental phenomena. The activation parameters were calculated at 298.2 K.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2008-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"72952378","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In presence of osmium(VIII), the reaction between L-tryptophan and diperiodatocuprate(III) DPC in alkaline medium exhibits 1:4 stochiometry (L-tryptophan:DPC). The reaction shows first-order dependence on [DPC] and [osmium(VIII)], less than unit order in both [L-tryptophan] and [alkali], and negative fractional order in [periodate]. The active species of catalyst and oxidant have been identified. The main products were identified by spectral studies and spot test. The probable mechanism was proposed and discussed.
{"title":"Mechanistic Aspects of Osmium(VIII) Catalyzed Oxidation of L-Tryptophan by Diperiodatocuprate(III) in Aqueous Alkaline Medium: A Kinetic Model","authors":"N. Shetti, R. R. Hosamani, S. Nandibewoor","doi":"10.1155/2008/216058","DOIUrl":"https://doi.org/10.1155/2008/216058","url":null,"abstract":"In presence of osmium(VIII), the reaction between L-tryptophan and diperiodatocuprate(III) DPC in alkaline medium exhibits 1:4 stochiometry (L-tryptophan:DPC). The reaction shows first-order dependence on [DPC] and [osmium(VIII)], less than unit order in both [L-tryptophan] and [alkali], and negative fractional order in [periodate]. The active species of catalyst and oxidant have been identified. The main products were identified by spectral studies and spot test. The probable mechanism was proposed and discussed.","PeriodicalId":14074,"journal":{"name":"International Journal of Inorganic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2008-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90503023","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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