Clay-catalyzed reactions of coagulant polymers during water chlorination

The influence of suspended clay/solid particles on organic–coagulant reactions during water chlorination was investigated by analyses of total product formation potential (TPFP) and disinfection by-product (DBP) distribution as a function of exchanged clay cation, coagulant organic polymer, and reaction time. Montmorillonite clays appeared to act as a catalytic center where the reaction between adsorbed polymer and disinfectant (chlorine) was mediated closely by the exchanged clay cation. The transition-metal cations in clays catalyzed more effectively than other cations the reactions between a coagulant polymer and chlorine, forming a large number of volatile DBPs. The relative catalytic effects of clays/solids followed the order Ti-Mont > Fe-Mont > Cu-Mont > Mn-Mont > Ca-Mont > Na-Mont > quartz > talc. The effects of coagulant polymers on TPFP follow the order nonionic polymer > anionic polymer > cationic polymer. The catalytic role of the clay cation was further confirmed by the observed inhibition in DBP formation when strong chelating agents (o-phenanthroline and ethylenediamine) were added to the clay suspension. Moreover, in the presence of clays, total DBPs increased appreciably when either the reaction time or the amount of the added clay or coagulant polymer increased. For volatile DBPs, the formation of halogenated methanes was usually time-dependent, with chloroform and dichloromethane showing the greatest dependence.     

Insertion of fluorophore dyes between Cloisite Na+ layered for preparation of novel organoclays

The aim of this study was to obtain novel photo-functional organomontmorillonites from the intercalation reaction of Cloisite Na⁺ and fluorescent dyes of auramine O, and safranin T in an aqueous solution. The insertion of surfactants in the interlamellar space of nanoclay was followed by Fourier transform infrared spectroscopy and X-ray measurements. An X-ray diffraction analysis established that incorporation of the organic dye cations into the Cloisite Na⁺ expands remarkably the mineral interplanar distances from 1.17 to 1.83–1.97 nm. Field emission scanning electron microscopy was used to study the morphology of the synthesized organoclays. The thermal behavior of the novel hybrid materials was investigated by thermogravimetric analysis and the results show that the organo modified clays verify stepwise decomposition corresponding to initial weight loss from residual water desorption, followed by decomposition of the fluorescent dyes and the dehydroxylation of structural water of the clay layers. Fluorescence properties of the cationic dyes, auramine O, and safranin T incorporated in the clay have significant differences from their behavior in organic solvents and water and the results show that both dyes exhibit a significant fluorescence emission at room temperature when adsorbed in clay.     

Adsorption, desorption and activities of acid phosphatase on various colloidal particles from an Ultisol

Adsorption, desorption and activity of acid phosphatase on various soil colloidal particles and pure clay minerals were studied. Higher adsorption amounts and low percentage of desorption of acid phosphatase were found on fine soil clays (<0.2 μm). Electrostatic force and ligand exchange are the major driving forces that are involved in the adsorption of enzymes on soil clays. More enzyme molecules were adsorbed on soil clays in the presence of organic components. However, enzymes on organic clays were more easily released. One-third of the enzyme on goethite was adsorbed via ligand exchange process. Some other interactions, such as van der Waals force, hydrophobic force and hydrogen bonding may be more important in the adsorption of enzyme on kaolinite and the enzyme in this system cannot be easily removed. Coarse clays (0.2–2 μm) and inorganic soil clays had higher affinities for enzyme molecules than fine clays and organic clays, respectively. The activity of enzyme bound on soil clays was inhibited and the thermal stability was increased in the presence of organic matter. Data obtained in this study are helpful for a better understanding of the interactions of enzymes with inorganic and organic constituents in soil and associated environments.     

Influence of the layer charge and clay particle size on the interactions between the cationic dye methylene blue and clays in an aqueous suspension

The spectroscopic behavior of the dye MB in suspensions of different clays have been used for evaluating layer charge density influence on the adsorption properties of the particles. The clays with higher charge density, like SAz-1 and SCa-3, promote a higher aggregation and do not show deaggregation at longer times, so that practically only the aggregate peak at approximately 570 nm is observed, without any change with time. This is due to, on one side, the larger particle size that decreases the surface area available for adsorption. Additionally, the clay layers will be held together more tightly, avoiding the migration of the dye to the interlamellar region. On the other hand, SWy-1, having a lower charge density, shows a completely different behavior. The dye molecules, initially adsorbed as aggregates on the outer surface of the clay, deaggregate to form monomers that migrate to the interlamellar spaces, giving rise to absorption bands at 670 and 760 nm. Experiments using Ca-exchanged SWy-1, variation of the ionic strength by addition of salt, and the use of different size fractions of the clays confirm the finding that the main factor ruling the adsorption behavior of the probe is the size of the clay particles.     

高岭石吸附乙烯和苯的Delft分子力学研究

运用Ｄｅｌｆｔ分子力学（ＤＭＭ）程序及其粘土和共轭烯烃力场，计算研究了高岭石对乙烯和苯的吸附作用，探讨了吸附对粘土晶体和有机分子的结构、电荷分布和能量的影响，求得了高岭石吸附乙烯和苯的吸附热等重要物理量．     

A review of post-column photochemical reaction systems coupled to electrochemical detection in HPLC

Post-column photochemical reaction systems have developed into a common approach for enhancing conventional methods of detection in HPLC. Photochemical reactions as a means of ‘derivatization’ have a significant number of advantages over chemical reaction-based methods, and a significant effort has been demonstrated to develop an efficient photochemical reactor. When coupled to electrochemical (EC) detection, the technique allows for the sensitive and selective determination of a variety of compounds (e.g., organic nitro explosives, beta-lactam antibiotics, sulfur-containing antibiotics, pesticides and insecticides). This review will focus on developments and methods using post-column photochemical reaction systems followed by EC detection in liquid chromatography. Papers are presented in chronological order to emphasize the evolution of the approach and continued importance of the application.     

Study on elastic modulus of crosslinked polyurethane/organoclay nanocomposites

In this paper, two polyurethane/clay nanocomposite systems with crosslinked structure were synthesized via in situ polymerization of a polyether‐ as well as a polyester‐based prepolymer with methylene‐bis‐ortho‐chloroanilline (MOCA). Two types of modified clays with different organic modifiers were used in order to see the effect of compatibility between polymer matrix and clays on elastic modulus of nanocomposites. The morphology and the dispersion of clay layers in polyurethanes have been characterized by X‐ray diffraction (XRD) and microscopic techniques. The changes of elastic modulus of nanocomposites with clay content were examined and compared with those predicted by some conventional composite models. The results showed a reasonable fitting of experimental and theoretical values only at very low clay contents. As the clay content exceeds 1.5 wt% in this system, a reduction in elastic modulus was experimentally observed due to insufficient dispersion degree of silicate layers throughout the crosslinked matrix. This behavior was not predicted with the conventional composite theories. A new model on the basis of Wu model was then developed in order to predict the reduction of elastic modulus at various clay contents in crosslinked PU matrix. This model fitted reasonably the experimental results. Copyright © 2010 John Wiley & Sons, Ltd.     

Intercalation of a nonionic surfactant (C10E3) bilayer into a Na-montmorillonite clay

A nonionic surfactant, triethylene glycol mono-n-decyl ether (C(10)E(3)), characterized by its lamellar phase state, was introduced in the interlayer of a Na-montmorillonite clay at several concentrations. The synthesized organoclays were characterized by small-angle X-ray scattering in conjunction with Fourier transform infrared spectroscopy and adsorption isotherms. Experiments showed that a bilayer of C(10)E(3) was intercalated into the interlayer space of the naturally exchanged Na-montmorillonite, resulting in the aggregation of the lyotropic liquid crystal state in the lamellar phase. This behavior strongly differs from previous observations of confinement of nonionic surfactants in clays where the expansion of the interlayer space was limited to two monolayers parallel to the silicate surface and cationic surfactants in clays where the intercalation of organic compounds is introduced into the clay galleries through ion exchange. The confinement of a bilayer of C(10)E(3) nonionic surfactant in clays offers new perspectives for the realization of hybrid nanomaterials, since the synthesized organoclays preserve the electrostatic characteristics of the clays, thus allowing further ion exchange while presenting at the same time a hydrophobic surface and a maximum opening of the interlayer space for the adsorption of neutral organic molecules of important size with functional properties.     

Adsorption of nitrobenzene andn-pentanol from aqueous solution on hydrophilic and hydrophobic clay minerals

The sorption of nitrobenzene andn-pentanol from dilute aqueous solution on swelling clay minerals and their organophilized derivatives (organo clays) was studied. Adsorption excess isotherms were obtained by the immersion method. The basal spacings of the clay minerals were determined by X-ray diffraction measurements. By combining these two independent methods, composition and structure of the interlamellar space could be calculated. On the hydrophilic surface of montmorillonite negative adsorption of the organic component was observed at low molar fractions of nitrobenzene or pentanol, i.e., water was preferentially adsorbed. On organophilized montmorillonite and vermiculite adsorption of nitrobenzene and pentanol was positive over the whole range of liquid composition. The amount of interlamellar alkyl chains which is determined by the surface charge of clay mineral inversely affected the adsorption of both solutes.     

Monte carlo study of the adsorption and aggregation of alkyltrimethylammonium chloride on the montmorillonite-water interface

Organically modified clays exhibit adsorption capacities for cations, anions, and nonpolar organic compounds, which make them valuable for various environmental technical applications. To improve the understanding of the adsorption processes, the molecular-scale characterization of the structures of organic aggregates assembled on the external basal surfaces of clay particles is essential. The focus of this Monte Carlo simulation study was on the effects of the surface coverage and the alkyl chain length n on the structures of alkyltrimethylammonium chloride ((C(n)TMA)Cl) aggregates assembled on the montmorillonite-water interface. We found that the amount of adsorbed C(n)TMA(+) ions is independent of the alkyl chain length and increases with the C(n)TMA(+) surface coverage. The C(n)TMA(+) ions predominantly adsorb as inner-sphere complexes; the fraction of outer-sphere adsorbed ions equals only about 10%. The conformational order of the C(n)TMA(+) alkyl chains substantially decreases with decreasing alkyl chain length. In agreement with previous experiments, the amount of C(n)TMA(+) ions that are aggregated at the mineral surface increases with increasing chain length. The maximum value of 0.66 C(n)TMA(+) adsorption complex per unit cell area of the clay surface considerably exceeds the amount of cations required to compensate the negative charge of the montmorillonite surface. Furthermore, in most of the studied systems, fractions of Na(+) surface cations remain adsorbed on montmorillonite. The resulting interfacial positive charge excess is counterbalanced by coadsorbed chloride ions forming ion pairs with both C(n)TMA(+) and Na(+).     

Characterization and assessment of Saudi clays raw material at different area

The general characteristics of three types of clays obtained from the different locations in Saudi Arabia have been investigated. These clays were compared with those of pure kaolin samples. Clays were analyzed by DTA, TGA, SEM, X-ray diffraction, chemical composition (XRF) and optical properties. Three clays are white clay (WC), red clay (RC) from Jeddah area and grey clay (GC) from Elmadina area. The comparison made with Spain clay as pure kaoline (KA). The clays contain kaolinite, illite, montmorillonite and quartz. Quartz is present in every class and varies between 45% and 20%. Montmorillonite is found mainly in the WC (50%) and are lacking only in sample RC and GC. Another important aspect with respect to the chemical composition of the clays is the low amounts of Na₂O and K₂O. The clay deposits (WC, RC, and GC) are suitable for use in industrial ceramics due to the low whiteness, high yellowness and high content of impurities as montmorillonite and iron. This is an important technological aspect that renders possible use of clay RC and GC in the fabrication of products with a cream tonality, especially in roofing tiles and rustic floor tiles. The results also, showed that the studied clays have adequate characteristics for ceramics wall, floor, roof tiles, tableware, earthenware and brick fabrication.     

Graphene-supported small-sized palladium nanoparticles made by facile photochemical approaches

To achieve small-sized and well-dispersed palladium (Pd) nanoparticles, we make use of effective photochemical approaches to synthesis of clean Pd nanoparticles on the surface of graphene at room temperature. By modulating the photochemical reaction conditions, the size and dispersion of graphene–Pd composites can be well controlled, where PdCl₄²⁻ and graphene oxide (GO) are the reaction precursors, Hantzsch 1,4-dihydropyridine (HEH) is used as an electron donor and an amine-type ligand to stabilize small Pd nanoparticles on the surface of graphene. As a result, the easy and effective photochemical approaches to the graphene–Pd composites with well-dispersed, small-sized Pd nanoparticles and highly conductive reduced GO, are established. Good to excellent yields have also been achieved with the graphene-supported Pd nanoparticles catalysts for the Suzuki coupling reaction.     

Synthesis, structure and properties of intercalation compounds containing perfluoroalkyl groups

Synthesis, structure and properties of various layered materials containing perfluoroalkyl groups in their interlayer space were summarized. They were obtained by ion exchange method for layered materials with ion exchange capacity and by silylation technique for those possessing acidic hydroxyl groups. The orientation of perfluoroalkyl groups greatly changed depending on their contents in the layered materials. The nature of the interlayer space of them changed from hydrophilic to hydrophobic and they were well dispersed in appropriate organic solvents. Some of them formed so called nanosheet solution and film samples were prepared from it. Organic molecules were introduced into the intercalation compounds by co-adsorption or exfoliation-restacking methods. The empty space surrounded by perfluoroalky chains where organic molecules are included showed unique properties. The weak interaction between perfluoroalkyl chains and included organic molecules lead the easy diffusion of them in the interlayer space, which caused the aggregation of them or affected the distribution of isomers obtained by photochemical reaction. The low vibrational C-F bonding in perfluoroalky groups reduced radiational quenching, accordingly enhanced the fluorescence from included organic dyes.     

Light-harvesting energy transfer and subsequent electron transfer of cationic porphyrin complexes on clay surfaces

A novel energy-transfer system involving nonaggregated cationic porphyrins adsorbed on an anionic-type clay surface and the electron-transfer reaction that occurs after light harvesting are described. In the clay-porphyrin complexes, photochemical energy transfer from excited singlet zinc porphyrins to free-base porphyrins proceeds. The photochemical electron-transfer reaction from an electron donor in solution (hydroquinone) to the adsorbed porphyrin in the excited singlet state was also examined. Because the electron-transfer rate from the hydroquinone to the excited singlet free-base porphyrin is larger than that to the excited singlet zinc porphyrin, we conclude that the energy transfer accelerates the overall electron-transfer reaction.     

Benzimidazolium surfactants for modification of clays for use with styrenic polymers

Nanocomposites of polystyrene (PS), acrylonitrile-butadiene-styrene copolymer (ABS) and high impact polystyrene (HIPS) were prepared with two new homologous benzimidazolium surfactants used as organic modifications for the clays. The morphology of the polymer/clay hybrids was evaluated by powder X-ray diffraction (XRD) and transmission electron microscopy (TEM), showing good overall dispersion of the clay. The thermal stability of the polymer/clay nanocomposites was enhanced, as evaluated by thermogravimetric analysis. From cone calorimetric measurements, the peak heat release rate of the nanocomposites was decreased by about the same amount as seen for other organically-modified, commercially available clays.     

Differential thermal study of Mg-bearing clays from saline lakes of Southern Tunisia

Clays high in Mg content occur frequently in the high saline environment of salt lakes in southern Tunisia. The DTA curves of these clays show a striking endothermic-exothermic reaction in the temperature range of 800–820°C. A strong correlation is observed between the intensity of these coupled reactions and the Mg content of the initial clay sample. The initial endothermic reaction is interpreted as the melting/dehydroxylation of the Mg-bearing smectites. The subsequent exothermic peak is interpreted as caused by the crystallisation of the new Mg-silicate phase enstatite. Therefore, the DTA is considered as a suitable method for the identification and relative quantification of high Mg clay minerals (e.g. trioctahedral smectites). Variations of the Mg content of the studied samples were well detectable by means of DTA, disclosing a distinct distribution pattern of the salt lake clays. Clues to bulk chemical composition of the initial clay assemblage can also be found in the results of the X-ray analysis of the firing products.     

Dynamic light scattering studies of poly(ethylene oxide) adsorbed on Laponite: layer conformation and its effect on particle stability

Dynamic light scattering has been used to determine the hydrodynamic thickness of poly(ethylene oxide) (PEO) adsorbed on synthetic anisotropic clay particles (Laponite) as a function of molecular weight. The layer thicknesses, and their increase with molecular weight, indicate that the conformation of the adsorbed layer is very compact and is much smaller than those normally observed for polymer adsorption on flat interfaces. The aggregation kinetics of the polymer coated particles in 5 mM NaCl was analyzed in a quantitative manner, revealing that the potential barrier to aggregation is strongly enhanced when polymer is present.     

端基含36个己氧基偶氮苯基元的二代碳硅烷光致变色液晶树状高分子的光化学研究

研究了含36个己氧基偶氮苯介晶基元的二代(G2)光致变色液晶树枝状高分子在氯仿和四氢呋喃溶液中的最大吸收波长,摩尔消光系数,反顺光异构化反应速率常数,光化学回复异构化正逆反应速率常数及其平衡常数,G2和G1的光致变色反应速率常数kp为10-1s-1,而含偶氮基元光致变色液晶聚硅氧烷的kp为10-8s-1,因此液晶树状高分子的光响应速率比后者快107倍.     

Generation of quinone methide from aminomethyl(hydroxy)arenes precursors in aqueous solution

o-Quinone methides (QMs) are an important reactive intermediate for organic synthetic and biological standpoints of view. Photochemical and thermal transformation of N,N-dialkyl-9-aminomethyl-10-phenanthrols and their naphthalene analogs, which act as QM precursors, has been studied. These precursors readily reacted with alkyl vinyl ethers to give 2-alkoxydibenzo[f,h]chroman and 2-alkoxybenzo[f]chroman, respectively. Thermal and photochemical generation of QM was accelerated by the presence of water molecule in reaction solvents and by the formation of anionic micelle and vesicle.