Use of water spin-spin relaxation rate to probe the solvation of cyclodextrins in aqueous solutions

1H spin-spin relaxation rate constant, R2, of water was measured by using the Carr-Purcell-Meiboom-Gill sequence in aqueous solutions of native cyclodextrins (alpha, beta, and gamma-CD) and chemically modified CDs in order to probe the structuring of the water surrounding these cyclic carbohydrate molecules. R2 values for water in solutions containing glucose and dextran were also measured for comparison. A two-site model for bonded and free water molecules was used to fit the results for the dependence of R2 on the solute concentrations. The order of relaxation rates for water in aqueous solution at a fixed specific hydroxyl group concentration is glucose>dextran congruent with CDs. No significant difference was observed for R2 of water in solutions containing native CDs, which indicates that the size and nature of the cavity has a small effect on the spin-spin relaxation times of water. The lower relaxation rate for water in CD solutions was attributed to the intramolecular hydrogen bonding formed between the secondary hydroxyl groups that line the rim of the CDs. For comparison, the relaxation rates for water in solutions of two chemically modified CDs were also studied.     

Effect of temperature on the fluorescence emission of carbazole-substituted methylcellulose in dilute aqueous solutions

Fluorescent-labeled polymers, carbazole-substituted methylcelluloses (Cz-MCs) were synthesized through a two-step reaction by firstly introducing epoxy group to carbazole, and then reacting with MC. Structure of Cz-MC was characterized by using FTIR, NMR, elemental analysis and UV–vis spectroscopy. Aggregation behavior of Cz-MCs in dilute aqueous solution was investigated by a thermotropic study performed with dynamic laser light scattering. Cz-MCs displayed concentration self-quenching properties of fluorescence spectra both in H₂O and DMSO. The temperature effect on the fluorescent emission in dilute aqueous solution was explored. The results showed that the degree of substitution of carbazole and thermal aggregation of Cz-MC contributed to the formation of network structure between the molecules, consequently leading to the enhancement or quenching in fluorescence intensity.     

Adsorption of citric acid from dilute aqueous solutions by hydroxyapatite

The role of citric acid in the demineralization of dental enamel, which is mainly constituted by hydroxyapatite, is important for periodontal regeneration and in the conditioning of enamel or dentin for bonding restorative resins. The adsorption of citric acid from aqueous solutions onto synthetic hydroxyapatite at 278, 288, 298, and 308 K and pH 4.8 has been studied by means of UV spectroscopy. The adsorption reaction, which takes place by an interaction between phosphate groups and citrate anions at the solid-solution interface, yields an adsorbate-adsorbent complex of high stability. The adsorption isotherms fit the Langmuirian shape. The proposed adsorption model, where citrate species interact in a bidentate manner (one citrate ion links two phosphate sites), is coherent with the experimental data. The activation standard heat and activation standard entropy were calculated. All the thermodynamic and kinetic parameters were in concordance with the adsorption reaction proposed in this work.     

Quenching of fluorescence from pyrene in micellar solutions by cationic quenchers

The fluorescence from the S₁ state of pyrene solubilized within the hydrophobic region of sodium dodecyl sulfate micelles has been studied as a function of concentration of some cationic additives to the aqueous phase. At concentrations of added quencher below ca. 10^?3 mol dm^?3 the fluorescence decay follows a complex rate law; at long time, the decay is exponential with the same time constant as that of pyrene (S₁) without added quencher. The initial slope of the decay curve depends linearly on the concentration of added cation. These results are discussed in terms of the recently proposed model which requires the water-hydrocarbon interface to penetrate the micelle in the region of the probe. An analytical treatment is presented which, on the premises stated, serves to explain the observed kinetic features.     

十二烷基磺酸钠增强的吡啶锉 对芘的荧光猝灭

水溶液中三种吡啶 盐(吡啶盐酸盐, HP+;N-苄基吡啶,BP^+; 苄基紫精, BV^2^+)对芘的荧光猝灭因十二烷基磺酸钠(SLS)的引入而增强, 且猝灭常数对SLS浓度的敏感性BV^2^+>BP^+>HP^+, 电导实验表明体系中无簇集体形成。认为SLS与吡啶 的静电作用及表面活性剂分子中烷基链的绕曲是导致猝灭增强的原因。     

Determination of thiabendazole in aqueous solutions using a cucurbituril-enhanced fluorescence method

The complexation of thiabendazole (TBZ) with the cucurbit[6]uril (Q[6]), cucurbit[7]uril (Q[7]) and symmetric tetramethyl-cucurbit[6]uril (TMeQ[6]) in aqueous solution has been investigated using UV–vis and fluorespectrometry. The experimental results show 1:1 host–guest inclusion complexes at pH 6.5 for all three macrocyclic hosts, and the corresponding formation constants by UV and fluorescence methods are (5.37?±?1.05)?×?10⁴?L?mol^?1 and (1.47?±?0.41)?×?10⁴?L?mol^?1 for the Q[6]-TBZ system (7.76?±?0.51)?×?10⁴?L?mol^?1 and (9.36?±?0.22)?×?10⁴?L?mol^?1 for the Q[7]-TBZ system (1.28?±?0.78)?×?10⁴?L?mol^?1 and (2.69?±?0.55)?×?10⁴?L?mol^?1 for the TMeQ[6]-TBZ system, respectively. Based on the enhancement of the fluorescence intensity of TBZ with the addition of Q[n]s in neutral media, a fluorespectrometry method for the determination of TBZ in aqueous solution in the presence of Q[n] was established. In the range of 6.0?×?10^?8?mol?L^?1–8.0?×?10^?6?mol?L^?1 a linear relationship was obtained between fluorescence intensity and TBZ concentration. The detection limit was found to be between 5.51 and 8.85?×?10^?9?mol?L^?1. The interference of coexisting ions was found to be slight. The proposed method has been successfully applied to the determination of TBZ in different aqueous solutions with satisfactory recoveries of 92–103%. The method seems to be suitable for environmental water analysis.     

Contribution of a pyrene fluorescence probe to the aggregation propensity of polypeptides

[structure: see text] Two synthetic polypeptides, TT1p and TT1b, have been used in comparative aggregation equilibrium studies. The findings reveal that a single alkylpyrene moiety in TT1p contributes about 30% of the polypeptide dimerization energy in aqueous media. This result not only is informative with regard to the aggregation properties of these particular photoactive polypeptides but also provides a quantitative understanding of the limitations on the use of pyrene chromophores as emission probes.     

Separation of ionic liquids from dilute aqueous solutions using the method based on CO2 hydrates

Ionic liquids (ILs) have been regarded as the potential novel solvents for improved analytical-and process-scale separation methods. The development of methods for the recovery of ILs from aqueous solutions to escape contamination and recycle samples will ultimately govern the viability of ILs in the future industrial applications. Therefore, in this paper a new method for separation of ILs from their dilute aqueous solutions and simultaneously purification of water was proposed on the basis of the CO2 hydr...     

Intensification of formic acid from dilute aqueous solutions using menthol based hydrophobic deep eutectic solvents

The fermentation of biomass and organic waste streams is the primary source of formic acid production. Formic acid is the hydrogen energy carrier and is used as a hydrogen storage medium in fuel cells. Sustainable production of formic acid makes the hydrogen-fuel cell entirely environmentally friendly and ensures the long-term storage of renewable energy. Therefore, green, economic, and sustainable production and recovery of formic acid are highly demanded. In this study, it was aimed to use a new generation, green, easily prepared, and designer hydrophobic deep eutectic solvents (HDES) for the removal of formic acid via reactive extraction. HDESs obtained by preparing binary mixtures of nonanoic acid, decanoic acid, dodecanoic acid (HBD), and menthol (HBA) were used as diluents; tri-n-octylamine (TOA) and Amberlite LA-2 (Amb.LA-2) were acted as extractants. Experiments were performed to investigate the effect of extractant type and concentration, initial acid concentration, and volume of the organic phase on extraction. Experimental data were presented by calculating the extraction efficiency (E%), distribution coefficient (D), and loading factor (Z). Results demonstrated that the extraction efficiency remained between 10 and 13% when performing physical extraction using M-NA, M-DA, and M-DDA, while TOA was diluted with the same HDESs reached around 90% and with Amb.LA-2 85%. The highest distribution coefficient was obtained that the organic phase consisting of TOA and M-DDA mixture was used. The efficiency of utilized HDESs was in the following order: M-DDA ?> ?M-DA ?> ?M-NA.     

Structural analysis of aggregates formed by a thermoresponsive homopolymer in dilute aqueous solutions

The aqueous solution of a thermoresponsive polymer, poly[2‐(2‐ethoxy) ethoxyethyl vinyl ether] poly(EOEOVE), contains a tiny amount of large polymer aggregates at low polymer concentrations far below the lower critical solution temperature (～40 °C). The molar mass M_w,slow, radius of gyration 〈S²〉, and hydrodynamic radius R_H,slow of the aggregating component of poly(EOEOVE) were obtained by simultaneous static and dynamic light scattering as functions of the polymer concentration and temperature, while the weight fraction w_slow of the component was estimated by size‐exclusion chromatography. The M_w,slow dependencies of 〈S²〉 and R_H,slow, as well as the ratio 〈S²〉/R_H,slow, indicated that the poly(EOEOVE) aggregate takes a sparsely branched polymer‐like conformation. We have analyzed the structure of the aggregate, using the branched polymer model of random type. The M_w,slow dependence of 〈S²〉 obtained was favorably compared with this model with reasonable structural parameters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1179–1187, 2006     

Probing the lateral organization of membranes: fluorescence repercussions of pyrene probe distribution

Phospholipids pyrene labeled are widely used to investigate dynamics and organizations of membranes. We studied pyrene probe lateral distribution by analyzing the variations of the molar absorption coefficient (epsilon) versus probe concentrations, in small unilamellar vesicles (SUV) made of phospholipids and/or glycolipids, with pyrene labeled phosphatidylcholine (PyPC) or phosphatidylglycerol (PyPG). The results were interpreted according to an infinite associative model. They indicated that an effective self-association process corresponding to K ranging from 30 to 100 M(-1) occurred with those probes incorporated in dimannosyl diacylglycerol (DMDG). In contrast, after SUV labeling of egg yolk phosphatidylcholine (EggPC) or phosphatidylglycerol (EggPG), K values < 1 M(-1) were determined. The corresponding percentages of various stacked forms of pyrene probes were calculated. They indicated that, for a 3% PyPG labeling, the monomer represented 21% of n-mers in DMDG and 94% in EggPC. The analysis of fluorescence experiments carried out on the same samples indicated that: (i) the fluorescence process of pyrene probes was generated by the monomers: and (ii) the excimer forming resulted from a diffusional encounter between one excited and one non-excited monomer. A correction of fluorescence data allowing a more correct interpretation of fluorescence measurements was proposed.     

Adsorption preconcentration of pyrene by silver nanoparticles and its determination in aqueous solutions

The reduction of silver nitrate with sodium borohydrate in an aqueous medium in the presence of cetyl trimethylammonium bromide gives a stable sol of silver, which can adsorb nonpolar organic compounds, e.g., polycyclic aromatic hydrocarbons, on the surface of metal nanoparticles. The subsequent luminescent determination demonstrated the effect of sensitized luminescence of silver nanoparticles, which could provide a basis for the determination of traces of polycyclic aromatic compounds in water.     

NMR chemical shifts of xenon in aqueous solutions of amphiphiles: A new probe of the hydrophobic environment

The chemical shift of elemental xenon in solution is sensitive to the environment. The shift arises from van der Waals interactions in most liquids, but an additional effect is present in aqueous media yielding a larger shift than expected. In water the shift is affected by the presence of low molecular weight amphiphiles, and its variation with composition can reveal the presence of hydrophobic hydration of the amphiphile. The results are similar to the conclusions drawn from other physical studies. Data are presented for aqueous solutions of methanol, ethanol, n-propanol, iso-propanol, tert-butanol, dimethylsulfoxide, p-dioxane, and acetonitrile.     

Investigation of the surface of a polymeric adsorbent with pyrene as a fluorescence probe

Pyrene was used as a fluorescence probe to study the surface and pyrene/surface interactions which occur on a polypropylene adsorbent. The surface interaction between this adsorbent and pyrene was found to be very similar to that found for pyrene in hydrocarbon solvents. In contrast to the surfaces of other types of adsorbents, the polypropylene surface presents an energetically homogeneous surface to adsorbing molecules. Consequently, adsorption takes place essentially randomly as opposed to being associated with activated sites.     

Determination of nucleic acids using fluorescence probe sensitized by microemulsion

Because the fluorescence of azur A can be quenched by adding nucleic acid, a sensitive fluorometric method for determination of nucleic acids at nanogram levels was established. Using optimal conditions, the calibration curves were linear in the range of 0-6.0 microg/mL for calf thymus deoxyribonucleic acid (ct DNA) and 0-7.0 microg/mL for herring sperm DNA (hs DNA). The limits of determination were 3.5 and 3.8 ng/mL, respectively, which shows the high sensitivity of this method. Triton X-100 microemulsion was applied as a sensitive media to enhance the sensitivity. The binding mode concerning the interactions of azur A with nucleic acids was also studied and the association constant with different binding numbers was obtained. The method has been applied to the determination of nucleic acid in both synthetic and real samples, such as cauliflower and pork liver, with satisfactory results.