Search PubMed⌕ Search

SEARCH · Search PubMed

Results for “macrocycles”

Search indexed PubMed citations on genomics, clinical trials, systematic reviews and public health. Explore titles, authors and supplied subject terms, then open the PubMed record.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 559 records · Page 31Linked to original sources
PubMed2004

Electrochemical anion recognition with ferrocene functionalised macrocycles.

The syntheses and characterization of two new redox active cyclam ligands ferrocenylmethyl-(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine (L3) and 1,1'-ferrocenylmethyl-bis(6-methyl-1,4,8,11-tetraazacyclotetradec-6-yl)-amine (L4) are reported. The compounds each possess a ferrocenyl group bearing one (L3) or two (L4) appended macrocycles linked by their exocyclic amino groups and the crystal structures of both compounds have been determined. Anion binding of L3 and L4 was investigated by electrochemical titrations where H-bonding to each macrocycle causing a shift in the Fc+/0 redox potential was used as a reporter of guest binding. The Zn(II) complex of L3 has also been isolated and characterized structurally. These compounds were analysed for their capacity to electrochemically recognize anions in both aqueous and non-aqueous solution. We have found that L3, L4 and [ZnL3]2+ sense Cl- and AcO- anions in MeCN-CH2Cl2, a function that is lost in aqueous solution.

Journal Article↗
PubMed2004

Pentaaza macrocyclic ytterbium(III) complex and solvent controlled supramolecular self-assembly of its dimeric mu-eta 2:eta 2 peroxo-bridged derivatives.

The unprecedented template action of ytterbium ion in the synthesis of pentaaza macrocyclic Schiff bases is exemplified by isolation and definitive identification of the seven-coordinate pentagonal bipyramidal complex with the formula of [YbLCl(2)]ClO(4) (1), where L is 2,14-dimethyl-3,6,10,13,19-pentaazabicyclo[13.3.1]nonadeca-1(19),2,13,15,17-pentaene, providing the first example of crystallographically characterized pentaaza macrocyclic ytterbium complex. For the first time the spectrum of the (2)F(7/2) --> (2)F(5/2) transition has been obtained for a molecular complex of ytterbium with organic ligands in which all ligand-field components of the ground and excited state are well displayed at room temperature. This complex is capable of forming a dimeric peroxo Yb(2)(mu-eta(2):eta(2)-O(2))L(2)(4+) (2) derivative containing the biologically significant planar side-on doubly bidentate coordination mode of the peroxide. Inclusion of the appropriate solvent molecule into the crystal structure generates supramolecular architectures (2a-d) in which the solvent controlled self-assembly is observed. Spectral properties of these complexes were found to be very important and promising in the area of ytterbium physicochemistry.

Journal Article↗
PubMed2004

Synthesis and coordination properties of new macrocyclic ligands: equilibrium studies and crystal structures.

The synthesis and characterization of two new macrocyclic ligands, the bis-macrocyclic compound 2,6-bis(1,4,13-triaza-7,10-dioxacyclopentadec-1-ylmethyl)phenol (L) and 38-methoxy-1,4,13,16,19,28-hexaaza-7,10,22,25-tetraoxatricyclo[14.14.7.1(32,36)]octatriconta-32,34,Delta(36,38)-triene (L1) are reported. Equilibrium studies of basicity and coordination properties toward metal ions such as Cu(II), Zn(II), Cd(II) and Pb(II) were performed for ligand by potentiometric measurements in aqueous solution (298.1 +/- 0.1 K, I= 0.15 mol dm(-3)). L behaves as a hexaprotic base (logK(1)= 10.93, logK(2)= 9.70, logK(3)= 8.79, logK(4)= 8.05, logK(5)= 6.83, logK(6)= 2.55). All metal ions form stable mono- and dinuclear complexes: logK(MLH(-1))= 25.61 for Cu(II), 15.37 for Zn(II), 12.58 for Cd(II) and 13.79 for Pb(II); logK(M(2)LH(-1))= 31.61 for Cu(II), 23.38 for Zn(II), 24.49 for Cd(II) and 23.68 for Pb(II). All these dinuclear species show a great tendency to add the OH(-) group: the equilibrium constant for the addition reaction was found to be logK(M(2)LH(-1)OH)= 4.77 for Cu(II), 5.66 for Zn(II), 2.8 for Cd(II) and 3.18 for Pb(II). In the case of Ni(II), kinetic inertness prevents the possibility of solution studies. The dinuclear solid adducts [Ni(2)H(-1)L(N(3))(3)].EtOH and [Cu(2)H(-1)L(N(3))](ClO(4))(2) were characterized by X-ray analysis.

Journal Article↗
PubMed2004

The formation of dimeric phosph(III)azane macrocycles [[P(mu-NtBu)]2.LL]2 [LL = organic spacer].

The dimeric macrocycles [[P(mu-NtBu)]2.LL]2 [LL = OCH2C(Me)2CH2O (1), 2,6-(NH)2C5H3N (2), 1,2-(NH)2C6H4(3)] have been obtained by the reactions of the appropriate diols and diamines (LLH2) with the dimeric phosph(III)azane [ClP(mu-NtBu)]2. Under different conditions the reaction of 1,2-(NH2)2C6H4 with [ClP(mu-NtBu)]2 gives the monomer [[P(mu-NtBu)]2.[1,2-(NH)2C6H4]] (4) (instead of the dimer 3). Contrary to the literature, the results illustrate that the formation of dimeric macrocycles is common in these reactions and dependent among other factors on the steric demands and length of the organic spacer (LL) as well as the reaction conditions.

Journal Article↗
PubMed2004

Preparation of macrocyclic 15N-labelled oligoaminodeoxysaccharides as probes for RNA-binding.

Two macrocyclic aminoglycosides were prepared from a 1,4-butanediol linked 2-deoxy-L-rhamnal which was O-allylated at the 4- and 4'-positions via the precursor allyl 3,4-di-O-acetyl-2,6-dideoxy-alpha-L-arabino-hexoside employing olefin metathesis and ring closing metathesis in a sequential manner. The macrocycles were 15N-labelled at all four amino groups in order to study interactions with regulatory RNA structures in solution by NMR spectroscopy. A key step for the introduction of the 15N-label was a reductive amination step using commercially available 15NH4OAc. The reductive amination proceeds with excellent stereocontrol. As a by-product the unusual acyclic amino nitrile was isolated which originated from intramolecular imine formation followed by cyanide addition to the intermediate C=N double bond.

Aminoglycosides↗
PubMed2004

A chiral [2]catenane self-assembled from meso-macrocycles of palladium(II).

Reaction of trans-[PdX2(SMe2)2](X = Cl or Br) with the chiral ligand LL = 1,1'-binaphthyl-2,2'-(NHC(= O)-3-C5H4N)2 gave the [2]catenane complexes trans-[{(PdX2)2(micro-LL)2}2], which are formed by self-assembly from 4 units each of trans-PdX2 and LL. The catenation is favored by the formation of multiple hydrogen bonds between the constituent macrocycles (4 x NHClPd, 2 x NHO double bond C). If the ligand LL is racemic, each macrocycle trans-[(PdX2)2(micro-LL)2] is formed in the meso form trans-[(PdX2)2(micro-R-LL)(micro-S-LL)] but the resulting [2]catenane is chiral as a direct result of the catenation step. This is the first time that this form of chiral [2]catenane has been observed. The enantiomers of the [2]catenane further self-assemble in the crystalline form, through secondary intermolecular PdX bonding, to form a racemic infinite supramolecular polymer of [2]catenanes.

Journal Article↗
PubMed2004

A study of the complexation and extraction of Cu(II) sulfate and Ni(II) sulfate by N3O2-donor macrocycles.

Comparative solvent extraction (water/chloroform) studies of Ni(II) and Cu(II) employing a dinonyl-substituted N3O2-donor macrocycle (L2) as extractant have been undertaken from sulfate, chloride, nitrate and acetate-containing aqueous media. Contrary to expectations, efficient extraction of both metal sulfates was observed, the degree of extraction being comparable (or slightly enhanced) relative to that observed for each of the other anionic systems. X-Ray diffraction studies of [NiL1(H2O)3]SO4 x 4H2O and [CuL1(H2O)]SO4 x 6.67 H2O (where L1 is the unsubstituted derivative of L2) show that each complex occurs as a hydrogen-bonded 'cluster', with the sulfate anions involved in hydrogen bonded networks that incorporate ligand amine protons and water molecules; in the copper complex, which adopts a dimeric arrangement, simultaneous sulfate binding to a copper site is also present. In each complex the macrocyclic ligand fails to coordinate via its ether oxygen donors but instead is arranged so that the metal ion and sulfate anions are somewhat shielded hydrophobically from the exterior of the complex cluster assembly.

Journal Article↗
PubMed2005

Synthesis of huge macrocycles using two calix[4]arenes as templates.

Macrocycles with up to 100 atoms have been synthesised using two calix[4]arenes as templates: first, (3,5-dialkenyloxy)phenyl groups are attached to the wide rim of a calix[4]arene via urea links, then the alkenyl groups are connected via a metathesis reaction using a tetratosylurea calix[4]arene for their correct prearrangement and finally the urea functions are cleaved to detach the newly formed macrocycles.

Journal Article↗
PubMed2005

Template synthesis of 9-membered triphospha-macrocycles with rigid o-phenylene backbone functions.

[eta(5)-Cp(R)Fe(CH3CN)(1,2-diphosphinobenzene)]+ complexes are readily formed from [eta(5)-Cp(R)FeL3]+ salts and act as template precursors for the intramolecular hydrophosphination of co-ordinated trivinylphosphine with 1,2-diphosphinobenzenes. This sequence constitutes a versatile synthetic route to a new class of co-ordinated triphosphacyclononanes bearing a rigid o-phenylene backbone link. The efficiency of the synthesis depends markedly upon the nature of the Cp(R) ligand. The new secondary phosphine macrocycles prepared by this route are readily alkylated to tritertiary triphosphine macrocycles bearing alkyl and pendant functions.

Journal Article↗
PubMed2006

Synthesis and structural characterization of lanthanide(III) nitrate complexes of a tetraiminodiphenol macrocycle in the solid state and in solution.

The lanthanide(III) complexes [Ln(LH2)(NO3)3] 1-11(La-Er), 15(Y) and [Ln(LH2)(NO3)2(H2O)](NO3) 12-14 (Tm-Lu) of the tetraiminodiphenolate macrocycle L2- have been prepared by the transmetallation reaction between [Pb(LH2)(NO3)2] and Ln(NO3)3.nH2O. In these compounds, the uncoordinated imino nitrogens are protonated and are hydrogen bonded to the phenolate oxygens. The X-ray crystal structures of the La (1), Ho (10) and Lu (14) compounds have been determined. Compounds 1 and 10, in which all the three nitrates are bound in bidentate fashion, are isostructural with distorted bicapped square antiprism geometry for the metal centre. In [Lu(LH2)(NO3)2(H2O)](NO3) 14, of the two metal bound nitrates one is bidentate and the other is unidentate, while the metal centre obtains a distorted square antiprism coordination environment. Proton NMR spectra of the paramagnetic lanthanide complexes have been studied in detail. Contributions of contact and pseudo-contact shifts to the lanthanide induced isotropic shifts (LIS) of the macrocycle protons have been separated and good agreement has been obtained between the calculated LIS values and the experimentally observed values. Analysis of the NMR data has led us to conclude that all the complexes in dimethyl sulfoxide solution attain similar configurations. The absorption and emission spectral characteristic of several compounds have been investigated. The complexes of samarium (5) and europium (6) on photoexcitation at 400 nm exhibit well-resolved luminescence spectra at 77 K both in the solid state and a methanol-ethanol (1 : 4) glassy matrix. For the terbium (8) and dysprosium (9) complexes, however, the observed luminescence peaks are less resolved and weak in intensity.

Journal Article↗
PubMed2006

Comparative study of donor atom effects on the thermodynamic and electron-transfer kinetic properties of copper(II/I) complexes with sexadentate macrocyclic ligands. [CuII/I([18]aneS4N2)] and [CuII/I([18]aneS4O2)].

Studies have been conducted on the copper complexes formed with two sexadentate macrocyclic ligands containing four thioether sulfur donor atoms plus either two nitrogen or two oxygen donor atoms on opposing sides of the ring. The resulting two ligands, L, designated as [18]aneS(4)N(2) and [18]aneS(4)O(2), respectively, represent homologues of the previously studied Cu(ii/i) system with a macrocycle having six sulfur donor atoms, [18]aneS(6). Crystal structures of [Cu(II)([18]aneS(4)O(2))](ClO(4))(2) and [Cu(I)([18]aneS(4)O(2))]ClO(4) have been determined in this work. Comparison of the structures of all three systems reveals that the oxidized complexes are six coordinate with two coordinate bonds undergoing rupture upon reduction. However, the geometric changes accompanying electron transfer appear to differ for the three systems. The stability constants and electrochemical properties of both of the heteromacrocyclic complexes have been determined in acetonitrile and the Cu(II/I)L electron-transfer kinetics have been studied in the same solvent using six different counter reagents for each system. The electron self-exchange rate constants have then been calculated using the Marcus cross relationship. The results are compared to other Cu(II/I)L systems in terms of the effect of ligand geometric changes upon the overall kinetic behavior.

Journal Article↗
PubMed2002

Thermolysin-linearized microcin J25 retains the structured core of the native macrocyclic peptide and displays antimicrobial activity.

Microcin J25 (MccJ25) is the single macrocyclic antimicrobial peptide belonging to the ribosomally synthesized class of microcins that are secreted by Enterobacteriaceae. It showed potent antibacterial activity against several Salmonella and Escherichia strains and exhibited a compact three-dimensional structure [Blond et al. (2001) Eur. J. Biochem., 268, 2124-2133]. The molecular mechanisms involved in the biosynthesis, folding and mode of action of MccJ25 are still unknown. We have investigated the structure and the antimicrobial activity of thermolysin-linearized MccJ25 (MccJ25-L1-21: VGIGTPISFY10GGGAGHVPEY20F), as well as two synthetic analogs, sMccJ25-L1-21 (sequence of the thermolysin-cleaved MccJ25) and sMccJ25-L12-11 (C-terminal sequence of the MccJ25 precursor: G12GAGHVPEYF21V1GIGTPISFYG11). The three-dimensional solution structure of MccJ25-L1-21, determined by two-dimensional NMR, consists of a boot-shaped hairpin-like well-defined 8-19 region flanked by disordered N and C termini. This structure is remarkably similar to that of cyclic MccJ25, and includes a short double-stranded antiparallel beta-sheet (8-10/17-19) perpendicular to a loop (Gly11-His16). The thermolysin-linearized MccJ25-L1-21 had antibacterial activity against E. coli and S. enteritidis strains, while both synthetic analogues lacked activity and organized structure. We show that the 8-10/17-19 beta-sheet, as well as the Gly11-His16 loop are required for moderate antibacterial activity and that the Phe21-Pro6 loop and the MccJ25 macrocyclic backbone are necessary for complete antibacterial activity. We also reveal a highly stable 8-19 structured core present in both the native MccJ25 and the thermolysin-linearized peptide, which is maintained under thermolysin treatment and resists highly denaturing conditions.

Amino Acid Sequence↗
PubMed2006

New macrocyclic lathyrane diterpenes, from Euphorbia lagascae, as inhibitors of multidrug resistance of tumour cells.

The new macrocyclic lathyrane diterpenes latilagascenes A and B ( 1 and 2), the diacetylated derivative of 2, latilagascene C ( 3), and the known diterpenes ent-16alpha,17-dihydroxyatisan-3-one ( 4) and ent-16alpha,17-dihydroxykauran-3-one ( 5), isolated from the methanol extract of Euphorbia lagascae, were examined for their effects on the reversal of multidrug resistance (MDR) on mouse lymphoma cells. Among the active lathyrane derivatives 1 - 3, compound 2 displayed the highest inhibition of rhodamine 123 efflux of human MDR1 gene transfected mouse lymphoma cells when compared to the untreated cells or the positive control verapamil. The new compounds are the first macrocyclic lathyrane diterpenes showing oxidation at C-16, whose structures were characterized by extensive spectroscopic methods, including 2D NMR experiments ( (1)H- (1)H COSY, HMQC, HMBC and NOESY). The known phenolic compounds vanillic acid ( 6), p-salicylic acid ( 7), isofraxidin ( 8) and cleomiscosin A ( 9) were also isolated from this species.

Animals↗
PubMed2001

Crystal structure of the macrocycle-forming thioesterase domain of the erythromycin polyketide synthase: versatility from a unique substrate channel.

As the first structural elucidation of a modular polyketide synthase (PKS) domain, the crystal structure of the macrocycle-forming thioesterase (TE) domain from the 6-deoxyerythronolide B synthase (DEBS) was solved by a combination of multiple isomorphous replacement and multiwavelength anomalous dispersion and refined to an R factor of 24.1% to 2.8-A resolution. Its overall tertiary architecture belongs to the alpha/beta-hydrolase family, with two unusual features unprecedented in this family: a hydrophobic leucine-rich dimer interface and a substrate channel that passes through the entire protein. The active site triad, comprised of Asp-169, His-259, and Ser-142, is located in the middle of the substrate channel, suggesting the passage of the substrate through the protein. Modeling indicates that the active site can accommodate and orient the 6-deoxyerythronolide B precursor uniquely, while at the same time shielding the active site from external water and catalyzing cyclization by macrolactone formation. The geometry and organization of functional groups explain the observed substrate specificity of this TE and offer strategies for engineering macrocycle biosynthesis. Docking of a homology model of the upstream acyl carrier protein (ACP6) against the TE suggests that the 2-fold axis of the TE dimer may also be the axis of symmetry that determines the arrangement of domains in the entire DEBS. Sequence conservation suggests that all TEs from modular polyketide synthases have a similar fold, dimer 2-fold axis, and substrate channel geometry.

Amino Acid Sequence↗
PubMed2002

Factors affecting the threading of axle molecules through macrocycles: binding constants for semirotaxane formation.

The threading of more or less linear axle molecules through macrocyclic molecules, a fundamental process relating to the formation of interlocked molecular structures, has been investigated through the study in acetone of the equilibrium constants for the formation of pseudorotaxanes by NMR methods. The 30 new axle molecules have in common a secondary ammonium group, present as the thiocyanate salt, and an anthracen-9-ylmethyl group, but are rendered unique by the second amine substituent. All rotaxanes involve the well known polyether macrocycle, benzo[24]crown-8. The constants for the binding of axles having linear groups ranging from 2 to 18 carbon atoms show little variation in binding constant but are divided into two groups by their equilibration rates. Those with less than five methylene groups react rapidly on the NMR timescale, whereas those having more than five methylene groups are slow. Branching inhibits binding, but the effect decreases as the branch is moved away from the amine. Phenyl groups weaken binding when close to the amine but strengthen binding when more remote. Some functional groups decrease pseudorotaxane stability (alcohol functions), whereas others increase binding (carboxylic acid groups).

Acetone↗
PubMed2003

Probable multigeneric resistance to macrocyclic lactone anthelmintics in cattle in New Zealand.

AIM: To establish the efficacy of topical formulations of eprinomectin and abamectin against naturally acquired abomasal and small intestinal nematode infections in cattle purchased from a North Island bull-beef property. METHODS: A controlled slaughter trial, involving eighteen 6-8-month-old mixed breed calves, was conducted in May 2002.The animals were randomly allocated on the basis of faecal egg count to one of three equal-sized groups (n=6), consisting of an untreated control group and two treatment groups. One of the treatment groups was treated with a topical formulation of eprinomectin, the other with abamectin. Both anthelmintics were administered as a single topical treatment on an individual liveweight basis, at the manufacturer's recommended dose rates of 0.5 mg/kg. All calves were housed in separate groups with no access to pasture throughout the entire trial and were slaughtered 7-10 days after treatment. RESULTS: Both anthelmintic treatments were highly effective(worm count reduction >98%) against Ostertagia ostertagi, Trichostrongylus axei and Cooperia punctata, but were not effective at reducing worm counts significantly of either Cooperia oncophora or Trichostrongylus longispicularis. Against these latter two parasites, worm count reductions of only 72% and 79%, and 81% and 76%, respectively, were recorded following treatment with eprinomectin or abamectin, respectively (all p>0.05). CONCLUSIONS: These results demonstrate evidence of resistance to macrocyclic lactone anthelmintics by C. oncophora and probably T. longispicularis also. CLINICAL RELEVANCE: As well as perhaps providing the first record of resistance to any anthelmintic by T. longispicularis, the present findings may also represent the first case of resistance to macrocyclic lactone anthelmintics exhibited by more than one parasite species at a time in cattle in New Zealand.

Journal Article↗