Macrocyclic Polyamine Complexes Research Articles

Synthesis, characterization, and biological activities of macrocyclic polyamine complexes

Two new dinuclear macrocyclic complexes, [Ni2L1(OAc)]·ClO4 (1) and [Co2L2(OAc)]·1.5(ClO4)·0.5Na·2(CH3OH) (2) (where H2L1 and H2L2 are the condensation products of N,N-bis(3-aminopropyl)-4-methoxybenzylamine with 2,6-diformyl-4-brominephenol and 2,6-diformyl-4-methylphenol in the presence of metal ions, respectively) have been synthesized and characterized by infrared spectra, elemental analysis, electrospray mass spectra, and X-ray single crystal diffraction. The interactions of the complexes with CT-DNA have been measured by UV-absorption titrations and fluorescence quenching experiments.

Research on Macro Cyclic Polyamine Complexes of Transition Metal and Catalytic Properties

This article Synthesis of carbohydrate ligands of coordination ability, to react with metal Chlorides to get more stable complexes, and elemental analysis, infrared, Ultraviolet Spectroscopic characterization and analysis of nuclear magnetic resonance. Characterization of its structure and study on the hydrolysis activity of pnitrophenyl picolinate lipid and the activity of pnitrophenol solution of phosphate, disodium macrocyclic polyamine catalyzed by macrocyclic polyamine metal complexes. The results show that the effect of hydrolytic activity of macrocyclic polyamine complexes is much larger than the hydrolysis activity of ordinary metal complexes; it can be important significance to find a better way of cutting nucleic acid by hydroxylation.

ChemInform Abstract: The First Gold(III) Macrocyclic Polyamine Complexes and Application to Selective Gold(III) Uptake.

ChemInform Abstract: The First Gold(III) Macrocyclic Polyamine Complexes and Application to Selective Gold(III) Uptake.

Chiral multinuclear macrocyclic polyamine complexes: Synthesis, characterization and their interaction with plasmid DNA

A series of multinuclear macrocyclic polyamine metal (Zn 2+, Cu 2+, Co 2+) complexes containing chiral dipeptide linkage were synthesized and used as artificial nuclease enzyme model. The interaction between the complexes and plasmid DNA (pUC19) was studied, and the results revealed that these complexes could act as powerful catalysts for the cleavage of plasmid DNA under physiological conditions.

Carboxyester hydrolysis promoted by dizinc(ii) macrocyclic polyamine complexes with hydroxyethyl pendants: a model study for the role of the serine alkoxide nucleophile in zinc enzymes

A novel dinuclear Zn(II) complex with hexaaza macrocycle bearing two hydroxyethyl pendants (L1), 3,6,9,16,19,22-hexaaza-6,19-bis(2-hydroxyethyl)-tricyclo[22,2,2,211,13]triaconta-1,11,13,24,27,29-hexaene), was synthesized as a model for alkaline phosphatase. The Zn(II) complex [Zn2L1(CH3CO2)2](ClO4)2(H2O)2 was isolated as a colorless crystal, triclinic, space group P-1. Both Zn(II) ions adopt the geometry of a distorted trigonal bipyramid in a pentacoordinated environment with Zn⋯Zn distance of 8.74 Å. The solution complexation study has revealed that the alcoholic hydroxyl group of the complex Zn2L1 exhibits a low pKa value at 25 °C. Zn(II)-bound alkoxides, which act as reactive nucleophiles toward the hydrolysis of 4-nitrophenyl acetate in 10% (v/v) CH3CN at 25 °C, with I = 0.10 M (NaNO3) and pH 9.0, have shown a second-order rate constant of 0.32 ± 0.01 M−1s−1, a value that is approximately 13 times greater than the value for the corresponding dinuclear Zn(II) complex formed by a hexaaza macrocycle without hydroxyethyl pendants (L2). The pH–rate profile for Zn2L1 gave a sigmoidal curve. A possible mechanism has been proposed: the Zn(II)–RO− function acts as a nucleophile in the first step of the hydrolytic mechanism, to give an acetyl intermediate, which is subsequently hydrolyzed to acetate by a Zn(II)–OH− group.

Why zinc in zinc enzymes? From biological roles to DNA base-selective recognition.

Intrinsic chemical properties of the zinc(II) ion in zinc enzymes have been investigated by the model of 1:1 Zn2+-macrocyclic polyamine complexes, including Zn2+-1,5,9-triazacyclododecane ([12]aneN3) and 1,4,7,10-tetraazacyclododecane (cyclen). The physiologically most suitable pKa values for the Zn2+-bound H2O in enzymes were illustrated by the first model Zn2+-[12]aneN3 complex, which mimics the essential kinetic and thermodynamic roles of Zn2+ in carbonic anhydrase. The activation of proximate serine residues (in alkaline phosphatase) and activation of alcohols for hydride transfer to NAD+ (in alcohol dehydrogenase) were also mimicked by Zn2+ -[12]aneN3 complexes. The functions of two zincs in dinuclear metallophosphatases were explained by a new dinuclear Zn2+-cryptate. For an aldolase type II model, a Zn2+-cyclen derivative showed facile enolate formation from a proximate carbonyl pendant under physiological conditions. The strong anion affinities, which Zn2+ intrinsically possesses, were exploited into novel selective nucleobase thymine (or uracil) recognition of Zn2+-cyclen complexes by the strong Zn2+ -imido anion bond formation. The Zn2+-aromatic-pendant cyclen complexes selectively bind to T (or U) in single- and double-stranded DNA (or RNA). Thus, Zn2+ complexes act like molecular zippers to break A-T pairs in DNA, which was proven by various physicochemical measurements and DNA footprinting assays. These Zn2+ complexes showed some relevant biochemical and biological properties such as inhibition of transcriptional factor, TATA binding protein, or strong antimicrobial activities to gram-positive bacterial strains.

ChemInform Abstract: Dynamic Anion Recognition by Macrocyclic Polyamines in Neutral pH Aqueous Solution: Development from Static Anion Complexes to an Enolate Complex

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Dynamic anion recognition by macrocyclic polyamines in neutral pH aqueous solution: development from static anion complexes to an enolate complex

Multiprotonated macrocyclic polyamines are useful host molecules for anion guests at neutral pH in aqueous solution. An intramolecular uracil anion complex with a diprotonated macrocyclic tetraamine recently provided a unique example of electrostatic stabilization of the uracil N1 anion at neutral pH, which may be relevant to the facile glycosylation and deglycosylation of uracil at N1 in DNA. Macrocyclic polyamine complexes with Zn2+ possess strong anion affinities and hence can deprotonate weak acids at neutral pH to bind with the resulting conjugate bases: e.g. H2O → HO–, ROH → RO–, ArSO2NH2 → ArSO2NH–, RCONHR′ → RCON–R′, RCONHCOR′ → RCON–COR′. The Zn2+–conjugate base complexes act as catalytic nucleophiles (i.e. HO––Zn2+, RO––Zn2+), fluorescence sensors (ArSO2NH––Zn2+), and thymine or barbital recognition hosts, which are often found in zinc–enzyme functions. Enolate anion complex formation has recently been observed in intramolecular interaction of carbonyl oxygen with Zn2+.

Inversion of DNA helicity induced by zinc (II)-macrocyclic polyamine complexes

Abstract Exposure of synthetic polynucleotide poly(dG-dC)·poly(dG-dC) to ZnII cyclen, 2 (cyclen = 1,4,7,10-tetraazacyclododecane), produces a dramatic change in its circular dichroism (CD) spectrum in H2O at pH 7.2, 24°C: the CD spectrum of the initial B form changes to that of the Z form (or a non-Z structure with a left-handed helix) at very low concentrations ([ZnII]/[base pair] in molar basis ≤ 1). By contrast, ZnII-[12]aneN3, 1 ([12]aneN3 = 1,5,9-triazacyclododecane), and ZnII-cyclam, 3 (cyclam = 1,4,8,11-tetraazacyclo-tetradecane), do not significantly have such a topological affect on the polynucleotide even at much higher concentrations. An increase in Na+ ionic strength nullified the effect of 2 on the CD spectrum, indicating an outside interaction (electrostatic and/or hydrogen bonding) of the DNA model. This study illustrates the significance of the macrocyclic ligand structure around the ZnII ion for specific interaction with DNA.

A model for catalytically active zinc(II) ion in liver alcohol dehydrogenase: a novel "hydride transfer" reaction catalyzed by zinc(II)-macrocyclic polyamine complexes

The role of Zn ion at the active center of liver alcohol dehydrogenase has been well-defined for the first time by the comparative studies of Zn( 12)aneN3, 1 ((12)aneN3 = 1,5,9-triazacyclododecane, L,), Zn( 12)aneN4, 2 (( 12)aneN4 = 1,4,7,10-tetraazacyclododecane, L2), Zn( 14)aneN4, 3 (( 14)aneN4 = 1,4,8,1 I-tetraazacyclotetradecane, LJ, and free Zn salts, 4. Variations in Zn acidity and coordination environment in these complexes result in varying degrees of catalytic activity in the reduction of p-nitrobenzaldehyde (9) and an NAD' model compound (18) with alcohols as the sources (e.g., 2-PrOH) to p-nitrobenzyl alcohol (10) and the corresponding NADH model compounds (19 and 20), respectively. Among Zn species tested, the Zn complex of macrocyclic triamine ( 1 2)aneN3, 5 (L,-Zn11-OH)3.(TfO)3.TfOH (TfO = CF3S03-), was by far the most effective catalyst: 10 was obtained from 9 in 7820% yield (based on the concentration of Zn) in the presence of 5 (0.8 mol %) in refluxing 2-PrOH for 24 h. The Zn complex 5, also promotes the from 2-PrOH to an NAD' model compound, N-benzylnicotinamide chloride (18), to yield the 1,4-adduct, N-benzyl-l,4-dihydronicotinamide (19), almost exclusively. It is concluded, from the comparison of 5 with other Zn complexes of ( 12)aneN4 and ( 14)aneN4, that the most acidic and coordinatively least saturated Zn in LI catalytically generates zinc( 11)-alkoxide complex to facilitate the hydride transfer to the hydride acceptor on the Zn coordination sphere. The present study provides the first chemical model illustrating the significance of the Zn acidity and the steric requirement around Zn coordination sphere in the hydride transfer reaction (from alcohol) catalyzed by Zn%ontaining alcohol dehydrogenases (ADH).

The first gold(III) macrocyclic polyamine complexes and application to selective gold(III) uptake

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTThe first gold(III) macrocyclic polyamine complexes and application to selective gold(III) uptakeEiichi Kimura, Yasuhisa Kurogi, and Toshikazu TakahashiCite this: Inorg. Chem. 1991, 30, 22, 4117–4121Publication Date (Print):October 1, 1991Publication History Published online1 May 2002Published inissue 1 October 1991https://doi.org/10.1021/ic00022a007RIGHTS & PERMISSIONSArticle Views269Altmetric-Citations42LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (595 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: Synthesis and Functions of Macrocyclic Polyamines.

Macrocyclic polyamines are a new class of functional molecules. They show (1) special features of mode of their proton uptake; (2) uptake of biological polyanions (such as TCA cycle polycarboxylates, phosphate, ATP and carbonate) and of catechols (such as dopa and dapamine); (3) selective inclusion of some transition metal ions (e. g. CuII); (4) selective uptake of hard metal ions (e. g. MgII); (5) peptide-like functions to stabilize unusual oxiadtion state of metal ions (e. g. CuIII, NiIII); (6) superoxide dismutase-like activities by macrocyclic polyamine complexes; (7) heme-like O2-uptake and activation functions by metal complexes; and (8) functions of phenolate-coordinate heme enzymes. These newly discovered properties will prove to be useful for the future development of entirely new type of medicines, chemicals, catalysts and so on.

大環状ポリアミン（アザクラウン）化合物の合成と機能について

Macrocyclic polyamines are a new class of functional molecules. They show (1) special features of mode of their proton uptake; (2) uptake of biological polyanions (such as TCA cycle polycarboxylates, phosphate, ATP and carbonate) and of catechols (such as dopa and dapamine); (3) selective inclusion of some transition metal ions (e. g. CuII); (4) selective uptake of hard metal ions (e. g. MgII); (5) peptide-like functions to stabilize unusual oxiadtion state of metal ions (e. g. CuIII, NiIII); (6) superoxide dismutase-like activities by macrocyclic polyamine complexes; (7) heme-like O2-uptake and activation functions by metal complexes; and (8) functions of phenolate-coordinate heme enzymes. These newly discovered properties will prove to be useful for the future development of entirely new type of medicines, chemicals, catalysts and so on.

Further studies on superoxide dismutase activities of macrocyclic polyamine complexes of copper(II)

The superoxide dismutase (EC 1.15.1.1) activities of new series of macrocyclic complexes with copper (II) have been measured. Chemical modifications in macroycyclic ring size, donor atom, donor atom number, substituents on the macrycyclic skeletons, and length of bridges linking two macrocycles are shown to have profound effects on the superoxide dismutase activities of the metal complexes. The quantitative measurement by the standard xanthine-xanthine oxidase assay, which depends on the conversion of nitroblue tetrazolium to formazan, has been corroborated by a direct assay method using an oxygen electrode.

Superoxide dismutase activity of macrocyclic polyamine complexes

Copper(II) and nickel(II) complexes of macrocyclic polyamine derivatives possessing partial oligopeptide-like structures are found to suppress the xanthine-xanthine oxidase-mediated reduction of nitroblue tetrazolium and also to suppress formazan formation by potassium superoxide. The activity in the superoxide dismutase assay is dependent on ring size, type and number of donor atoms, metal ion, and substituents on the macrocycles. Some of those are more active than the known O 2 − scavengers such as copper(II)-salicylate and copper(II)-amino acid (or peptide) complexes. Nickel (II)-naphthylmethyl-dioxo-[16]ane N 5, 13, 1 : 1 complex (NiH −2L) is the most active among the 30 chelates examined.