Investigation of copper-azamacrocyclic complexes by high-performance liquid chromatography

The use of copper radioisotopes in imaging and therapy has prompted an increased interest in chelators which form stable copper complexes, such as Cu(II)-azamacrocyclic complexes. The effects of charge, stability and the size of the macrocyclic backbone of the Cu(II)-azamacrocyclic complexes on biological behavior have been evaluated. Here we report a reversed-phase high-performance liquid chromatography (HPLC) method to separate several Cu(II)-azamacrocyclic complexes, including Cu(II) complexes of 1,4,8,11-tetraazacyclotetradecane-1,4,8,11-tetraacetic acid (TETA), 4,11-bis(carboxymethyl)-1,4,8,11-tetraazabicyclo[6.6.2]hexadecane (CB-TE2A) and 4,10-bis(carboxymethyl)-1,4,7,10-tetraazabicyclo[5.5.2]tetradecane (CB-DO2A). Absorbance at 280 nm was used to monitor the complexes as they eluted from the reversed-phase column. The effects of the concentration of the buffer, the pH of the buffered mobile phase and the concentration of the organic modifier, methanol, on the separation were investigated. Separation of these copper complexes by ion-pair HPLC with the use of a mass spectrometry-compatible ion-pair reagent, triethylammonium acetate, in the mobile phase at pH 6.3 is also presented. The reversed-phase chromatographic conditions utilized also allow the pK(a)s of Cu-TETA and the log(k'w) values of Cu-CB-TE2A, Cu-TETA and Cu-CB-DO2A to be estimated.     

Reactivity of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine with CuI and [Cu(MeCN)4][PF6]: Benzimidazole Formation vs. Cu Oxidation

The reaction of 2,2′‐Bis(2N‐(1,1′,3,3′‐tetramethyl‐guanidino))diphenylene‐amine (TMG₂PA) ( 1 ) with CuI in MeCN results in the formation of [Cu^II(TMG₂PA^amid)I] ( 2 ) indicatingthat Cu^I is the target of an oxidative attack of the N‐H proton of the ligand which itself is converted to molecular hydrogen. In contrast, if [Cu(MeCN)₄][PF₆] is used as the Cu^I source, [Cu^I₂(TMGbenz)₂][PF₆]₂ ( 3 ) is obtained instead. The use of the non‐coordinating counterion [PF₆]^– apparently prevents Cu^I from oxidation but induces itself a cyclisation reaction within the ligand which results in the formation of a benzimidazole‐guanidine ligand.     

The unusual stability of H-bonded complexes in solvent caused by greater solvation energy of complex compared to those of isolated fragments

Here, the effect of solvent on the stability of non-covalent complexes, was studied. These complexes were from previously published S22, S66, and X40 datasets, which include hydrogen-, halogen- and dispersion-bonded complexes. It was shown that the charge transfer in the complex determines whether the complex is stabilized or destabilized in solvent.     

Effect of a metal ion on intramolecular spin exchange in spin-labeled complexes

The characteristic features of intramolecular spin exchange in 14 complexes of Ag^I, Hg^II, Ni^II, Pd^II, Pt^II, Au^III, and Pt^IV with spin-labeled ligands were studied by ESR spectroscopy. The measured values of the exchange integral ‖J‖ and the differences between the enthalpies of the efficient conformations (ΔH) were compared with the electronic polarization (refraction)R _f of the Ni^II, Pd^II, and Pt^II ions and Klopman's rigidity parameters σ_K, which characterize the total polarazibility of the ions and the degree of covalence of the bond between the metal atom and the donor atom of the ligand, respectively. Delocalization of the electron spin density and the efficiency of spin exchange are determined by the relative contributions of the s, p, and d orbitals, which produce the overlap integral of wave functions, ‖J‖, and by the geometric features of the coordination polyhedron, which affect the mutual orientation of the N−O fragments. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2005–2009, October, 1999.     

Synthesis of 3‐Acyl‐4‐alkenylpyrrolidines by Platinum‐Catalyzed Hydrative Cyclization of Allenynes

A series of nitrogen‐tethered allenynes (‘5‐aza‐1,2‐dien‐7‐ynes’) 1 were transformed to the corresponding 3‐acyl‐4‐alkenylpyrrolidines 3 when treated with a catalytic amount of PtCl₂ in MeOH at 70°. Initial Pt‐promoted cyclization forms a nonclassical carbocationic intermediate. In contrast to the cycloisomerization in toluene, which produced the bicyclic cyclobutenes 2 , the intermediate is intercepted by addition of an oxygen nucleophile to achieve the formal hydrative cyclization.     

Novel polyelectrolyte complexes between N-carboxyethylchitosan and synthetic polyelectrolytes

Novel polyelectrolyte complexes (PEC) between the polyampholyte N-carboxyethylchitosan (CECh) and polyacid or polybase have been prepared. The complex formation between CECh and poly(2-acryloylamido-2-methylpropanesulfonic acid) (PAMPS), poly(acrylic acid) (PAA) or poly(ethylene imine) (PEI) has been studied. The complex CECh/PAMPS is formed in the pH range from 1.2 to 6.0. The complex CECh/PAA is formed in the range 4.8-6.0 and CECh/PEI—from pH 5.4 to 7.0. The stoichiometry of the complexes depends on the pH value of the medium. In case of CECh/PAMPS and CECh/PAA the maximum quantity of complex is formed in excess of CECh and in the case of CECh/PEI—in excess of PEI. It has been shown that PEC formation between CECh and PAMPS improves the haemocompatibility of CECh.     

Binding of hairpin polyamides to DNA studied by fluorescence correlation spectroscopy for DNA nanoarchitectures

We have recently constructed a “DNA strut” consisting of two DNA-binding hairpin polyamides of Dervan-type connected via a long flexible linker and were able to show that this strut can be used to sequence-selectively connect DNA helices. This approach provides a second structural element (besides the Watson–Crick base pairing) for the assembly of higher-order DNA nanoarchitectures from smaller DNA building blocks. Since none of the existing analytical techniques for studying this kind of system were found suitable for detection and quantification of the formation of the resulting complexes, we chose fluorescence correlation spectroscopy (FCS). In the present study we show that FCS allowed us in a versatile and fast way to investigate the binding of Dervan polyamides to DNA. In particular it also shows its power in the quantitative detection of the formation of multimeric complexes and the in investigation of binding under nonphysiological conditions. Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Density functional study of magnetic exchange of dinuclear manganese complexes with the heteropoly-molyanion:[Mn~(II)_2(X~(n )Mo_9O_(33))_2]~(2(n-10)-) (X=P~V, As~V, Se~VI)

The magnetic exchange interactions between the dimanganese(II)-substituted complexes and the het-eropolymolyanion, [MnII2(Xn Mo9O33)2]2(n-10)-(X = PV(I), AsV(II) and SeVI(III)), are investigated by using density functional theory combined with broken-symmetry approach (DFT-BS) method. The calculated magnetic exchange coupling constant (J) of complex II is in reasonable agreement with the responding experimental value and the negative J values indicate that antiferromagnetic exchange interactions exist in these complexes. Furthermore, the influence of the central heteroatom on the exchange cou-pling within the dimanganese core unit is studied from standpoints of geometry, spin density and fron-tier orbitals. It demonstrates that the change of the heteroatom X via PV-AsV-SeVI elongates the dis-tances of Mn1···Mn2 and shortens the distances of Ob···Ob, and reduces the effectiveness of the super-exchange pathways, consequently, decreasing the magnitude of the antiferromagnetic coupling constant, J, of these species.     

Correlation between thermal and mass spectral techniques for the characterization of allenylidene and carbene complexes

The fragmentation pathways of allenylidene and carbene complexes have been studied using FAB mass spectrometry in comparison with thermal analyses (TGA, DrTG and DTA). Both the decomposition modes are investigated and the possible fragmentation pathways are suggested. The use of mass and thermal analyses (TGA and DTA) in the analyses of allenylidene and carbene complexes allowed the characterization of the fragmentation pathways in MS. The major pathway includes successive loss of carbon monoxide followed by fragmentation of the organic part of the allenylidene or carbene molecules. This is also confirmed by thermogravimetric analysis (TGA) where the first step involves the loss of carbon monoxide followed by the organic ligand. The nature of each step; exothermic or endothermic, is also studied using DTA technique. The kinetic parameters of the thermal decomposition are also studied using the Coates-Redfern method.