First Reaction of a Chiral Gly-Ni(Ⅱ) Complex in Water

The amination of a chiral Ni(II) complex as a model reaction was studied to develop a highly practical, efficient, and stereospecific approach for Ni(II) complex reactions in an aqueous phase. A convenient and clean water‐mediated reaction of the Ni(II) complex has been reached, and a broad spectrum of substrates could participate in the process effectively to produce desired products in good yields and excellent diastereoselectivities. Significantly, it is the first report of chiral gly‐Ni(II) complex reaction in aqueous media.     

Phase Behavior of Poly(Oxyethylene)–Poly(Oxypropylene)–Poly(Oxyethylene) Block Copolymer in Water and Water–C12EO5 Systems

Abstract

The binary phase diagram of a triblock copolymer poly(oxyethylene) (PEO) poly(oxypropylene) (PPO) poly(oxyethylene) (PEO), (PEO)₃₇(PPO)₅₈(PEO)₃₇ or P105 in water and the ternary system of P105, water, and pentaoxyethylene dodecyl ether (C₁₂EO₅) has been studied to understand the miscibility of a small amphiphile, C₁₂EO₅ and a copolymer, as well as the mixing effect on the formed liquid crystalline structures. Phase diagrams, small angle x‐ray scattering (SAXS) and differential scanning calorimetry (DSC) were used to characterize these systems. The phase diagram of the binary system is presented together with the characteristic parameters for founded phases, namely, cubic, hexagonal, and lamellar phases. In the ternary system it was found that the small amphiphile and the block copolymer, despite having very different chain lengths are essentially miscible forming single phases. A large amount of C₁₂EO₅ can be solubilized in the P105 aggregates whereas P105 is most difficult to dissolve in the C₁₂EO₅ aggregates because of the difference in the molecular size. The copolymer is practically insoluble in the lamellar phase of C₁₂EO₅ due to the packing constraint. Hence, two lamellar phases coexist in a surfactant‐rich region, at W _s  = 0.66, where W _s is the weight fraction of the total amphiphile in the system. This indicates that the thickness of the lipophilic part of the C₁₂EO₅ lamellar phase is too small to allocate the large lipophilic chain of the P105 triblock copolymer.     

Solvation Behaviors of Poly(acrylic acid) in Mixed Solvents of 2-Butoxyethanol + Water

Poly(acrylic acid) (PAA) is a well known weak polyelectrolyte in water but little is known about the solvation behavior of PAA in the mixtures of alcohol?+?water. In this study, the solvation behavior of PAA in the mixed solvents composed of 2-butoxyethanol (2BE)?+?water were investigated by measurements of volumetric properties, electrical conductivity, resonance light scattering and dynamic light scattering. All the measured experimental properties showed extrema or abrupt changes at a 2BE mole fraction of about 0.017 in 2BE?+?water. This may be explained by the formation of aggregates of 2BE and water, which is a poor solvent for PAA and results in cononsolvency of PAA in the mixture of the two good solvents, 2BE and water. We found that the volumetric property is sensitive to the occurrence of the specific aggregate of 2BE and water and the interactions in the complex fluid mixtures.     

Biomimetic Synthesis of Water Soluble Conductive Polypyrrole and Poly(3,4‐Ethylenedioxythiophene)

Abstract

A novel biomimetic method for the synthesis of conducting molecular complexes of polypyrrole (PPYR) and poly(3,4‐ethylenedioxythiophene) (PEDOT) in the presence of a polyelectrolyte, such as polystyrene sulfonate (SPS) is presented. A poly(ethylene glycol) modified hematin (PEG‐Hematin) was used to catalyze the polymerization of pyrrole (PYR) and 3,4‐ethylenedioxythiophene (EDOT) in the presence of SPS to form PPYR/SPS and PEDOT/SPS complexes. UV‐VIS, FT‐IR, and electrical conductivity studies for all complexes indicated the presence of a stable and electrically conductive form of these polymers. Furthermore, the presence of SPS in this complex provides a unique combination of properties such as processability and water‐solubility.     

Tuning of Water and Hydroxide Content of Intercalated Ruddlesden-Popper-type Oxides in the PrSr(3)Co(1.5)Fe(1.5)O(10-δ) System

A series of hydration experiments of the Ruddlesden-Popper phase PrSr(3)Co(1.5)Fe(1.5)O(10-δ) with varying levels of oxygen nonstoichiometry were performed with the goal to clarify phase formation and underlying mechanisms and driving forces. The hydration reaction is most intense for partly reduced samples with a vacancy concentration corresponding to δ ≈ 1. Fully oxidized samples show little or no tendency toward hydration. Presence of oxygen vacancies acts as a prerequisite for hydration. Probably, the basicity of the materials owing to A-site cations is another contributing factor to the hydration ability. Under CO(2) free conditions pure hydrates and oxide hydroxides are formed. In CO(2)-containing atmosphere, additional carbonate anions are easily incorporated into the hydrate, probably at the expense of hydroxyl groups. The I-centered PrSr(3)Co(1.5)Fe(1.5)O(8)(OH)(2)·1H(2)O achieves a highly expanded c-axis upon the topochemical insertion reactions. In situ powder synchrotron X-ray diffraction (SXRD) shows that the hydrate converts to an oxide hydroxide, PrSr(3)Co(1.5)Fe(1.5)O(8)(OH)(2), at 70 °C with a primitive orthorhombic unit cell. Upon heating above 170 °C, an I-centered product is formed for which further dehydroxylation occurs at around 400-500 °C. Rietveld refinement of SXRD data shows that the absorbed water molecules fill the tetrahedral voids of the [AO](RS) rock salt layer of the monoclinic hydrate.     

Complexation of Dioxovanadium (V) with CDTA in the Water + Methanol Solvent System

The solvent effect has been studied in this research for the interaction of the $ {\text{VO}}_{2}^{ + } $ VO 2 + cation with trans-1,2-diaminocyclohexane-N, N, N′, N′- tetraacetic acid monohydrate at T = 298 K, I = 0.10 mol·dm^?3 sodium perchlorate, and in the range of 0–45 % water + methanol mixtures. UV absorbance data as a function of pH and dissociation constants, obtained from potentiometric titrations, were used for the determination of stability constants. The Kamlet–Abboud–Taft (KAT) model has been investigated for a plausible interpretation and calculation of the linear solvation energy relationship coefficient contribution to the formation of three species VO₂H₂L, VO₂HL^? and VO₂L^2?, which were identified in this work.     

Conductance Determination of the Ion Association of Tris-(ethylenediamine)chromium(III) Chloride in Dimethyl Sulfoxide–Water Mixtures at Various Temperatures

The electrical conductances of tris-(ethylenediamine)chromium chloride, ([Cr(en)₃]Cl₃; en = ethylenediamine) were measured as functions of temperature and concentration in 20–80 wt% dimethyl sulfoxide (DMSO)–water mixtures. Conductance data were analyzed by the Kraus–Bray and Shedlovsky models. Also, density and viscosity values for 20–80 wt% DMSO–water mixtures have been determined experimentally at temperatures varying from (288.15 to 318.15) K. The limiting molar conductance, Λ ⁰, and the association constant, K _A, for ([Cr(en)₃]Cl₃ were computed by using Shedlovsky’s equation. The Λ ⁰ values decrease with increase in the percentage of DMSO in the mixed solvent. The K _A values increase with increasing temperature and increasing percentage of DMSO in the mixed solvent at all temperatures. This may be attributed to the increase in association constant with the decrease in the relative permittivity of the mixed solvent. Thermodynamic parameters (Gibbs energy, enthalpy and entropy changes) were determined from the temperature dependence of K _A for ([Cr(en)₃]Cl₃. The results of the study have been interpreted in terms of ion–solvent interactions and solvent properties.     

Ternary Complexes of Cadmium(II) with Phenylalanine and Phenylalkylmalonates in Dioxane–Water Mixtures

The formation and stability of ternary complexes of cadmium(II) with phenylalanine and malonate, phenylmalonate benzylmalonate, 2-phenylethylmalonate, and 3-phenylpropylmalonate, have been studied by the potentiometric pH titration technique in 40% (v/v) dioxane–water at 25°C and 0.10—ionic strength (NaNO₃). All systems give stable ternary complexes, and the log K and _K values demonstrated that the complexes possess enhanced stability. The possible reasons that lead to these results are discussed in terms of –electron back donation from metal ions to ligands and intramolecular ligand–ligand aromatic ring-stacking interactions present in the complexes. The relative contribution of each interactions to the enhanced stability have also been evaluated.     

Potentiometric Studies of Copper(II) Complexes of Some Substituted Benzylidene-2-Hydroxyanilines in Dioxane–Water Media

The formation and protonation constants of 17 Schiff bases-derived 2-hydroxyaniline with some substituted benzaldehydes, and the stability constants of Cu(II) complexes of these Schiff bases, have been determined potentiometrically in 20, 40, and 60% dioxane–water media. The data from the potentiometric titrations were evaluated with the BEST computer program. For all Schiff bases studied, it was observed that the log K_OH values related to the protonation equilibria of the phenolic oxygen are increased, and the log K_NH values related to the protonation equilibria of the azomethine nitrogen are decreased, as the dioxane content is increased. The variation of these constants is discussed on the basis of specific solute–solvent interactions and structural changes of Schiff bases from water to the dioxane–water media. Also, titrimetric-pH investigation of substituted benzilidene-2-hydroxyaniline systems has revealed the formation of stable mono-Schiff base complexes with the metal ion Cu(II).     

Interaction of Chromium(III) with Chrome Azurol S in Water–Glycerol Media

The interaction of Cr(III) with Chrome azurol S (CAS) in water–glycerol binary mixtures has been investigated by spectrophotometry. The absorption electronic spectra of Chrome azurol S and its complex with Cr(III) in water–glycerol media with glycerol contents from 10 to 50% by vol. have been measured. The stability constant of the complex in water–glycerol binary mixtures has been determined. It has been shown that the rate of reaction increases as the organic solvent content increases.     

Dilational Rheological Properties of P-(n-alkyl)-benzyl Polyoxyethylene Ether Carboxybetaine at Water–Decane Interface

The dilational rheological behaviors of absorbed films of p-(n-alkyl)-benzyl polyoxyethylene ether carboxybetaine C_xBE₂CB (x = 8, 10, 12) at the water–decane interface have been investigated by the drop-shape analysis method. The influences of time, oscillation frequency, and bulk concentration on dilational modulus and phase angle have been expounded. The experimental results show that the phase angle of C_xBE₂CB (x = 10, 12) decreases with the increase of time, the slope of the log ? ? log ω curve and phase angle of C_xBE₂CB (x = 10, 12) decrease in a wide concentration range. These phenomena become more and more apparent with the increase of hydrocarbon chain length and it cannot be attributed to the diffusion-exchange process between the bulk and the interface. It is reasonable to consider that ethylene oxide groups are flexible and can be compressed and expanded, just like a spring. Therefore, the compression and expansion of the ethylene oxide groups in the interfacial layer and the exchange between interface and sublayer play a more important role for C_xBE₂CB (x = 10, 12) adsorption film. The dependence of dilational modulus on interfacial pressure can support our provided mechanism strongly.     

A Porous 3D Supramolecular Architecture of Cd(Ⅱ) Complex with Water Clusters as Pillars

A supramolecular complex of Cd(Ⅱ) with 1D water tapes as pillars[Cd2(dpa)2(phen)2- (H2O)2]·6H2O 1 (H2dpa = diphenic acid, phen = phenanthroline), has been synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group Pī with a = 9.7029(4), b = 11.9601(5), c = 12.1788(4) A, a = 71.6990(10), β = 71.8740(10), γ = 74.4680(10)°, V = 1252.39(8) A3 C52H48Cd2N4O16, Mr = 1209.76, Z = 1, Dc = 1.604 g/cm3,μ = 0.925 mm-1, F(000) = 612, R = 0.0679 and wR = 0.2514 for 3870 observed reflections (Ⅰ > 2σ(Ⅰ)). Two intramolecular Cd(Ⅱ) centers of this complex are encircled by two dpa2- ligands forming an 18-membered ring, which is further assembled into a pillared three-dimensional (3D) supramolecular architecture through the synergetic effect of intermolecular face-to-face π…π stacking and weak O-H…O hydrogen-bonding interactions. Moreover, this complex exhibits photoluminescence with the main emission bands located at about 456 nm upon excitation at 355 nm in the solid state at room temperature.     

The Effect of Concentration Parameters on Complexation in the Iron(0)–Iron(II)–Glycine–Water System

The processes of formation of iron(II) complexes in aqueous glycine solutions in the pH range of 1.0–8.0 at 298 K and ionic strength of 1 mol/L (NaClO₄) are studied using Clark and Nikolskii’s oxidation potential method. The type and number of coordinated ligands, the nuclearity, and the total composition of the resulting complexes are determined. The following complex species are formed in the investigated system: [Fe(OH)(H₂O)₅]⁺, [FeHL(H₂O)₅]²⁺, [Fe(HL)(OH)(H₂O)₄]⁺, [Fe(OH)₂(H₂O)₄]⁰, [Fe₂(HL)₂(OH)₂(H₂O)₈]²⁺, and [Fe(HL)₂(H₂O)₄]²⁺. Their formation constants are calculated by the successive iterations method using Yusupov’s theoretical and experimental oxidation function. The model parameters of the resulting coordination compounds are determined.     

Coordination Features of a Polyaza-Bipyridine-Macrocyclic Ligand toward Co(II) and Cd(II) in Water and Dimethylsulfoxide

The coordination features of a polyaza macrocycle, containing the diverse bipyridine unit 4,4′-(2,5,6,11,14-pentaaza[15]-[15](2,2′)-bipyridylophane (L3), with Co(II) and Cd(II) have been studied in aqueous solution and in the aprotic solvent dimethylsulfoxide (DMSO). The study was carried out at 298 K by means of potentiometric, spectrophotometric and calorimetric techniques. The formation of the dinuclear species M₂ L3 is observed for Co(II) both in water and in DMSO, whereas Cd(II) is able to form this type of dinuclear complex only in DMSO. The FT-IR spectra of the mononuclear species ML3, formed in both solvents, provide evidence that the rigid structure of the polyaminic chain prevents metal ions from being coordinated by all of the nitrogens of the macrocyclic cavity, in good agreement with the behavior suggested by the thermodynamic parameters. The results are compared with those for the complexation of Co(II) and Cd(II) with similar polyazamacrocycles containing a bipyridine unit directly inside the cavity. Semi-empirical calculations were also performed to obtain structural information.     

Fabrication of N-(Amino-Ethyl)-Amino-Propyl Functionalized Magnetite Nanoparticles for Oil–Water Separation of Wastewater From Tertiary Oil Recovery

N-(amino-ethyl)-amino-propyl trimethoxy silane (AEAPTMS) is used to modify Fe₃O₄ with a one-pot coprecipitation method. Powder X-ray diffraction measurements show the spinel structure of magnetite nanoparticles. A high positive charge of +33.96 mV was obtained on the surfaces of modified magnetic nanoparticles, with the diameter ranging from 6.5 to 22.5 nm. The modified Fe₃O₄ was first applied to the treatment of wastewater from tertiary oil recovery. The obtained results indicated that the oil removal rate increased with the dosage of modified Fe₃O₄ and slightly increased with the separation time. The mechanism of modified Fe₃O₄ toward wastewater from tertiary oil recovery was attributed to the electrostatic interaction between negatively charged microemulsion oil in wastewater and the positively charged surfaces of magnetic nanoparticles.     

Factors Affecting the Droplet Size of Water‐in‐Oil Emulsions (W/O) and the Oil Globule Size in Water‐in‐Oil‐in‐Water Emulsions (W/O/W)

Multiple emulsions of the W₁/O/W₂ type are promising tools for encapsulating bioactive ingredients in the inner aqueous droplets. It is necessary, however, to control the factors influencing their encapsulation efficiency. One important factor is the particle size because it determines the surface area available for mass transport. Because of the coexistence of water and oil droplets in multiple emulsions, there are numerous factors that have an impact on particle size, for example, oil phase composition, interfacial properties, and viscosity of the phases. The purpose of this study was to systematically investigate the effect of these factors on particle sizes in multiple emulsions.     

A Study on the Preparation of Konjac Glucomannansilk Fibroin Composite Aerogels and Its Adsorption of Water Pollutant Cr(Ⅲ)

It is emergent to develop a green waste water adsorbent with high efficiency.Therefore,a type of low-cost,green and environmentally friendly konjac glucomannan(KGM)-silk fibroin(SF)composite aerogels were compounded via simple chemical grafting and vacuum freeze drying,and a study on its adsorption capacity was also conducted.The characterizations of FT-IR,SEM,XRD and DSC indicate that the modified aerogels show a porous network space structure and there is a strong hydrogen bond effect between the KGM and SF molecules,which improves the density,compressive strength and thermal stability of aerogel materials.The adsorption experiments show that KGM-SF aerogels can effectively adsorb the water pollutants Cr(Ⅲ)with a maximal adsorption capacity of 82 mg·g^-1.In addition,the adsorption isotherm and dynamic model analysis are used to elaborate the adsorption mechanism of KGM-SF aerogels and explain that the composite aerogels can be single molecule chemisorption.KGM-SF aerogels have potential adsorption capacity.     

Structure of Hexakis(imidazole)nickel(II) Nitrate Water Solvate:[Ni(Im)_6] (NO_3)_2·4H_2O

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