Synthesis of wheat straw-g-poly(acrylic acid) superabsorbent composites and release of urea from it

Wheat straw (WS) was used as raw material for synthesizing a novel wheat straw-g-poly(acrylic acid) (WS/PAA) superabsorbent composite by graft polymerization with wheat straw powder and acrylic acid in aqueous solution. The effect of wheat straw on water absorbency was discussed and the highest water absorbency was obtained when the amount of wheat straw in the feed was 20%. The superabsorbent composite was characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). The results of FTIR spectra showed OH of WS participated in graft polymerization with acrylic acid. The influences of pH, cations and anions on equilibrium water absorbency of WS/PAA were investigated. The superabsorbent composite was swollen in aqueous solution of urea to load urea, and the results showed urea concentration had no obvious effect on the swelling behaviors of WS/PAA. Furthermore, the release of urea from loaded WS/PAA was analyzed in water and in soil. Urea diffusion coefficient D was calculated.     

Preparation and properties of a double-coated slow-release NPK compound fertilizer with superabsorbent and water-retention

A double-coated slow-release NPK compound fertilizer with superabsorbent and water-retention was prepared by crosslinked poly(acrylic acid)/diatomite - containing urea (the outer coating), chitosan (the inner coating), and water-soluble granular fertilizer NPK (the core). The effects of the amount of crosslinker, initiator, degree of neutralization of acrylic acid, initial monomer and diatomite concentration on water absorbency were investigated and optimized. The water absorbency of the product was 75 times its own weight if it was allowed to swell in tap water at room temperature for 2 h. Atomic absorption spectrophotometer and element analysis results showed that the product contained 8.47% potassium (shown by K(2)O), 8.51% phosphorus (shown by P(2)O(5)), and 15.77% nitrogen. We also investigated the water-retention property of the product and the slow release behavior of N, P and K in the product. This product with excellent slow release and water-retention capacity, being nontoxic in soil and environment-friendly, could be especially useful in agricultural and horticultural applications.     

Effect of carboxymethylation conditions on the water-binding capacity of chitosan-based superabsorbents

A superabsorbent polymer (SAP) from chitosan was provided via carboxymethylation of chitosan, followed by cross-linking with glutaraldehyde and freeze-drying. This work was focused on an investigation of the effects of monochloroacetic acid (MCAA), sodium hydroxide, and reaction time on preparation of carboxymethyl chitosan (CMCS). The CMCS products were characterized using FTIR spectroscopy, and their degrees of substitution (DS) were measured using conductimetry and FTIR analysis. The highest DS value was obtained when the carboxymethylation reaction was carried out using 1.75 g MCAA and 1.75 g NaOH per g of chitosan in 4 h. The water solubilities of the CMCS products at various pHs were also evaluated, and the results indicated a significant impact of the reaction parameters on the solubility of CMCS. The CMCSs with the highest DS value resulted in SAPs having the highest water-binding capacity (WBC). The WBC of the best SAP measured after 10 min exposure in distilled water, 0.9% NaCl solution, synthetic urine, and artificial blood was 104, 33, 30, and 57 g/g, respectively. The WBC of this SAP at pH 2-9 passed a maximum at pH 6.     

Enzyme immobilization on ultrafine cellulose fibers via poly(acrylic acid) electrolyte grafts

Ultrafine cellulose fiber (diameter 200-400 nm) surfaces were grafted with polyacrylic acid (PAA) via either ceric ion initiated polymerization or methacrylation of cellulose with methacrylate chloride (MACl) and subsequent free-radical polymerization of acrylic acid. PAA grafts by ceric ion initiated polymerization increased with increasing reaction time (2-24 h), monomer (0.3-2.4 M), and initiator (1-10 mM) concentrations, and spanned a broad range from 5.5-850%. PAA grafts on the methacrylated cellulose fibers also increased with increasing molar ratios of MACl to cellulosic hydroxyl groups (MACl/OH, 2-6.4) and monomer acrylic acid (AA) to initiator potassium persulfate (KPS) ratios ([AA]/[KPS], 1.5-6), and were in a much narrower range between 12.8% and 29.4%. The adsorption of lipase (at 1 mg/ml lipase and pH 7) and the activity of adsorbed lipase (pH 8.5, 30 degrees C), in both cases decreased with increasing PAA grafts. The highest adsorption and activity of the lipase on the ceric ion initiated grafted fibers were 1.28 g/g PAA and 4.3 U/mg lipase, respectively, at the lowest grafting level of 5.5% PAA, whereas they were 0.33 g/g PAA and 7.1 U/mg lipase, respectively, at 12.8% PAA grafts on the methacrylated and grafted fibers. The properties of the grafted fibers and the absorption behavior and activity of lipase suggest that the PAA grafts are gel-like by ceric-initiated reaction and brush-like by methacrylation and polymerization. The adsorbed lipase on the ceric ion-initiated grafted surface possessed greatly improved organic solvent stability over the crude lipase. The adsorbed lipases exhibited 0.5 and 0.3 of the initial activity in the second and third assay cycles, respectively.     

Crosslinked carboxymethylchitosan-g-poly(acrylic acid) copolymer as a novel superabsorbent polymer

A novel carboxymethylchitosan-g-poly(acrylic acid) (CMCTS-g-PAA) superabsorbent polymer was prepared through graft polymerization of acrylic acid onto the chain of carboxymethylchitosan and subsequent crosslinking. It was demonstrated by FTIR spectroscopy that acrylic acid had been graft polymerized with carboxymethylchitosan. The thermal stability of the polymer was characterized by thermogravimetric analysis. By studying the swelling ratio of the polymer synthesized under different conditions, optimization conditions were found for a polymer with the highest swelling ratio. The rate of water absorption of the polymer was high, and the swelling of the polymer fitted the process of first dynamics. The swelling ratio of the polymer was pH-dependent.     

Utilization of starch and clay for the preparation of superabsorbent composite

Starch and attapulgite were utilized as raw material for synthesizing starch-graft-poly(acrylic acid)/attapulgite superabsorbent composite by graft copolymerization reaction of starch and acrylic acid (AA) in the presence of attapulgite micropowder in aqueous solution. Major factors affecting on water absorbency such as weight ratio of AA to starch, initial monomer concentration, neutralization degree of AA, amount of crosslinker, initiator and attapulgite were investigated. The superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10 wt% exhibit absorption of 1077 g H(2)O/g sample and 61 g H(2)O/g sample in distilled water and in 0.9 wt% NaCl solution, respectively. This superabsorbent composite with excellent water absorbency and water retention under load, being biodegradable in nature, economical and environment-friendly, could be especially useful in agricultural and horticultural applications.     

Synthesis,characterization and swelling behaviors of sodium alginate-g-poly(acrylic acid)/sodium humate superabsorbent

A novel sodium alginate-g-poly(acrylic acid)/sodium humate superabsorbent was prepared by graft copolymerization with sodium alginate, acrylic acid and sodium humate in aqueous solution, using N,N’-methylenebisacrylamide as a crosslinker and ammonium persulfate as an initiator. The effects of crosslinker, sodium alginate and sodium humate content on water absorbency of the superabsorbent were studied. The swelling behavior in solutions of various pH and the swelling kinetics in saline solutions (5 mmol/L NaCl and CaCl₂) were also investigated. The results from IR analysis showed that both sodium alginate and sodium humate react with the acrylic acid monomer during the polymerization process. The introduction of sodium humate into the sodium alginate-g-poly(acrylic acid) system could enhance the water absorbency and the superabsorbent containing 10 wt% sodium humate acquired the highest water absorbency (1380 g/g in distilled water and 83 g/g in 0.9 wt% NaCl solution).     

Chlorella sorokiniana immobilized on the biomatrix of vegetable sponge of Luffa cylindrica: a new system to remove cadmium from contaminated aqueous medium

A new sorption system of microalgal cells immobilized on the biostructural matrix of Luffa cylindrica for sequestering cadmium is reported. Free and immobilized Chlorella sorokiniana removed cadmium from 10 mgl(-1) solution at the efficiency of 92.7% and 97.9% respectively. Maximum cadmium sorption was observed to be 39.2 mgg(-1) at equilibrium (C(eq)) of 112.8 mgl(-1) by immobilized microalgal biomass as compared to 33.5 mgg(-1) at C(eq) of 116.5 mgl(-1) by free biomass from initial concentration of 150 mgl(-1). In continuous liquid flow column, the cadmium sorption capacity of immobilized C. sorokiniana was 192 mgg(-1), which was 73.2% of the total metal passed in 51.5 l. Metal desorption with 0.1 M HCl was 100% and the desorbed immobilized system was reusable with a similar efficiency in the subsequent cycle.     

Activated carbon from Eucalyptus camaldulensis Dehn bark using phosphoric acid activation

The powdered activated carbon prepared by phosphoric acid activation was significantly affected by the carbonization temperature and the weight ratio between raw material and phosphoric acid. With an activation time of 1h and an impregnation ratio of 1:1, the activated carbons with better adsorption capacity were obtained at 500 degrees C. A reduction in the adsorption capacity of the carbon product at higher acid content than this was observed, possibly due to the collapse of the micropore structure. The properties of the resulting activated carbon were: bulk density 0.251gcm(-3), ash content 4.88%, yield 26.2%, iodine adsorption 1043mgg(-1), methylene blue adsorption number 427mgg(-1), and BET surface area 1239m(2)g(-1).     

Use of superabsorbent polymer gels for surface decontamination of Bacillus anthracis spores

Aims:  This study evaluated the inactivation of Bacillus anthracis Vollum spores dried on a nonporous surface using a superabsorbent polymer (SAP) gel containing commercially available liquid decontaminants.
Methods and Results:  The first phase determining the availability of the liquid decontaminant within the SAP showed that the SAP gel containing pH-adjusted sodium hypochlorite (NaOCl) inhibited B. anthracis growth while the water control SAP gel had no affect on growth. For testing surface decontamination, B. anthracis spores were dried onto steel coupons painted with chemical agent resistant coating and exposed to SAP containing either pH-adjusted NaOCl, chlorine dioxide (ClO₂) or hydrogen peroxide/peracetic acid (H₂O₂/PA) for 5 and 30 min. At contact times of both 5 and 30 min, all of the SAP gels containing pH-adjusted NaOCl, ClO₂ or H₂O₂/PA inactivated B. anthracis spores at levels ranging from 2·2 to ≥7·6 log reductions.
Conclusions:  Incorporation of three commercially available decontaminant technologies into a SAP gel promotes inactivation of B. anthracis spores without observable physical damage to the test surface.
Significance and Impact of the Study:  This work provides preliminary data for the feasibility of using SAP in inactivating B. anthracis spores on a nonporous surface, supporting the potential use of SAP in surface decontamination.     

Conducting polyamic acid membranes for sensing and site-directed immobilization of proteins

A biosensor platform based on polyamic acid (PAA) is reported for oriented immobilization of biomolecules. PAA, a functionalized conducting polymer substrate that provides electrochemical detection and control of biospecific binding, was used to covalently attach biomolecules, resulting in a significant improvement in the detection sensitivity. The biosensor sensing elements comprise a layer of PAA antibody (or antigen) composite self-assembled onto gold (Au) electrode via N-hydroxysuccinimide (NHS) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) linking. The modified PAA was characterized by Fourier transform infrared (FTIR), (1)H nuclear magnetic resonance (NMR), and electrochemical techniques. Cyclic voltammetry and impedance spectroscopy experiments conducted on electrodeposited PAA on Au electrode using ferricyanide produced a measurable decrease in the diffusion coefficient compared with the bare electrode, indicating some retardation of electron transfer within the bulk material of the PAA. Thereafter, the modified PAA surface was used to immobilize antibodies and then to detect inducible nitric oxide synthase and mouse immunoglobulin G (IgG) using enzyme-linked immunosorbent assay (ELISA), surface plasmon resonance (SPR), and amperometric techniques. ELISA results indicated a significant amplified signal by the modified PAA, whereas the SPR and amperometric biosensors produced significant responses as the concentration of the antigen was increased. Detection limits of 3.1×10(-3)ng/ml and 2.7×10(-1)ng/ml were obtained for SPR and amperometric biosensors, respectively.     

Synthesis and self-assembly of well-defined poly(amino acid) end-capped poly(ethylene glycol) and poly(2-methyl-2-oxazoline)

Poly(ethylene glycol) (PEG) and poly(2-methyl-2-oxazoline) (PMOx) are water-soluble, biocompatible polymers with stealth hemolytic activities. Poly(amino acid) (PAA) end-capped PEG and PMOx were prepared using amino-terminated derivatives of PEG and PMOx as macroinitiators for the ring-opening polymerization of γ-benzyl protected l-glutamate N-carboxyanhydride and S-benzyloxycarbonyl protected l-cysteine N-carboxyanhydride, respectively, in the presence of urea, at room temperature. The molecular weight of the PAA moiety was kept between M(n) = 2200 and 3000 g mol(-1). PMOx was polymerized by cationic ring-opening polymerization resulting in molecular weights of M(n) = 5000 and 10,000 g mol(-1), and PEG was a commercial product with M(n) = 5000 g mol(-1). Here, we investigate the self-assembly of the resulting amphiphilic block copolymers in water and the effect of the chemical structure of the block copolymers on the solution properties of self-assembled nanostructures. The PEG-block-poly(amino acid), PEG-b-PAA, and PMOx-block-poly(amino acid), PMOx-b-PAA, block copolymers have a narrow and monomodal molecular weight distribution (PDI < 1.3). Their self-assembly in water was studied by dynamic light scattering and fluorescence spectroscopy. In aqueous solution, the block copolymers associate into particles with hydrodynamic radii (R(H)) ranging in size from R(H) 70 to 130 nm, depending on the block copolymer architecture and the polymer molecular weight. Larger R(H) and critical association concentration values were obtained for copolymers containing poly(S-benzyloxycarbonyl-l-cysteine) compared to their poly(γ-benzyl-L-glutamate) analogue. FTIR investigations revealed that the poly(γ-benzyl-L-glutamate) block adopts a helical conformation, while the poly(S-benzyloxycarbonyl-L-cysteine) block exists as β-sheet.     

Polyelectrolyte brushes grafted from cellulose nanocrystals using Cu-mediated surface-initiated controlled radical polymerization

Herein we report the synthesis of cellulose nanocrystals (CNCs) grafted with poly(acrylic acid) (PAA) chains of different lengths using Cu-mediated surface initiated-controlled radical polymerization (SI-CRP). First, poly(tert-butylacrylate) (PtBA) brushes were synthesized; then, subsequent acid hydrolysis was used to furnish PAA brushes tethered onto the CNC surfaces. The CNCs were chemically modified to create initiator moieties on the CNC surfaces using chemical vapor deposition (CVD) and continued in solvent phase in DMF. A density of initiator groups of 4.6 bromine ester groups/nm(2) on the CNC surface was reached, suggesting a dense functionalization and a promising starting point for the controlled/living radical polymerization. The SI-CRP of tert-butylacrylate proceeded in a well-controlled manner with the aid of added sacrificial initiator, yielding polymer brushes with polydispersity values typically well below 1.12. We calculated the polymer brush grafting density to almost 0.3 chains/nm(2), corresponding to high grafting densities and dense polymer brush formation on the nanocrystals. Successful rapid acid hydrolysis to remove the tert-butyl groups yielded pH-responsive PAA-polyelectrolyte brushes bound to the CNC surface. Individually dispersed rod-like nanoparticles with brushes of PtBA or PAA were clearly visualized by AFM and TEM imaging.     

Poly(amidoamine) salt form: effect on pH-dependent membrane activity and polymer conformation in solution

On exposure to an acidic pH, linear poly(amidoamine)s (PAAs) cause membrane perturbation and consequently have potential as endosomolytic polymers for the intracellular delivery of genes and toxins. Previous studies used PAAs in the hydrochloride form only. The aim of this study was to investigate systematically the effect of the PAA counterion on pH-dependent membrane activity, general cytotoxicity, and PAA solution properties to help guide optimization of PAA structure for further development of PAA-protein conjugates. PAAs (ISA 1, 4, 22, and 23; M(w) 10000-50000 g/mol) were synthesized to provide a library of PAAs having different counterions including the acetate, citrate, hydrochloride, lactate, phosphate, and sulfate salts. pH-Dependent membrane activity was assessed using a rat red blood cell haemolysis assay (conducted at a starting pH of 7.4, 6.5, or 5.5; 1 mg/mL; 1 h), and general cytotoxicity was investigated using a murine melanoma cell line (B16F10) and a human bladder endothelial-like cell line (ECV-304). Whereas poly(ethyleneimine) was haemolytic at the starting pH of 7.4 at 1 h [ approximately 50% haemoglobin (Hb) release], none of the PAA salts were haemolytic at a starting pH of 7.4 or 6.5. Although PAA acetate, citrate, and lactate were also non-haemolytic at the starting pH of 5.5, the sulfate and hydrochloride forms caused significant haemolysis (up to 80% Hb release) and ISA 22 and 23 phosphate were also markedly haemolytic ( approximately 70% Hb release). These counterion-specific differences were also clearly visible using scanning electron microscopy, which was used to visualize the red blood cell morphology. All PAAs were relatively nontoxic (IC(50) >or= 300-5000 microg/mL) compared to poly-l-lysine (IC(50) = 2-10 microg/mL), the PAA hydrochloride salts produced the greatest cytotoxicity, and the B16F10 cells were more sensitive than the ECV-304 cells. Small-angle neutron scattering suggested that ISA 23 hydrochloride had a larger hydrodynamic radius (5.1 +/- 0.2 nm) than the citrate salt (3.1 +/- 0.2 nm). These results provide indirect evidence for the salt- and pH-dependent changes in the conformation of the polymer coil. This study clearly demonstrates the importance of optimization of the counterion form when developing endosomolytic polymers designed to mediate pH-dependent membrane permeabilization.     

Hydroxypropylcellulose templated synthesis of surfactant-free poly(acrylic acid) nanogels in aqueous media

We report the synthesis and study of surfactant-free poly(acrylic acid) (PAA) nanogels using hydroxypropylcellulose (HPC) as a template in aqueous HPC solutions at room temperature or above. Through the hydrogen bonding interaction of acrylic acid (AA) with hydroxypropylcellulose (HPC), AA absorbed on the HPC polymer chains and triggered the phase transition of HPC at a lower temperature, with increasing AA concentration, than the HPC intrinsic phase transition temperature 41 °C. As AA polymerized to form PAA, the much stronger interpolymer hydrogen bonding triggered the phase transition of HPC at a temperature around room temperature, causing HPC coil-global phase transition to collapse and form nanospheres at room temperature, PAA hydrogen-bonded HPC chains collapsed and formed nanogels chemically crosslinked by poly(ethylene glycol) diacrylate (PEGDA) or methylenebisacrylamide (BIS). The results showed that all the PAA nanogels demonstrated a narrow size distribution with diameters ranging from 60 nm to 600 nm.     

Silicon Composite Electrodes with Dynamic Ionic Bonding

Silicon (Si) composite electrodes are developed with increased cycle lifetimes and reliability through dynamic ionic bonding between active Si nanoparticles and a polymer binder. Amine groups are covalently attached to Si nanoparticles via surface functionalization. Si composite electrodes are fabricated by combining the Si nanoparticles with a poly(acrylic acid) (PAA) binder. The formation of ionic bonds between amine groups on Si particles and carboxylic acid groups on the PAA binder is characterized by X‐ray photoelectron spectroscopy and Raman spectroscopy. Si composite anodes with ionic bonding demonstrate long term cycling stability with capacity retention of 80% at 400 cycles at a current density of 2.1 A g^?1 and good rate capability. The dynamic ionic bonds effectively mitigate the deterioration of electrical interfaces in the composite anodes as suggested by stable impedance over 300 cycles.     

Leachate Characterization and Phytoremediation Using Water Hyacinth (Eichorrnia crassipes) in Pulau Burung,Malaysia

Leachate from Pulau Burung landfill site was analyzed and treated using phytoremediation technique while water hyacinth (Eichhornia crassipes) was used as the phytoremediator. Some parameters analyzed included ammonia nitrogen (NH₃-N), nitrate, nitrite, total Kjeldahl nitrogen (TKN), phosphate, and zinc. The range of values of nutrients such as the pH, ammonia nitrogen, TKN, phosphate and zinc during leachate characterization were 8.72 and 8.58, 1810 and 1070 mg/L, 1183 and 1120 mg/L, 46.4 and 31.2 mg/L, 11.1 and 5.4 mg/L, respectively. After phytoremediation, significant reduction was noticed in all the nutrients and zinc. Nitrite, phosphate and zinc values were between 91.9% and 98.2%, 4.4 to 0.6 mg/L and 1.1 and 0.1 mg/L, respectively. Statistical analyses showed significant differences between the planted and unplanted systems (p ≤ .05). It was established that Eichhornia crassipes had the capacity to remove nutrients and heavy metals from leachate, which requires treatment to minimize pollutants to an acceptable level before discharging into water courses.     

Formulation of a liquid fertilizer for sorghum (Sorghum bicolor (L.) Moench) using vermicompost leachate

Leachate from vermicomposting contains large amounts of plant nutrients and can be used as liquid fertilizer, but normally diluted to avoid plant damage. The amount of nutrients applied is thus reduced so that an additional fertilizer is required. We investigated how dilution of vermicompost leachate combined with different concentrations of NPK triple 17 fertilizer, and polyoxyethylene tridecyl alcohol as dispersant and polyethylene nonylphenol as adherent to increase efficiency of fertilizer uptake, affected sorghum plant development. The vermicomposting leachate with pH 7.8 and electrolytic conductivity 2.6 dS m(-1), contained 834 mg K(+) l(-1), 247 mg NO(3)(-)l(-1) and 168 mg PO(4)(3-) l(-1), was free of pathogens and resulted in a 65 % germination index. Vermicompost leachate can be used as liquid fertilizer for the cultivation of sorghum without dilution and mixed with 140-170 g l(-1) of NPK triple 17 fertilizer and 2-3 ml(-1) of dispersant and 0-1 ml l(-1) adherent. It was found that vermicompost leachate stimulated plant development, but fertilization with NPK was required for maximum growth.     

Compensating effect of fulvic acid and super-absorbent polymer on leaf gas exchange and water use efficiency of maize under moderate water deficit conditions

A field-based pot experiment with maize plants was conducted to examine the effect of combined fulvic acid (FA) and super-absorbent polymer (SAP) on leaf gas exchange, water use efficiency, and grain yield under soil water deficit. SAP (45 kg hm^?2) was applied to the topsoil at sowing. Plants were well-watered (80% field capacity), but subjected to water deficit (50% field capacity) from tassel stage to grain-fill. FA solution (2 g L^?1) was sprayed onto plant leaves at 2 and 9 days after imposing water deficit. Under water deficit, SAP and FA application did not affect evapotranspiration, but increased leaf abscisic acid and decreased leaf transpiration rate with a little change in photosynthesis, thus improving instantaneous water use efficiency. Applying SAP and FA under water deficit also increased grain yield by 19% and grain water use efficiency by 24%, largely attributed to an increase in kernel number. In contrast, under well-watered condition the two chemicals increased stomatal conductance, leaf transpiration, photosynthesis and chlorophyll content, but did not change kernel number and were relatively less effective in respect to water use efficiency compared to water-stressed condition. This study showed that application of foliar FA and soil SAP had little effect on evapotranspiration but maintained high photosynthesis and kernel number, and improved water use efficiency under soil water deficit.