High-sensitive determination of coenzyme Q(10) in iodinate-beta-cyclodextrin medium by inclusion reaction and catalytic polarography

A novel polarographic method for the determination of coenzyme Q(10) in beta-cyclodextrin (beta-CD) and iodinate system is proposed. The stability of coenzyme Q(10) to light was improved by the formation of coenzyme Q(10)-beta-CD inclusion complex. In addition, the sensitivity for the determination of coenzyme Q(10) was enhanced by both the formation and the polarographic catalytic wave of the inclusion complex in the presence of iodinate. In 0.1 mol/L HAc-NaAc (pH 4.7)-5.0 x 10(-5) mol/L beta-CD-1.2 x 10(-3) mol/L potassium iodinate-ethanol/water (60:40, v/v) medium, coenzyme Q(10)-beta-CD inclusion complex yielded a sensitive association/parallel catalytic wave. The second-order derivative peak current of the catalytic wave was proportional to coenzyme Q(10) concentration in the range of 6.0 x 10(-8)-2.5 x 10(-7) mol/L, and the detection limit was 1.0 x 10(-8) mol/L. The proposed method has high analytical sensitivity and is allowed to determine coenzyme Q(10) under light.     

Binding behavior of aliphatic oligopeptides by bridged and metallobridged bis(beta-cyclodextrin)s bearing an oxamido bis(2-benzoic) carboxyl linker

beta-Cyclodextrin dimers bearing an oxamido bis(2-benzoic) carboxyl linker (1) or its metal complexes (2 and 3) were newly synthesized, and their inclusion complexation behavior with a series of representative aliphatic oligopeptides, i.e., Leu-Gly, Gly-Leu, Gly-Pro, Glu-Glu, Gly-Gly, Gly-Gly-Gly, and Glu(Cys-Gly), was elucidated by means of UV/vis, circular dichroism, fluorescence, and 2D NMR spectroscopy in Tris-HCl buffer solution (pH 7.4) at 25 degrees C. The results obtained indicated that metallobridged bis(beta-cyclodextrin)s 2 or 3 could significantly enhance the original molecular binding abilities of parent bis(beta-cyclodextrin) 1 toward model substrates through the cooperative binding of two cyclodextrin moieties and the additional chelation effect supplied by the coordinated metal centers. It is interesting that hosts 2 and 3 displayed an entirely different fluorescence behavior upon complexation with guest oligopeptides. Among the guest peptides examined, 3 showed the highest complex formation constant of 68 200 M(-)(1) for Glu-Glu, up to 510-fold as compared with 1 (135 M(-)(1)), while 1 gave excellent molecular selectivity for Glu(Cys-Gly)/Glu-Glu pair, up to 51-fold. The molecular binding ability and selectivity were discussed from the viewpoints of the induced-fit and multiple recognition mechanism between host and guest.     

Efficient fluorescent sensors of oligopeptides by dithiobis(2-benzoylamide)-bridged bis(beta-cyclodextrin)s: structure in solution, binding behavior, and thermodynamic origin

Two 6,6'-bis(beta-cyclodextrin)s linked by 2,2'-dithiobis[2-(benzoylamino)ethyleneamino] and 2,2'-dithiobis[2-(benzoylamino)diethylenetriamino] bridges (1 and 2) have been synthesized as cooperative multipoint recognition receptor models for non-aromatic oligopeptides. Their structures in solution and inclusion complexation mechanism are comprehensively investigated by means of circular dichroism, 2D NMR spectra and temperature-dependent fluorescence titrations. The results show that the cooperative 'host-linker-guest' binding mode and the extensive desolvation effect jointly contribute to the guest-induced fluorescence enhancement of bis(beta-cyclodextrin)s. Further examinations on the binding behavior of hosts 1-2 with a series of di- and tri-peptides demonstrate that bis(beta-cyclodextrin) 1 can recognize not only the size/shape of oligopeptides but also the dipeptide sequence, giving an exciting residue selectivity up to 37.5 for Gly-Gly-Gly/Glu-Glu pair and a high sequence selectivity up to 5.0 for Gly-Leu/Leu-Gly pair. These fairly good selectivities are discussed from the viewpoint of cooperative binding, multiple recognition and induced-fit interactions between host and guest.     

Molecular binding behavior of pyridine-2,6-dicarboxamide-bridged bis(beta-cyclodextrin) with oligopeptides: switchable molecular binding mode

Bridged bis(beta-cyclodextrin) 1 with a pyridine-2,6-dicarboxamide linker was synthesized, and its inclusion complexation behavior with some aliphatic oligopeptides was investigated in aqueous buffer solution of pH 2.0 and 7.2 at 25 degrees C by means of circular dichroism, fluorescence, and 2D NMR techniques. The results show that the resulting inclusion complexes of 1 with oligopeptides adopt a cooperative "cyclodextrin-guest-cyclodextrin" sandwich binding mode in a neutral media, but a "guest-linker-cyclodextrin" coinclusion binding mode in an acidic media. These switchable binding modes consequently rationalize the binding ability of bis(beta-cyclodextrin) 1 at different pH values; that is, 1 shows the stronger association with oligopeptides in a neutral media. Because of the simultaneous contributions of hydrophobic, hydrogen bond, and electrostatic interactions, bis(beta-cyclodextrin) 1 affords length-selectivity up to 4.7 for the Gly-Gly/Gly-Gly-Gly pair at pH 2.0 and sequence-selectivity up to 4.2 for the Gly-Leu/Leu-Gly pair at pH 7.2. These phenomena are discussed from the viewpoint of the size-fit concept and the multipoint recognitions between host and guest.     

The rate constants of the reaction of hydroxyl radicals (*OH) with alcohol dehydrogenase and Glyceraldehyde-3-phosphate dehydrogenase

The rate constants of the reactions of alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase with hydroxyl radicals were determined using the method of steady-state competitive reactions. Ethanol was used as a scavenger of hydroxyl radicals. The rate constants of the reactions of hydroxyl radicals with alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase were found to be 2.8 x 10(12) dm(3) mol(-1) s(-1), and 1.6 x 10(12) dm(3) mol(-1) s(-1), respectively.     

Electron paramagnetic resonance, kinetics of formation and decomposition studies of (bis(hydroxyethyl)amino-tris(hydroxymethyl)-methane)oxochromate(V): a model chromium(V) complex for DNA damage studies

A new chromium complex, (bis(hydroxyethyl)amino-tris(hydroxymethyl)methane)oxochromate(V), has been characterized by epr spectroscopy. The chromium(V) complex was formed by the ligand displacement reaction of bis(2-ethyl-2-hydroxybutanato) oxochromate(V) with bis(hydroxyethyl)amino-tris(hydroxy-methyl)methane (BT). Both epr and kinetic data indicate that the reaction proceeds through a chromium(V) intermediate. Kinetics of formation of the intermediate exhibit a rate saturation at higher [BT] (> 30 mM) indicating a rate law constituting an equilibrium between the parent Cr(V) complex and the bis-tris ligand followed by a pure first order process. The g-value of the intermediate is consistent with a Cr(V) complex in which the BT is coordinated in a bidentate fashion replacing a coordinated hydroxy butanoic acid ligand, affording a mixed ligand complex. The equilibrium step (K = 36 M-1) consists of monodentate coordination by the BT ligand and the limiting first order rate constant (1.9 x 10(-2) s-1) manifests the rate of chelation by the polydentate ligand. The intermediate is converted to the product upon further chelation through the complete displacement of the remaining 2-ethyl-2-hydroxy butanoic acid by a first order process (k = 0.023 s-1). The epr data support a pair of products that are in rapid equilibrium. In these products, BT functions either as a tetra or a penta-dentate ligand coordinating through four or five alkoxy sites. The enthalpy and entropy of activations related to the two chelation steps were found to be 32 +/- 2 kJ/mol and -(1.7 +/- 0.2) x 10(2) J/mol K for the intermediate, and 36 +/- 1 kJ/mol and -(1.5 +/- 0.2) x 10(2) J/mol K for the product. Our data support an associative mechanism for the chelation steps. The Cr(V)-BT product is more stable than the parent complex. The second order disproportionation rate constant for the Cr(V)-BT complex was evaluated to be 0.1 M-1 s-1 compared to 8.0 M-1 s-1 for the parent complex. This is the first example of a chromium(V) complex with a non-macrocyclic ligand coordinating through oxygen donor atoms which is stable in aqueous solution at neutral pH over a long period of time.     

Antioxidant properties of Plumbago zeylanica, an Indian medicinal plant and its active ingredient, plumbagin

Plumbago zeylanica (known as "Chitrak") is a useful Indian medicinal plant. The root of the plant and its constituents are credited with potential therapeutic properties including anti-atherogenic, cardiotonic, hepatoprotective and neuroprotective properties. To examine possible mechanisms of action of P. zeylanica (Chitrak), in relation to its reported beneficial properties, antioxidant effects of the aqueous/alcoholic extracts of root, corresponding to medicinal preparations, and the active ingredient, plumbagin, were studied. Methods used included: ferric reducing/antioxidant power (FRAP), radical scavenging of 1,1-diphenyl-2-picryl hydrazyl (DPPH) and 2,2'-azobis-3-ethylbenzthiazoline-6-sulfonic acid (ABTS), lipid peroxidation in rat liver mitochondria induced by different agents, and estimating phenolic and flavonoid content. In FRAP/DPPH assays, boiled ethanolic extracts were the most effective, while in the ABTS assay boiled aqueous extracts were the most efficient. These extracts also significantly inhibited lipid peroxidation induced by cumene hydroperoxide, ascorbate-Fe(2+) and peroxynitrite and contained high amounts of polyphenols and flavonoids. To examine the mechanisms of action in detail, antioxidant and pulse radiolysis studies with plumbagin were conducted. The hydroxyl (.OH), alkyl peroxyl (CCl(3)OO.), linoleic acid peroxyl (LOO.), and glutathiyl (GS.) radicals generate a phenoxyl radical upon reaction with plumbagin. The bimolecular rate constants were: .OH, 2.03 x 10(9) dm(3)mol(-1)s(-1); CCl(3)OO., 1.1 x 10(9) dm(3)mol(-1)s(-1); LOO., 6.7 x 10(7) dm(3)mol(-1)s(-1); and GS., 8.8 x 10(8) dm(3)mol(-1)s(-1). In conclusion, our studies reveal that extracts of P. zeylanica and its active ingredient plumbagin have significant antioxidant abilities that may possibly explain some of the reported therapeutic effects.     

Synthesis of ethylenediamine linked beta-cyclodextrin dimer and its analytical application for tranilast determination by spectrofluorimetry

A synthesis of beta-cyclodextrin (beta-CD) dimer, containing two beta-CD moieties that are linked through their sides by ethylenediamine, was presented. The dimer was characterized by means of IR, (1)H NMR, (13)C NMR, and elemental analysis. The inclusion complexation behavior of beta-cyclodextrin dimer with tranilast was studied in an aqueous KH(2)PO(4)-citric acid buffer solution of pH 2.00 at room temperature by spectrofluorimetry. Based on the significant enhancement of fluorescence intensity of tranilast, a spectrofluorimetric method with high sensitivity and selectivity was developed for the determination of tranilast in bulk aqueous solution in the presence of ethylenediamine beta-CD dimer. The apparent association constant of the complex was 8.39 x 10(3) L mol(-1), and the linear range was 10.8-1.40 x 10(4) ng mL(-1) with the detection limit 3.2 ng mL(-1). There was no interference from the excipients normally used in tablets and serum constituents. The proposed method was successfully applied to the determination of tranilast in serum.     

Reactivity of halides with triplets of 6-chloro and 6-bromopicolinic acids: contrasting effects of bromide and chloride.

The reactivity of Br(-) and Cl(-) with triplet of anionic 6-chloropicolinic acid (pH = 5.4) and with triplets of 6-chloro and 6-bromopicolinic acids in zwitterionic forms (pH = 0.9) was studied by laser flash photolysis and steady-state irradiation. Br(-) was found to trap the three triplets. Triplet lifetime measurements gave quenching rate constants of 8 x 10(8) mol(-1) dm(3) s(-1) for the zwitterion of 6-chloropicolinic acid and of 3.4 x 10(5) mol(-1) dm(3) s(-1) for the anionic counterpart. No secondary transient species were observed indicating that the charge transfer intermediates are subject to dissipative processes. Cl(-) trapped triplet of zwitterions only, and reactions were found to be associated with a high quantum yield of radicals. The photolysis of 6-bromopicolinic acid photolysis was drastically enhanced by Cl(-), 6-chloropicolinic acid being produced with a chemical yield of about 90%. The 6-bromo-2-carboxypyridinyl radical could be characterized (lambda(max)/nm = 318 with shoulder at 370 nm and epsilon/mol(-1) dm(3) cm(-1) = 8100).     

Selective binding of chiral molecules of cinchona alkaloid by beta- and gamma-cyclodextrins and organoselenium-bridged bis(beta-cyclodextrin)s

The inclusion complexation behavior of chiral members of cinchona alkaloid with beta- and gamma-cyclodextrins (1 and 2) and 6,6(')-trimethylenediseleno-bridged bis(beta-cyclodextrin) (3) was assessed by means of fluorescence and 2D-NMR spectroscopy. The spectrofluorometric titrations have been performed in aqueous buffer solution (pH 7.20) at 25.0 degrees C to determine the stability constants of the inclusion complexation of 1-3 with guest molecules (i.e., cinchonine, cinchonidine, quinine, and quinidine) in order to quantitatively investigate the molecular selective binding ability. The stability constants of the resulting complexes of 2 with guest molecules are larger than that of 1. As a result of cooperative binding, the stability constants of inclusion complexation of dimeric beta-cyclodextrin 3 with cinchonidine and cinchonine are higher than that of parent 1 by factor of 4.5 and 2.4, respectively. These results are discussed from the viewpoint of the size-fit and geometric complementary relationship between the host and guest.     

Temperature-responsive cellulose by ceric(IV) ion-initiated graft copolymerization of N-isopropylacrylamide

Temperature-responsive cellulose has been obtained by graft copolymerization of N-isopropylacrylamide (NIPAAm) monomer using ceric ammonium nitrate (CAN) as initiator at 25.0 +/- 0.1 degrees C in acidic medium. Kinetic and grafting parameters were evaluated at different concentrations of NIPAAm ranging from 1.25 x 10(-3) to 12.5 x 10(-3) mol dm(-3) and varying concentrations of CAN from 1.5 x 10(-3) to 9.0 x 10(-3) mol dm(-3) at constant concentration of nitric acid (2.5 x 10(-2) mol dm(-3)). The graft copolymerization of NIPAAm onto cellulose has shown a significant increasing trend below lower critical solution temperature (LCST) of poly(N-isopropylacrylamide) (PNIPAAm) and shown low energy of activation (18.0 kJ mol(-1)) for graft copolymerization within the temperature range of 10-35 degrees C as determined with Arrhenius plot. The PNIPAAm-grafted cellulose has shown improved thermal stability and shown temperature-dependent degree of swelling. Variation in degree of swelling of PNIPAAm-grafted cellulose as a function of temperature has been used to determine LCST of PNIPAAm-grafted cellulose. The contact angle (theta) has shown variation on increasing the graft yield and temperature. On the basis of experimental observations, the reaction steps for graft copolymerization have been proposed and a rate expression has been derived.     

Use of cyclodextrins as a cosmetic delivery system for fragrance materials: Linalool and benzyl acetate

The aim of this study was to increase the stability and water solubility of fragrance materials, to provide controlled release of these compounds, and to convert these substances from liquid to powder form by preparing their inclusion complexes with cyclodextrins (CDs). For this purpose, linalool and benzyl acetate were chosen as the fragrance materials. The use of beta-cyclodextrin (beta CD) and 2-hydroxypropyl-beta-cyclodextrin (2-HP beta CD) for increasing the solubility of these 2 fragrance materials was studied. Linalool and benzyl acetate gave a B-type diagram with beta CD, whereas they gave an A(L)-type diagram with 2-HP beta CD. Therefore, complexes of fragrance materials with 2-HP beta CD at 1:1 and 1:2 molar ratios (guest:host) were prepared. The formation of inclusion complexes was confirmed using proton nuclear magnetic resonance ((1)H-NMR) spectroscopy and circular dichroism spectroscopy. The results of the solubility studies showed that preparing the inclusion complex with 2-HP beta CD at a 1:1 molar ratio increased the solubility of linalool 5.9-fold and that of benzyl acetate 4.2-fold, whereas the complexes at a 1:2 molar ratio increased the solubility 6.4- and 4.5-fold for linalool and benzyl acetate, respectively. The stability and in vitro release studies were performed on the gel formulations prepared using uncomplexed fragrance materials or inclusion complexes of fragrance materials at a 1:1 molar ratio. It was observed that the volatility of both fragrance materials was decreased by preparing the inclusion complexes with 2-HP beta CD. Also, in vitro release data indicated that controlled release of fragrances could be possible if inclusion complexes were prepared.     

Chemical properties of water-soluble porphyrins. 4. The reaction of a 'picket-fence-like' iron (III) complex with the superoxide oxygen couple

Solution properties of the iron-(III) 'picket-fence-like' porphyrin, Fe(III)-alpha,alpha,alpha, beta-tetra-ortho (N-methyl-isonicotinamidophenyl) porphyrin, (Fe(III)PFP) were investigated. These were acid/base properties of the aquo complex with pKa of 3.9 and its aggregation (formation of dimer with K = 1 X 10(-10) dm3 mol-1), complex formation with cyanide ions and 1-methyl imidazole (1-MeIm), spectral properties of the three iron complexes in their ferric and ferrous form and the one-electron reduction potential of these complexes. Knowing these properties, the reaction of the ferric complexes, aquo, dicyano and bis (1-MeIm), with the superoxide radical and other reducing radicals were studied using the pulse radiolysis technique. The second-order reaction rate constant of O2- with the iron (III) aquo complex which governs the catalytic efficiency of the metalloporphyrin upon the disproportionation of the superoxide radical was 7.6 X 10(7) dm3 mol-1 s-1, two orders of magnitude faster when compared to the reaction of each of the other complexes. The reduction by other radicals with all iron (III) complexes had similar second-order rate constants (10(9) to 10(10) dm3 mol-1 s-1). The reduction reaction in all cases produced Fe(II)PEP and no intermediate was found. The oxidation reaction of Fe(II)PEP by O2- was one order of magnitude faster when compared to the reduction of Fe(III)PFP by the same radical. Since the reactivity of O2- toward the three iron (III) porphyrin complexes follows their reduction potentials, it is suggesting the formation of a peroxo Fe(II) porphyrin as an intermediate. The reactions of the Fe(II)PFP complexes with dioxygen were also studied. The aquo complex was found to be first order in O2 and second order in Fe(II)PFP, suggesting the formation of a peroxo Fe(II) porphyrin as an intermediate. The intermediate formation was corroborated by evidence of the rapid CO binding reaction to the aquo complex of Fe(II)PFP. The two other complexes reacted very slowly with O2 as well as with CO.     

Inclusion complexes of azadirachtin with native and methylated cyclodextrins: solubilization and binding ability

The inclusion complexation behavior of azadirachtin with several cyclodextrins and their methylated derivatives has been investigated in both solution and the solid state by means of XRD, TG-DTA, DSC, NMR, and UV-vis spectroscopy. The results show that the water solubility of azadirachtin was obviously increased after resulting inclusion complex with cyclodextrins. Typically, beta-cyclodextrin (beta-CD), dimethyl-beta-cyclodextrin (DMbetaCD), permethyl-beta-cyclodextrin (TMbetaCD), and hydroxypropyl-beta-cyclodextrin (HPbetaCD) are found to be able to solubilize azadirachtin to high levels up to 2.7, 1.3, 3.5, and 1.6 mg/mL (calculated as azadirachtin), respectively. This satisfactory water solubility and high thermal stability of the cyclodextrin-azadirachtin complexes, will be potentially useful for their application as herbal medicine or healthcare products.     

Synthesis,biodistribution and antitumor activity of hematoporphyrin-platinum(II) conjugates

A new series of platinum(II) complexes of pegylated hematoporphyrin derivatives with controlled hydrophobic/hydrophilic balance were synthesized by introducing different kinds of poly(ethylene glycol) and amine ligands to the porphyrin ring. The antitumor activity of the porphyrin-platinum(II) conjugates was assayed in vitro and in vivo against leukemia L1210 cell line and various human tumor cell lines. The present complexes exhibited high antitumor activity and improved water solubility as well as considerable lipophilicity. In particular, complex 16 showed not only higher in vivo activity (T/C%=258) than cisplatin (T/C%=184) and carboplatin (T/C%=168), but also excellent solubility in water and organic solvent. The antitumor activity of complex 20 was superior to that of carboplatin against all human tumor cell lines tested. Moreover, some amphiphilic complexes (7 and 12) exhibited elevated tumor-localizing effect (tumor/muscle ratio>2).     

Inclusion complexation behavior of dyestuff guest molecules by a bridged bis(cyclomaltoheptaose)[bis(beta-cyclodextrin)] with a pyromellitic acid diamide tether

A novel bridged bis(beta-cyclodextrin) with a pyromellitic acid 2,5-diamide tether (2) has been synthesized by reaction of 6(I)-(2-aminoethyleneamino)-6-deoxycyclomaltoheptaose [mono 6-(2-aminoethyleneamino)-6-deoxy-beta-cyclodextrin] with 1,2,4,5-benzenetetracarboxylic dianhydride. Its inclusion complexation behavior with some representative dyestuffs, i.e., Acridine Red (AR), Rhodamine B (RhB), Neutral Red (NR), Brilliant Green (BG), was studied by using UV-absorption, fluorescence, and 2D NMR spectroscopy. Fluorescence titrations have been performed at 25 degrees C in pH 7.2 buffer solution to calculate the binding constants of resulting complexes. These results obtained indicated that bis(beta-cyclodextrin) 2 exhibits the strongly enhanced binding ability with all dye molecules examined compared with natural cyclodextrins. The binding modes of 2 with dye molecules have been deduced by 2D NMR experiments to establish the correlations between molecular conformations and binding constants of inclusion complexation. It is found that the improved binding ability and molecular selectivity of 2 could be attributed to double-cavity cooperative inclusion interaction and the size/shape matching between the host and guest.     

Solubilization of cholesterol and polycyclic aromatic compounds into sodium bile salt micelles (part 2)

The aqueous solubility of cholesterol was determined over the temperature range from 288.2 to 318.2 K with intervals of 5 K by the enzymatic method. The solubility was (3.7+/-0.3)x10(-8) mol dm(-3) (average +/- S.D.) at 308.2 K. The maximum additive concentrations of cholesterol into the aqueous micellar solutions of sodium deoxycholate (NaDC), sodium ursodeoxycholate (NaUDC), and sodium cholate (NaC) were spectrophotometrically determined at different temperatures. The cholesterol solubility increased in the order of NaUDC相似文献   

A novel metallobridged bis(beta-cyclodextrin)s fluorescent probe for the determination of glutathione

A novel metallobridged bis(beta-cyclodextrin)s 2 [bis(beta-CD)s 2] was synthesized and characterized by means of (1)H NMR, IR, element analysis and redox iodometric titration. The fluorescence of metallobridged bis(beta-CD)s 2 was weak compared with bis(beta-CD)s 1 because of the paramagnetism of copper (II) ions. Glutathione was able to form complexes with copper (II) derived from the metallobridged bis(beta-CD)s 2. This competitive complexation with copper (II) may lead to a significant fluorescence recovery of the bis(beta-CD)s. Therefore, a rapid and simple spectrofluorimetric method was developed for the determination of glutathione. The analytical application for glutathione was investigated in NaCl/P(i) (pH 6.00) at room temperature. The linear range of the method was 0.30-20.0 micromol.L(-1) with a detection limit of 63.8 nmol.L(-1). There was no interference from the plasma constituents. The proposed method had been successfully used to determine glutathione in human plasma.     

Pulse radiolysis studies of beta-carotene in oxygenated DMSO solution. Formation of beta-carotene radical cation

The spectroscopic and kinetic characteristics of beta-carotene radical cation (beta-carotene(.+)) were studied by pulse radiolysis in aerated DMSO solution. The buildup of beta-carotene(.+) with k(1) = (4.8 +/- 0.2) x 10(8) dm(3) mol(-1) s(-1) [lambda(max) = 942 nm, epsilon = (1.6 +/- 0.1) x 10(4) dm(3) mol(-1) cm(-1)] results from an electron transfer from beta-carotene to DMSO(.+). The beta-carotene(.+) species decays exclusively by first-order reaction, k = (2.1 +/- 0.1) x 10(3) s(-1), probably by two processes: (1) at low substrate concentration by hydrolysis and (2) at high concentrations also by formation of dimer radical cation (beta-carotene)(2)(.+). Under the experimental conditions, a small additional beta-carotene triplet-state absorption ((3)beta-carotene) in the range of 525 to 660 nm was observed. This triplet absorption is quenched by oxygen (k = 7 x 10(4) s(-1)), resulting in singlet oxygen ((1)O(2)), whose reactions can also lead to additional formation of beta-carotene(.+).     

Metal complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid and benzohydroxamic acid. Crystal and molecular structure of [Cu(phen)2(Cl)]Cl x H2Sha, a model for a peroxidase-inhibitor complex

Stability constants of iron(III), copper(II), nickel(II) and zinc(II) complexes of salicylhydroxamic acid (H2Sha), anthranilic hydroxamic acid (HAha) and benzohydroxamic acid (HBha) have been determined at 25.0 degrees C, I=0.2 mol dm(-3) KCl in aqueous solution. The complex stability order, iron(III) > copper(II) > nickel(II) approximately = zinc(II) was observed whilst complexes of H2Sha were found to be more stable than those of the other two ligands. In the preparation of ternary metal ion complexes of these ligands and 1,10-phenanthroline (phen) the crystalline complex [Cu(phen)2(Cl)]Cl x H2Sha was obtained and its crystal structure determined. This complex is a model for hydroxamate-peroxidase inhibitor interactions.