Interaction of inorganic anions with iron-mineral adsorbents in aqueous media — A review

A number of inorganic anions (e.g., nitrate, fluoride, bromate, phosphate, and perchlorate) have been reported in alarming concentrations in numerous drinking water sources around the world. Their presence even in very low concentrations may cause serious environmental and health related problems. Due to the presence and significance of iron minerals in the natural aquatic environment and increasing application of iron in water treatment, the knowledge of the structure of iron and iron minerals and their interactions with aquatic pollutants, especially inorganic anions in water are of great importance. Iron minerals have been known since long as potential adsorbents for the removal of inorganic anions from aqueous phase. The chemistry of iron and iron minerals reactions in water is complex. The adsorption ability of iron and iron minerals towards inorganic anions is influenced by several factors such as, surface characteristics of the adsorbent (surface area, density, pore volume, porosity, pore size distribution, pH_pzc, purity), pH of the solution, and ionic strength. Furthermore, the physico-chemical properties of inorganic anions (pore size, ionic radius, bulk diffusion coefficient) also significantly influence the adsorption process. The aim of this paper is to provide an overview of the properties of iron and iron minerals and their reactivity with some important inorganic anionic contaminants present in water. It also summarizes the usage of iron and iron minerals in water treatment technology.     

Possible link of the V-shaped phase diagram to the glass-forming ability and fragility in a water-salt mixture

Water is a very poor glass former, but its link to the thermodynamic and kinetic anomalies remains elusive. We experimentally reveal that the glass-forming ability and fragility of a water-salt mixture are closely related to its equilibrium phase diagram. We propose that frustration between local and global orderings controls both the glass-forming ability and the fragility. Relying on the same role of salt and pressure, which commonly break tetrahedral order, we apply this idea to pure water under pressure. This scenario not only explains unusual behavior of water-type liquids such as water, Si, and Ge but also provides a mechanism for a link between the equilibrium phase diagram, glass-forming ability, and fragility for various materials including oxides, chalcogenides, and metallic glasses.     

Supramolecular Engineering of Oligothiophene Nanorods without Insulators: Hierarchical Association of Rosettes and Photovoltaic Properties

Supramolecular rosettes of oligothiophenes that do not bear long aliphatic tails have been designed as semiconducting nanomaterials for solution‐processable bulk heterojunction solar cells. The rosettes consist of six barbiturated thienyl[oligo(hexylthiophene)] units (Bar‐T‐hT_n; n=3,4,5) aggregated by multiple hydrogen bonds, which have been directly visualized by scanning tunneling microscopy (STM) at a solid–liquid interface. ¹H NMR spectroscopy in [D₈]toluene showed that Bar‐T‐hT_n exists as a mixture of monomers and small hydrogen‐bonded aggregates. Hierarchical organization of the hydrogen‐bonded aggregates took place through π–π stacking interactions upon casting their toluene solutions, resulting in the growth of highly ordered nanorods whose widths are consistent with the diameters of the rosettes. The nanorods could be generated in the presence of soluble fullerene derivatives via solution casting or the annealing of the resulting thin films. The solar cells fabricated based on these bulk heterojunction films showed power conversion efficiencies of 1–3 %, which are far higher than those of the non‐hydrogen‐bonded reference oligothiophene and the derivative that possesses long aliphatic tails.     

Laser Molding in Polymeric Materials Using Femto-Second Laser Pulse and Replication via Electroforming

The upheaval structure on the surface of polymer induced by the irradiation of a near-infrared (NIR) femto-second laser pulse in polymer bulk was investigated. Copolymers, such as poly(acrylonitrile-styrene) (AS) and poly(acrylonitrilebutadiene-styrene-methyl methacrylate) (ABSM) produced upheaval structures with a flattop just like the crater of a volcano, whereas homopolymers with relatively high glass transition temperature (T_g), such as polycarbonate (PC) and polyether imide (PEI) were more often formed a bell-shaped upheaval structure. A micro-lens effect was observed for the bell-shaped upheaval structure, but that effect was not observed in the case of copolymers with a flattop structure. Replication of the bell-shaped upheaval structure in PC was carried out by electroforming (non-electrolytic plating of Ni and the following electrolytic plating of Ni) and potting approximately 30 wt% THF solution of AS copolymer. A micro-scale bell-shaped upheaval structure in PC induced by a laser pulse was replicated using a Ni mother mold with suitable precision, and the replicated bell-shaped structure also showed a micro-lens effect.     

Diffusion limit for the linear boltzmann equation of the neutron transport theory

In this paper we present the asymptotic analysis of the linear Boltzmann equation for neutrons with a small positive parameter ? related to the mean free path, based upon the Chapman–Enskog procedure of the kinetic theory. We prove that if proper initial conditions derived by considering initial layer solutions are used, the diffusion equation gives the uniform approximation to the neutron density function with the O(?²) accuracy.     

Asymptotic analysis of the linear Boltzmann equation

The stiff boundary value problem for the time-independent linear Boltzmann equation is considered in the variational formulation in terms of the coercive symmetric bilinear form. It is shown that it is asymptotically equivalent to the related variational diffusion problem when the stiffness parameter tends to zero. Higher order perturbations are also discussed.     

Calculation of the salt separation by negatively charged gel-filled membranes

The salt separations of negatively charged gel-filled membranes composed of poly(2-acrylamido-2-methylpropanesulfonic acid) gels anchored within a polypropylene microporous substrate have been determined experimentally and modeled theoretically. The separation of these membranes were calculated by both the Teorell, Meyer and Sievers (TMS) model and the Donnan–Steric Pore (DSP) model coupled with the extended Nernst–Planck equation. For modeling, the membrane effective thickness, effective charge density, and pore radius were either directly measured or calculated from theories without the use of fitting procedures. Good agreement between the experimental measurements and the theoretical calculations of salt separation was observed. For the theoretical calculations, the TMS model is suitable for membranes with moderate gel polymer volume fractions, while the DSP model is more suitable for membranes with high gel polymer volume fractions. Moreover, with a calculated constant effective charge density, the salt separation with different salt concentrations could be accurately predicted. The separation of various other salts could also be predicted with good accuracy.     

Accurate quantitation of salivary and pancreatic amylase activities in human plasma by microchip electrophoretic separation of the substrates and hydrolysates coupled with immunoinhibition

A high-performance determination system for alpha-amylase isoenzyme activities in human plasma involving microchip electrophoresis with a plastic chip was developed. The combination of microchip electrophoresis for substrate and hydrolysate separation and an immunoinhibition method for the differentiation of isoenzyme activities using antihuman salivary amylase (S-AMY) mAb allowed the highly selective determination of amylase isoenzyme (S-AMY and pancreatic amylase (P-AMY)) activities even in a complex matrix such as a crude plasma sample. We used 8-aminopyrene-1,3,6-trisulfonic acid (APTS)-labeled maltohexaose (G6) as a substrate. Amylase in a human plasma sample hydrolyzed APTS-G6 into APTS-maltotriose (G3) and G3, which was measured as the fluorescence intensity of APTS-G3 on microchip electrophoresis. A double logarithm plot revealed a linear relationship between amylase activity and fluorescence intensity in the range of 5-500 U/L of amylase activity (r2=0.9995, p<0.01), and the LOD was 4.38 U/L. Amylase activities in 13 subjects determined by the present method were compared with the results obtained by conventional methods with nitrophenylated oligosaccharides as substrates, respectively. Good correlations were observed for each method on simple linear regression analysis (both p<0.01). The reproducibilities of within-days for total amylase and P-AMY were 2.98-6.27 and 3.83-6.39%, respectively, and these between-days were 2.88-5.66 and 3.64-5.63%, respectively. This system enables us to determine amylase isoenzyme activities in human plasma with high sensitivity and accuracy, and thus will be applicable to clinical diagnosis.     

Potentiometric titration behavior of poly(acrylic acid) within a cross-linked polymer network having amide groups

This study aimed to investigate the effect of COOH group distribution within a polymer network having amide groups, with which the COOH could form hydrogen bonds. We employed here two polyelectrolyte gels composed of N-isopropylacrylamide (NIPA) networks, either copolymerized with acrylic acid (AA) or within which poly(acrylic acid) (PAA) was entrapped. Both gels (AA–NIPA ∼ 1:4 mol/mol) were prepared by aqueous red-ox polymerization with N,N’-methylenebisacrylamide as the cross-linker. Finely divided gels in NaCl solutions (0.025 and 0.1 M) were titrated with NaOH and back-titrated with HCl at 25 °C. The results of the copolymer gel (CG) agreed well with those of a linear copolymer and a nanoscale gel which had a similar AA content to CG. However, marked differences were observed in the titration behaviors of the AA-copolymerized and PAA-entrapped gels, mainly due to the hydrogen bonding between the entrapped PAA chain and its surrounding NIPA network.     

Ion mobility spectrometers with doped gases

Ion mobility spectrometry (IMS) is an instrumental technique used successfully for the detection of wide range of organic compounds in the gas phase. In this paper, advances in using special substances called dopants for gases flowing through IMS detectors are reviewed. These substances influence the ion-molecule chemistry in sample ionisation region as well as change conditions for the drift of ions. Improved selectivity and sensitivity of detection can be obtained by the use of dopants. In some cases, especially when measurements are conducted in the presence of different substances disturbing detection, the use of dopants is indispensable. The theory of the function of dopants is based on the knowledge of ion-molecule reactions. Fundamental information about these reactions is presented here. Mechanisms of changing the composition of ions produced in reactant section of IMS detector are explained on this basis. The most commonly used dopants are acetone and ammonia for positive mode and chloride for negative mode IMS. Other substances, such as higher ketones, organophosphorous compounds or methyl salicylate are used for special purposes and are selected for given analytical problem. Particular examples for the application of these substances are described.