Polyamino acids and cytochrome C anchored rhodium complexes

Polyamino acids (amino acid = valine, alanine, lysine and arginine) and the protein cytochrome C (Cyt C) have been treated with [Rh(CO)₂Cl]₂ (1) to give polymersupportedcis-dicarbonyl species. The polymer-supported rhodium complexes, characterised on the basis of infrared and ESCA data, have been found to undergo reversible decarbonylation reaction. The Cyt C-supported rhodium complex acts as a hydrogenation catalyst of low to moderate activity. In the hydrogenation of 3-methyl cyclohexanone no stereoselectivity has been observed.     

Kinetics of heat-induced transformation of copper complexes with amino acids

We have studied the effect of substituent R on the rate and mechanism of thermal decomposition of copper(II) complexes with L-α-amino acids anions H₂NCH(R)COO^?. The homolytic decomposition rate increases in the series of CuL₂ complexes with alanine, glycine, valine, isoleucine, leucine, phenylalanine, and serine. Intramolecular redox formation of ^·+CuGly cation-radical upon reduction of Cu(II) to Cu(I) and oxidation of H₂NCH₂COO^? into H₂NCH₂COO^· carboxylamine radical is the primary stage of heat-induced decomposition.     

Oxidation of L‐amino acids by metal ion (Mn3+) in sulfuric acid medium: Effect of nucleophilicity and hydrophobicity on reaction rate

The kinetics of oxidation of L ‐amino acids (AAs) glycine( 1a ), alanine( 1b ), valine( 1c ), isoleucine( 1d ), leucine( 1e ), proline( 1f ), and phenylalanine( 1g ) by a transition metal ion (Mn³⁺) was studied in the presence of sulfuric acid medium at 26°C by a spectrophotometrical (λ_max = 500 nm) method. In all cases, the kinetics of reactions was of first‐order with respect to each [AA] and [Mn³⁺]. Increased [H⁺], [Mn²⁺] (the reduction product of Mn³⁺), sulfate, and chloride had no effect on the reaction rate. However, the reaction rate increased with increased dielectric constant of the medium. Oxidation rate increased for 1a–g and an apparent correlation was observed between the rate of oxidation and nucleophilicty of AAs except for 1a and 1g . The reaction rate also linearly depended on the hydrophobicity of AAs except for 1f and 1g . The thermodynamic parameters for AA‐metal ion complex formation and activation parameters for the rate‐limiting steps have been evaluated. Analysis of the oxidation products indicated that the AAs underwent oxidative deamination and decarboxylation to form corresponding aldehydes. Based on these data, plausible mechanisms involved in the oxidation of AAs are proposed. © 2011 Wiley Periodicals, Inc. Int J Chem Kinet 43: 599–607, 2011     

Studies on some radical transfer reactions by entrapping the radicals as polymer end groups. II. Reactions of ȮH radicals with amino acids

The reaction of ?H radicals with a number of aliphatic amino acids has been studied by entrapping the resultant radicals as end groups of poly(methyl methacrylate) that have been detected and estimated by the sensitive dye partition technique. The rate constants of the reaction (in mol^?1 L S^?1) of 7 amino acids at 25°C and at pH 1.00 have been determined as 8.33 × 10⁸ for glycine, 2.56 × 10⁹ for β-alanine, 2.01 × 10⁹ for β-alanine, 3.99 × 10⁹ for 4-amino butyric acid, 7.56 × 10⁹ for (1+) valine, 1.42 × 10¹⁰ for (1?) leucine, and 5.98 × 10¹⁰ for 6-amino caproic acid. Glycine, α-alanine, β-alanine, and 4-amino butyric acid produced radicals that underwent deamination and incorporated only carboxyl-bearing end groups in the polymer. The other amino acids, leucine, valine, and 6-amino caproic acid, produced at least two types of radicals, radicals that underwent deamination and those that remained intact, and incorporated in the polymer both carboxyl- and amine-bearing end groups but in different amounts. The latter type of radicals were about 29% from 6-amino caproic acid, 23% from leucine, and 18% from valine. The change of pH from 0.80 to 2.72 did not produce any significant change in the end group profile of the polymer obtained, indicating no appreciable change in the rate of the reaction of ?H radicals with the simplest amino acid glycine in the pH range studied.     

磺酰氨基酸钛配合物对Diels-Alder反应的对映选择性催化作用

研究了对甲苯磺酰基-L-缬氨酸、对甲苯磺酰基-L-苯丙氨酸、对甲苯磺酰基-L-亮氨酸、对甲苯磺酰基-L-异亮氨酸、对甲苯磺酰基-L-脯氨酸、1-萘磺酰基-L-缬氨酸、1-萘磺酰基-L-苯丙氨酸、1-萘磺酰基-L-亮氨酸和1-萘磺酰基-L-异亮氨酸与钛的配合物对环戊二烯与丙烯酸甲酯的环加成反应的对映选择性催化作用。萘磺酰基氨基酸钛配合物的对映选择性比对甲苯磺酰基氨基酸钛配合物好,氨基酸与钛比为2:1时比1:1要好得多。1-萘磺酰基-L-异亮氨酸与钛的2:1配合物的对映选择性最好,e.e.值为56%。     

Nuclease activity of mixed ligand complexes of copper(II) with heteroaromatic derivatives and picoline

New picoline adducts with carbamic acid [(furan-2-yl)methylene]hydrazide–Cu^II (CFMH) (1); thiocarbamic acid [(furan-2-yl)methylene]hydrazide–Cu^II (TFMH) (2); carbamic acid [(furan-2-yl)ethylidene]hydrazide–Cu^II (CFEH) (3), thiocarbamic acid [(furan-2-yl)ethylidene]hydrazide–Cu^II (TFEH) (4); carbamic acid [(thiophene-2-yl) methylene]hydrazide–Cu^II (CTMH) (5), thiocarbamic acid [(thiophene-2-yl)methylene]hydrazide–Cu^II (TTMH) (6), carbamic acid [(thiophene-2-yl)ethylidene]hydrazide–Cu^II (CTEH) (7), thiocarbamic acid [(thiophene-2-yl)ethylidene]hydrazide–Cu^II (TTEH) (8) have been prepared and characterized by analytical, i.r., electronic, e.s.r. and c.v. spectral data. The electronic spectra suggest distorted octahedral geometry for all the picoline adducts. E.s.r. g values lie between 2.251–2.286 at l.n.t. All the adducts undergo a quasi-reversible one-electron reduction in the range +0.47 to +0.51 V versus s.c.e., attributable to the Cu^III/Cu^II redox couple. The electron transfer is much faster in the semicarbazone complexes than in the thiosemicarbazone complexes. All adducts showed increased nuclease activity in the presence of oxidant; the nuclease activity is compared with that of the parent copper(II) complexes.     

Amino-substituted gem-diphosphonic acids: structures of complexes with divalent metal cations in aqueous solutions

A comparative study of complexation of acids R₂N(CH₂)_nCR"(PO₃H₂)₂ (R = H or Me; R" = OH or H; n = 1 or 2) with the Ca²⁺, Mg²⁺, Zn²⁺, and Cu²⁺ cations in aqueous solutions was carried out by vibrational (IR and Raman) and electronic spectroscopy using the data of ESR spectroscopy and conformational analysis (molecular mechanics). The MOPCPO chelate ring is formed in all ML and MHL complexes. The involvement of the N atom in coordination was found only in the Cu²⁺ complexes and is determined by the structure of the ligand. The relationship between the stability constants and the structures of the complexes in aqueous solutions is analyzed.     

Carbohydrates, amino acids, phytin, and macroelements of the herbage ofTrifolium pratense

Two monosaccharides have been found by paper chromatography in an aqueous extract of the herbage of red clover (Trifolium pratense). One of them has been identified as glucose. After hydrolysis of a dry water-soluble extract by paper chromatography in the presence of markers, galactose, arabinose, xylose, and mannose were detected. By paper chromatography in the presence of markers the amino acids phenylalanine, leucine (isoleucine), methionine, aspartic acid, proline, alanine, and histidine have been identified. Phytin with decomp. p 276°C has been isolated and identified, giving, after hydrolysis, inositol with mp 225–226°C, and Ca²⁺, Mg²⁺, and PO ₄ ^3– have been detected. The amount of ash in the herbage of clover is 8.4% and the amount insoluble in HC1 1.5%. The amounts of macroelements were determined by the flame photometry of a solution of the ash (mg–%): K⁺ 1620; Na⁺ 310; Ca²⁺ 1240; Mg²⁺ 1090.Pyatigorsk Pharmaceutical Institute. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 483–485, July–August, 1980.     

Metal complexes with macrocyclic ligands. XIII. The complexation of Cu2+ with triazacycloalkanes

The potentiometric study of the complexation of Cu²⁺ with 1,4,7-triazacyclononane ( 1 ), 1,4,8-triazacyclodecane ( 2 ) 1,5,9-triazacyclododecane ( 3 ) has shown that CuL, CuL₂ and (CuLOH)₂ are the main species present in solution. Their stabilities (Table 1) and their absorption spectra (Table 2) indicate facial coordination of the cyclic triamines in a distorted octahedral geometry. The formation and dissociation kinetics have been measured by stopped-flow techniques. The formation in acetate buffer can be described by the reaction of Cu²⁺ and CuAcO⁺ with the monoprotonated species of the ligand. The bimolecular rate constants for these complexations (Table 3) decrease when the ring size increases. In contrast the dissociation induced by acid is only little affected by the ring size. Thus for these complexes the rate of formation and not that of the dissociation determines the overall stability.     

Catalytic cleavage of p-nitrophenyl picolinate by metallomicelles made up of copper(II) complexes of small molecular ligands bearing hydroxyl or carboxyl groups

The esterolytic activities of Cu²⁺ complexes (Cu²⁺L1, Cu²⁺L2 and Cu²⁺L3) of three small molecular ligands: N-(2-hydroxyethyl)ethylenediamine (L1), 2,2-iminodiethanol (L2) and iminodiacetic acid (L3), in the presence of the nonionic micelle (Brij35) towards the substrate p-nitrophenyl picolinate (PNPP) have been investigated. The catalytic reactivity order is: Cu²⁺L1 > Cu²⁺L2 > Cu²⁺L3, which can be attributed to the similarity of and the difference between their catalytic mechanisms, most likely resulting from the analogy and the discrepancy of the structure of the three complexes. The critical feature of the catalytic process is, quite likely, the formation of a ternary complex involving a binary metal ion complex and the substrate, followed by pseudo-intramolecular nucleophilic attack of the alcoholic hydroxyl (for Cu²⁺L1 and Cu²⁺L2) or metal ion bound hydroxide ion (for Cu²⁺L3), at carbonyl of the substrate. Detailed kinetic analyses are given for the hydrolysis of PNPP catalyzed by the three complexes.     

Simultaneous dual wavelength spectrophotometric determination of citric and ascorbic acids using an artificial neural network

In this study, a very simple spectrophotometric method for the simultaneous determination of citric and ascorbic acid based on the reaction of these acids with a copper(II)-ammonia complex is presented. The Cu²⁺-NH₃ complex (with λ_max = 600 nm) was decomposed by citrate ion and formed a Cu²⁺-citrate complex (with λ_max = 740 nm). On the other hand, during the reaction of ascorbic acid with copper(II)-ammonia complex, ascorbic acid is oxidized and the copper(II)-ammonia complex is reduced to the copper(I)-ammonia complex and the absorbance decreases to 600 nm. Although there is a spectral overlap between the absorbance spectra of complexes Cu²⁺-NH₃ and Cu²⁺-citrate, they have been simultaneously determined using an artificial neural network (ANN). The absorbances at 600 and 740 nm were used as the input layer. The ANN architectures were different for citric and ascorbic acid. The output of the citric acid ANN architecture was used as an input node for the ascorbic acid ANN architecture. This modification improves the capability of the ascorbic acid ANN model for the prediction of ascorbic acid concentrations. The dynamic ranges for citric and ascorbic acid were 1.0–125.0 and 1.0–35.0 mM, respectively. Finally, the proposed method was successfully applied to the determination of citric and ascorbic acids in vitamin C tablets and some powdered drink mixes. The text was submitted by the authors in English.     

Novel Flame‐Retardant and Thermally Stable Poly(Amide‐imide)s Based on Bicyclo[2,2,2]oct‐7‐Ene‐2,3,5,6‐Tetracarboxylic Diimide and Phosphine Oxide in the Main Chain: Synthesis and Characterization

Six novel poly(amide‐imide)s PAIs 5a‐f were synthesized through the direct polycondensation reaction of six chiral N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L‐amino acids 3a‐f with bis(3‐amino phenyl) phenyl phosphine oxide 4 in a medium consisting of N‐methyl‐2‐pyrrolidone (NMP), triphenyl phosphite (TPP), calcium chloride (CaCl₂) and pyridine. The polymerization reaction produced a series of flame‐retardant and thermally stable poly(amide‐imide)s 5a‐f with high yield and good inherent viscosity of 0.39–0.83 dLg^?1. The resultant polymers were fully characterized by means of FTIR, ¹H NMR spectroscopy, elemental analyses, inherent viscosity, specific rotation and solubility tests. Thermal properties and flame retardant behavior of the PAIs 5a‐f were investigated using thermal gravimetric analysis (TGA and DTG) and limited oxygen index (LOI). Data obtained by thermal analysis (TGA and DTG) revealed that these polymers show good thermal stability. Furthermore, high char yields in TGA and good LOI values indicated that resultant polymers exhibited good flame retardant properties. N,N′‐(bicyclo[2,2,2]oct‐7‐ene‐tetracarboxylic)‐bis‐L‐amino acids 3a‐f were prepared in quantitative yields by the condensation reaction of bicyclo[2,2,2]oct‐7‐ene‐2,3,5,6‐tetracarboxylic dianhydride 1 with L‐alanine 2a , L‐valine 2b , L‐leucine 2c , L‐isoleucine 2d , L‐phenyl alanine 2e and L‐2‐aminobutyric acid 2f in acetic acid solution. These polymers can be potentially utilized in flame retardant thermoplastic materials.     

Catalytic reduction of 4-nitrophenol by means of nanostructured polymeric Schiff base complexes

Polymeric Schiff base ligands were synthesized using 2-hydroxybenzaldehyde (L²), 4-hydroxy-3-methoxybenzaldehyde (L⁴), and 5-aminoisophthalic acid. The nanostructured complexes were then synthesized using Ni²⁺, Cu²⁺, and Mn³⁺. The ligands and complexes thus synthesized were characterized using Fourier-transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis (TGA), and field-emission scanning electron microscopy. The thermal stability of the complexes was confirmed using TGA. The synthesized complexes were used as catalysts in the reduction of 4-nitrophenol (4-NP) to 4-aminophenol in an aqueous phase in the presence of sodium borohydride. In this work, the catalytic reactivity of nanostructured complexes was compared using the rate constant (k) of the reaction. The reaction time for the reduction of 4-NP was 5–14 min for different complexes. The catalytic system based on Ni²⁺/2-hydroxybenzaldehyde was the most active and displayed reusability in the reduction of 4-NP.     

Ternary complexes of N-(2-acetamido)iminodiacetic acid and some aromatic acids. Isolation and stability constants in solution

Summary Ternary 1:1:1 complexes of Y^III, Co^II, Ni^II, Cu^II, La^III, Ce^III and UO ₂ ²⁺ with N-(2-acetamido)iminodiacetic acid (H₂ADA) as primary ligand and salicylic, anthranilic or phthalic acid as secondary ligand are described. The complexes of Co^II and Cu^II were isolated and characterized by microanalysis, molar conductance measurements, thermal analysis, i.r. and u.v.-vis. spectra. The formation constants of the 111 ternary complexes were determined potentiometrically in 20% (w/w) EtOH-H₂O at 24 °C. The stabilities of the 111 M ⁿ⁺ :ADA^2–:aromatic acid ternary complexes are higher than those of the corresponding 11 M ⁿ⁺ :aromatic acid binary complexes.     

BODIPY Immobilized MCM-41 Based Multianalyte Sensor: Application in Detection and Removal of Trivalent (Al3+, Cr3+) and Divalent (Cu2+, Hg2+) Metal Ions in Aqueous Media

In the present study, a novel p-phenylcarboxylic acid BODIPY ( L ) immobilized MCM-41 based solid chemosensor material L-propylsilyl@MCM-41 ( MS4 ) was developed to detect multiple metal ions in a pure aqueous medium. The synthesized solid chemosensor material MS4 shows high sensitivity and removal ability towards trivalent (Al³⁺, Cr³⁺) and divalent (Cu²⁺, Hg²⁺) metal ions. The emission intensity of MS4 enhanced multifold selectively in the presence of trivalent (Al³⁺, Cr³⁺) metal ions and shows quenching in the presence of divalent (Cu²⁺, Hg²⁺) metal ions. The limit of detection was calculated to be in the nanomolar range with Al³⁺, Cr³⁺, Cu²⁺_, and Hg²⁺ metal ions in the aqueous medium. The spectroscopic and analytical results suggest that MS4 selectively binds with Al³⁺ and Cr³⁺ through −NH functionality and with Hg²⁺ and Cu²⁺ through −COOH functionality of p-phenylcarboxylic acid BODIPY ( L ). Further, MS4 selectively removes Al³⁺, Cr³⁺, Cu²⁺, and Hg²⁺ metal ions from the aqueous media with removal efficiency of 97.28 %, 96.34 %, 87.19 %, and 95.63 %, respectively. No noticeable change in the concentration was observed for other metal ions. The recycling potential of MS4 was evaluated using EDTA for up to seven cycles with no significant reduction in sensing capability.     

Synthesis, characterization and liquid–liquid extraction properties of new methoxyaminobiphenylglyoxime derivatives and their complexes with some transition metals

In this study, three new aminobiphenylglyoximes, [L¹H₂] N-(2-methoxy)aminobiphenylglyoxime, [L²H₂] N-(3-methoxy)aminobiphenylglyoxime and L[³H₂] N-(4-methoxy)aminobiphenylglyoxime have been synthesized by the reaction of (E,E)-4′-biphenylchloroglyoxime with 2-Methoxyaniline, 3-Methoxyaniline and 4-Methoxyaniline in absolute ethanol. The preparation Ni^II, Co^II and Cu^II complexes of these ligands are described. The ligands and their complexes were characterized by elemental analyses, IR, mass, H¹ and ¹³C NMR spectra, thermogravimetric analyses (t.g.a) and magnetic susceptibility measurements. Ligands complexing properties were studied by the liquid–liquid extraction of selected alkali (Li⁺, Na⁺, K⁺, Cs⁺) and transition metals (Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺). It has been observed that all ligands show a high affinity to Cu²⁺ ions, whereas almost no affinity to alkali metals. The extraction equilibrium constants (K _ex) for complexes of ligands with Cu²⁺ metal picrates between dichloromethane and water have been determined at 25°C.     

Catalytic decomposition of aliphatic peroxy acids

The catalytic decomposition of peroxy acids is studied in various solvents in the presence of manganese, cobalt, chromium, nickel, and copper acetates and cerium benzoate. The catalytic activity of the salts in peroxy acid decomposition decreases in the order Mn²⁺ > Co²⁺ > Ce³⁺ > Cr³⁺ > Ni²⁺ > Cu²⁺. The apparent activation energies of the catalytic decomposition of peroxydecanoic acid range between 45.9 and 88.0 kJ/mol. The reaction medium has an effect both on the apparent rate constant and on the activation energy of the reaction. The reaction mechanism includes the fast formation of a catalyst-peroxy acid intermediate complex, which decomposes to release a catalyst molecule and forms the reaction products. The oxidation state of the metal ion of the catalyst can change. The introduction of compounds capable of forming complexes with metal ions of the catalyst substantially slows down the catalytic decomposition.     

Studies on copper(II) complexes of some polyaza macrocycles derived from 1,2-diaminoethane

Syntheses of copper(II) complexes of 20-membered and 15-membered aza macrocycles 1,3,6,8,11,13,16,18-octaaza-2,7,12,17-tetrachlorocycloeicosane (OTCE, [20]-N₈) and 1,3,6,8, 11,13-hexaazacyclopentadecane (HCPD, [15]-N₆) involving metal template condensation between 1,2-diaminoethane, trichloromethane and dichloromethane, respectively, are reported. Formulation of [Cu₄(OTCE)(H₂O)₈]Cl₈ and [Cu₃(HCPD)(H₂O)₆]Cl₆ · 2H₂O and the ligand hydrochlorides OTCE · 8HCl and HCPD · 6HCl are supported by elemental analyses, conductivity measurements, and spectral studies. For a comparative cavity size effect on the stability constant, potentiometric measurements on the copper complexes of the generated macrocycles [15]-N₆ and [20]-N₈ and the structurally related larger macrocycle 1,3,6,8,11,13,16,18,21,23-decaaza-2,2,7,7,12,12,17,17,22,22-decachlorocyclopentacosane (DDCP, [25]-N₁₀, prepared recently) have been performed in aqueous solution at 25°C (μ = 0.1 M KNO₃). Very high stability constants obtained for reaction Cu²⁺ + A ? CuA²⁺ (A = ligand, log K = 20.51 and 25.87, respectively, for OTCE and DDCP systems) are a reflection on the folding of the ligand to provide a small cavity suitable for fitting of the copper ion. Further, a high equilibrium constant value for CuA²⁺ + Cu²⁺ ? Cu₂A⁴⁺ (OTCE system, log K = 14.59) or Cu₂A⁴⁺ + Cu²⁺ ? Cu₃A⁶⁺ (DDCP system, log K = 16.69) is due to suitable fitting of two and three copper ions in the 20-membered and 25-membered ring cavity of OTCE and DDCP, respectively.     

Cu2+-complexes of polyamino acids in aqueous solutions catalytic activity (H202-decomposition) and structure

The decomposition of H₂O₂ (8 · 10^?3M ) catalyzed by complexes of Cu²⁺ (4 · 10^?4M ) with various oligomers and polymers of glycine, L-lysine or L-glutamic acid was investigated in aqueous solution in the pH range 5–11, at 24°C and at low ionic strength. Previous investigations have shown that the decomposition of H₂O₂ is catalyzed by Cu²⁺-complexes capable of forming Cu²⁺-peroxocomplexes. With increasing pH the catalytic activity of Cu²⁺-complexes with glycine or glycylglycine (1:1) increases while the activity of Cu²⁺-complexes with tri- or tetraglycine (1:1) is comparatively small at higher pH values apparently because in the latter cases the coordination positions of the copper become progressively occupied by the peptides. This interpretation is in accordance with the pH-dependence of the light-absorption spectra of the latter complexes. Cu²⁺-complexes with poly-α, L -lysines of various molecular weights (molar ratios Cu²⁺: lysine residues = 1:15) have a catalytic activity comparable to or higher than that of the complex Cu²⁺-ethylenediamine (1:1), indicating two available coordination positions for formation of peroxo-complexes. On the other hand, the system Cu²⁺-L -lysine (1:15) showed no significant activity probably because all coordination positions at the Cu²⁺ are occupied by lysine. Despite the excess of ligand groups over Cu²⁺ in the polylysine systems the structure of this polyamino acid apparently does not allow its full coordination with these groups under the conditions investigated. Two adjacent chelating ε-amino groups are considered as the main ligand groups of the polymer to each copper ion. The Cu²⁺-poly-α, L -glutamic acid complex examined (Cu²⁺: glutamic acid residues = 1:5) shows comparatively little activity. In this case, absorption spectra indicate formation of hydroxo-complexes at higher pH. Besides the effects of structure, the electrostatic fields of the charged polyelectrolytes polylysine or polyglutamic acid are also considered to affect the rates of catalysis.     

Cofluorescence of Eu in complexes of aromatic carboxylic acids

The fluorescence of Eu³⁺ in certain Eu³⁺–aromatic acid complexes were enhanced by over two orders of magnitude, by the addition of La³⁺; a process referred to as cofluorescence. Cofluorescence was observed only with certain aromatic acid ligands; trismesic acid, pyromellitic acid and mellitic acid; thereby clearly establishing a correlation between the structure of the ligand and the process of cofluorescence. While cofluorescence has been extensively studied using β-diketones as ligands, our studies demonstrate cofluorescence for the first time in ligands other than β-diketones. Furthermore, the mechanism of cofluorescence in the aromatic acid complexes studied by us appears to be different from that operating in the β-diketones. While intermolecular energy transfer is believed to occur in the β-diketones, formation of polynuclear complexes appears to be responsible for cofluorescence in the aromatic acid ligands.