纤维素中空纤维膜气体加湿性能的研究

采用纤维素N甲基吗啉N氧化物(NMMO)水三元纺丝体系,以去离子水为芯液,自来水为凝胶浴,湿法纺制了纤维素中空膜.经自然干燥后该膜的轴向、径向都明显收缩,断面呈现均质致密结构.干膜在水中会明显溶胀,重新润湿后具有气密性.考察了加湿水温、水气压力差等因素对膜的水渗透通量的影响,并初步测试了膜对质子交换膜燃料电池(PEMFC)反应气体H2和O2的加湿性能.实验结果表明该膜透水性能较优,气体加湿效果明显,具有应用于PEMFC反应气体加湿系统的潜力.     

Rapid monitoring and sensitive determination of DDT and its metabolites in water sample using solid-phase extraction followed by ion mobility spectrometry

Dichlorodiphenyl trichloroethane (DDT) as an organochlorine compound has been globally used as a pesticide for controlling soil-dwelling insects and treating diseases such as malaria and typhus. The degradation products of DDT and its metabolites have also negative effects on the environment. The present study has investigated the determination of DDT and its metabolites in water sample using ion mobility spectrometry (IMS) as a rapid and sensitive detection technique. For this purpose, DDT and its metabolites were extracted using reverse phase solid-phase extraction (SPE) from water samples. The samples were then recovered by eluting with methanol and finally, quantified using the corona discharge IMS technique. Injection and oven temperatures and the effect of dopant were optimized as experimental parameters influencing both detection and determination efficiencies. Degradation of DDT in IMS drift tube was studied and reduced mobility values of DDT and its metabolites were calculated. The developed method was validated using water sample to obtain good results for the determination of DDT at low levels (1 ng ml^?1) while spiked recoveries were obtained to be between 95.0–96.7%. The proposed method based on IMS proved to be a simple, inexpensive, rapid and sensitive procedure for the fast monitoring and determination of DDT and its main metabolites in water sample.     

Isopiestic Study of Water + Mannitol(sat) + Sodium Chloride + Ammonium Chloride + Barium Chloride at <Emphasis Type="Italic">T</Emphasis> = 298.15 K and Comparison with the Ideal-Like Solution Model

Isopiestic measurements have been carried out at the temperature 298.15 K for the quinary system (water + mannitol(sat) + sodium chloride + ammonium chloride + barium chloride) saturated with mannitol and its ternary sub-systems (water + mannitol(sat) + sodium chloride), (water + mannitol(sat) + ammonium chloride) and (water + mannitol(sat) + barium chloride). Taking aqueous sodium chloride as reference solutions, osmotic coefficients of the other aqueous solutions were determined. The experimental results show that the isopiestic activities of the quinary system in relation to its ternary sub-systems are in excellent agreement with the ideal-like solution model.     

Dependence of the number of hydrogen bonds per water molecule on its distance to a hydrophobic surface and a thereupon-based model for hydrophobic attraction

A water molecule in the vicinity of a hydrophobic surface forms fewer hydrogen bonds than a bulk molecule because the surface restricts the space available for other water molecules necessary for its hydrogen-bonding. In this vicinity, the number of hydrogen bonds per water molecule depends on its distance to the surface. Considering the number of hydrogen bonds per bulk water molecule (available experimentally) as the only reference quantity, we propose an improved probabilistic approach to water hydrogen-bonding that allows one to obtain an analytic expression for this dependence. (The original version of this approach [Y. S. Djikaev and E. Ruckenstein, J. Chem. Phys. 130, 124713 (2009)] provides the number of hydrogen bonds per water molecule in the vicinity of a hydrophobic surface as an average over all possible locations and orientations of the molecule.) This function (the number of hydrogen bonds per water molecule versus its distance to a hydrophobic surface) can be used to develop analytic models for the effect of hydrogen-bonding on the hydration of hydrophobic particles and their solvent-mediated interaction. Presenting a model for the latter, we also examine the temperature effect on the solvent-mediated interaction of two parallel hydrophobic plates.     

From a localized H3O radical to a delocalized H3O+···e- solvent-separated pair by sequential hydration

The impact of microhydration on the electronic structure and reactivity of the H(3)O moiety is investigated by ab initio calculations. In the gas phase, H(3)O is a radical with spin density localized on its hydrogen end, which is only kinetically stable and readily decomposes into a water molecule and a hydrogen atom. When solvated by a single water molecule, H(3)O preserves to a large extent its radical character, however, two water molecules are already capable to shift most of the spin density to the solvent. With three solvating water molecules this shift is practically completed and the system is best described as a solvent-separated pair of a hydronium cation and a hydrated electron. The electronic structure of this system and its proton transfer reactivity leading to formation of a hydrogen atom already resemble those of a proton-electron pair in bulk water.     

Kinetics of hydrogen bonds in aqueous solutions of cyclodextrin and its methyl-substituted forms

Molecular dynamics simulations of β-cyclodextrin (BCD) and its two methyl-substituted derivatives, namely, heptakis(2,6-di-O-methyl)-β-cyclodextrin (DIMEB) and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin (TRIMEB) have been performed in aqueous solutions. Detailed analyses were carried out to investigate the effects of substitution on the kinetics of cyclodextrin-water and water-water hydrogen bonds formed by water present in the hydration layers around these macromolecules as well as those formed by water inside their cavities. It is observed that increased geometrical constraints due to substitution of the OH groups of the glucose rings of the BCD molecule result in rapid establishment of hydrogen bond breaking and reformation equilibria for DIMEB and TRIMEB. This has been found to be the microscopic origin of highly rigid arrangement of water around TRIMEB and inside its cavity, as against water in and around BCD and DIMEB.     

Determination of MTBE in drinking water using corona discharge ion mobility spectrometry

Methyl tertiary-butyl ether (MTBE) is an organic compound which is used as a gasoline additive. Contamination of ground and surface water can occur due to large scale use of MTBE and its high solubility in water. According to United State Environmental Protection Agency (USEPA), MTBE is a possible human carcinogen at high doses and its detection and measurement in the water is important as concerned about human health. In this work, ion mobility spectrometry (IMS) equipped with a corona discharge ionization source was used for determination of MTBE in drinking water. Both pure and aqueous solutions of MTBE were studied and their ion mobility spectra were obtained at different temperatures. Using a calibration curve for detection of MTBE in drinking water, a detection limit (LOD) of 1 mg/L was obtained by IMS. This work proved that, IMS with corona discharge can be used for fast and direct detection of MTBE in water sample without any sample preparation.     

Blank values, adsorption, pre-concentration, and sample preservation for arsenic speciation of environmental water samples

Arsenic is the focus of public attention because of its toxicity. Arsenic analysis, its toxicity, and its fate in the environment have been broadly studied, still its blank values, adsorption to sampling materials and pre-concentration of water samples as well as stabilization of arsenic compounds in water samples under field conditions have been very little investigated. In this study, we investigate the blank values and adsorption of arsenic compounds for different laboratory materials. We focused our work onto pre-concentration of water samples and how to stabilize arsenic compounds under field conditions. When using glassware for arsenic analysis, we suggest testing arsenic blank values due to the potential release of arsenic from the glass. Adsorption of arsenic compounds on different laboratory materials (<10%) showed little influence on the arsenic speciation. Pre-concentration of methanol-water solutions could result in potential overestimation of arsenic compounds concentrations. Successful pre-concentration of water samples by nitrogen-purge provides an analytical possibility for arsenic compounds with high recoveries (>80%) and low transformation of arsenic compounds. Thus, concentrations as low as 1 ng As l⁻¹ can be determined. Addition of ethylenediaminetetraacetic acid (EDTA) and storage in the dark can decrease the transformation among arsenic compounds in rainwater and soil-pore water for at least a week under field conditions.     

Predicting solute adsorption on activated carbon: phenol

Activated carbon (AC), the most widely used adsorbent in water and in wastewater treatment, comprises a high surface area of very small, convoluted and interconnected pores. Despite the wide use of AC, there is little fundamental atomic-level understanding of its adsorption capacity and selectivity as well as its pore structure. The purpose of this work is to suggest the methodology for calculation of equilibrium adsorption capacity of common water organic pollutants and use it for phenol as a model. The effects of various functional groups, pore size, and coverage on thermodynamics of phenol adsorption from the gas phase and from water media are calculated using molecular mechanics (MM) and density functional theory (DFT) approaches.     

Design, synthesis, structure, and dehydrogenation reactivity of a water-soluble o-iodoxybenzoic acid derivative bearing a trimethylammonium group

5-Trimethylammonio-1,3-dioxo-1,3-dihydro-1λ(5)-benzo[d][1,2]iodoxol-1-ol anion (AIBX 1a), an o-iodoxybenzoic acid (IBX) derivative having the trimethylammonium moiety on its phenyl ring, possesses very good solubility in water and distinct oxidative properties from IBX, which is demonstrated in the oxidation of various β-keto esters to the corresponding dehydrogenated products using water as cosolvent. The regeneration of AIBX 1a can be easily realized from the reaction mixture due to its good water solubility.     

State of irremovable water in solid polymer films examined by fourier transform infrared spectroscopy I: poly(ethylene glycol) dimethyl ether

The state of the sorbed water, including the water that cannot be removed by the reduced pressure and water-sorption processes, into poly(ethylene glycol) dimethyl ether (PEG-DME) film was examined by Fourier transform infrared (FT-IR) spectroscopy. The spectrum of the irremovable water could be obtained without a thermal treatment frequently used as the dehydration procedure. It was found that the irremovable water mainly existed in the crystalline region of PEG-DME film, and that its hydrogen-bonding (HB) structure differed from that of the water sorbed from the air. Moreover, the amount of water having the same HB structure as the irremovable water increased with the water contents. These findings could not be revealed by the spectrum of the sorbed water obtained by the conventional dehydration procedure. The experimental procedure examined here allowed us to investigate the true aspects of the irremovable water and the water-sorption processes.     

Dynamics of a protein and water molecules surrounding the protein: hydrogen-bonding between vibrating water molecules and a fluctuating protein

Internal and rigid-body motions of bovine pancreatic trypsin inhibitor (BPTI) and of water molecules surrounding the BPTI are studied in a vicinity of an energy minimum using a normal mode analysis proposed as the independent molecule model. Water's rigid-body motion is predominant in comparison to its internal motions. We have derived information about the relationship between the magnitude of a thermal ellipsoid of an H-bonding atom and the anisotropy of its ellipsoid, and the relationship between the magnitude of the ellipsoid and the H-bond strength. We see a relationship between vibrational frequencies (assuming rigid-body motion of the water molecules) and the H-bond strength of the water taking part in this H-bonding. Analyzing the H-bond strength, we found that a hydrogen in water is likely to H-bond to oxygen in the protein, whereas an oxygen in water has a less strong preference to H-bond to the protein. For water molecules acting as the hydrogen acceptor, strong H-bonding has longer lifetimes than weak H-bonding.     

Chemistry of alumina, reactions in aqueous solution and its application in water treatment

Due to the presence and significance of alumina in the natural aquatic environment and its increasing application in drinking and wastewater purification, the knowledge of the structure of alumina and its possible interactions with organic and inorganic compounds in water are of great importance. This is of particular importance in both the understanding of natural aquatic environment processes and efficient industrial applications. The chemistry of alumina reactions in water is complex. The adsorption ability of alumina towards organic and inorganic compounds might be influenced by several factors such as: surface characteristics of the adsorbent (surface area, density, pore volume, porosity, pore size distribution, pH(PZC) as well as mechanical strength and purity), pH of the solution, ionic strength, composition of water and the physicochemical properties of adsorbates. The aim of this paper is to give a brief review of the properties of alumina and its reactivity with organic and inorganic compounds present in aqueous solutions. It also summarises the usage of alumina and alumina supported phases in water treatment technology.     

The role of glycerol and phosphatidylcholine in solubilizing and enhancing insulin stability in reverse hexagonal mesophases

The potential of reverse hexagonal mesophases based on monoolein (GMO) and glycerol (as cosolvent) to facilitate the solubilization of proteins, such as insulin was explored. H(II) mesophases composed of GMO/decane/water were compared to GMO/decane/glycerol/water and GMO/phosphatidylcholine (PC)/decane/glycerol/water systems. The stability of insulin was tested, applying external physical modifications such as low pH and heat treatment (up to 70°C), in which insulin is known to form ordered amyloid-like aggregates (that are associated with several neurodegenerative diseases) with a characteristic cross β-pleated sheet structure. The impact of insulin confinement within these carriers on its stability, unfolding, and aggregation pathways was studied by combining SAXS, FTIR, and AFM techniques. These techniques provided a better insight into the molecular level of the "component interplay" in solubilizing and stabilizing insulin and its conformational modifications that dictate its final aggregate morphology. PC enlarged the water channels while glycerol shrank them, yet both facilitated insulin solubilization within the channels. The presence of glycerol within the mesophase water channels led to the formation of stronger hydrogen bonds with the hosting medium that enhanced the thermal stability of the protein and remarkably affected the unfolding process even after heat treatment (at 70°C for 60 min).     

Polyelectrolyte Hydrogels Based on Radiation-Modified Polyacrylamide and Products of Its Alkali Hydrolysis

The effect of molecular mass on the formation of polyelectrolyte hydrogels made from polyacrylamide (PAAm) and products of its alkali hydrolysis and on their water sorption capacity was studied. It was found that the efficiency of crosslinking of both the initial polymer and its hydrolyzates noticeably decreased on passing from high-molecular-mass to low-molecular-mass PAAm. Hydrogels prepared from high-molecular-mass PAAm and its hydrolyzates exhibited a greater limiting water uptake as compared with hydrogels made from low-molecular-mass PAAm and its hydrolyzates. A change in the degree of conversion of amide to acrylate groups from 35–41 to 47–54% had a slight effect on the maximum water uptake.     

Hydrophobic hydration

The problem of interaction between organic and water moieties (neutral or ionized water molecular species) is of particular interest in chemistry in view of its implications to physico-chemical behavior of chemical and biological systems. Hydration patterns which result from interaction between hydrophilic and hydrophobic species are non trivial in chemistry. The key issue is that water molecules are able to aggregate in extremely large variety of structural modes. Tetrahedral geometry of intermolecular bonding around water molecule is analogous in geometrical terms to that of intramolecular geometry of carbon atom, known as a source of infinite number of organic structures. In general, space filling with hydrogen bonded water molecules is rather low. It may be illustrated in the following way: volume of neonium atoms is comparable to that of water molecules whilst having atomic mass just 10% higher than molecular mass of water. Thus, liquid neonium and liquid water would have similar densities if molecular packing is of comparable efficiency. The real values are much different, however. Liquid neonium at its boiling temperature has density of 1.20 g cm^–3 , thus displaying significantly denser packing that that of water molecules. It certainly means that solid or liquid water has a ‘porous’ structure and may lead to molecular inclusion of foreign (guest) species in the intermolecular space of water framework. This property is not that simple, however, since inclusion of foreign (guest) species is, as a rule, associated with rearrangement of the host framework structure [1]. Anyway, inefficient packing of the mono-component host solid phases may be considered as a prerequisite for its pronounced clathration ability.     

高吸水性树脂

高吸水性树脂,可以吸收其本身重量的几百倍水。将水溶性高分子如羧甲基纤维素、聚丙烯酸钠盐或聚乙烯醇进行轻微的交联可以得到。由于其高吸水性、在压力下的高保水性和高增稠性,被广泛应用于纸尿布、生理巾、土壤保水剂、工业脱水剂、增稠剂等。     

Preparation of a thermosensitive cobalt phthalocyanine/N-isopropylacrylamide copolymer and its catalytic activity on thiol

A thermosensitive copolymer of cobalt tetra(N-acryliccarbonyl)aminophthalocyanine (Co-TACAPc) and N-isopropylacrylamide (NIPA) was prepared through redox polymerization in aqueous solution, and its catalytic activity for oxidation of 2-mercaptoethanol was investigated. The products of Co-TACAPc and its copolymer were characterized by elemental analysis, IR, UV/vis, and TGA. The copolymer can be dissolved into most solvents, particularly into water over a wide range of pH. The copolymer also revealed a lower critical solution temperature (LCST) phenomenon at 32.6 degrees C in water; i.e., it was soluble in cold water (below 32.6 degrees C) but insoluble in hot water (above 32.6 degrees C). As a result, in contrast to Co-TACAPc, the copolymer is able to serve as a homogeneous catalyst on oxidation of 2-mercaptoethanol below 31.0 degrees C and be recovered with increasing temperature due to its lower solubility above 31.0 degrees C.     

Development of high quality Fe_3O_4/rGO composited electrode for low energy water treatment

Electrochemical water treatment is an attractive technology for water desalination and softening due to its low energy consumption. Especially, capacitive Deionization(CDI) is promising as a future technology for water treatment. Graphene(rGO) has been intensively studied for CDI electrode because of its advantages such as excellent electrical conductivity and high specific surface area. However, its 2D dimensional structure with small specific capacitance, high resistance between layers and hydrophobicity degrades ion adsorption efficiency. In this work, we successfully prepared uniformly dispersed Fe_3O_4/rGO nanocomposite by simple thermal reactions and applied it as effective electrodes for CDI. Iron oxides play a role in uniting graphene sheets, and specific capacitance and wettability of electrodes are improved significantly;hence CDI performances are enhanced. The hardness removal of Fe_3O_4/rGO nanocomposite electrodes can reach 4.3 mg/g at applied voltage of 1.5V, which is 3 times higher than that of separate r GO electrodes.Thus this material is a promising candidate for water softening technology.     

Nonaqueous catalytic water oxidation

The complex [Ru(Mebimpy)(bpy)(OH(2))](2+) [Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine; bpy = 2,2'-bipyridine] and its 4,4'-(PO(3)H(2)CH(2))(2)bpy derivative on oxide electrodes are water oxidation catalysts in propylene carbonate and 2,2,2-trifluoroethanol (TFE) to which water has been added as a limiting reagent. The rate of water oxidation is greatly enhanced relative to that with water as the solvent and occurs by a pathway that is first-order in H(2)O; an additional pathway that is first-order in acetate appears when TFE is used as the solvent.