Host–guest control on the formation of pinacyanol chloride H-aggregates in anionic polyelectrolyte solutions

The interactions of pinacyanol chloride (PIN), a cationic cyanine dye, with the anionic polyelectrolyte poly(acrylic acid, sodium salt) (PAA) towards enhancing H-aggregation were investigated by electronic absorption spectroscopy. We employed the cucurbit[7]uril (CB7) host to control the formation of these aggregates via host–guest binding interactions with the dye molecules. Absorption spectroscopic studies clearly demonstrate that PAA enhances the formation of PIN H-aggregates. Electrostatic interactions between the cyanine dye molecules and the polyelectrolyte chains assist the formation of H-aggregates at very low dye concentrations (ca. 10 μM). Furthermore, the presence of CB7 was found to effectively disrupt the interactions responsible for dye aggregation. Thus, CB7 completely disrupts the H-aggregates (as well as lower concentrations of J-aggregates) by forming inclusion complexes with PIN. A competing guest, 1-aminoadamantane (AD), was utilised to adjust the extent of aggregation of the cyanine dye. AD regulates aggregate formation by forming an extremely stable complex with CB7 and exerting a tight control on the CB7 concentration available to interact and bind with the dye. Our spectroscopic data clearly indicate that by varying the relative molar ratios of CB7 host, AD and polyelectrolyte acid groups, we can quantitatively control the extent of formation of PIN H-aggregates in these solutions.     

Secondary environment effects on the first step of the protonation of SO 4 2− in saline aqueous solutions

The solubility of strontium sulfate in the mixtures of isomolar LiClO₄(NaClO₄) and HClO₄ aqueous solutions was determined at 25°C and ionic strengths of I = 0.5, 1.0, 2.0, 3.0, and 4.0. At I>-2, the solubility of SrSO₄ as a function of the hydrogen ion (HClO₄) concentration passes through a maximum, clearly showing a substantial contribution from environment effects (H⁺ substitution for Li⁺ or Na⁺), which counteract complexation (i.e., HSO ₄ ^? formation). A correct method for separating these two effects was proposed, and the parameters of the environment effect and the standard values of pSP° and logβ° were evaluated.     

Application of BU4N+HSO4 − as an Ionic Liquid and Acid Catalyst for Thioacetalization of Aldehydes and Ketones

A variety of carbonyl containing compounds have been successfully reacted with 1,2-ethanedithiol in a thioacetylization reaction using tetrabutylammonium hydrogensulfate as a mild and efficient catalyst. Aldehydes and ketones react with good to excellent yields under mild conditions.     

Electrochemical signal modulation in homogeneous solutions using the formation of an inclusion complex between ferrocene and β-cyclodextrin on a DNA scaffold

Two DNA conjugates modified with ferrocene and β-cyclodextrin were prepared as a pair of probes that work cooperatively for DNA sensing, in which the electrochemical signal of ferrocene on one probe was significantly "quenched" by the formation of an inclusion complex with β-cyclodextrin of the other probe on the DNA templates.     

Coordination model,stability constant,and kinetics study of cystamine and l-cystine with [PdCl4]2− in hydrochloric aqueous solutions

Stoichiometry, equilibria, and kinetics of [PdCl₄]^2?interactions with l-cystine (H₄CysS²⁺) and cystamine (H₂Cyst²⁺) have been investigated spectrophotometrically in strong hydrochloric acidic media. Interactions lead to the formation of highly stable S/(S,N)-coordinated binuclear, and then with excess [PdCl₄]^2? trinuclear (S,S,N) or tetranuclear (S,S,N,N) species without disulfide bond cleavage. The reaction of [PdCl₄]^2? with H₄CysS²⁺ or H₂Cyst²⁺ at [PdCl₄]^2? excess has irreversible first-order kinetics, and with H₄CysS²⁺ or H₂Cyst²⁺ excess, by irreversible parallel reaction of [PdCl₄]^2? addition to the ligand. The influence of leaving groups on the kinetics has been explained in terms of formation of stable ionic pairs with complex species and of efficient overlap of d and π orbitals in a transition state. The reactions proceed through an associative mechanism with the first step being formation of the S-coordinated complex. Coordination models and mechanisms have been proposed. Applicability of spectrophotometry for establishment of disulfide bond state in organic disulfides in complexation processes has been demonstrated.     

Dispersion of single-walled carbon nanotubes in dimethylacetamide and a dimethylacetamide–cholic acid mixture

A way of dispersing single-walled carbon nanotubes in preparing stable suspensions with high concentrations of individual nanotubes in amide solvents is described. The obtained suspensions are studied via Raman spectroscopy. The dependence of the degree of single-walled carbon nanotube (SWNT) dispersion in individual and mixed amide solvents on the type of solvent, the mass of nanotubes, and the concentration of cholic acid is established. A technique for processing spectral data to estimate the diameters and chiralities of individual nanotubes in suspension is described in detail.     

Conversion of xylose and xylan into furfural in biorenewable choline chloride–oxalic acid deep eutectic solvent with the addition of metal chloride

An environmentally benign processing approach for furfural production from xylose and xylan under very mild conditions(353–373 K) was developed with the addition of metal chlorides in ChCl–oxalic acid(a deep eutectic solvent(DES)) synthesized from cheap and renewable starting materials). ChCl–oxalic acid acted as both a Br?nsted acid catalyst and a reaction medium in this catalytic route. In addition, a biphasic system with methyl isobutyl ketone as an extracting reagent(DES/MIBK) to further increase furfural yield was also proposed. This processing approach for producing furfural eliminated the large energy consumption for high pressure saturated steam and the generation of acidic effluent, which was very difficult to handle. The whole catalytic system was more environmentally friendly compared with the commercial process for furfural production.     

Hydration of α-alanine in aqueous sodium chloride and urea solutions

The hydration number of α-alanine in aqueous urea solutions is greater than in aqueous NaCl solutions; the ratio of the hydration numbers increases from 0.2 (m = 1) to ≈2 (m = 6). Given the same partial volumes of water, the hydration numbers of α-alanine in the two systems are close to each other.     

The dissociation quotients of formic acid in sodium chloride solutions to 200°C

The dissociation quotients of formic acid were measured potentiometrically from 25 to 200°C in NaCl solutions at ionic strengths of 0.1, 0.3 1.0, 3.0, and 5.0 mol-kg^–1. The experiments were carried out in a concentration cell with hydrogen electrodes. The resulting molal acid dissociation quotients for formic acid, as well as a set of infinite dilution literature values and a calorimetrically-determined enthalpy of reaction, were fitted by an empirical equation involving an extended Debye Hückel term and seven adjustable parameters involving functions of temperature and ionic strength. This regressional analysis yielded the following thermodynamic quantities for 25°C: logK=–3.755±0.002, H^o=–0.09±0.15 kJ-mol^–1, S^o=–72.2±0.5 J-K^–1-mol^–1, and C _p ^o =–147±4 J-K^–1-mol^–1. The isocoulombic form of the equilibrium constant is recommended for extrapolation to higher temperatures.     

Standard enthalpies of formation of α-aminobutyric acid and products of its dissociation in an aqueous solution

Heats of solution of crystalline α-aminobutyric acid in water and in aqueous solutions of potassium hydroxide at 298.15 K are measured by means of direct calorimetry. Standard enthalpies of formation of the amino acid and products of its dissociation in an aqueous solution are calculated.     

Synergistic effects of alkali metals in the alkylation of naphthalene and toluene with ethene in the ArH–alkali metal systems in THF (ArH – naphthalene,phenanthrene)

The use of mixtures of metallic lithium and sodium in the naphthalene–alkali metal systems in THF leads to a synergistic acceleration of the naphthalene alkylation with ethene at room temperature and atmospheric pressure. The greatest synergistic effect is observed at a Li:Na molar ratio of 2:1. Under these conditions, the overall conversion of naphthalene into alkylation products (linear 1-alkylnaphthalenes and their dihydro derivatives) attains 88% after 24 h (a (Li + Na):C₁₀H₈ ratio is 2:1). The use of mixtures of metallic lithium and potassium in such systems results, however, in a synergistic retardation of the alkylation process. The strongest retarding effect is observed at a Li:K molar ratio of 1:1. The efficiency of the toluene alkylation with ethene in the naphthalene–alkali metal systems in THF is also increased on the replacement of lithium or sodium by their mixtures. The best results are obtained at a Li:Na molar ratio of 1:3. With this Li:Na ratio, toluene is almost quantitatively converted into linear and α-branched higher monoalkylbenzenes (24 h, (Li + Na):C₁₀H₈ = 2:1). The rate of the naphthalene alkylation with ethene in the presence of toluene is enhanced as well on an introduction of mixtures of lithium and sodium into the system. However the maximum of the activity is shifted here towards higher lithium content (Li:Na = 1:1). A similar synergistic effect of lithium and sodium was found on studying the toluene alkylation with ethene in the phenanthrene–Li–Na systems in THF (a (Li + Na):phenanthrene ratio is 3:1). An addition of potassium to sodium also considerably increases the efficiency of the toluene and naphthalene alkylation with ethene in the naphthalene-based systems. The possible mechanism of the alkali metal synergism in the above-mentioned alkylation reactions is discussed.     

The ionization of sulfurous acid in Na−Mg−Cl solutions at 25°C

The stoichiometric pK ₁ ^* and pK ₂ ^* for the ionization of sulfurous acid has been determined from emf measurements in NaCl solutions with varying concentrations of added MgCl₂ (m=0.1, 0.2 and 0.3) from I=0.5 to 6.0 molal at 25°C. These experimental results have been treated using both the ion pairing and Pitzer's specific ion-interaction models. The Pitzer parameters for the interaction of Mg²⁺ with SO₂ and HSO ₃ ^– yielded =0.085±0.004, ⁽⁰⁾ = 0.35±0.02, ⁽¹⁾ = 1.2±0.04, and C = –0.072±0.007. The Pitzer parameters ⁽⁰) = –2.8±0.4, ⁽¹⁾ = 12.9±2.9 and ⁽²⁾ = –2071±57 have been determined for the interactions of Mg²⁺ with SO ₃ ^2– . The calculated values of pK ₁ ^* and pK ₂ ^* using Pitzer's equations reproduce the measured values to within ±0.04 pK units. The ion pairing model with log K_MgSO3=2.36±0.02 and log_MgSO3 = 0.1021, reproduces the experimental values of pK ₂ ^* to ±0.01. These results demonstrate that treating the data by considering the formation of MgSO₃ yields a better fit of the experimental measurements with fewer adjustable parameters. With these derived coefficients obtained from the Pitzer equations and the ion pairing model, it is possible to make reliable estimates of the activity coefficients of HSO ₃ ^– and SO ₃ ^2– in seawater, brines and marine aerosols containing Mg²⁺ ions.     

Aqueous solutions of a “green” ionic liquid and of lithium chloride compared and contrasted

Aqueous solutions of (a) a “green” ionic liquid and (b) lithium chloride are considered here. Proposals are made in respect to momentum transfer as characterized by shear viscosity, η. Arrhenius-type behavior as a function of temperature is contrasted with possible power-law form. More generally, η?is written as a product of mass density, the velocity of sound squared, and a characteristic time. Experiments are proposed for testing present ideas also involving the Debye–Hückel screening length.     

Rapid formation of metal−monophenolic networks on polymer membranes for oil/water separation and dye adsorption

Surface deposition based on metal-phenolic networks (MPNs) has received increasing interest in recent years. The catechol structure is generally considered to be essential to the formation of MPNs. Our most recent results have demonstrated that some kinds of monophenols can form MPNs on substrate surfaces. Herein, we report a fast and effective surface-coating system based on the coordination of 3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid, a kind of monophenol, with Fe³⁺. Compared with other metal ions such as Cu²⁺ and Ni²⁺, Fe³⁺ with stronger electron acceptability can coordinate with the monophenol more strongly to form MPNs, and moreover, the deposition time significantly decreases to 40 min from generally 24 h. It is demonstrated that the deposition process is controlled by the coordination, Fe³⁺ hydrolysis, and deprotonation of the monophenol. The coatings endow substrates such as polypropylene microfiltration membrane with underwater superoleophobicity, which can be applied in oil/water separation with high separation efficiency and great long-term stability. In addition, the coated membranes are positively charged and thus are useful in selective adsorption of dyes. The present work not only provides a novel, fast, and one-step deposition method to fabricate MPNs, but also demonstrates that the fabrication efficiency of monophenol-based MPNs is comparable with that of polyphenol-based MPNs.     

Thermodynamic study on salt effects on complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid

The aim of this work was to gain a deeper understanding of salt effects in the inclusion complex formation of cyclodextrins. For this purpose, thermodynamic study of complex formation of α-, β- and γ-cyclodextrins with p-aminobenzoic acid was carried out in water and solutions of KCl, KBr, KH₂PO₄ and K₂SO₄ (0.2 mol/kg). Stability constants were calculated from the binding isotherms obtained on the basis of ¹H NMR measurements. Enthalpy and entropy of complex formation were estimated from the van’t Hoff plots. It was found that effects of KCl, KH₂PO₄ and K₂SO₄ are insignificant, while the influence of KBr on complex formation of cyclodextrins with p-aminobenzoic acid is more pronounced and results in a decrease of the stability constants. Specific action of Br⁻ is caused by the ability of these anions to penetrate into macrocyclic cavity. Coexistence of two complexation equilibria in KBr solution is accompanied by significant solvent reorganization originated from more intensive dehydration of the interacting species. This results in an increase of the enthalpy and entropy of complex formation. Manifestation of Br⁻ effect was found to be the same in the binding of p-aminobenzoic acid with α-, β- and γ-cyclodextrins.