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DMSO Solution (dmso + solution)
Selected AbstractsMetal Ion Complementarity: Effect of Ring-Size Variation on the Conformation and Stability of Lead(II) and Cadmium(II) Complexes with Pendant-Armed CrownsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2007Martín Regueiro-Figueroa Abstract The binding tendencies of the pendant-armed crown ethers L1,L3 [L1 = N,N, -bis(benzimidazol-2-ylmethyl)-1,7-diaza-12-crown-4, L2 = N,N, -bis(benzimidazol-2-ylmethyl)-1,10-diaza-15-crown-5) and L3 = N,N, -bis(benzimidazol-2-ylmethyl)-4,13-diaza-18-crown-6] towards PbII and CdII have been investigated. The X-ray crystal structure of [Cd(L3)](ClO4)2·EtOH shows that, in the solid state, the CdII ion is eight-coordinate and fits quite well into the crown hole, favouring an anti arrangement of the organic receptor. NMR measurements recorded in acetonitrile solution indicate that increasing the crown size induces a conformational change in the series of CdII complexes. The conformation goes from a syn arrangement for L1 to an anti arrangement for L3, passing through a syn [lrarr2] anti equilibrium in the complex derived from L2. On the contrary, no conformational change was observed for the corresponding PbII complexes, which have a syn conformation in all cases. These results have been confirmed by means of density functional theory (DFT) calculations performed by using the B3LYP model. The binding constants obtained from UV/Vis titration experiments in DMSO solution demonstrate that a decrease in the crown size provokes a 102 -fold enhancement of the stability for this series of CdII complexes, whereas for PbII a gradual decrease of the binding constants is observed. Receptor L1 shows a certain degree of selectivity for CdII over PbII, with a selectivity factor > 102. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007) [source] Self-Assembly by Ligand-Exchange ReactionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 16 2005Dillip Kumar Chand Abstract An interesting phenomenon of ligand exchange is observed in the DMSO solution of certain self-assembled molecules generated from cis -protected PdII and organic ligands. Upon heating, assemblies such as [{Pd(en)}x(ligand)y](NO3)2x change to [Pdm(ligand)n](NO3)2m and [Pd(en)2](NO3)2. The change is also possible at room temperature when 0.5 equiv. Pd(en)(NO3)2 is added in excess to the system. The transformation is incomplete when the ligand moiety is monodentate in nature, for example in the case of 4-phenylpyridine. However, multinuclear assemblies containing nonchelating, polydentate ligands used in this study entirely favor the transformation. This process is not possible with some related PtII compounds. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Coordination Modes of 9-Methyladenine in cis -Platinum(II) Complexes with Dimethyl(phenyl)phosphanes as Ancillary Ligands , Synthesis and Characterization of cis -[PtL2(9-MeAd)2](NO3)2, cis -[PtL2{9-MeAd(,H)}]3(NO3)3, and cis -[L2Pt{9-MeAd(,H)}PtL2](NO3)3EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2003Bruno Longato Abstract Treatment of 9-methyladenine (9-MeAd) with cis -[PtL2(NO3)2] (1) (L = PMe2Ph) in a 2:1 molar ratio generated the bis(adduct) cis -[PtL2(9-MeAd)2](NO3)2 (2), which was isolated and fully characterized by multinuclear (1H, 31P, 13C, 195Pt and 15N) NMR analysis, which showed that the two nucleobases are selectively coordinated through the N1 atom. Small amounts of a mono(adduct) cis -[PtL2(S)(9-MeAd)]2+ (3) (S = solvent) and of a diplatinated species cis -[L2Pt(S){9-MeAd(,H)}PtL2]3+ (4) are formed in DMSO solution when 9-MeAd is present in smaller quantities than 1. Complex 3 is platinated at N1, with a solvent molecule representing the fourth ligand around the metal center. Complex 4 contains an adenine molecule deprotonated and platinated at N1,N6,N7, with two cis -L2Pt units bonded to nitrogen atom N1 and to nitrogen atoms N6 and N7, respectively. With increasing relative concentration of the nucleobase, both complexes 3 and 4 progressively convert into the bis(adduct) 2, the only species detectable in solution when the Ad/Pt molar ratio is 2:1. The trinuclear compound cis -[L2Pt{9-MeAd(,H)}]3(NO3)3 (5) (L = PMe2Ph), containing an NH2 -deprotonated nucleobase bridging the metal centers through the N1 and N6 atoms, is quantitatively formed when the dinuclear hydroxo complex cis -[Pt(,-OH)L2]2(NO3)2 (6) reacts with 9-MeAd in CH3CN solution. The isolated complex was fully characterized by multinuclear NMR spectroscopy and mass spectrometry. It appears to be stable in solution in CH3CN and chlorinated solvents, whereas in DMSO it partially converts into a new species, probably the dinuclear analog cis -[PtL2{9-MeAd(,H)}]2(NO3)2, in which the adenine maintains its coordination mode. At equilibrium the trinuclear/dinuclear species molar ratio is 20:1. Through the addition of a stoichiometric amount of nitrate 1 to a DMSO solution of 5 we were able to generate the diplatinated compound 4 in high yield. Complex 4 displays a new coordination mode for the adeninate ion, with N1 bonded to one platinum atom whereas N6 and N7 are chelated to a second one. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] Towards Selective Recognition of Sialic Acid Through Simultaneous Binding to Its cis -Diol and Carboxylate FunctionsEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 17 2010Martín Regueiro-Figueroa Abstract A series of receptors containing phenylboronic acid and urea or thiourea units have been designed for simultaneous recognition of the cis -diol and carboxylate functions of sialic acids, which are known to be overexpressed on the surfaces of tumor cells. The interaction of the receptors with 5-acetylneuraminic acid (Neu5Ac) and 2-,- O -methyl Neu5Ac (MeNeu5Ac) in DMSO solution has been investigated bymeans of spectrophotometric titrations and 1H, 13C, and 11B NMR spectroscopy. Additionally, we have also investigated the binding of these receptors with competing monosaccharides such as D -(+)-glucose, D -fructose, methyl ,- D -galactoside, and methyl ,- D -mannoside. Our results show that 2-{[3-(4-nitrophenyl)thioureido]methyl}phenylboronic acid (3a) recognizes both Neu5Ac and MeNeu5Ac with good selectivity with regard to the remaining monosaccharides investigated. DFT calculations performed at the B3LYP/6-31G(d) level show that this selectivity is due to a cooperative two-site binding of Neu5Ac through 1) ester formation by interaction at the phenylboronic acid function of the receptor and 2) hydrogen-bond interaction between the thiourea moiety and the carboxylate group of Neu5Ac. Compound 3a can therefore be considered a promising synthon for the design of contrast agents for magnetic resonance imaging of tumors. In contrast, the analogue of 3a containing a urea moiety , compound 3b , displays strong binding to all monosaccharides investigated, due to two-site binding through interaction on the phenylboronic acid function of the receptor and a hydrogen-bond interaction between the urea moiety and the sugar hydroxy groups. [source] NMR, solvation and theoretical investigations of conformational isomerism in 2-X-cyclohexanones (X=NMe2, OMe, SMe and SeMe)JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 11 2003Matheus P. Freitas Abstract The conformational equilibria of 2- N,N -dimethylamino- (1), 2-methoxy- (2), 2-methylthio- (3) and 2-methylselenocyclohexanone (4) were determined in various solvents by measurement of the 3JH-2,H-3 couplings. The observed couplings were analyzed using theoretical and solvation calculations to give both the conformer energies in the solvents studied plus the vapor-phase energies and the coupling constants for the distinct conformers. These gave the conformer energies and couplings of 2,4. The intrinsic couplings for the 2- N,N -dimethylamino compound were determined by the molecular mechanics PCMODEL program. The axial conformation in 1 is the most polar and also more stable in DMSO solution (Eeq,Eax=0.05,kcal,mol,1) and the pure liquid, while the equatorial conformer predominates in the remaining solvents studied (except in CCl4, where self-association is observed). In the methoxy ketone (2) the equatorial conformation is more stable in the vapor (Eeq,Eax=,0.30,kcal,mol,1) and in all solvents. The opposite behavior is shown by 3 and 4, where the axial conformation is the more stable one in the vapor phase (Eeq,Eax=1.60 and 2.95,kcal,mol,1 for 3 and 4, respectively) and is still the prevailing conformer in solution. The axial predominance for 3 and 4 is attributed to hyperconjugation between the electron lone pair of the hetero-substituent and the ,*CO orbital. This interaction is stronger for 3 and 4 than in the case of 1 and 2, where the ,gauche effect' in the equatorial conformation should be more effective in stabilizing this conformation. Copyright © 2003 John Wiley & Sons, Ltd. [source] Biocomplementary interaction behavior in DNA-like and RNA-like polymersJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2009Chih-Chia Cheng Abstract A series of nucleobased polymers and copolymers were synthesized through atom transfer radical polymerization (ATRP). Biocomplementary DNA- and RNA-like supramolecular complexes are formed in dilute DMSO solution through nucleobase recognition. 1H NMR titration studies of these complexes in CDCl3 indicated that thymine-adenine (T-A) and uracil-adenine (U-A) complexes form rapidly on the NMR time scale with high association constants (up to 534 and 671 M,1, respectively) and result in significant Tg increase. WAXD and differential scanning calorimetry analyzes in the bulk state indicate the presence of highly physical cross-linked structures and provide further details into the nature of the self-assembly of these systems. Furthermore, this study is of discussion on the difference in the hydrogen bond strength between T-A and U-A base pairs within polymer systems, indicating that the strength of hydrogen bonds in RNA U-A pairs is stronger than that in DNA T-A base pairs. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6388,6395, 2009 [source] Effects of some trivalent metal ions on the fluoride-induced chemiluminescence from a phenylphosphate-substituted dioxetane Lumigen PPDLUMINESCENCE: THE JOURNAL OF BIOLOGICAL AND CHEMICAL LUMINESCENCE, Issue 5 2002Mojtaba Shamsipur Abstract The chemiluminescene generated from the reaction of a thermally stable phenylphosphate-substituted dioxetane Lumigen PPD at ambient temperature was studied in DMSO solution. The presence of trivalent metal ions Cr3+, Ga3+, Fe3+ and Al3+ was found to quench the resulting chemiluminescence dramatically. The system resulted in nice Stern,Volmer plots in the quencher concentration range 1.5,×,10,4,1.8,×,10,3,mol/L. The KQ values decreased in the order Cr3+,>,Ga3+,>,Fe3+,>,Al3+. Copyright © 2002 John Wiley & Sons, Ltd. [source] Preparation and Characterisation of Pd Nanoclusters in Hyperbranched Aramid Templates to be used in Homogeneous CatalysisMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 12 2003Daniela Tabuani Abstract In the present paper the potential use of hyperbranched (HB) aramids as metallic solution stabilisers and carriers for homogeneous catalysis is outlined. Aramids, synthesised either from A2,+,B3 reagents [namely, p -phenylenediamine (PPD) and trimesic acid (TMA)] or from an AB2 monomer [i.e., 5-(4-aminobenzamido)isophtalic acid, named ABZAIA], have been used to stabilise palladium nanoclusters dispersed in two solvent media, namely N,N, -dimethylformamide (DMF) and dimethyl sulfoxide (DMSO). The influence of the nature of the polymeric support as well as of the solvent medium on both cluster dimensions and stability of the solutions has been investigated. Indeed, the interactions between the polymeric support and the metallic precursor (PdCl2), as revealed by 1H NMR spectroscopy, involve only the amino groups of the HB aramids. Metal nanocluster dimensions and stability are strongly dependent on the polymer used as a stabilizer. Transmission electron microscopy (TEM) analysis has shown that the presence of HB polymer in the solution reduces cluster dimensions and allows the obtaining of stable systems. The low concentration of NH2 end groups in the poly(AB2) system leads to the formation of Pd particles of rather low dimensions with a high tendency to aggregate. All prepared solutions are stable under inert atmosphere for at least a month, with an improved stabilisation when using the poly(A2,+,B3) system for more than five months. A TEM micrograph of poly(ABZAIA)/Pd from a DMSO solution. [source] 13C assignments of the carbon atoms in the aromatic rings of lignin model compounds of the arylglycerol ,-aryl ether typeMAGNETIC RESONANCE IN CHEMISTRY, Issue 10 2006Michel Bardet Abstract The 13C NMR signals from the aromatic ring carbons in a series of lignin model compounds of the arylglycerol ,-aryl ether type in DMSO solution have been assigned. The model compounds investigated are representative of the erythro and threo forms of differently substituted arylglycerol ,-aryl ethers. Copyright © 2006 John Wiley & Sons, Ltd. [source] 1H chemical shifts in NMR: Part 22,,Prediction of the 1H chemical shifts of alcohols, diols and inositols in solution, a conformational and solvation investigationMAGNETIC RESONANCE IN CHEMISTRY, Issue 8 2005Raymond J. Abraham Abstract The 1H NMR spectra of a number of alcohols, diols and inositols are reported and assigned in CDCl3, D2O and DMSO- d6 (henceforth DMSO) solutions. These data were used to investigate the effects of the OH group on the 1H chemical shifts in these molecules and also the effect of changing the solvent. Inspection of the 1H chemical shifts of those alcohols which were soluble in both CDCl3 and D2O shows that there is no difference in the chemical shifts in the two solvents, provided that the molecules exist in the same conformation in the two solvents. In contrast, DMSO gives rise to significant and specific solvation shifts. The 1H chemical shifts of these compounds in the three solvents were analysed using the CHARGE model. This model incorporates the electric field, magnetic anisotropy and steric effects of the functional group for long-range protons together with functions for the calculation of the two- and three-bond effects. The long-range effect of the OH group was quantitatively explained without the inclusion of either the CO bond anisotropy or the COH electric field. Differential , and , effects for the 1,2-diol group needed to be included to obtain accurate chemical shift predictions. For DMSO solution the differential solvent shifts were calculated in CHARGE on the basis of a similar model, incorporating two-bond, three-bond and long-range effects. The analyses of the 1H spectra of the inositols and their derivatives in D2O and DMSO solution also gave the ring 1H,1H coupling constants and for DMSO solution the CHOH couplings and OH chemical shifts. The 1H,1H coupling constants were calculated in the CHARGE program by an extension of the cos2, equation to include the orientation effects of electronegative atoms and the CHOH couplings by a simple cos2, equation. Comparison of the observed and calculated couplings confirmed the proposed conformations of myo -inositol, chiro -inositol, quebrachitol and allo -inositol. The OH chemical shifts were also calculated in the CHARGE program. Comparison of the observed and calculated OH chemical shifts and CH. OH couplings suggested the existence of intramolecular hydrogen bonding in a myo -inositol derivative. Copyright © 2005 John Wiley & Sons, Ltd. [source] Synthesis and Characterization of the Nitrogen-Rich Hyperbranched Polymers , Poly([1,2,3]-Triazole-[1,3,5]-Triazine)sPROPELLANTS, EXPLOSIVES, PYROTECHNICS, Issue 6 2008Georgiy Abstract Novel hyperbranched poly([1,2,3]-triazole-[1,3,5]-triazine)s (HBP TT) were synthesized by a 1,3-dipolar cycloaddition reaction from AB2 monomer , 2-azido-4,6-bis-prop-2-yn-1-yloxy- [1,3,5]-triazine (ABPOT). The monomer contains one azide group A and two terminal alkyne units B. Thermal polymerization of ABPOT in bulk or in DMF solution leads to hyperbranched polymers containing both 1,4- and 1,5-disubstituted [1,2,3]-triazoles. The monomer was also polymerized catalytically in the presence of Cu(I) salts under mild reaction conditions in DMSO solution and in bulk affording hyperbranched poly-[1,2,3]-triazoles 1,4-disubstituted only. The reactions lead to the products soluble in aprotic polar solvents like DMSO or DMF. Side reactions can proceed in a few cases, particularly: (i) homocoupling of alkyne groups, leading to the formation of insoluble products as a result of cross-linking, (ii) isomerization of propynyloxytriazine fragments to propynyl- or propadienyltriazinone ones, and (iii) hydrolysis of triple bonds without the loss of solubility. Heats of formation of monomer and synthesized polymers were calculated from their combustion heats. All products were characterized by NMR-, IR-spectroscopy, and size exclusion chromatography (SEC) data. The obtained results open the prospect for the use of HBP TT as the high-enthalpy modifiers for energetic and non-energetic binders. [source] Anion Recognition by Neutral Macrocyclic AmidesCHEMISTRY - A EUROPEAN JOURNAL, Issue 20 2005J. Chmielewski Dr., Micha Abstract Although amides often serve as anchoring groups in natural and synthetic anion receptors, the structure,affinity relationship studies of amide-based macrocyclic receptors are still very limited. Therefore, we decided to investigate the influence of the size of the macroring on the strength and selectivity of anion binding by uncharged, amide-based receptors. With this aim, we synthesized a series of macrocyclic tetraamides derived from 2,6-pyridinedicarboxylic acid and aliphatic ,,,-diamines of different lengths. X-ray analysis shows that all ligands studied adopt expanded conformations in the solid state with the convergent arrangement of all four hydrogen-bond donors. 1H NMR titrations in DMSO solution revealed a significant effect of the ring size on the stability constants of anion complexes; the 20-membered macrocyclic tetraamide 2 is a better anion receptor than its both 18- and 24-membered analogues. This effect cannot be interpreted exclusively in terms of matching between anion diameter and the size of macrocyclic cavity, because 2 forms the most stable complexes with all anions studied, irrespective of their sizes. However, geometric complementarity manifests in extraordinarily high affinity of 2 towards the chloride anion. The results obtained for solutions were interpreted in the light of solid-state structural studies. Taken together, these data suggest that anion binding by this family of macrocycles is governed by competitive interplay between their ability to adjust to a guest, requiring longer aliphatic spacers, and preorganization, calling for shorter spacers. The 20-membered receptor 2 is a good compromise between these factors and, therefore, it was selected as a promising leading structure for further development of anion receptors. Furthermore, the study of an open chain analogue of 2 revealed a substantial macrocyclic effect. X-ray structure of the acyclic model 14 suggests that this may be due to its ill-preorganized conformation, stabilized by two intramolecular hydrogen bonds. [source] Enol Forms of 1,3-Indanedione, Their Stabilization by Strong Hydrogen Bonding, and Zwitterion-Assisted InterconversionEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 14 2010Mark Sigalov Abstract By analyzing NMR spectroscopic data, and supported by IR, UV/Vis, Raman, dielectrometry, and DFT techniques, a comprehensive study of the 1:2 adducts of picolinaldehyde and 1,3-indanediones is presented. The parent indanedione derivative 5 exists in an equilibrium between all-keto and enol forms, the latter being stabilized by an intramolecularO,H···N hydrogen bond. Only the all-keto form was observed in the 5,6-dimethoxy compound 6, whereas solely the enol tautomer was observed with its 5,6-dichloro analogue 7. Polar solvents and low temperatures shift the equilibrium towards the enol tautomer in 5. The structure of adduct 8, formed with isonicotinaldehyde, prevents the formation of intramolecular O,H···N hydrogen bonds and thus it exists in the all-keto form in low polar solvents. However, in DMSO solutions it adopts a zwitterionic form with a strong anionic O,···H···O hydrogen bond. Thus, the enol form in indanedione adducts was unequivocally characterized in solution and the factors that determine the keto,enol tautomerism, namely electronic effects, solvent, temperature, and intramolecular hydrogen bonds, have been methodically studied by spectroscopic and quantum mechanical methods. [source] Poly(urethanes) containing silarylene and/or germarylene unitsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 1 2008C. A. Terraza Abstract A series of 10 poly(urethanes) were synthesized by solution polymerization from bis(chloroformates) and aromatic diamines, containing both silicon or germanium as central atom. So, the polymers prepared contain two silicon atoms or two germanium atoms exclusively or combinations of both. Me, Et, and Ph groups were bonded to the central atoms according to the nature of the monomers employed. Poly(urethanes) were characterized by FTIR, 1H, 13C, and 29Si NMR spectroscopy and the results agreed with the proposed structures. Additionally, intrinsic viscosity values were established in DMSO solutions and thermal analyses were developed. In all cases, thermostable oligomers were obtained, which showed a degradation process beginning at ,240,260°C. Polymers showed a thermal dependence with the nature of the heteroatom employed. Thus, in general, when germanium was used as central atom, the thermal stability was higher than the polymers containing silicon which agrees with the lower polarity and higher energy of the CGe bond in comparison with the CSi one. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008. [source] Study of carvedilol by combined Raman spectroscopy and ab initio MO calculationsJOURNAL OF RAMAN SPECTROSCOPY, Issue 10 2002M. P. M. Marques The novel cardioprotective drug carvedilol was studied by both Raman spectroscopy and ab initio molecular orbital methods (using the density functional theory approach). The spectra, acquired both for the solid samples and DMSO solutions as a function of pH, were assigned in view of the calculated wavenumbers and intensities, and also based on the experimental data obtained for individual compounds which comprise the molecule, namely carbazole and 1,2-dimethoxybenzene. The pH dependence of the Raman pattern of carvedilol was studied, and the pKa value of its secondary amine group was determined (pKa = 8.25) through pH titration experiments. This kind of information is of great significance for the understanding of the biochemical role of carvedilol, which is strongly determined by the acid,base behaviour of the molecule. Copyright © 2002 John Wiley & Sons, Ltd. [source] | |||||||||||||||||||||||||