Hierarchical tungsten-doped bimetallic selenides nanosheets arrays/nickel foam composite electrode as efficient gallic acid electrochemical sensor.

The development of effective and accurate gallic acid (GA) electrochemical sensors is critical for food and pharmaceutical industry and health perspectives. Multi-step hydrothermal treatments of bimetallic (Ni/Co) flaky bimetallic hydroxides (NiCo FBHs) were employed to prepare tungsten-doped cobalt-nickel selenides nanosheets arrays (W-Co0.5Ni0.5Se2 NSAs) serving  as the main active substance of GA detection. The morphology and composition of the W-Co0.5Ni0.5Se2 NSAs/NF were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), Raman spectroscopy, X-ray powder diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The GA electrochemical sensor constructed by the W-Co0.5Ni0.5Se2 NSAs/NF composite electrode exhibits two linear concentration ranges of 1.00-36.2 µM and 36.2-1.00×103 µM for GA electrochemical detection with a limit of detection of  0.120 µM (S/N=3) at the working potential of 0.05 V (vs. SCE). The W-Co0.5Ni0.5Se2 NSAs/NF shows high selectivity, good long-term stability, high recovery in the range 97.9-105%, and a relative standard deviation (RSD) between 0.60 and 2.7%.

Enhancement of the Catalytic Activity of Double Metal Cyanides for the Oxidation of Styrene by the Presence of Included Alcohols.

In recent years, people have focused on the development of simple and efficient heterogeneous catalysts for the styrene epoxidation reaction. In this work, a FeCo double metal cyanide (DMC) was modified with C1 to C6 linear alcohols, and the prepared materials were used to catalyze the reaction of styrene epoxidation in various solvents. It is noteworthy that the styrene conversion is mainly affected by modification with alcohols, while the selectivity in styrene oxide (SO) is obviously influenced by the solvent. FeCo DMC along with MeOH exhibits the best catalytic performance, with a conversion rate of 96% and a SO selectivity of 86%, in N,N-dimethylformamide (DMF) solvent. Various physical and chemical methods were used to analyze the structures and compositions of the materials. To clarify the mechanism of the improvement, we set up an original approach to investigate the kinetics of the adsorption process between the oxidant and the catalyst, using isothermal titration calorimetry (ITC). The obtained results illustrate that the adsorption process of the oxidant on the surface of FeCo DMC can be dramatically promoted by the presence of MeOH. Such a difference in adsorption thus explains the significant improvement of its catalytic activity by modification with MeOH. This study thus provides a new fundamental understanding of DMC catalysts for the styrene epoxidation reaction.

Autosetting soliton pulsation in a fiber laser by an improved depth-first search algorithm.

Soliton pulsation is one of the most fascinating phenomena in ultrafast fiber lasers, owing to its rich nonlinear dynamics and potential generation of high peak power pulse. However, it is still a challenge to efficiently search for pulsating soliton in fiber lasers because it requires a fine setting of laser cavity parameters. Here, we report the autosetting soliton pulsation in a passively mode-locked fiber laser. The parameters of electronic polarization controller are intelligently adjusted to search for pulsating soliton state by the improved depth-first search algorithm. Moreover, the intensity modulation depth of pulsating soliton could be flexibly controlled. These findings indicate that the intelligent control of a fiber laser is an effective way to explore on-demand soliton dynamics and is also beneficial to the optimization of ultrafast laser performance.

In Situ Growth of 3D/2D (CsPbBr3/CsPb2Br5) Perovskite Heterojunctions toward Optoelectronic Devices.

Two-dimensional (2D) CsPb2Br5 exhibits intriguing functions in enhancing the performance of optoelectronic devices in terms of environmental stability and luminescence properties when composited with other perovskites in different dimensionalities. We built a type I three-dimensional (3D) CsPbBr3/2D CsPb2Br5 heterojunction through phase transition where CsPbBr3 quantum dots in situ grew into 2D CsPb2Br5. A thorough growth mechanism study in combination with excited state dynamic investigations via femtosecond spectroscopy and first-principles calculations revealed that the type I hierarchy enhanced the stability of the heterojunction and spurred its luminous quantum yield by prolonging the lifetime of photogenerated carriers. Mixing the heterojunction with other phosphors yielded white-light-emitting diodes with a color rendering index of 94%. The work thus not only offered one new avenue for building heterojunctions by using the "soft crystal" nature of perovskites but also disentangled the enhanced luminescence mechanism of the heterojunction that can be harnessed for promising applications in the luminescence and display fields.

The inter-micellar interaction enthalpies of DTAB/TX100 mixed micelles and their structural transitions.

The heats of mixing for a series of DTAB/TX100 mixed surfactant aqueous solutions were measured by flow-mixing calorimetry and isothermal titration calorimetry (ITC) at 298.15 K and 85 kPa, which were used to calculate the inter-micellar interaction enthalpies (-ΔHC). The signs of -ΔHC for pure DTAB and TX100 micellar systems were contrary to the inter-micellar interaction parameters reported for the same systems in the literature, suggesting that these interaction parameters might have a Gibbs free energy character dominated by entropy changes. It was found that the inter-micellar interaction enthalpies varied with the total surfactant concentration and the mixed ratio of the two surfactants, and characterized different structures of the mixed micelles. These phenomena were discussed based on the effects of structural water around the micellar interface, the hydration of counterions, and the repulsive Coulombic interaction.

Critical Anomalies of Two SN1 Hydrolysis Reactions in Critical Binary Solutions.

Rates of SN1 hydrolysis reactions for 2-chloro-2-methylbutane in the critical solution of isobutyric acid + water and for 2-bromo-2-methylpropane in the critical solution of triethylamine + water in the one-phase region and at various temperatures have been determined respectively by conductance measurements. It was found that the reaction rates at different temperatures for those two SN1 reactions were well described by the Arrhenius equation in the noncritical region, whereas near the critical points the critical slowing down was clearly detected. These results are inconsistent with a previous report in the literature (J. Phys. Chem. A 2003, 107, 8435 - 8443). Reanalyzing the literature data, we found that if an Arrhenius equation appropriate to either the one-phase region or the two-phase region being examined was used as the background, a critical slowing down rather than a speeding up was detected for the reaction in both the one-phase region and the two-phase region. The experimental data from different sources were fitted with a simplified crossover formalism characterizing the critical effect on the reactions to determine the critical slowing down exponents, which were found to be about 0.04, showing that only a dynamic critical slowing down could be detected for these reaction systems. This phenomenon was attributed to the fact that the SN1 hydrolysis reaction is neither a first-order nor a pseudo-first-order reaction in the reverse direction and the kinetic measurements were carried out in a region quite far from the equilibrium of the reactions.

Effects of water content and chain length of n-alkane on the interaction enthalpy between the droplets in water/sodium bis(2-ethylhexyl)-sulfosuccinate/n-alkane microemulsions.

The concentration-dependent enthalpies of mixing for water/sodium bis(2-ethylhexyl)-sulfosuccinate (AOT)/n-alkane microemulsions with different water contents ω0 and chain lengths n of n-alkane were determined by isothermal titration microcalorimetry (ITC) and flow-mixing microcalorimetry at 298.15 K and used to calculate the interaction enthalpies (-ΔH(C)) between the droplets. It was found that -ΔH(C) increased with ω0, and changed from negative to positive at about ω0 = 10. The investigation of the dependence of -ΔH(C) on n revealed that the values of -ΔH(C) were negative and had a minimum for ω0 = 5; while they were positive and had a maximum for ω0 = 15. These phenomena were discussed based on the competition of the overlapping contribution of the surfactant tails between two neighbouring droplets and the penetration contribution of the solvent molecules into the surfactant tails. These results indicated the important role of entropy in the stability of the microemulsion systems.

Solvent dependent interactions between droplets in water-in-oil microemulsions.

In this paper, we investigated the dilution enthalpies of the droplets in water/AOT/oil microemulsions with oil being isooctane, decane, or cyclohexane by isothermal titration microcalorimetry (ITC). Combining with the results obtained from the study of the water/AOT/toluene system in our previous work, it was found that the enthalpy interactions between droplets for isooctane and decane systems were repulsive, while the enthalpy interactions were attractive for cyclohexane and toluene systems. The repulsive droplet interaction for the isooctane system was also confirmed by static light scattering. The solvents appear to play important roles in varying the droplet enthalpy interactions from positive to negative, and the entropy contribution seems to be dominant for the stability of these microemulsion droplet systems.

The interactions of ι-carrageenan with cationic surfactants in aqueous solutions.

The interactions between the anionic polymer ι-carrageenan (IC) and the cationic surfactants 1-dodecyl-3-methylimidazolium bromide (C12mimBr), dodecyltrimethylammonium bromide (DTAB) and ethyl-α,ω-bis(dodecyldimethylammonium)dibromide (12-2-12) have been studied by fluorimetry and isothermal titration calorimetry. Our experimental results showed that at a low surfactant concentration, the monomers adsorbed on the IC chains through the electrostatic attraction, followed by the formation of induced micelles on the IC chains through the hydrophobic interaction until the IC chains are saturated by surfactant molecules; after that the added surfactant formed free micelles in the solution. A pseudo-phase-equilibrium thermodynamic model was proposed to explain the experimental results and to understand the mechanisms of the interactions in these three systems. Moreover, the salt effect on the interactions was investigated and found that it changed the critical concentrations but not the interaction mechanism.

Thermodynamics of mixed surfactant solutions of N,N'-bis(dimethyldodecyl)-1,2-ethanediammoniumdibromide with 1-dodecyl-3-methylimidazolium bromide.

Mixed surfactant solutions are studied to understand their synergistic effects. Here we report the micellization properties of mixed surfactant solutions of the gemini surfactant N,N'-bis(dimethyldodecyl)-1,2-ethanediammoniumdibromide (12-2-12) with the imidazolium ionic liquid 1-dodecyl-3-methylimidazolium bromide (C12mimBr) investigated by isothermal titration calorimetry (ITC), conductometry, fluorimetry, and dynamic light scattering (DLS). A two-parameter Margules model was successfully used to correlate the cmc values and calculate the compositions and activity coefficients of the two components in the mixed micelle phase for 12-2-12/C12mimBr aqueous solutions with different overall surfactant compositions. The dissociation degree of counterion, the thermodynamic quantities of micellization, and the excess thermodynamic quantities for the mixed micelle were calculated and discussed. The ITC experiment in the low overall surfactant composition region showed a second phase transition. A thermodynamic model was proposed to explore phase behaviors of two different types of micelle and their solution, which was further confirmed by fluorescence and DLS studies.

Critical anomalies of alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water.

We have used three-wavelength UV-spectrophotometry to study the reaction of the alkaline fading of phenolphthalein in the critical solution of 2-butoxyethanol + water. It was found that when the temperature was far away from the critical point, the values of the natural logarithm of the rate constant k and the natural logarithm of the chemical equilibrium K determined in our experiments had good linear relationships with the reciprocal of temperature, which served as the backgrounds and were used for correcting k and K in the critical region. The critical slowing down of the reaction and the critical anomaly of the chemical equilibrium were detected near the critical point. The value of the critical exponent characterizing the slowing down effect of the reaction rate was obtained to be 0.156, which was close to the value 0.11 associated with the heat capacity divergence and agreed with the theoretical prediction. The experimental result also confirmed the theoretical prediction of 0.11 for the critical exponent characterizing the weak divergence of the singularity of the chemical equilibrium.

The effect of the spacer rigidity on the aggregation behavior of two ester-containing Gemini surfactants.

Two Gemini surfactants with very similar structure but different spacer rigidity, namely 1-dodecanaminium,N,N'-[[(2E)-1,4-dioxo-2-butene-1,4-diyl]bis(oxy-2,1-ethanediyl)]bis[N,N-dimethyl-,bromide] (12-fo-12) and 1-dodecanaminium, N,N'-[(1,4-dioxo-1,4-butanediyl)bis(oxy-2,1-ethanediyl)] bis[N,N-dimethyl-, bromide] (12-su-12), and their monomeric counterpart 1-dodecanaminium, N-[2-(acetyloxy)ethyl]-N,N-dimethyl-, bromide (DTAAB) were synthesized and their aggregation behavior in aqueous solutions was studied by measurements of surface tension, conductivity, isothermal titration calorimetry, dynamic light scattering, and transmission electron microscopy. It was found that the Krafft point of 12-fo-12 was 18.6°C, significantly higher than that of 12-su-12 (7.6°C) and DTAAB (<0°C). The minimum surface areas per surfactant A(min) at the water-air interface of DTAAB, 12-su-12, and 12-fo-12 were determined. It was found that the value of A(min) of DTAAB was larger than half that of 12-su-12 but smaller than half that of 12-fo-12. The values of the degree of association ß of the three surfactants were found to be in a sequence of DTAAB>12-su-12>12-fo-12, which was in accord with the sequence of the entropy of micellization. The enthalpies of micellization of the two Gemini surfactants were found to be more negative than double that of DTAAB, and 12-fo-12 had the most negative standard enthalpy of micellization. It was also found that 12-su-12 and DTAAB formed micelles in aqueous solutions, while 12-fo-12 could form micelles and vesicles dependent on the concentration.

Determination of the interaction enthalpy between microemulsion droplets by isothermal titration microcalorimetry.

A new experimental design for the measurement of the real heat of dilution of the microemulsion droplets by isothermal titration microcalorimetry (ITC) has been reported and used to study the interaction enthalpies of the droplets for the system of water/sodium bis(2-ethylhexyl)-sulfosuccinate (AOT)/toluene. The results are in good agreement with those determined from light-scattering experiments.

Interactions and aggregations in aqueous and brine solutions of poly(diallydimethylammonium chloride)/sodium bis(2-ethylhexyl) sulfosuccinate.

The interactions between the anionic surfactant sodium bis(2-ethylhexyl) sulfosuccinate (AOT) and the polycation poly(diallydimethylammonium chloride) (PDDAC), the aggregations of AOT and PDDAC-bound AOT in PDDAC/AOT aqueous solutions, and the influence of salt on the interactions and aggregations have been studied by isothermal titration calorimetry (ITC), dynamic light scattering (DLS), and negative staining transmission electron microscopy (TEM). The adsorptions of AOT onto PDDAC and the formations of PDDAC-bound AOT micelles, free AOT micelles, and AOT vesicles were examined, and the corresponding critical concentrations were determined. Combining calculations of thermodynamic parameters with the above three experimental techniques, it was shown that the micellization of free AOT is driven by entropy gain, while the adsorption of AOT onto PDDAC and the micellization of PDDAC-bound AOT are driven by both enthalpy and entropy. It was also found that addition of salt enhances the binding of AOT onto PDDAC through the ion exchange and favors the formations of PDDAC/AOT micelles, free AOT micelles, and free AOT vesicles but prevents the transition of PDDAC/AOT micelles to the vesicles. Thermodynamic analysis suggested that the adsorption of AOT onto PDDAC and the micellization of PDDAC/AOT in PDDAC/AOT brine solutions are different in mechanism compared with that in corresponding aqueous solutions.