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51.
52.
Valente AJ Burrows HD Cruz SM Pereira RF Ribeiro AC Lobo VM 《Journal of colloid and interface science》2008,323(1):141-145
Aggregation properties of sodium dodecyl sulfate (SDS) in the presence of cerium(III) chloride, at various temperatures (298.15-323.15 K) have been measured by the electrical conductance technique. The experimental data on aqueous solutions as a function of SDS concentration show the presence of two inflexion points indicating the presence of two distinct interaction mechanisms: the first, occurring at SDS concentrations below the critical micelle concentration of the pure surfactant, which can be explained by the formation of aggregates between dodecyl sulfate (DS-) and Ce(III), while the second one, at SDS concentrations around the critical micelle concentration (cmc) of the pure surfactant which is due to the SDS micellization. The aggregation between DS- and Ce(III) was confirmed by static light scattering. The binding ratio of DS-/Ce(III) changes from 6 to 4, shows a slight dependence on the Ce(III) concentration and is independent of the temperature. The thermodynamic micellization parameters, Gibbs energy, enthalpy and entropy of micellization were calculated on the basis of the experimental data for the aggregation concentration, and the degree of counterion dissociation of the micelles. The SDS micellization is energetically favoured by increasing either the concentration of CeCl3 or the temperature. Such behaviour is clearly dominated by a decrease of the micellization (exothermic) enthalpy. The entropy of micellization approaches zero as the cerium(III) chloride concentration and temperature increase. 相似文献
53.
Xu X Fleming AM Muller JG Burrows CJ 《Journal of the American Chemical Society》2008,130(31):10080-10081
8-Oxo-7,8-dihydro-2'-deoxyguanosine (OG), a prevalent product of oxidative stress on cellular DNA, is readily further oxidized forming adducts with nucleophiles. In the presence of tyrosine or p-cresol, an unusual tricyclo[4.3.3.0] adduct has been characterized in both nucleoside and oligodeoxynucleotide studies. The adduct is more stable in oligomers than nucleosides and undergoes slow reversion and hydration to spiroiminodihydantoin. 相似文献
54.
The potential energy surface for formation of 2-amino-5-hydroxy-7,9-dihydropurine-6,8-dione (5-OH-OG), guanidinohydantoin (Gh) and spiroiminodihydantoin (Sp) from 8-oxoguanine (8-oxoG) has been mapped out using B3LYP density functional theory, the aug-cc-pVTZ and 6-31+G(d,p) basis sets and the IEF-polarizable continuum model (PCM) solvation model. Three pathways for formation of 5-OH-OG from 8-oxoG were evaluated: (A) stepwise loss of two electrons and two protons to form the quinonoid intermediate 2-amino-7,9-dihydro-purine-6,8-dione (8-oxoG(ox)) followed by hydration; (B) stepwise loss of two electrons and one proton and net addition of hydroxide, in which the key step is nucleophilic addition to the 8-oxoG radical cation; and (C) stepwise loss of one electron and one proton and addition of hydroxyl radical to the 8-oxoG radical cation. The data suggest that all three pathways are energetically feasible mechanisms for the formation of 5-OH-OG, however, Pathway A may be kinetically favored over Pathway B. Although lower in energy, Pathway C may be of limited biological significance since it depends on the local concentration of hydroxyl radical. Pathways for hydrolysis and decarboxylation of 5-OH-OG to form Gh via either a carboxylic acid or substituted carbamic acid intermediate have been evaluated with the result that cleavage of the N1-C6 bond is clearly favored over that of the C5-C6 bond. Formation of Sp from 5-OH-OG via stepwise proton transfer and acyl migration or ring opening followed by proton transfer and ring closure have also been explored and suggest that deprotonation of the hydroxyl group facilitates a 1,2 acyl shift. Results of the calculations are consistent with experimental studies showing dependence of the Gh/Sp product ratio on pH. Under neutral and basic conditions, the data predict that formation of Sp is kinetically favored over the pathways for formation of Gh. Under acidic conditions, Gh is predicted to be the kinetically favored product. 相似文献
55.
Burrows AD Dodds D Kirk AS Lowe JP Mahon MF Warren JE Whittlesey MK 《Dalton transactions (Cambridge, England : 2003)》2007,(5):570-580
Facile substitution reactions of the two water ligands in the hydrophilic tetradentate phosphine complex cis-[Fe{(HOCH2)P{CH2N(CH2P(CH2OH)2)CH2}2P(CH2OH)}(H2O)2](SO4) (abbreviated to [Fe(L1)(H2O)2](SO4), 1) take place upon addition of Cl-, NCS-, N3(-), CO3(2-) and CO to give [Fe(L1)X2] (2, X = Cl; 4, X = NCS; 5, X=N3), [Fe(L1)(kappa2-O(2)CO)], 6 and [Fe(L1)(CO)2](SO4), 7. The unsymmetrical mono-substituted intermediates [Fe(L1)(H2O)(CO)](SO(4)) and [Fe(L(1))(CO)(kappa(1)-OSO(3))] (8/9) have been identified spectroscopically en-route to 7. Treatment of 1 with acetic anhydride affords the acylated derivative [Fe{(AcOCH2)P{CH2N(CH2P(CH2OAc)2)CH2}2P(CH2OAc)}(kappa2-O(2)SO2)] (abbreviated to [Fe(L2)(kappa2-O(2)SO2)], 10), which has increased solubility over 1 in both organic solvents and water. Treatment of 1 with glycine does not lead to functionalisation of L1, but substitution of the aqua ligands occurs to form [Fe(L(1))(NH(2)CH(2)CO(2)-kappa(2)N,O)](HSO(4)), 11. Compound 10 reacts with chloride to form [Fe(L(2))Cl(2)] 12, and 12 reacts with CO in the presence of NaBPh4 to form [Fe(L2)Cl(CO)](BPh4) 13b. Both of the chlorides in 12 are substituted on reaction with NCS- and N3(-) to form [Fe(L2)(NCS)2] 14 and [Fe(L2)(N3)2] 15, respectively. Complexes 2.H2O, 4.2H2O, 5.0.812H2O, 6.1.7H2O, 7.H2O, 10.1.3CH3C(O)CH3, 12 and 15.0.5H2O have all been crystallographically characterised. 相似文献
56.
García-Zubiri IX Burrows HD Seixas de Melo JS Pina J Monteserín M Tapia MJ 《Photochemistry and photobiology》2007,83(6):1455-1464
The complexation of beta-carboline-3-carboxylic acid N-methylamide (betaCMAM) with the sodium salts of the nucleotides polyadenylic (Poly A), polycytidylic (Poly C), polyguanylic (Poly G), polythymidylic (Poly T) and polyuridylic (Poly U) acids, and with double stranded (dsDNA) and single stranded deoxyribonucleic acids (ssDNA) was studied at pH 4, 6 and 9. Predominant 1:1 complex formation is indicated from Job plots. Association constants were determined using the Benesi-Hildebrand equation. BetaCMAM-sensitized singlet oxygen quantum yields were determined at pH 4, 6 and 9, and the effects on this of adding oligonucleotides, dsDNA and ssDNA were studied at the three pH values. With dsDNA, the effect on betaCMAM triplet state formation was also determined through triplet-triplet transient absorption spectra. To evaluate possible oxidative damage of DNA following singlet oxygen betaCMAM photosensitization, we used thiobarbituric acid-reactivity assays and electrophoretic separation of DNA assays. The results showed no oxidative damage at the level of DNA degradation or strand break. 相似文献
57.
Pina J de Melo JS Burrows HD Batista RM Costa SP Raposo MM 《The journal of physical chemistry. A》2007,111(35):8574-8578
A comprehensive study has been made in solution at room temperature (293 K), low temperature (77 K), and in thin films (Zeonex matrixes) of the spectral and photophysical properties of six arylthienyl- and bithienyl-benzothiazole derivatives functionalized with different donor groups. Similar experiments have been carried out with two related precursors (containing the arylthienyl and aryl-bithienyl conjugated systems), and results are compared. Singlet-singlet and triplet-triplet absorption spectra, emission spectra together with lifetimes and quantum yields have been obtained, and from these data the rates for all the radiative and nonradiative processes determined, providing information on the dominant decay processes. The arylthienyl-benzothiazole derivatives show high fluorescence quantum yields (phi(F)) with negligible internal conversion (phi(IC)), whereas the bithienyl-benzothiazoles display lower but still significant phi(F) values, but now radiationless processes (phi(IC) and phi(ISC)) are competitive. A comparison with the analogous oligothiophenes is made. Singlet oxygen yields were also determined and the triplet energy transfer to (3)O2 to produce (1)O2 was found to be highly efficient with values of S(Delta)(= phi(Delta)/phi(T)) varying from 0.4 to 1. 相似文献
58.
M. E. C. D. Real Oliveira Graham Hungerford E. M. S. Castanheira M. da G. Miguel H. D. Burrows 《Journal of fluorescence》2000,10(4):347-353
The phase transition of microemulsions involving the nonionic surfactant C12E5 [C12H25(OCH2-CH2)5OH], water, and alkanes (heptane, decane and tetradecane) has been investigated through the excimer formation of pyrene. On going to the microemulsion bicontinuous phase, by changing either composition or temperature, pronounced changes in the pyrene excimer-to-monomer fluorescence intensity ratio, I
E/I
M, are observed. Several differences in the steady-state emission spectra and in fluorescence decay curves show that as a probe pyrene is well suited to follow the transition from the water continuous to the oil continuous phase, through an intermediate bicontinuous (continuous in both water and oil) region. The results provide information about the different characteristics and structure of these three regions (water continuous, bicontinuous, and oil continuous) of the phase diagram for C12E5/water/alkane systems. 相似文献
59.
Artur J. M. Valente Cesar M. C. Filho Adley Rubira Edvani C. Muniz Hugh D. Burrows 《Colloid and polymer science》2014,292(7):1665-1673
Equilibrium and transport properties have been investigated of ephedrines, a class of sympathomimetic amines, through cryogel membranes of poly(vinyl alcohol) (PVA). The effect of the PVA (10 to 18 % (w/v)) on the release properties of (1S,2R)-(+)-ephedrine hydrochloride has been discussed on the basis of partition–diffusion and power-law models. The effect of PVA concentration on the swelling degree of PVA–ephedrine matrices have been measured, allowing the estimation of the volume fraction of polymer in the gel. Ephedrine release rate constants, computed by using a first-order kinetics approach, have been modeled by using free-volume and hydrodynamic-scaling models. Differences in the release properties of the ephedrine isomers, (1S,2R)-(+)- and (1R,2S)-(?)-ephedrine as their hydrochlorides, have also been studied at different temperatures. The release kinetic constants and the corresponding activation energies show a marked discrimination between the two ephedrine isomers. This suggests that PVA cryogel membranes possess high potential for enantiomeric differentiation. 相似文献
60.
Donohoe TJ Harris RM Burrows J Parker J 《Journal of the American Chemical Society》2006,128(42):13704-13705
The double oxidative cyclization of dienes is a viable procedure for making complex natural products containing cis-THF units. A double deprotection/double oxidative cyclization strategy using catalytic osmium tetroxide was used to construct the bisheterocyclic core of cis-sylvaticin and ultimately confirm its structure. The natural product was then prepared by a short sequence of reactions that is exceptionally concise: the final route being just 13 linear steps and 19 chemical operations in total. 相似文献