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Reaction of 1,4,7,10-tetraazacyclododecane (cyclen) and Cu(ClO4)2·6H2O with nucleobases (adenine, hypoxanthine, xanthine, theophylline, cytosine, or uracil) under alkaline conditions gave four ternary cyclen-metal-nucleobase complexes, [Cu(cyclen)(adeninato)]·ClO4·2H2O (1), [{Cu(cyclen)}2(hypoxanthinato)]·(ClO4) 3 (2), [Cu(cyclen)(theophyllinato)]3·(ClO4) 3·2H2O (3), and [Cu(cyclen)(xanthinato)]·(0.7ClO4)·(0.3ClO 4)·3H2O·(0.5H2O)3 (4), whose crystal structures were determined by X-ray diffraction. In the adenine complex 1, a cyclen-capped square-pyramidal Cu2+ ion binds to an adeninato ligand through N(9) with the formation of an intramolecular interligand hydrogen bond between the secondary amino nitrogen of cyclen and N(3) of the base. In the hypoxanthine complex 2, two cyclen-capped Cu2+ ions bind to a hypoxanthinato ligand, one through N(7) with the formation of an intramolecular N(cyclen)-H···O(6) hydrogen bond and the other through N(9) to form an intramolecular N(cyclen)-H···N(3) hydrogen bond. Similarly, in both the theophylline complex 3 and the xanthine complex 4, each cyclen-capped Cu2+ ion binds to a theophyllinato or xanthinato ligand through N(7) with the formation of an intramolecular N(cyclen)-H···O(6) hydrogen bond. However, unlike in 2, steric constraints between amino group(s) of cyclen and the methyl group at N(3) of theophylline in 3 or the proton attached to N(9) of xanthine in 4 preclude the metal bonding to N(9) in 3 or N(3) in 4. The significance of intramolecular interligand interaction as a factor that affects metal-binding site(s) on nucleobases is emphasized.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

Simple exploration of 1,4,7,10-Tetraazacyclododecane tetrahydrochloride

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The kinetics and the mechanism of the cyanide-induced demetallation of a series of Ni2+ complexes with macrocyclic ligands of different ring size (12- to 14-membered; see 1-4) and steric constraints was studied. Although the rates differ by almost five orders of magnitude when compared to each other under fixed experimental conditions (pH 10.5, [CN-] = 10-2 M). all reactions proceed through the relatively rapid formation of cyano adducts [Ni(CN)nL] (n = 1, 2), which then react with additional CN- or HCN to give the final products. Of paramount importance for the reaction rate is the geometry and configuration of the cyano adducts [Ni(CN)nL] (n = 1,2). cis-Dicyano derivatives with a folded macrocycle react faster than trans-compounds. In the case of (1,4,8,11-tetraazacyclotetradecane)nickel(2+) ([Ni (4)]2+), which gives a trans- dicyano adduct, the base-catalyzed N-inversion necessary to obtain the cis-dicyano derivative becomes rate determining at high CN – concentrations.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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(Chemical Equation Presented) Cholesterol-armed cyclens worked as octadentate receptors for Na+, Ca2+, and Y3+ complexes in which four chiral cholesterol-functionalized sidearms were bundled and asymmetrically twisted above cyclen-metal complex platforms. Since the resulting helical metal complexes included chiral, hydrophobic cholesterol residues and charged, hydrophilic metal sites as well as asymmetric coordination geometries, they exhibited unique amphiphilic properties and provided chiral self-aggregates in aqueous solutions. Light scattering, fluorescence, and TEM characterizations demonstrated that Na+ complex with cholesterol-armed cyclen gave a particularly stable self-aggregate in aqueous solution and offered supramolecular environments effective for sensing and detection of amino acid anions. Various dansylamino acid derivatives (dansyl = 5-(dimethylamino)-1-naphthalenesulfonyl) were nicely accommodated in the helicate aggregates to give highly enhanced fluorescence signals, which could be detected by the naked eye at 10-7 mol/L level. Their inclusion behaviors were analyzed by a Langmuir-type equation, indicating that enantiomer-selective inclusion occurred. MM/MD calculations and circular dichroism (CD) studies further suggested that cholesterol-armed cyclen helicates have chiral and hydrophobic cavities upon self-aggregation, in which the dansylamino acid anions were specifically accommodated. Since these helicates exhibited nonselective binding abilities in solvent extraction experiments of dansylamino acid anions, uncommon chiral recognition and sensing functions were generated by supramolecular alignments of the chiral metal helicates in the aqueous solutions.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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The bicyclic tetraamine 1,4,7,10-tetraazabicyclo<5.5.3>pentadecane (L1) has been synthesized by the reaction of the ditosylate of cyclen <1,7-bis(p-toluenesulfonyl)-1,4,7,10-tetraazacyclododecane> with the ditosylate of 1,3-propanediol followed by removal of the tosyl groups.The amine isolated as the trihydrobromide, L1*3HBr, in an overall yield of 23percent (based upon cyclen).The structure of L1*2HBr*HClO4 has been solved by X-ray diffraction techniques at T=120 K; Mr=474.6, orthorhombic, Pnma, a=17.583(4), b=8.664(3), c=11.707(3) Angstroem, Z=4, Dx=1.77 g cm-3, MoKalpha=0.71073 Angstroem, mu=46.7 cm-1, F(000)=960.R(F)=0.0471 for 1815 reflections with I>2?(I) and wR(F2)=0.0803 for all 2761 unique reflections.The H3L13+ cation exhibits a mirror plane, the secondary nitrogen atoms and a carbon atom lying in the plane.The distance between the tertiary nitrogen atoms is 2.567(4) Angstroem, with one of the acidic hydrogen atoms situated midway between the two nitrogens.The distance between the two secondary nitrogen atoms is 5.194(7) Angstroem, giving rise to a rather elongated conformation of the cyclen ring.The free base L1 behaves as a proton sponge, being a stronger base than hydroxide in water.The concentration protonation constants were determined by potentiometric measurements, which combined with 13C NMR studies gave pK1>15, pK2=7.242(8), pK3=3.202(7) and pK4<-1. (1M NaBr, 25 deg C).The 13C NMR spectra of the mono- and triprotonated species correspond to a time-averaged C2v symmetry in solution. One of the oldest and most widely used commercial enzyme inhibitors is aspirin, Reference of 10045-25-7, which selectively inhibits one of the enzymes involved in the synthesis of molecules that trigger inflammation. you can also check out more blogs about 10045-25-7

Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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A catalyst don’t appear in the overall stoichiometry of the reaction it catalyzes, category: catalyst-ligand, but it must appear in at least one of the elementary reactions in the mechanism for the catalyzed reaction. 10045-25-7, Name is 1,4,7,10-Tetraazacyclododecane tetrahydrochloride, molecular formula is C8H24Cl4N4. In a Article, authors is Bhattacharyya, Arunasis,once mentioned of 10045-25-7

A multiple diglycolamide (DGA)-containing ligand having four DGA arms tethered to a tetraaza-12-crown-4 ring, viz. 2,2?,2??,2???-(((1,4,7,10-tetraazacyclododecane-1,4,7,10-tetrayl)tetrakis(2-oxoethane-2,1-diyl)) tetrakis (oxy)) tetrakis(N,N-dioctylacetamide) (T12C4ODGA), was synthesized and evaluated for the extraction of different actinide and lanthanide ions, viz. Am3+, Eu3+, Pu4+, Np4+, and UO22+. The extraction efficiency of the present ligand was found to be the highest reported so far, more specifically for the trivalent metal ions Am3+ and Eu3+, when one considers the very low ligand concentration used in the present study, compared to that of the various previously reported multiple DGA-based ligands. The nature of the complexes formed during the extraction of Eu3+ was investigated using time-resolved fluorescence (TRFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Both the solvent extraction and TRFS studies indicated the presence of 1:1 and 1:2 complexes during the extraction of Am3+ and Eu3+ having three inner-sphere water molecules in the 1:1 complex. Density functional theoretical (DFT) studies were performed on the Am3+ and Eu3+ complexes of both T12C4ODGA and an analogous compound having methyl groups in place of the n-octyl groups, and the DFT results of the T12C4ODGA nicely explain the extraction behavior of Am3+ and Eu3+

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Complexes between cobalt(III) and eight different 1,4,7,10- tetraazacyclododecane (cyclen) as well as two tris(3-aminopropyl)amine (trpn) derivatives are reported with varying numbers and structures of peralkylammonium groups in side chains of the ligands. The presence of additional positive charges has small effects on hydrolysis rates of nitrophenyl- and bis(nitrophenyl)phosphate esters but leads to substantially enhanced cleavage of plasmid DNA. Increasing the number of the charged side groups and/or their distance to the metal ion center provides for better binding to the DNA groove, as shown also by affinity measurements with calf- thymus DNA. In line with this, saturation kinetics of plasmid DNA cleavage yield a corresponding increase of efficiency in Michaelis-Menten-type K(M) values, with rather constant k(ca1) parameters. A binuclear cobalt complex with two cyclen centers separated by a -(CH2)6-N+(CH3)2-(CH2)6- N+(CH3)2-(CH2)6- spacer shows, with only 5 x 10-5 M catalyst concentration, the largest known rate enhancement factor of > 107 (corresponding to > 1011 at 1 M) against DNA; incubation with 0.05 mM at 37 C for only 2 h leads to almost complete cleavage without appearance of products typical for redox cleavage. These results are in contrast to experiments with corresponding copper(II) complexes with added hydrogen peroxide, which has no effect with corresponding Co, Zn, Cd, or Ni complexes.

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Reference:
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI

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Ester-armed cyclens having quadruplicated helical geometry: Remarkably stable and selective encapsulation of Na+ ion

A new series of ester-armed cyclens nicely accommodated a Na+ ion in their quadruplicated helical binding spheres and effectively discriminated the cation from Li+ and K+ ions. Crystallographic studies revealed that four ester-functionalized sidearms provided effective coordination with the Na+ ion trapped in the 12-membered cyclen ring. Log K values for their Na+ complexes were estimated as 9-11 in CD3CN or C2D5OD, which were comparable to those of common bicyclic cryptands. FAB-MS, liquid-liquid extraction, and NMR binding experiments demonstrated that the cooperative action of the parent cyclen ring and ester-functionalized sidearms offered stable and selective encapsulation of the Na+ ion based on unique quadruplicated helical geometry.

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Reference£º
Metal catalyst and ligand design,
Ligand Template Strategies for Catalyst Encapsulation – NCBI