Ethylenediamine at air/liquid and air/silica interfaces: protonation versus hydrogen bonding investigated by sum frequency generation spectroscopy

The adsorption process on mineral oxide surfaces is one of the most important factors influencing the migration and distribution of contaminants in the environment. Although there have been numerous studies carried out at the macroscopic scale, there is a lack of molecular-scale interfacial information. The molecular-scale information is often crucial for the determination of sorption mechanisms. In this study, sum frequency generation spectroscopy (SFG), a surface specific vibrational spectroscopy, has been employed to investigate the adsorption of ethylenediamine (H2N(CH2)2NH2, EDA) onto the amorphous SiO2 surface and EDA protonated products at air/liquid interfaces. The SFG spectra of EDA adsorbed on the silica surface and the singly protonated EDA solution are similar in both CH and NH stretching regions. These spectral similarities indicate that EDA molecules are strongly chemisorbed to the silica surface through the protonation of one EDA amine group by surface silanol OH groups, thereby forming a (H2N(CH2)2NH3)+(O-Si[triple bond])- surface complex. The SFG results also indicate that the surface acidity of the silanol OH groups (pKa (HOSi[triple bond])) is between the two pKa values of EDA (in the range of 7.56-10.71) at the air/silica interface.     

Adsorption of ethylene glycol vapor on (alpha-AI2O3 (0001) and amorphous SiO2 surfaces: observation of molecular orientation and surface hydroxyl groups as sorption sites

Vapor adsorption is an important process influencing the migration and the fates of many organic pollutants in the environment. In this study, adsorption of ethylene glycol (EG) vapor onto single crystal alpha-Al2O3 (0001) and fused SiO2 (amorphous) surfaces was studied with sum frequency generation spectroscopy, a well-suited surface specific technique for probing interfacial phenomena atthe molecular scale. Air-aqueous EG solutions were also investigated to compare to the adsorption at the air-solid interface in the presence of water vapor. The gauche conformer of EG molecules dominates the air-aqueous EG solution interface, and EG molecules act as hydrogen acceptors at the air-liquid interface. Water and surface hydrophilic/ hydrophobic properties play important roles for the adsorption of EG onto silica and alumina surfaces. The adsorbed EG molecules interact in different ways at the two different oxide surfaces. EG molecules weakly physisorb onto the alpha-Al2O3 (0001) surface by forming relatively weak hydrogen bonds with surface water molecules. On the silica surface, the suppression of the silanol OH stretching peak indicates that EG molecules form hydrogen bonds with silanol OH groups.     

Reaction of polycyclic aromatic hydrocarbons adsorbed on silica in aqueous chlorine

The reaction of polycyclic aromatic hydrocarbons (PAHs) previously adsorbed on silica gel or diatomaceous earth with sodium hypochlorite was carried out to elucidate their reactivity to aqueous chlorine. It was demonstrated that the PAHs adsorbed on silica reacted more rapidly than the PAHs themselves in water, leading to the formation of many chlorinated and oxidized derivatives. A similar reaction in the presence of potassium bromide was found to preferentially produce corresponding brominated derivatives. These reactions seem to proceed through PAHs adsorbed on the silica surface and halogenating agents, the electrophilicity of which may be raised by the catalytic effect of the silanol group of the silica surface. These findings from the environmental viewpoint suggest that the reaction of hydrophobic compounds adsorbed on sediment cannot be neglected.     

Influence of phosphate on bacterial adhesion onto iron oxyhydroxide in drinking water

The transport and storage of drinking water in water distribution systems can modify its initial composition and properties. The accumulation of bacteria on corroded pipes is prejudicial and may lower the microbiological quality of the water. Previous results have shown that when pipes are highly corroded, the addition of phosphate, used as an anticorrosion treatment, decreases the bacterial concentration in the water. We studied the possibility of using phosphate to reverse the surface charge of iron oxyhydroxide (FeOOH) to limit bacterial adhesion. Iron oxyhydroxide (IOH) particles and Escherichia coli SH 702 were used as models of corrosion products and bacterial contamination, respectively. Electrophoresis was used to characterize the initial surface charges of both types of particles and the modifications that occurred after the addition of phosphate anions. Flow cytometry and adhesion assays were used to build adsorption isotherms of bacteria on IOH versus (phosphated-) IOH. X-ray photoelectron spectroscopy permitted to determine the chemical composition of the E. coli envelope and to discuss on functional groups responsible for bacterial surface properties. In the present conditions, adding phosphate to water allowed a decrease of 75% of the bacteria adhering to IOH.     

Mesoporous Silica‐Based Supports for the Controlled and Targeted Release of Bioactive Molecules in the Gastrointestinal Tract

Mesoporous silica particles (MSPs) have attracted increasing interest as supports in the design of controlled delivery materials. Besides their excellent properties as loading supports (that is, large surface area and pore volume), the modification of their external surface with molecular/supramolecular ensembles allows the design of gated MSPs. Delivery systems based on gated MSPs show “zero delivery” until an adequate stimulus is present and triggers gate opening and the cargo is released. Encapsulation of bioactive molecules in gated MSPs may improve biological stability, facilitate component handling, mask unpleasant sensorial properties, and modulate the bioaccessibility of target molecules along the gastrointestinal tract. These properties make gated MSPs excellent candidates for encapsulating bioactive molecules and their subsequent utilization in the formulation of functional foods. This text highlights the most significant endogenous triggering stimuli that might be applied to design these site‐specific delivery systems, as well as the strategies to develop them. Given the novelty of using MSPs in the food sector, the benefits and current potential limitations of employing MSPs in human food have been identified and discussed.     

Adsorption of 4-picoline and piperidine to the hydrated SiO2 surface: probing the surface acidity with vibrational sum frequency generation spectroscopy

Vapor adsorption is an important process influencing the migration and the fate of many organic pollutants in the environment. In this study, vibrational sum frequency generation (SFG) spectroscopy was used to study the adsorption of two surface acidity probe molecules, 4-picoline (pKa = 5.94) and piperidine (pKa = 11.24), onto the amorphous SiO2 surface. The adsorption of 4-picoline onto the silica surface occurs by forming weak hydrogen bonds between the nitrogen atoms of 4-picoline molecules and the hydrogen atoms of surface silanol OH groups. Piperidine molecules are strongly chemisorbed onto the SiO2 surface through the protonation of piperidine molecules by surface silanol OH groups. The SFG results indicate that the surface acidity constant of silanol OH groups (pKa-(HOSi triple bond)) is in the range of 5.94-11.24 at the air/solid interface. Although this range of surface acidity constants is quite wide, it is possible to narrow it by choosing probe molecules with a smaller pKa range. Together with theoretical prediction methods, adsorption studies using vibrational SFG spectroscopy are capable of quantifying the surface acidity of mineral oxides by carefully choosing the acidity probe molecules.     

Synthesis of mono-dispersed spherical silica particles containing covalently bonded chromophores

Organic-inorganic ultraviolet (UV) active hybrid materials have been prepared by a sol-gel process from benzophenone derivatives and tetraethylorthosilicate. The silica particles are spherical in shape and have a narrow size distribution which remains unchanged up to organic chromophore concentrations of 0.2 mmol g(-1). At higher concentrations the spheres become less regular and fuse. A dependence of the material absorption properties on the particle size (at the same organic chromophore concentration) and on the concentration of surface grafted chromophores was noted. The most effective UV filter materials were found in a combination of silica incorporated chromophores and surface grafted chromophores at an overall low chromophore concentration. A comparison of the photostability of chromophores at standardized UV irradiation revealed an increase in stability for silica incorporated and surface immobilized benzophenone compared to benzophenone in a homogeneous solution.     

Probing the surface structure of divalent transition metals using surface specific solid-state NMR spectroscopy

Environmental and geochemical systems containing paramagnetic species could benefit by using nuclear magnetic resonance (NMR) spectroscopy due to the sensitivity of the spectral response to small amounts paramagnetic interactions. In this study, we apply commonly used solid-state NMR spectroscopic methods combined with chemometrics analysis to probe sorption behavior of the paramagnetic cations Cu(2+) and Ni(2+)at the amorphous silica surface. We exploit the unique properties of paramagnets to derive meaningful structural information in these systems at low, environmentally relevant cation surface loadings by comparing the NMR response of sorption samples to paramagnetic free samples. These data suggest that a simple sorption model where the cation sorbs as inner sphere complexes at negatively charged, deprotonated silanol sites is appropriate. These results help constrain sorption models that are used to describe metal fate and transport.     

Investigation of the inhibitory effect of silica on the degradation of 1,1,1-trichloroethane by granular iron

Although iron-based permeable reactive barriers are gaining importance for treating groundwater contaminants, little is currently known about the effect of cosolutes on barrier longevity. Because of their corrosion inhibiting properties, dissolved silica species are of particular concern. This research investigates the effect of silica on the reduction of 1,1,1-trichloroethane by granular iron as a function of added silica concentration, pH, and duration of iron exposure to dissolved silica. Batch studies reveal that, at pH 8.5 and above, added silica concentrations as low as 0.17 mM cause a 30% reduction in the reactivity of iron. At higher silica concentrations, reactivity decreases by 65-75%. The inhibitory effect is greater at higher pH: 0.83 mM silica has no apparent adverse effect at pH 7.5, but leads to a 46% decrease in reaction rate at pH 8 and 90% at pH 9. This corresponds to observed trends in silica adsorption onto iron, which is low at pH 7.3 but increases at higher pH. Extending the duration of iron exposure to silica solutions also leads to a more pronounced inhibitory effect. This is in good agreement with the increase in silica coverage on the iron surface as revealed by X-ray photoelectron spectroscopy.     

Implications of aqueous silica sorption to iron hydroxide: mobilization of iron colloids and interference with sorption of arsenate and humic substances

This work highlighted practical implications of aqueous silica sorption to iron hydroxide in natural and engineered systems. Two types of surfaces were prepared by exposing 10 mg/L preformed Fe(OH)3 to aqueous silica (0-200 mg/L as SiO2) for periods of 1.5 h or 50 days. After 1.5 h, the concentration of iron passing through a 0.45 microm pore size filter at pH 6.0-9.5 was always negligible, but if zeta potential < or =-15 mV as much as 35% of the iron passed through filters after 50 days of aging. When arsenate was added to 10 mg/L iron hydroxide particles equilibrated with aqueous silica for 1.5 h, percentage arsenate removals were high. In contrast, if silica was preequilibrated with iron for 50 days, arsenate removals decreased markedly at higher pH and aqueous silica concentrations. Similar trends were observed for humic substances, although their removal was nearly completely prevented at pH 8.5 at SiO2 concentrations above 50 and 10 mg/L at 1.5 h and 50 days exposure, respectively. The mechanism of interference was hindered sorption to the iron hydroxide surface.     

Prebiotics and Iron Bioavailability—Is There a Connection?

ABSTRACT: Poor bioavailability of dietary iron, especially from diets rich in cereals and legumes, is a major factor contributing to the high prevalence of nutritional iron deficiency in developing countries. Dietary modification to increase intake of components that promote iron absorption from low-bioavailability meals is an effective strategy for combating nutritional iron deficiency. Prebiotics are nondigestible oligosaccharides that selectively stimulate the growth and activity of specific species of bacteria in the colon with benefits to human health. Common prebiotics such as inulin and fructooligosaccharides occur naturally in a wide variety of plant-based foods and have recently been suggested to have an enhancing effect on iron absorption. The hypothesis that prebiotics enhance iron absorption is biologically plausible because fermentation of prebiotics by natural microflora present in the colon may decrease the pH of the luminal content, promote reduction of Fe(III) to Fe(II), stimulate proliferation of epithelial cells to expand the absorptive surface area, and potentially stimulate expression of mineral-transport proteins in epithelial cells. However, data available in the literature characterizing the enhancing properties of prebiotics on iron absorption are inconsistent, and mechanisms of actions involved are poorly understood. The notion that the colon can function as a significant site of iron absorption in response to stimulation by prebiotics, and the effect of long-term exposure to prebiotics on the iron status of iron-deficient subjects remain to be clarified. This review discusses the functional properties of prebiotics as a promising dietary factor that enhances iron absorption. Keywords: prebiotics, iron, colon, oligosaccharides, inulin     

Rapid and extensive debromination of decabromodiphenyl ether by smectite clay-templated subnanoscale zero-valent iron

Subnanoscale zerovalent iron (ZVI) synthesized using smectite clay as a template was utilized to investigate reduction of decabromodiphenyl ether (DBDE). The results revealed that DBDE was rapidly debrominated by the prepared smectite-templated ZVI with a reaction rate 10 times greater than that by conventionally prepared nanoscale ZVI. This enhanced reduction is plausibly attributed to the smaller-sized smectite-templated ZVI clusters (～0.5 nm) vs that of the conventional nanoscale ZVI (～40 nm). The degradation of DBDE occurred in a stepwise debromination manner. Pentabromodiphenyl ethers were the terminal products in an alkaline suspension (pH 9.6) of smectite-templated ZVI, whereas di-, tri-, and tetrabromodiphenyl ethers formed at the neutral pH. The presence of tetrahydrofuran (THF) as a cosolvent at large volume fractions (e.g., >70%) in water reduced the debromination rates due to enhanced aggregation of clay particles and/or diminished adsorption of DBDE to smectite surfaces. Modification of clay surfaces with tetramethylammonium (TMA) attenuated the colsovent effect on the aggregation of clay particles, resulting in enhanced debromination rates. Smectite clay provides an ideal template to form subnanoscale ZVI, which demonstrated superior debromination reactivity with DBDE compared with other known forms of ZVIs. The ability to modify the nature of smectite clay surface by cation exchange reaction utilizing organic cations can be harnessed to create surface properties compatible with various contaminated sites.     

Effect of silica particle loading on shape distortion in glass/vinyl ester-laminated composite plates

Fibre-reinforced composites loaded with micro/nano particles are being employed in industry for their functional properties. However, behaviour of such composites is different while fabrication is due to the presence of particles. One major parameter needs to be investigated is process-induced residual stress which cause shape distortion in the part. These stresses are generated due to the mismatch of thermal expansion behaviour between the plies, resulting in shape distortion of the composite part. The current study focuses to determine the effect of silica fillers on shape distortion of glass/vinyl ester-laminated composite plates. The resin samples reinforced with 0, 2, 4, 5 and 6% (vol%) of silica particles were prepared and their thermal expansion coefficients (CTE) were determined using Dilatometer. The fillers tend to decrease the CTE of reinforced resin and increase its modulus, as determined using UTM. Composite plates with UD glass were prepared with and without fillers to investigate the distortion behaviour. The experimental results showed that the curvature reduced from 4.3243 to 2.0973 mm by addition of 5% silica particles. The curvature in plates was also simulated in COMSOL Multiphysics, and results are correlated with the experimental values.     

The state of nano-sized titanium dioxide (TiO2) may affect sunscreen performance

In the past several years, there has been a trend in the sunscreen/cosmetics industry to replace micron-sized titanium dioxide (TiO(2)) particles with nanoscale materials. The increased use of nanoscale TiO(2) has resulted in questions about these and other nanoproducts. This study examines the effects of using nanoscale TiO(2) on ultraviolet (UV) attenuation in simple to complex sunscreen formulations. UV light attenuation, product stability, and potential damage to the skin barrier were examined with both nanoscale and microscale TiO(2) particles. Results indicate that none of the formulations decreased the barrier function of the skin and the best UV attenuation occurs when the TiO(2) particles are stabilized with a coating and evenly distributed such as with non-agglomerated coated nanoscale materials. This indicates that nanoscale TiO(2) may have better efficacy while lacking toxicity.     

Development of a trajectory model for predicting attachment of submicrometer particles in porous media: stabilized NZVI as a case study

A new trajectory simulation algorithm was developed to describe the efficiency of a single collector (pore) to catch submicrometer particles moving through saturated porous media. A constricted-tube model incorporating the deterministic (interception, hydrodynamic retardation, van der Waals force and gravitational sedimentation), stochastic (Brownian diffusion), and thermodynamic (electrostatic and steric repulsion force) mechanisms was established to predict the transport and deposition of surface modified nanoscale zerovalent iron (NZVI) particles by applying Lagrangian trajectory analytical approach. The simulation results show good agreement with the results predicted by existing energy-barrier-free models except for the particle size less than 100 nm at low approach velocity. The number of realizations per start location could be decreased down to 100 with the simulations still exhibiting acceptable relative standard deviation for engineering purposes. With the consideration of energy barriers, the model successfully describes the breakthrough curve of polymer-modified NZVI in a benchtop soil column as well. The novel simulation scheme can be a useful tool for predicting the behavior of the nanoscale colloidal particles moving through filter beds or saturated soil columns under conditions with repulsion and attraction forces among surfaces.     

Removal of heavy metals from aqueous systems with thiol functionalized superparamagnetic nanoparticles

We have shown that superparamagnetic iron oxide (Fe3O4) nanoparticles with a surface functionalization of dimercaptosuccinic acid (DMSA) are an effective sorbent material for toxic soft metals such as Hg, Ag, Pb, Cd, and Tl, which effectively bind to the DMSA ligands and for As, which binds to the iron oxide lattices. The nanoparticles are highly dispersible and stable in solutions, have a large surface area (114 m2/g), and have a high functional group content (1.8 mmol thiols/g). They are attracted to a magnetic field and can be separated from solution within a minute with a 1.2 T magnet. The chemical affinity, capacity, kinetics, and stability of the magnetic nanoparticles were compared to those of conventional resin based sorbents (GT-73), activated carbon, and nanoporous silica (SAMMS) of similar surface chemistries in river water, groundwater, seawater, and human blood and plasma. DMSA-Fe3O4 had a capacity of 227 mg of Hg/g, a 30-fold larger value than GT-73. The nanoparticles removed 99 wt% of 1 mg/L Pb within a minute, while it took over 10 and 120 min for Chelex-100 and GT-73 to remove 96% of Pb.     

Coal fly ash as a source of iron in atmospheric dust

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.     

Oxidative degradation of the carbothioate herbicide, molinate, using nanoscale zero-valent iron

Degradation of the carbothiolate herbicide, molinate, has been investigated in oxic solutions containing nanoscale zero-valent iron particles and found to be effectively degraded by an oxidative pathway. Both ferrous iron and superoxide (or, at pH < 4.8, hydroperoxy) radicals appearto be generated on corrosion of the zero-valent iron with resultant production of strongly oxidizing entities capable of degrading the trace contaminant.     

Effect of particle age (Fe0 content) and solution pH on NZVI reactivity: H2 evolution and TCE dechlorination

Subsurface injection of nanoscale zerovalent iron (NZVI) has been used for the in situ remediation of chlorinated solvent plumes and DNAPL source zones. Due to the cost of materials and placement,the efficacy of this approach depends on the NZVI reactivity and longevity, selectivity for the target contaminant relative to nonspecific corrosion to yield H2, and access to the Fe0 in the particles. Both the reaction pH and the age of the particles (i.e., Fe0 content) could affect NZVI reactivity and longevity. Here, the rates of H2 evolution and trichloroethene (TCE) reduction are measured over the lifetime of the particles and at solution pH ranging from 6.5 to 8.9. Crystalline reactive nanoscale iron particles (RNIP) with different initial Fe0 weight percent (48%, 36%, 34%, 27%, and 9.6%) but similar specific surface area were studied. At the equilibrium pH for a Fe(OH)2/H2O system (pH = 8.9), RNIP exhibited first-order decay for Fe0 corrosion (H2 evolution) with respect to Fe0 content with a Fe0 half-life time of 90-180 days. A stable surface area-normalized TCE reduction rate constant 1.0 x 10(-3)L x hr(-1) x m(-2) was observed after 20 days and remained constant for 160 days, while the Fe0 content of the particles decreased by half, suggesting that TCE reduction is zero-order with respect to the Fe0 content of the particle. Solution pH affected H2 evolution and TCE reduction to a different extent. Decreasing pH from 8.9 to 6.5 increased the H2 evolution rate constant 27 fold from 0.008 to 0.22 day(-1), but the TCE dechlorination rate constant only doubled. The dissimilarities between the reaction orders of H2 evolution and TCE dechlorination with respect to both Fe0 content and H+ concentration suggest that different rate controlling steps are involved for the reduction reactions.     

Preparation of estriol-molecularly imprinted silica nanoparticles for determining oestrogens in milk tablets

In this paper, the molecularly imprinted polymer layer of estriol at the silica nanoparticles surface with selective recognition had been constructed. The methacryl groups of functional monomer at the silica nanoparticles surface were acted as reactive sites to induce imprinting polymerisation. The absorption capacity results showed that the molecularly imprinted polymers had an excellent combining affinity, recognition selectivity and fast kinetics. Furthermore, the molecularly imprinted polymers were successfully used as absorbent of dispersive solid-phase extraction coupled with high-performance liquid chromatography to determinate trace estriol and estradiol in milk tablets. The high recoveries yielded of 89.1-93.5% were achieved with the relative standard deviations less than 9.4%. So, the molecularly imprinted polymers are the effective absorbents for the separation and enrichment of oestrogens in the complex matrices samples.