Página 14 dos resultados de 7330 itens digitais encontrados em 0.011 segundos

Thermal properties and physicochemical behavior in aqueous solution of pyrene-labeled poly(ethylene glycol)-polylactide conjugate

Chen, Wei-Lin; Peng, Yun-Fen; Chiang, Sheng-Kuo; Huang, Ming-Hsi
Fonte: Dove Medical Press Publicador: Dove Medical Press
Tipo: Artigo de Revista Científica
Publicado em 08/04/2015 EN
Relevância na Pesquisa
462.1827%
A fluorescence-labeled bioresorbable polymer was prepared by a coupling reaction of poly(ethylene glycol)-polylactide (PEG-PLA) with carboxyl pyrene, using N,N’-diisopropylcarbodiimide/1-hydroxy-7-azabenzotriazole (DIC/HOAt) as a coupling agent and 4-dimethylaminopyridine (DMAP) as a catalyst. The obtained copolymer, termed PEG-PLA-pyrene, was characterized using various analytical techniques, such as gel permeation chromatography (GPC), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), proton nuclear magnetic resonance (1H-NMR), infrared spectroscopy (IR), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA), to identify the molecular structure and to monitor the thermal property changes before and after the reaction. The presence of a pyrene moiety at the end of polylactide (PLA) did not alter the crystallization ability of the poly(ethylene glycol) (PEG) blocks, indicating that the conjugate preserved the inherent thermal properties of PEG-PLA. However, the presence of PEG-PLA blocks strongly reduced the melting of pyrene, indicating that the thermal characteristics were sensitive to PEG-PLA incorporation. Regarding the physicochemical behavior in aqueous solution...

Spontaneous CO Release from RuII(CO)2–Protein Complexes in Aqueous Solution, Cells, and Mice**

Chaves-Ferreira, Miguel; Albuquerque, Inês S; Matak-Vinkovic, Dijana; Coelho, Ana C; Carvalho, Sandra M; Saraiva, Lígia M; Romão, Carlos C; Bernardes, Gonçalo J L
Fonte: WILEY-VCH Verlag Publicador: WILEY-VCH Verlag
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
462.1827%
We demonstrate that RuII(CO)2–protein complexes, formed by the reaction of the hydrolytic decomposition products of [fac-RuCl(κ2-H2NCH2CO2)(CO)3] (CORM-3) with histidine residues exposed on the surface of proteins, spontaneously release CO in aqueous solution, cells, and mice. CO release was detected by mass spectrometry (MS) and confocal microscopy using a CO-responsive turn-on fluorescent probe. These findings support our hypothesis that plasma proteins act as CO carriers after in vivo administration of CORM-3. CO released from a synthetic bovine serum albumin (BSA)–RuII(CO)2 complex leads to downregulation of the cytokines interleukin (IL)-6, IL-10, and tumor necrosis factor (TNF)-α in cancer cells. Finally, administration of BSA–RuII(CO)2 in mice bearing a colon carcinoma tumor results in enhanced CO accumulation at the tumor. Our data suggest the use of RuII(CO)2–protein complexes as viable alternatives for the safe and spatially controlled delivery of therapeutic CO in vivo.

NMR Studies of Hetero-Association of Caffeine with di-O-Caffeoylquinic Acid Isomers in Aqueous Solution

D’Amelio, Nicola; Papamokos, George; Dreyer, Jens; Carloni, Paolo; Navarini, Luciano
Fonte: Springer US Publicador: Springer US
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
462.1827%
Caffeine hetero-association with 3,5-di-O-caffeoylquinic acid, 3,4-di-O-caffeoylquinic acid and 4,5-di-O-caffeoylquinic acid in aqueous solution has been investigated by one-dimensional (1D) and two-dimensional (2D) high resolution 1H and 13C NMR spectroscopy. Self-association of the di-O-caffeoylquinic acid isomers has been studied as well. Caffeine-di-O-caffeoylquinic acid isomers association constants were measured. The value of the association constant of the caffeine-di-O-caffeoylquinic acid complexes is compatible with previous studies and within the typical range of reported association constants for other caffeine-polyphenols complexes. Structural features of the three different complexes have also been investigated by NMR spectroscopy combined with quantum chemical calculations, and the complex conformation is discussed. Our results show that stacking interactions drive the formation of the complexes and that multiple equilibria are present in the interaction of caffeine with 3,4-di-O-caffeoylquinic acid and 4,5-di-O-caffeoylquinic acid while the complex with 3,5-di-O-caffeoylquinic acid seems to be better defined.

Synthesis and Self-assembly of [60]Fullerene Containing Sulfobetaine Polymer in Aqueous Solution

Ravi, P.; Dai, S.; Tam, K. C.
Fonte: MIT - Massachusetts Institute of Technology Publicador: MIT - Massachusetts Institute of Technology
Tipo: Artigo de Revista Científica Formato: 296315 bytes; application/pdf
EN
Relevância na Pesquisa
462.1827%
A series of well-defined stimuli responsive water soluble [60]fullerene (C₆₀) containing polymers such as polyelectrolytes (polyacids and polybases), polyampholyte and polyzwitterionic polymers were synthesized using atom transfer radical polymerization. The aqueous solution properties of these polymers with respective external stimuli such as pH, temperature and salt were studied using potentiometric and conductivity titration, light transmittance, laser light scattering and transmission electron microscopic techniques. The influence of polymer concentration, temperature, pH and electrolyte on the hydrodynamic radius (Rh), radius of gyration (Rg) and aggregation number (Nagg) of the particles were investigated in detail to elucidate the morphology of the particles. The morphology of the aggregates was further confirmed by the TEM micrographs. The cytotoxicity of the pH responsive C₆₀ containing well-defined polymers (PAA-b-C₆₀, C₆₀-b-PAA-b-C₆₀ and PEO-b-PAA-b-C₆₀) was studied to confirm the suitability of these particles as potential drug delivery vehicles. The binding interaction between the anti-cancer drug (doxorubicin) and C₆₀ containing pH responsive polymers was studied using isothermal titration calorimetry...

Estudo da remoção de compostos orgânicos, benzeno e tolueno, em solução aquosa por processo oxidativo avançado do tipo Fenton; Study of removal of organics compounds, benzene and toluene, in aqueous solution by advanced oxidation processes of the type Fenton

Evangelista, Zuzilene da Silva
Fonte: Universidade Federal do Rio Grande do Norte; BR; UFRN; Programa de Pós-Graduação em Engenharia Química; Pesquisa e Desenvolvimento de Tecnologias Regionais Publicador: Universidade Federal do Rio Grande do Norte; BR; UFRN; Programa de Pós-Graduação em Engenharia Química; Pesquisa e Desenvolvimento de Tecnologias Regionais
Tipo: Dissertação Formato: application/pdf
POR
Relevância na Pesquisa
462.1827%
The oil and petrochemical industry is responsable to generate a large amount of waste and wastewater. Among some efluents, is possible find the benzene, toluene, ethilbenze and isomers of xilenes compounds, known as BTEX. These compounds are very volatily, toxic for environment and potencially cancerigenous in man. Oxidative advanced processes, OAP, are unconventional waste treatment, wich may be apply on treatment and remotion this compounds. Fenton is a type of OAPs, wich uses the Fenton s reactant, hydrogen peroxide and ferrous salt, to promove the organic degradation. While the Photo-Fenton type uses the Fenton s reactant plus UV radiation (ultraviolet). These two types of OAP, according to literature, may be apply on BTEX complex system. This project consists on the consideration of the utilization of technologies Fenton and Photo-Fenton in aqueous solution in concentration of 100 ppm of BTEX, each, on simulation of condition near of petrochemical effluents. Different reactors were used for each type of OAP. For the analyticals results of amount of remotion were used the SPME technique (solid phase microextraction) for extraction in gaseous phase of these analytes and the gas chromatography/mass espectrometry The arrangement mechanical of Photo-Fenton system has been shown big loss by volatilization of these compounds. The Fenton system has been shown capable of degradate benzene and toluene compounds...

Formation of metallo-6A-((2-(bis(2-aminoethyl)amino)ethyl)amino)-6A-deoxy-b-cyclodextrins and their complexation of tryptophan in aqueous solution

Lincoln, S.; Haskard, C.; Easton, C.; May, B.
Fonte: AMER CHEMICAL SOC Publicador: AMER CHEMICAL SOC
Tipo: Artigo de Revista Científica
Publicado em //1996 EN
Relevância na Pesquisa
462.1827%
A pH titration study shows that 6(A)-((2-(bis(2-aminoethyl)amino)ethyl)amino)-6(A)-deoxy-beta-cyclodextrin (betaCDtren) forms binary metallocyclodextrins, [M(betaCDtren)](2+), for which log(K/dm(3) mol(-)(1)) = 11.65 +/- 0.06, 17.29 +/- 0.05, and 12.25 +/- 0.03, respectively, when M(2+) = Ni(2+), Cu(2+), and Zn(2+), where K is the stability constant in aqueous solution at 298.2 K and I = 0.10 mol dm(-)(3) (NaClO(4)). The ternary metallocyclodextrins [M(betaCDtren)Trp](+), where Trp(-) is the tryptophan anion, are characterized by log(K/dm(3) mol(-)(1)) = 8.2 +/- 0.2 and 8.1 +/- 0.2, 9.5 +/- 0.3 and 9.4 +/- 0.2, and 8.1 +/- 0.1 and 8.3 +/- 0.1, respectively, where the first and second values represent the stepwise stability constants for the complexation of (R)- and (S)-Trp(-), respectively, when M(2+) = Ni(2+), Cu(2+), and Zn(2+). From comparisons of stabilities and UV-visible spectra, the binary and ternary metallocyclodextrins appear to be six-coordinate when M(2+) = Ni(2+) and Zn(2+) and five-coordinate when M(2+) = Cu(2+). The factors affecting the stoichiometries and stabilities of the metallocyclodextrins, are discussed and comparisons are made with related systems.

Self-assembly of triblock copolymers in aqueous solution

Urbano, Bruno; Silva, Patricio; Olea, Andrés F.; Fuentes, Irma; Martínez, Francisco
Fonte: Sociedad Chilena de Química Publicador: Sociedad Chilena de Química
Tipo: Artículo de revista
EN
Relevância na Pesquisa
462.1827%
Indexación: Scielo; The aggregation of PE4VP-b-PS-b-PE4VP block copolymers was studied in aqueous solution. Triblock copolymers P4VP-b-PS-b-P4VP were synthesized by sequential anionic polymerization of poly(styrene) and poly(4-vinylpirydine) using sodium naphthalene as a bifunctional initiator. Subsequently, the 4-vinylpyridine units were quaternized with ethyl bromide to obtain cationic PE4VP-b-PS-b-PE4VP block copolymers. Both star and crew-cut micelles were formed. The concentrations at which micelles are formed cmc were determined, by steady-state and time-resolved fluorescence probing methods, as a function of quatemization degree. The results indicate that cmc of crew-cut micelles increases with increasing charge density of the PE4VP blocks. For star micelles there is not a clear dependency of cmc with the percentage of quatemization. The lifetime of pyrene fluorescence and the ratio I1/I3 were determined at concentrations of copolymers well above the cmc, and the results show that the location of pyrene into the micelle changes with the charge density of the micelle corona. The micropolarity sensed by pyrene decreases with increasing quatemization degree. The presence of aggregates was confirmed by transmission electronic microscopy.

Synthesis, thermal behavior, and aggregation in aqueous solution of poly(methyl methacrylate)-b-poly(2-hydroxyethyl methacrylate)

ACEVEDO, B.; MARTINEZ, F.; OLEA, A. F.
Fonte: 2014 Sociedad Chilena de Química Publicador: 2014 Sociedad Chilena de Química
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
462.1827%
Indexación: Scielo; ABSTRACT Amphiphilic block copolymers of poly(methyl methacrylate) PMMA and poly(2-hidroxyethyl methacrylate) PHEMA were synthesized by a two-step atom transfer radical polymerization (ATRP). Copolymers with various degrees of polymerization and different relative block sizes were obtained. The structure of the resulting polymers have been characterized and verified by FT-IR and 1H-NMR, molecular weight were determined by size exclusion chromatography analyses. The thermal properties of these polymers were investigated by differential scanning calorimetry DSC and thermogravimetric analysis TGA. The glass transition temperature of mono halogenated PMMA increases from 116 °C to 123 °C with increasing molecular weight, whereas the glass transition temperature of block copolymers depends slightly on polymer structure. The derivatives of TGA curves indicate that thermal degradation occurs in one stage. The self-assembly of PMMA-b-PHEMA in aqueous solution have been investigated by fluorescence probing methods. The critical micelle concentrations are in the range 10-6 - 10-7 M. The micropolarity sensed by pyrene is higher than in aggregates formed by block copolymers based on polystyrene. Keywords: Block copolymers...

Self-assembly in aqueous solution of amphiphilic graft copolymers from oxidized carboxymethylcellulose

Bordallo, Eduardo; Rieumont, Jacques; Tiera, Marcio José; Gómez, Manuel; Lazzari, Massimo
Fonte: Elsevier B.V. Publicador: Elsevier B.V.
Tipo: Artigo de Revista Científica Formato: 43-49
ENG
Relevância na Pesquisa
462.1827%
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES); A series of oxidized carboxymethylcellulose-graft-poly(ethylene glycol)-dodecylamine (0CMC-g-PEG-DDA) was prepared by using an appositely prepared PEG with terminal amino groups and different amounts of DDA. The nanoaggregates formed in aqueous solution were characterized by surface tension measurements, fluorescence spectroscopy, dynamic light scattering (DES) and scanning electron microscopies (SEM and TEM). The micelles showed narrow hydrodynamic size distributions and diameters varying from 163 to 193 nm depending on the ratio of DDA to PEG chains. The DDA content in the graft copolymers also affected the core shell interfacial compactness.

Effective removal and fixation of Cr(VI) from aqueous solution with Friedel's salt

Dai, Y.; Qian, G.; Cao, Y.; Chi, Y.; Xu, Y.; Zhou, J.; Liu, Q.; Xu, Z.; Qiao, S.
Fonte: Elsevier Science BV Publicador: Elsevier Science BV
Tipo: Artigo de Revista Científica
Publicado em //2009 EN
Relevância na Pesquisa
462.1827%
Friedel's salt (3CaO x Al2O3 x CaCl2 x 10 H2O or Ca4Al2(OH)12Cl2(H2O)4) is a calcium aluminate hydrate formed by hydrating cement or concrete in seawater at a low cost. In the current study, we carefully examined the adsorption behaviors of Friedel's salt for Cr(VI) from aqueous solution at different concentrations and various initial pHs. The adsorption kinetic data are well fitted with the pseudo-first-order Lageren equation at the initial Cr(VI) concentration from 0.10 to 8.00 mM. Both the experimental and modeled data indicate that Friedel's salt can adsorb a large amount of Cr(VI) (up to 1.4 mmol Cr(VI)/g) very quickly (t1/2 = 2-3 min) with a very high efficiency (>99% Cr(VI) removal at [Cr] < 4.00 mM with 4.00 g/L of adsorbent) in the pH range of 4-10. In particular, the competitive adsorption tests show that the Cr(VI) removal efficiency is only slightly affected by the co-existence of Cl(-) and HCO3(-). The Cr(VI)-fixation stability tests show that only less than 0.2% adsorbed Cr(VI) is leaching out in water at pH 4-10 for 24 h because the adsorption/exchange of Cr(VI) with Friedel's salt leads to the formation of a new stable phase (3CaO x Al2O3 x CaCrO4 x 10 H2O). This research thus suggests that Friedel's salt is a potential cost-effective adsorbent for Cr(VI) removal in wastewater treatment.; Yingchun Dai...

Equilibrium studies of 2,2'-(5-bromo-6-methylpyrimidine-2,4-diyl)bis(azanediyl)dipropanoic acid with some transition-metal ions in aqueous solution

Sajadi,Seyed A. A.; Bagherzadeh,Ghodsieh; Khaleghian,Marzieh; Mirbagheri,Maryam; Safaie,Hosein
Fonte: Sociedade Brasileira de Química Publicador: Sociedade Brasileira de Química
Tipo: Artigo de Revista Científica Formato: text/html
Publicado em 01/06/2014 EN
Relevância na Pesquisa
462.1827%
The stability constants of the 1:1 complexes formed between M2+ (M2+: Mn2+, Ni2+, Cu2+, or Cd2+) and BMADA2- (BMADA: 2,2'-(5-bromo-6-methylpyrimidine-2,4 diyl)bis(azanediyl)dipropanoic acid) were determined by potentiometric pH titration in aqueous solution (I = 0.1 mol L-1, NaNO3, 25 °C). The stability of the binary M - BMADA complexes is determined by the basicity of the carboxyl or amino groups. All the stability constants reported in this work exhibit the usual trend, and the order obtained was Mn2+< Ni2+ < Cu2+ > Cd2+. The observed stability order for BMADA approximately follows the Irving - Williams sequence. In the M - BMADA complexes, the M ion is able to form a macrochelate via the pyrimidine group of BMADA.

Spatial configuration of deoxyribotrinucleoside diphosphates in aqueous solution.

Cheng, D M; Dhingra, M M; Sarma, R H
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em /11/1978 EN
Relevância na Pesquisa
462.1827%
The detailed conformational features and dynamics of the naturally occurring deoxyribotrinucleoside diphosphates d-TpTpT and d-TpTpC have been investigated at 20 degrees C and 80 degrees C in aqueous solution by nuclear magnetic resonance spectroscopy. The observed NMR parameters indicate that the conformational properties of the trimers are very similar to those of the constituent dimers and monomers, i.e., the monomers and dimers conserve their intrinsic conformational features when they become incorporated into oligomers. Model building indicate that the distant shieldings can originate from spatial configurations in which the central nucleotidyl unit is bulged out and the w'1w1, w'2w2 occupy /g+g+, g+g+/ domains.

A simple procedure for constructing 5'-amino-terminated oligodeoxynucleotides in aqueous solution.

Bruick, R K; Koppitz, M; Joyce, G F; Orgel, L E
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 15/03/1997 EN
Relevância na Pesquisa
462.1827%
A rapid method for the synthesis of oligodeoxynucleotides (ODNs) terminated by 5'-amino-5'-deoxythymidine is described. A 3'-phosphorylated ODN (the donor) is incubated in aqueous solution with 5'-amino- 5'-deoxythymidine in the presence of N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide hydrochloride (EDC), extending the donor by one residue via a phosphoramidate bond. Template- directed ligation of the extended donor and an acceptor ODN, followed by acid hydrolysis, yields the acceptor ODN extended by a single 5'-amino-5'-deoxythymidine residue at its 5'terminus.

Conformational analysis of r(CGCGCG) in aqueous solution: an A-type double helical conformation studied by two-dimensional nuclear Overhauser effect spectroscopy.

Westerink, H P; van der Marel, G A; van Boom, J H; Haasnoot, C A
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 25/05/1984 EN
Relevância na Pesquisa
462.1827%
The conformation of the hexanucleoside pentaphosphate r( CGCGCG ) in aqueous solution was studied by circular dichroism, 1H- and 31P-NMR spectroscopy. The base-, H1'- and H2'-proton resonances were assigned by means of 2D-NOE spectroscopy. The base- and H1'-proton chemical shifts were studied as a function of temperature. Proton-proton distances are computed in A- and A'-RNA as well as in A-, B- and Z-DNA. A qualitative interpretation of the observed 2D-NOE intensities shows that r( CGCGCG ) adopts a regular A-type double helical conformation under our experimental conditions. The CD- and 31P-NMR experiments described in this paper are in agreement with this structure both under low- and high-salt conditions.

Pulse-radiolysis studies on the interaction of one-electron-reduced species with ascorbate oxidase in aqueous solution.

O'Neill, P; Fielden, E M; Finazzi-Agrò, A; Avigliano, L
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 01/01/1983 EN
Relevância na Pesquisa
462.1827%
The interaction of e-aq., CO2-. and one-electron reduced nitroaromatics (RNO2-.) with ascorbate oxidase (AAO) was studied in aqueous solution at pH 6.0 and 7.5 by using the technique of pulse radiolysis. From observations at 330, 410 and 610 nm, interaction of e-aq. and CO2-. with AAO results in non-specific reduction of the protein followed by reduction of Type 1 Cu in a rate-determining intramolecular step. Only a few per cent of the reducing equivalents ultimately results in reduction of Type 1 Cu. With large excesses of reducing equivalents (e-aq. and CO2-.) with respect to the copper concentration, the amount of Type 1 copper reduced never exceeds 50% of the total amount of Type 1 copper after a single radiation pulse. With less-powerful reducing agents, e.g. RNO2-. reduction of Type 1 Cu occurs via a bimolecular step, and there is no evidence for formation of radicals on protein residues. From observations at 330 nm it is evident that Type 2 and/or Type 3 Cu may also be reduced along with Type 1 Cu. Almost stoichiometric reduction of AAO by RNO2-. was observed, e.g. the protein accepts 6-7 reducing equivalents. It is inferred that the various types of redox couples Cu2+/Cu+ are in equilibrium and that intramolecular electron transfer between the different types of Cu is not rate-determining when using RNO2-. as reducing agent.

Oligoaminonucleoside phosphoramidates. Oligomerization of dimers of 3'-amino-3'-deoxy-nucleotides (GC and CG) in aqueous solution.

Zielinski, W S; Orgel, L E
Fonte: PubMed Publicador: PubMed
Tipo: Artigo de Revista Científica
Publicado em 25/02/1987 EN
Relevância na Pesquisa
462.1827%
The self-complementary 5'-phosphorylated dinucleoside 3' (N)----5' (P)-linked phosphoramidates with sequence GC (8a), CG (8b) and the tetranucleoside triphosphoramidate with sequence GCGC (10a) and CGCG (10b) have been synthesized and characterized by physicochemical and enzymatic methods. The dinucleosides 8a or 8b oligomerize in aqueous solution in the presence of a water-soluble carbodiimide. This process is efficient and regiospecific. In the case of GC it produces alternating 3' (N)----5' (P)-linked phosphoramidates up to 15 dimeric units in length with a yield in excess of 70%. The oligomerization of the CG isomer is much less efficient. The mechanism of oligomerization is discussed.

Guest-Host Chemistry with Dendrimers—Binding of Carboxylates in Aqueous Solution

Ficker, Mario; Petersen, Johannes F.; Hansen, Jon S.; Christensen, Jørn B.
Fonte: Public Library of Science Publicador: Public Library of Science
Tipo: Artigo de Revista Científica
Publicado em 08/10/2015 EN
Relevância na Pesquisa
462.1827%
Recognition and binding of anions in water is difficult due to the ability of water molecules to form strong hydrogen bonds and to solvate the anions. The complexation of two different carboxylates with 1-(4-carbomethoxypyrrolidone)-terminated PAMAM dendrimers was studied in aqueous solution using NMR and ITC binding models. Sodium 2-naphthoate and sodium 3-hydroxy-2-naphthoate were chosen as carboxylate model compounds, since they carry structural similarities to many non-steroidal anti-inflammatory drugs and they possess only a limited number of functional groups, making them ideal to study the carboxylate-dendrimer interaction selectively. The binding stoichiometry for 3-hydroxy-2-naphthoate was found to be two strongly bound guest molecules per dendrimer and an additional 40 molecules with weak binding affinity. The NOESY NMR showed a clear binding correlation of sodium 3-hydroxy-2-naphthoate with the lyophilic dendrimer core, possibly with the two high affinity guest molecules. In comparison, sodium 2-naphthoate showed a weaker binding strength and had a stoichiometry of two guests per dendrimer with no additional weakly bound guests. This stronger dendrimer interaction with sodium 3-hydroxy-2-naphthoate is possibly a result of the additional interactions of the dendrimer with the extra hydroxyl group and an internal stabilization of the negative charge due to the hydroxyl group. These findings illustrate the potential of the G4 1-(4-carbomethoxy) pyrrolidone dendrimer to complex carboxylate guests in water and act as a possible carrier of such molecules.

Spectroscopic and Crystal Field Consequences of Fluoride Binding by [Yb⋅DTMA]3+ in Aqueous Solution

Blackburn, Octavia A; Chilton, Nicholas F; Keller, Katharina; Tait, Claudia E; Myers, William K; McInnes, Eric J L; Kenwright, Alan M; Beer, Paul D; Timmel, Christiane R; Faulkner, Stephen
Fonte: WILEY-VCH Verlag Publicador: WILEY-VCH Verlag
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
462.1827%
Yb⋅DTMA forms a ternary complex with fluoride in aqueous solution by displacement of a bound solvent molecule from the lanthanide ion. [Yb⋅DTMA⋅F]2+ and [Yb⋅DTMA⋅OH2]3+ are in slow exchange on the relevant NMR timescale (<2000 s−1), and profound differences are observed in their respective NMR and EPR spectra of these species. The observed differences can be explained by drastic modification of the ligand field states due to the fluoride binding. This changes the magnetic anisotropy of the YbIII ground state from easy-axis to easy-plane type, and this change is easily detected in the observed magnetic anisotropy despite thermal population of more than just the ground state. The spectroscopic consequences of such drastic changes to the ligand field represent important new opportunities in developing fluoride-responsive complexes and contrast agents.

Preferred peptide backbone conformations in the unfolded state revealed by the structure analysis of alanine-based (AXA) tripeptides in aqueous solution

Eker, Fatma; Griebenow, Kai; Cao, Xiaolin; Nafie, Laurence A.; Schweitzer-Stenner, Reinhard
Fonte: National Academy of Sciences Publicador: National Academy of Sciences
Tipo: Artigo de Revista Científica
EN
Relevância na Pesquisa
462.1827%
We have combined Fourier transform IR, polarized Raman spectroscopy, and vibrational CD measurements of the amide I′ band profile of alanyl-X-alanine tripeptides in 2H2O to obtain the dihedral angles of their central amino acid residue. X represents glycine, valine, methionine, histidine, serine, proline, lysine, leucine, tryptophan, tyrosine, and phenylalanine. The experimental data were analyzed by means of a recently developed algorithm, which exploits the excitonic coupling between the amide modes of the two peptide groups. The results were checked by measuring the respective electronic CD spectra. The investigated peptides can be sorted into three classes. Valine, phenylalanine, tryptophan, histidine, and serine predominantly adopt an extended β-strand conformation. Cationic lysine and proline prefer a polyproline II-like structure. Alanine, methionine, glycine, and leucine populate these two conformations with comparable probability. Our results are in variance with the prediction of the random-coil model, but supportive of Flory's isolated-pair hypothesis. We combined the obtained structural propensities of the investigated residues and similar information about other residues in the literature (i.e., glutamate, aspartate...

Nickel(II), Copper(II) and Zinc(II) Complexes of 9-[2- (Phosphonomethoxy)ethyl]-8-azaadenine (9,8aPMEA), the 8-Aza Derivative of the Antiviral Nucleotide Analogue 9-[2-(Phosphonomethoxy)ethyl] adenine (PMEA). Quantification of Four Isomeric Species in Aqueous Solution

Gómez-Coca, Raquel B.; Holý, Antonín; Vilaplana, Rosario A.; González-Vílchez, Francisco; Sigel, Helmut
Fonte: Hindawi Publishing Corporation Publicador: Hindawi Publishing Corporation
Tipo: Artigo de Revista Científica
Publicado em //2004 EN
Relevância na Pesquisa
462.1827%
The acidity constants of the twofold protonated acyclic nucleotide analogue 9-[2-(phosphonomethoxy)- ethyl]-8-azaadenine, H2(9,8aPMEA)±, as well as the stability constants of the M(H;9,8aPMEA)+ and M(9,8aPMEA) complexes with the metal ions M2+ =Ni2+, Cu2+ or Zn2+, have been determined by potentiometric pH titrations in aqueous solution at I=0.1 M (NaNO3) and 25℃. The result for the release of the first proton from H2(9,8aPMEA)+ (pKa= 2.73), which originates from the (N1)H+ site, was confirmed by UV-spectrophotometric measurements. Application of previously determined straight-line plots of log KMM(R-PO3) versus PKH3(R-HPO3)' for simple phosph(on)ate ligands, R- PO-, where R represents a residue without an affinity for metal ions, proves that the primary binding site of 9,8aPMEA2- is the phosphonate group for all three metal ions studied. By stability constant comparisons with related ligands it is shown, in agreement with conclusions reached earlier for the Cu(PMEA) system [PMEA2-=dianion of 9-[2- (phosphonomethoxy)ethyl]adenine], that in total four different isomers are in equilibrium with each other, i.e. (i) an open isomer with a sole phosphonate coordination, M(PA)op, where PA2-=PMEA2-or 9,8aPMEA2-, (ii) an isomer with a 5-membered chelate involving the ether oxygen...