Effect of Particle-Substrate Interactions on Colloidal Layer Structure Prepared by Convective Self-Assembly Using Polyelectrolyte-Grafted Silica Particles.

Cationic and anionic polyelectrolytes, poly(vinylbenzyl trimethylammonium chloride) (PVBTA) and poly(sodium styrene sulfate) (PSSS), were grafted on the surface of the silica particles, respectively, and then these two types of polyelectrolyte-grafted silica particles were applied to the colloidal layer preparation by convective self-assembly (CSA) using hydrophilic or hydrophobic glass substrates to investigate the effect of the interactions between the particles and the substrate surface on the resultant layer structures. When the PVBTA-grafted silica particle (PVBTA-Si) was used, the colloidal monolayers with a non-close-packed (NCP) structure were formed on both hydrophilic and hydrophobic glass substrates, where the NCP colloidal layers on the hydrophobic glass substrate have a somewhat more ordered structure than those on the hydrophilic glass substrate. In the case of the PSSS-grafted silica particle (PSSS-Si), on the other hand, stripe patterns with close-packed (CP) colloidal layers were obtained on both types of the glass substrates. The number of layers of the stripes on the hydrophilic glass substrate was less than that on the hydrophobic glass substrate, while the spacing and width of the stripes on both substrates were similar to each other. The difference in the structures of the colloidal layers obtained here indicates that an attractive interaction, such as an electrostatic attraction and a hydrophobic interaction, between the particle and the substrate surface is necessary to achieve the NCP structure by the CSA process using polyelectrolyte-grafted silica particles.

Efficient separation of phycocyanin of Nostoc commune by multistep diafiltration using ultra-filtration membrane modules.

Diafiltration (DF) is a separation method used to separate and concentrate macromolecules, such as polysaccharides and proteins. To obtain high-purity target molecules by DF, appropriate conditions should be used. In this study, a mathematical model was developed to suggest appropriate ultra-filtration (UF) membrane modules for the separation of phycocyanin (PC) by multistep DF. PC is a protein produced by microalgae. The contribution of each UF membrane module to PC productivity and purity at each stage of the multistep DF process was quantified by the proposed model. The parameters required as model inputs (k, Fα1, and Fα2) were experimentally determined by permeating PC-containing solution through UF membrane modules (150, 30, and 10 kDa cutoffs). The resulting analytical solutions and those predicted by the model were in close agreement. The PC purity increased from 0.20 to 0.30 when a 10 kDa UF membrane module was used in two-step DF. An orthogonal table was used to determine the combination of UF membrane modules needed to achieve higher purity of PC. The model predicted that the 30 kDa UF membrane module would have the highest contribution to PC productivity and purity at any position in a three-step DF. The developed model can help identify appropriate conditions for separating macromolecules by DF.

Separation of microalgae using a compacted magnetite-containing gel bed.

Separation of microalgae of various sizes and shapes is an important process that enables subsequent production of useful compounds. Herein, the separation of microalgae was accomplished using a magnetite-containing gel (42 µm) packed into a column. An algal suspension was injected into the top of the gel bed, after which water was passed through the column. The pressure generated during the process caused the lower domain of the gel bed to deform, resulting in narrowed gaps between the gel beads. When a suspension of Nannochloropsis sp. (0.0069-0.69 g L-1) was loaded and water was passed through the column at an applied pressure of 0.01-0.10 MPa, the majority of microalgae were captured within the upper domain of the gel bed, while only 20% were captured within the lower domain. The amount of Nannochloropsis sp. captured was expressed by an ordinary differential equation to determine the capture coefficient, K, and the maximum capture amount, Qmax. As pressure increased, gel gaps narrowed, K increased, and Qmax decreased because of a reduction in the number of effective capture sites upon compaction of the gel. When a mixed suspension of Anabaena sp., Monoraphidium sp., and Desmodesmus sp. (0.069 g L-1 each) was injected into the gel bed at an applied pressure of 0.01 MPa, only Anabaena sp. was captured at the bottom of the gel bed. This device can be applied for the separation of microalgae in rivers and the sea.

Surfactant-Assisted Synthesis of Pt Nanocubes Using Poly(N-isopropylacrylamide) Nanogels.

Poly(N-isopropylacrylamide) (PNIPAM) nanogels were prepared by emulsion polymerization using sodium dodecyl sulfate (SDS) and employed as a capping agent in platinum nanoparticle (Pt NP) synthesis by liquid-phase reduction with hydrogen gas. When the PNIPAM nanogels were used without removing SDS, that is, a slight amount of SDS was included in the reaction solution, Pt nanocubes (NCs) were predominantly produced (>80%). The proportion of the resultant Pt NCs was much higher than that obtained using the PNIPAM linear polymer (∼60%). To clarify the effects of the three-dimensional polymer network and SDS, we synthesized Pt NPs using the PNIPAM nanogel without SDS (SDS-free PNIPAM nanogel) and found that Pt NCs are rarely formed, and most NPs obtained have an irregular shape. When only SDS was used as a capping agent, NCs were hardly obtained, but other polyhedral NPs were formed. Furthermore, the use of SDS together with the PNIPAM polymer led to the decrease in the proportion of the Pt NCs compared with that obtained using only the linear polymer. These results indicate that the enhancement of the Pt NC proportion using the PNIPAM nanogel with SDS is attributable to not only the three-dimensional polymer network of the PNIPAM nanogel but also the assist of SDS as a capping agent.

Recovery of Filtered Particles by Elastic Flat-Sheet Membrane with Cross Flow.

After filtration, filtered residue is recovered by a spoon, during which, the structure of the residue is destroyed, and the activity of the microorganism would be reduced. Thus, a more efficient recovery method of filtered residue is required. This study addressed the recovery method of filtered residue by the restoration of an elastic membrane, followed by cross flow. An elastic membrane composed of a copolymer of poly(ethylene glycol) diacrylate and polyacrylonitrile was prepared by photopolymerization. The pore diameter of the obtained membrane was about 10 µm. Silica particle (1 and 10 µm) and Nannochloropsis sp. (2 µm) suspension was filtered, demonstrating that silica particles of 10 µm were filtered perfectly, whereas the filtration percentage of 1 µm silica particles and Nannochloropsis sp. was lower. After the filtration, the applied pressure was released to restore the elastic membrane which moved the filtered particles up, then the filtered residue was recovered by cross flow above the membrane, demonstrating that 71% of the filtered 10 µm silica particles was recovered. The elastic behavior of the membrane, along with the cross flow, has the potential to be used as a technique for the recovery of the filtered residues. This proposed scheme would be used for the particle recovery of ceramics, cells, and microorganisms from a lab scale to a large-scale plant.

Filtration of Elastic Polymers and Spherical Gels through a Silica-Deposited Layer on a Porous Membrane.

A 120-nm silica suspension was permeated through a porous polyethylene (PE) hollow-fiber membrane, as was a solution of deformable elastic particles of poly(N-isopropylacrylamide) (PNIPAM) gel and dextran. The amount adsorbed and flux of permeation were analyzed with ordinary differential equations to obtain adsorption coefficients, maximum amounts adsorbed, and pore-narrowing factors. The thickness of the "silica-deposited layer" on the membrane was 1 µm. In a batch adsorption mode, 5.0 mg of PNIPAM gel and 30 mg of dextran were adsorbed on the PE membrane, with no adsorption on the silica. The PE membrane pores were narrowed by a secondary layer of adsorbed PNIPAM gel. When filtered through the silica-deposited layer, PNIPAM gel occupies gaps, resulting in a reduced permeation flux. Dextran passed through the silica-deposited layer and was partially adsorbed on the PE membrane. The modified membrane can control adsorption, filtration, and flux permeation, which leads to dynamic membrane separations.

Dewatering of algal suspension using microfiltration with cross flow in the presence of magnetite as a filter aid.

Dewatering algal suspensions is an important step in the extraction of oil and other useful substances from algae. In this study, spherical Nannochloropsis sp. and ellipsoidal Monoraphidium sp. suspensions were dewatered in the presence of different amounts of 350-nm magnetite particles using a microfiltration membrane with 360-nm pores in cross-flow mode. Magnetite functions as a filter aid by reducing the deformation of the cake of filtered algae on the membrane and providing paths for water to flow through the filtration cake of algae. In the case of Nannochloropsis sp., the highest dewatering rate was obtained when the number ratio, defined based on the size and ideal density, between Nannochloropsis sp. and magnetite was 1:12.5, but the addition of magnetite had no observable effect on the filtration of ellipsoidal Monoraphidium sp. suspensions through the membrane. After dewatering, magnetite was effectively separated from the concentrated algal suspension by the application of a magnetic field in an open flow system. Magnetite has the potential to enhance dewatering performance using a cross-flow membrane system.

Hydrothermal preparation of a platinum-loaded sulphated nanozirconia catalyst for the effective conversion of waste low density polyethylene into gasoline-range hydrocarbons.

A platinum-loaded sulphated nanozirconia (Pt/nano ZrO2-SO4) bifunctional metal-acid catalyst was synthesized using a hydrothermal process. The nano ZrO2-SO4 was initially prepared by dispersing the nano ZrO2 in H2SO4, followed by wet impregnation via heating in an aqueous PtCl4 solution. This material was subsequently calcined and reduced under hydrogen gas to produce the catalyst. The Pt/nano ZrO2-SO4 was found to be a highly active, selective and stable solid acid catalyst for the conversion of waste low density polyethylene (LDPE) to high value hydrocarbons. The catalytic activity and stability of this material were evaluated during the hydrocracking of waste LDPE while optimizing the reaction temperature, time and catalyst-to-feed ratio. The activity of catalyst prepared by hydrothermal was attributed to highly dispersion of Pt species interacting with the support and inhibition of the agglomeration process. The impregnation method of hydrothermal generated highly active and selective catalyst with Pt loads of 1 wt%. The hydrocracking of waste LDPE over Pt/nanoZrO2-SO4 at 250 °C for 60 min with a catalyst-to-feed proportion of 1 wt% gave the largest gasoline fraction.

Comparison of interfacial behavior and silver extraction kinetics with various types calix[4]arene derivatives at heterogeneous liquid-liquid interfaces.

Various p-tert-octylcalix[4]arene derivatives as hydrophobic extractants have been prepared to investigate Ag(I) extraction efficiency in a batch-wise process in nitric acid media. The influence of the functional groups of the hydrophobic extractants on the interfacial behavior and Ag(I) extraction efficiency in nitric acid media has been investigated using the drop-volume method. Fitting of the interfacial tension isotherms to the Gibbs and Szyszkowski equations has provided parameters characterizing the interfacial activity of the extractants, in particular the Gibbs free energy of adsorption at the interface, the interface excess on saturation (Г∞) and the average area per the adsorbed extractant molecule (Amin). The amido-type p-tert-octylcalix[4]arene derivatives have strong interfacial activity and fast extraction rates. The interface excess at saturation (Г∞) increased with the type of functional groups in the following order: methyl ketonic < phenyl ketonic < dibenzyl amido < diethyl amido < quinolyl < pyridyl. The relationship between the interfacial activity and the dependence of the Ag(I) extraction efficiency on the different functional groups is discussed. The interfacial behavior of the extractants affected both the solvent extraction equilibrium and the kinetics and the overall results are consistent with a mass transfer mechanism at the heterogeneous liquid-liquid interfaces.

Recovery of Silver Using Adsorption Gels Prepared from Microalgal Residue Immobilized with Functional Groups Containing Sulfur or Nitrogen.

Although biodiesel oil extracted from microalgae attracts much attention as one of the most promising green energies, its high production cost is a big problem, impeding its extensive use. In order to lower the production cost, the effective use of microalgal residue after extracting biofuel was investigated as a feed material of functional materials. In the present work, a new adsorbent for silver(I) was prepared by immobilizing functional groups of polyethylene-polyamine or dithiooxamide, which exhibita high affinity for soft Lewis acids such as silver(I) ions. Their adsorption behaviors for silver(I) were investigated from aqueous nitrate and acidothiourea media. The effects of the concentrations of nitrate and thiourea, as well as of sulfuric acid, were qualitatively interpreted. From the study of adsorption isotherms on these gels, they were found to exhibita higher adsorption capacity than the majority of those reported to date.

Biosorbents for Removing Hazardous Metals and Metalloids.

Biosorbents for remediating aquatic environmental media polluted with hazardous heavy metals and metalloids such as Pb(II), Cr(VI), Sb(III and V), and As(III and V) were prepared from lignin waste, orange and apple juice residues, seaweed and persimmon and grape wastes using simple and cheap methods. A lignophenol gel such as lignocatechol gel was prepared by immobilizing the catechol functional groups onto lignin from sawdust, while lignosulfonate gel was prepared directly from waste liquor generated during pulp production. These gels effectively removed Pb(II). Orange and apple juice residues, which are rich in pectic acid, were easily converted using alkali (e.g., calcium hydroxide) into biosorbents that effectively removed Pb(II). These materials also effectively removed Sb(III and V) and As(III and V) when these were preloaded with multi-valent metal ions such as Zr(IV) and Fe(III). Similar biosorbents were prepared from seaweed waste, which is rich in alginic acid. Other biosorbents, which effectively removed Cr(VI), were prepared by simply treating persimmon and grape wastes with concentrated sulfuric acid.

Adsorption and Elution of Glucuronic Acid and Chondroitin Sulfate Using Amino-Group-Containing Spherical Gel.

A spherical gel containing amino groups was prepared using monomers of N,N-dimethylacrylamide and N,N-dimethylaminoethyl methacrylate, with a cross-linker composed of N,N'-methylenebisacrylamide prepared by suspension polymerization for the adsorption of glucuronic acid and chondroitin sulfate. The prepared gel was immersed in glucose, glucuronic acid, and chondroitin sulfate solutions to determine the adsorption performance in batch mode, which demonstrated that 20 % of the chondroitin sulfate was adsorbed to the amino-group-containing gel. The amino-group-containing gel was packed into a column to permeate the chondroitin sulfate-containing solution (0.40 g/L) at pH 2.0, and it adsorbed chondroitin sulfate to the gel at a space velocity of 4.5 h-1. When the space velocity was changed to 1.5 h-1, the amount of chondroitin sulfate increased. When 0.50 M NaCl solution was permeated through the chondroitin-sulfate-adsorbed gel in column mode, 70 % of the chondroitin sulfate was eluted. This spherical gel may be applicable for acidic glycan recovery using batch and permeation modes.

Enhancement of immobilized lipase activity by design of polymer brushes on a hollow fiber membrane.

A polymer brush possessing aminoethanol (AE) functional groups for lipase immobilization was grafted onto a hollow fiber membrane by radiation-induced graft polymerization. Almost the AE groups-grafted polymer brushes unfold through positive charge repulsion between the AE groups, enabling multi-layer immobilization of lipase. The hydroxyl groups in AE can also retain water molecules around hydrophilic part of the lipase. In this study, we controlled the length and density of the polymer brushes consisting of the glycidyl methacrylate (GMA) by changing the concentration of GMA monomer during radiation-induced graft polymerization. Immobilized lipase showed the highest activity on the grafted membrane when 5 wt% of glycidyl methacrylate as monomer for the radiation-induced graft polymerization was used. Consequently high efficiency esterification (approximately 1600 mmol/h/g-membrane) was achieved in five-layer lipase on AE polymer brush than that in monolayer lipase on the polymer brush possessing only hydroxyl groups. Moreover, the polymer brush possessing AE functional groups for lipase immobilization maintained high activity on the reuse for several times.

Adsorptive removal of cesium using bio fuel extraction microalgal waste.

An adsorption gel was prepared from microalgal waste after extracting biodiesel oil by a simple chemical treatment of crosslinking using concentrated sulfuric acid. The adsorbent exhibited notably high selectivity and adsorption capacity towards Cs(+) over Na(+) from aqueous solutions, within the pH range of slightly acidic to neutral. The adsorption followed Langmuir isotherm and the maximum adsorption capacity of the gel for Cs(+) calculated from Langmuir model was found to be 1.36 mol kg(-1). Trace concentration of Cs(+) ions present in aqueous streams was successfully separated from Na(+) ions using a column packed with the adsorbent at pH 6.5. The adsorption capacity of the gel towards Cs(+) in column operation was 0.13 mol kg(-1). Although the adsorbed Cs(+) ions were easily eluted using 1M hydrochloric acid solution, simple incineration is proposed as an alternative for the treatment of adsorbent loaded with radioactive Cs(+) ions due to the combustible characteristics of this adsorbent.

Preparation of novel alginate based anion exchanger from Ulva japonica and its application for the removal of trace concentrations of fluoride from water.

A green seaweed, Ulva japonica, was modified by loading multivalent metal ions such as Zr(IV) and La(III) after CaCl2 cross-linking to produce metal loaded cross-linked seaweed (M-CSW) adsorbents, which were characterized by elemental analysis, functional groups identification, and metal content determination. Maximum sorption potential for fluoride was drastically increased after La(III) and Zr(IV) loading, which were evaluated as 0.58 and 0.95 mmol/g, respectively. Loaded fluoride was quantitatively desorbed by using dilute alkaline solution for its regeneration. Mechanism of fluoride adsorption was inferred in terms of ligand exchange reaction between hydroxyl ion on co-ordination sphere of the loaded metal ions of M-CSW and fluoride ion in aqueous solution. Application of M-CSW for the treatment of actual waste plating solution exhibited successful removal of fluoride to clear the effluent and environmental standards in Japan, suggesting high possibility of its application for the treatment of fluoride rich waste water.

Adsorptive removal of fluoride from aqueous medium using a fixed bed column packed with Zr(IV) loaded dried orange juice residue.

The potential of the adsorbent prepared from DOJR marketed as cattle food in Japan was identified as an efficient and low cost adsorbent for fluoride using fixed bed column. DOJR was loaded with Zr(IV) ions to develop active adsorption sites for fluoride. Fluoride adsorption performance of column packed with Zr(IV) loaded DOJR was assessed under variable operating conditions such as Zr(IV) loading temperature, initial fluoride concentration, bed depth, initial pH, and flow rate. Breakthrough curve modeling showed that Thomas and bed depth service time (BDST) models were in good agreement with the experimental data. Application of adsorbent investigated in this study to the treatment of actual waste plating solution containing fluoride ion showed successful removal below acceptable standard in Japan using a fixed bed column, hence, Zr(IV)-DOJR can be expected to be a promising candidate for the treatment waste water containing trace amount of fluoride ion in fixed bed column.

N-aminoguanidine modified persimmon tannin: a new sustainable material for selective adsorption, preconcentration and recovery of precious metals from acidic chloride solution.

A new adsorption gel has been developed by immobilizing N-aminoguanidine (AG), a chelating ligand, on persimmon tannin extract through consecutive reactions. Adsorption behavior of the gel was investigated for the adsorptive separation and recovery of precious metal ions from varying concentration of HCl medium. The adsorption isotherms of precious metal ions on the gel were described by the typical monolayer type of Langmuir model and the maximum adsorption capacities were evaluated as 8.90 mol kg(-1) for Au(III), 2.01 mol kg(-1) for Pd(II) and 1.01 mol kg(-1) for Pt(IV). Real time applicability of the gel was examined for the recovery of precious metals from actual leach liquor of e-waste leached with chlorine containing hydrochloric acid. The gel was found to be highly efficient and selective for the uptake of targeted metal ions in the presence of excess base metal ions and also exhibited superior selectivity over commercially available anion exchange resins.

Self-pulsation observed in pH-sensitive microcapsules.

In this study, self-pulsating microparticles have been successfully prepared using a pH-sensitive and permselective membrane system.

Optimization of an adsorption process for tetrafluoroborate removal by zirconium (IV)-loaded orange waste gel from aqueous solution.

This investigation provides new insights into the effective removal of tetrafluoroborate (BF4-) by means of bio-sorption on waste generated in the orange juice industry. It was undertaken to evaluate the feasibility of zirconium (IV)-loaded saponified orange waste gel for BF4- removal from an aqueous solution. Batch adsorption experiments were carried out to study the influence of various factors such as pH, presence of competing anions, contact time, initial BF4- concentration and temperature on the adsorption of BF4-. The optimum BF4- removal was observed in the equilibrium pH region 2-3. The presence of coexisting anions showed no adverse effect on BF4- removal except SO4(2-). The equilibrium data at different temperatures were reasonably interpreted by the Langmuir adsorption isotherm and the maximum adsorption capacities were evaluated as 2.65, 3.28, 3.87 and 4.77 mmol g(-1) at 293, 298, 303 and 313 K, respectively. Thermodynamic parameters such as deltaGo, deltaHo and deltaSo indicated that the nature of BF4- adsorption is spontaneous and endothermic. The results obtained from this study demonstrate the potential usability of orange waste after juicing as a good BF4- selective adsorbent.

Allosteric coextraction of sodium and metal ions with calix[4]arene derivatives 2: first numerical evaluation for the allosteric effect on alkali metal extraction with crossed carboxylic acid type calix[4]arenes.

Crossed carboxylic acid types of calix[4]arene derivatives with two longer carboxylic acids and two acetic acids at the distal position have been prepared to investigate the solvent extraction of three alkali metal ions in individual and competitive systems. These extractants selectively extracted sodium ions among other alkali ions at low pH, and the first extracted sodium ion acted as a "trigger" causing a change in extraction ability and metal selectivity. Spacer groups with different lengths induced significant differences in the extraction behavior. The extraction equilibrium constants, K(ex1) and K(ex2), between the present cyclic tetramers and the extracted two alkali metal ions were estimated in order to obtain a numerical evaluation of the allosteric effect.