Biological de-inking of waste paper using modified cellulase with polyoxyethylene

Modified cellulase with polyoxyethylene was applied to de-ink waste papers and the weight ratio of modified cellulase to paper was varied from 0.05 to 2% (w/w). During mechanical pulping, the cellulase enhanced the detachment of the ink particle from the paper by partial hydrolysis of the fiber. Polyoxyethylene caused foaming and removed the detached ink particles by floatation. The new biological de-inking process improved the physical properties while maintaining the same de-inking ability. Reprocessed paper freeness, whiteness, and tensile strength increased by 31%, 13%, and 24%, respectively.     

Saccharification and adsorption characteristics of modified cellulases with hydrophilic/hydrophobic copolymers.

Saccharification and adsorption characteristics of native and modified cellulases were investigated. Copolymers, containing polyoxyalkylene and maleic anhydride (MA) were used to modify cellulase. Amino groups of the cellulase were covalently coupled with the MA. As the degree of modification (DM) increased, the activity of modified cellulase slightly decreased. At the maximum DM, the modified cellulase activity retained more than 75% of the unmodified native cellulase activity. In saccharification, native cellulase rapidly adsorbed onto the substrate at initial reaction time. Native cellulase adsorbed tightly onto the substrate surface and did not desorb as reaction time proceeded. The strong adsorption of cellulase onto the substrate can, however, be controlled by the modification. As the hydrophilicity of modified cellulase increased, free modified enzyme concentration also increased. As a result, the conversion rate of modified cellulase was higher than the native one.     

Development of effective modified cellulase for cellulose hydrolysis process

Cellulase was modified with amphilic copolymers made of alpha-allyl-omega-methoxy polyoxyalkylene (POA) and maleic acid anhydride (MAA) to improve the cellulose hydrolytic reactivity and cellulase separation. Amino groups of the cellulase molecule are covalently coupled with the MAA functional groups of the copolymer. At the maximum degree of modification (DM) of 55%, the modified cellulase activity retained more than 80% of the unmodified native cellulase activity. The modified cellulase shows greater stability against temperature, pH, and organic solvents, and demonstrated greater conversion of substrate than native cellulase does. Cellulase modification is also useful for controlling strong adsorption of cellulase onto substrate. Moreover, cellulase modified with the amphiphilic copolymer displays different separation characteristics which are new. One is a reactive two-phase partition and another is solubility in organic solvents. It appears that these characteristics of modified cellulase work very effectively in the hydrolysis of cellulose as a total system, which constitutes the purification of cellulase from culture broth, hydrolysis of cellulose, and recovery of cellulase from the reaction mixture. (c) 1995 John Wiley & Sons, Inc.     

Improvement of cellulase stability by the covalent modification of copolymer of polyalkylene derivative

Summary Stability of cellulase was improved by modification with synthetic copolymers of polyoxyalkylene derivative and maleic anhydride. The modified cellulases under 50% degree of modification showed higher initial activities than did native cellulase. Modified cellulase showed excellent stability of activity against wide pH variation and insoluble solvent. Moreover, cellulase modified with hydrophobic copolymer could be dissolved in these solvents.     

Mycelial paper: A potential resource recovery process?

Eleven species of fungi representative of a broad range of cell-wall compositions were evaluated with respect to their papermaking potential as additives to woodpulp furnishes. Some of these species were also examined for their ability to grow on a spent liquor from the pulp-and-paper industry. Handsheets with various levels of incorporated mycelia exhibited a wide range of species-dependent properties. Behavior of the mycelia in the sheets can be modified to a degree by physical and chemical treatments. The overall results suggest that small amounts (5–10% of the sheet constituents) of mycelia, grown inexpensively on waste effluents, might be incorporated into wood fiber paper without serious deleterious effects on paper strength properties. In some cases improved paper is obtained, and larger quantities of mycelia might be used to impart specific properties to the product.     

Citric acid and maleic anhydride as compatibilizers in starch/poly(butylene adipate-co-terephthalate) blends by one-step reactive extrusion

Starch/poly(butylene adipate-co-terephthalate) films were obtained by one-step reactive extrusion using maleic anhydride (MA) and citric acid (CA) as compatibilizers. The mechanical, structural, optical and barrier properties of the films were analyzed when glycerol (GLY), CA and MA were added to the starch/PBAT (55:45, w/w) according to mixture design. FTIR analysis showed that CA and MA were able to promote esterification/transesterification reactions and that CA induced them more efficiently. When a greater proportion of compatibilizer (1.5 wt%) was used, the resulting films were more opaque and had a greater tensile strength. A greater proportion of GLY (10.0%, w/w) improved the elongation at the break of the films. The barrier properties to water vapor of the films were improved by high levels of CA (1.5 wt%) and intermediate levels of GLY (9.25 wt%). The inclusion of compatibilizers resulted in blends with improved properties, representing a potential replacement for non-biodegradable films.     

Enzymatic deinking of various types of waste paper: Efficiency and characteristics

The aim of the present study was to characterize the enzymatic deinking of various types of waste paper. Studies on the optimization of enzymatic deinking have been performed previously using commercially available enzyme preparations containing cellulase and hemicellulase. The enzymatic deinking of different types of waste paper demonstrated a high efficiency of 86.6% on laser-printed paper, but a low deinking efficiency of 12.9% was obtained with newspaper. All enzymatic treatments significantly improved the drainage rate of the deinked waste paper. Enzymatic deinking increased the tensile index of magazine paper but reduced the tensile index of bubble jet-printed paper, photocopy paper and newspaper. Enzymatic hydrolysis caused a 21.1% reduction in the tear index for bubble jet-printed paper, but a 3.1% increase in the tear index was obtained for laser-printed paper relative to respective blank. In addition, enzymatic hydrolysis increased the burst index by 4.7% relative to blank for laser-printed paper. However, photocopy paper showed the highest reduction (8.3%) in the burst index relative to blank. Taken together, these results suggest that enzymatic hydrolysis is both advantageous and detrimental to the mechanical properties of deinked paper. Thus, the proper regulation of enzymatic hydrolysis is crucial to improve the quality of recycled paper.     

Improving the quality of municipal organic waste compost

The effects of different municipal organic waste (MOW) management practices (shredding, addition of carbon-rich materials and inoculation with earthworms) on organic matter stabilization and compost quality were studied. Four static piles were prepared with: (i) shredded MOW; (ii) shredded MOW+woodshavings; (iii) non-shredded MOW; and (iv) non-shredded MOW+woodshavings. After 50 days, a part of each pile was separated for vermistabilization, while the rest continued as traditional thermophilic composting piles. At different sampling dates, and in the finished products, the following parameters were measured: pH, electrical conductivity, carbon dioxide evolution, and concentrations of organic matter, total nitrogen, water-soluble carbon, nitrate nitrogen, ammonium nitrogen, and extractable phosphorus. Shredded treatments exhibited faster organic matter stabilization than non-shredded treatments, evidenced specially by earlier stabilization of carbon dioxide production and shorter thermophilic phases. Woodshavings addition greatly increased quality of final products in terms of organic matter concentration, and pH and electrical conductivity values, but decreased total nitrogen and available nutrient concentrations. Vermicomposting of previously composted material led to products richer in organic matter, total nitrogen, and available nutrient concentrations than composting only, probably due to the coupled effect of earthworm activity and a shorter thermophilic phase.     

Immobilization of Escherichia coli cells with penicillin-amidohydrolase activity on solid polymeric carriers

Whole cells of Escherichia coli containing the enzyme penicillinamidohydrolase EC 3.5.1.11 were immobilized on the surface of modified macroporous copolymers of glycidylmethacrylate with ethylenedimethacrylate and of copolymers of methacrylaldehyde (MA) with divinylbenzene (DVB) by means of glutaraldehyde. These polymeric carriers were modified before cell binding by using ammonia or polyamines, especially ethylenediamine and hexamethylenediamine (HMDA). The highest specific activity and the largest yield in cell immobilization were achieved with the macroporous copolymer of MA and DVB modified with HMDA. The material thus obtained was used in repeated conversions of benzylpenicillin to 6-aminopenicillanic acid in a stirred batch reactor.     

Enzymatic treatment of primary municipal sludge with Trichoderma viride cellulase

Enzymatic hydrolysis of the cellulose in raw primary settled municipal sludge by Trichoderma viride cellulase achieved conversions of up to 75% of the cellulose, primarily to cellobiose, in 24 hr. Simultaneously the gel-like characteristic of raw primary sludge was changed to that of a slurry of fine particles in less than 2 hr, causing a radical change in the ability to ultrafilter the sludge. The use of raw primary sludge as a growth medium for T. viride cellulase production was also investigated. It was possible, with nitrogen supplements, to obtain an enzyme with a filter paper activity (FPA) of two compared to over four which is attainable on defined medium of similar strength. The potential use of cellulase treatment as a pretreatment or integral part of waste treatment processes is discussed and the alternatives evaluated.     

Mechanical properties of poly(lactic acid)/starch composites compatibilized by maleic anhydride

Blending poly(lactic acid) (PLA) with wheat starch compatibized by maleic anhydride (MA) was performed with a lab-scale co-extruder. An initiator, 2,5-bis(tert-butylperoxy)-2,5 dimethylhexane (L101), was used to improve compatability among PLA, starch and MA. Interfacial adhesion between PLA and starch was significantly improved. Mechanical properties increased markedly compared to the virgin composites of PLA/starch. The PLA/starch composites at a constant ratio of 55/45 compatibilized by 1% MA and initiated by 10% L101 (MA basis) resulted in the highest tensile strength and elongation.     

Simultaneously physically and chemically gelling polymer system utilizing a poly(NIPAAm-co-cysteamine)-based copolymer

The objective of this work was to create an in situ physically and chemically cross-linking hydrogel for in vivo applications. N-Isopropylacrylamide (NIPAAm) was copolymerized with N-acryloxysuccinimide (NASI) via free radical polymerization. Poly(NIPAAm-co-NASI) was further modified to obtain poly(NIPAAm-co-cysteamine) through a nucleophilic attack on the carbonyl group of the NASI by the amine group of the cysteamine. Modification was verified by nuclear magnetic resonance. In addition to thermoresponsive physical gelling due to the presence of NIPAAm, this system also chemically gels via a Michael-type addition reaction when mixed with poly(ethylene glycol) diacrylate. The presence of both physical and chemical gelation resulted in material properties that are much improved compared to purely physical gels. The chemical gelation time of the copolymers was not significantly affected by the amount of thiol present due to the increased pKa of the copolymer containing more thiols. In addition, the swelling of the copolymers was highly dependent on the temperature and thiol content. Last, the rate of nucleophilic attack in the Michael-type addition reaction was shown to be highly dependent on pH and on the mole ratio of thiol to acrylate. Due to the improved mechanical properties, this material may be better suited for long-term functional replacement applications than other thermosensitive physical gels. With further development and biocompatibility testing, this material could potentially be applied as a temperature-responsive injectable biomaterial for functional embolization.     

Biodegradable films of partly branched poly(l-lactide)-co-poly(epsilon-caprolactone) copolymer: modulation of phase morphology, plasticization properties and thermal depolymerization

We report on the modulation of phase morphology, plasticization properties, and thermal stability of films of partly branched poly(l-lactide)-co-poly(epsilon-caprolactone) copolymer (PLLA-co-PCL) with additions of low molecular weight compounds, namely, triethyl citrate ester, diethyl phthalate, diepoxy polyether (poly(propylene glycol) diglycidyl ether), and with epoxidized soybean oil (ESO). The PLLA-co-PCL/polyether films showed significant stability against thermal depolymerization, high film flexibility, and good plasticizing properties, probably due to cross-linking and chain branching formation between diepoxy groups with both the end carboxyl and hydroxyl groups of the PLLA copolymer (initially present or generated during the degradation process) to produce primary ester and ether bonds, respectively. Diethyl phthalate and triethyl citrate ester were found to be efficient plasticizers for PLLA copolymer in terms of glass transition and mechanical properties, but the more water-soluble plasticizer triethyl citrate induced a dramatic loss in the molecular weight of the copolymer. Although ESO cannot play the role of a plasticizer, it substantially stabilizes and retards thermal depolymerization of the PLLA copolymer matrix, possibly because of a reaction between epoxy groups with the end carboxyl and hydroxyl groups of the PLLA copolymer. The presence of ESO in PLLA-co-PCL/ESO/triethyl citrate blends enhanced the compatibility and miscibility of the plasticizer with the PLLA copolymer matrix, considerably improved the mechanical properties (elongation at break), and substantially stabilized the copolymer against thermal depolymerization. It seems likely that the epoxy groups interact not only with the end hydroxyl and carboxyl group of the copolymer but as well with the hydroxyl group of triethyl citrate plasticizer to produce a new ether bond (C-O-C) as the cross-linking unit. On the other hand, for PLLA-co-PCL/ESO/polyether blends, (80/10/10) epoxidized oil distorts the compactness of the blend by diminishing the proposed entanglements between carboxyl, hydroxyl, and diepoxy groups of polyether and reduces the high elongation properties otherwise observed in the PLLA-co-PCL/polyether films. The multicomponent approach toward modulating poly(l-lactide)-co-poly(epsilon-caprolactone) copolymer films using epoxy compounds and plasticizers and the insight into the nature of various PLLA matrixes presented here offer advantages to a broad engineering of PLLA copolymer films having desirable physical properties and multiphase behavior for efficient uses in future technical applications.     

The properties of enzyme-hydrolyzed cellulose in aqueous sodium hydroxide

Pure natural cellulose (softwood pulp) modified with cellulase is allowed to react with sodium hydroxide in a muller, and changes in structure and properties are investigated by FTIR and DSC. The reactivity of cellulose for some dissolving and derivatization processes is shown to be improved by an enzymatic hydrolysis and admixture with sodium hydroxide. The modified cellulose dissolved at 9% (wt) sodium hydroxide at -10 degrees C at 6% pulp consistency, while the DP of cellulose is >350.     

Modification of high-lignin softwood kraft pulp with laccase and amino acids

This study demonstrates the potential of laccase-facilitated grafting of amino acids to high-lignin content pulps to improve their physical properties in paper products. Research studies have recently reported that increases in anionic fiber charge can improve strength properties of paper. In an effort to increase carboxylic acid groups, we developed a unique two-stage laccase grafting protocol in which fibers were initially treated with laccase followed by grafting reactions with amino acids. The bulk acid group content was measured, and a variety of amino acids including glycine (Gly), phenylalanine (Phe), serine (Ser), arginine (Arg), histidine (His), alanine (Ala), and aspartic acid (Asp) were examined. The effects of optimizing laccase dose, and amino acid structures, on fiber modification chemistry were studied. Histidine provided the best yield of acid groups on pulp fiber, and was used for the preparation of handsheets for physical strength testing. Laccase-histidine treated pulp showed an increase in strength properties of the resulting paper.     

Colloidal ionic assembly between anionic native cellulose nanofibrils and cationic block copolymer micelles into biomimetic nanocomposites

We present a facile ionic assembly between fibrillar and spherical colloidal objects toward biomimetic nanocomposites with majority hard and minority soft domains based on anionic reinforcing native cellulose nanofibrils and cationic amphiphilic block copolymer micelles with rubbery core. The concept is based on ionic complexation of carboxymethylated nanofibrillated cellulose (NFC, or also denoted as microfibrillated cellulose, MFC) and micelles formed by aqueous self-assembly of quaternized poly(1,2-butadiene)-block-poly(dimethylaminoethyl methacrylate) with high fraction of the NFC reinforcement. The adsorption of block copolymer micelles onto nanocellulose is shown by quartz crystal microbalance measurements, atomic force microscopy imaging, and fluorescent optical microscopy. The physical properties are elucidated using electron microscopy, thermal analysis, and mechanical testing. The cationic part of the block copolymer serves as a binder to NFC, whereas the hydrophobic rubbery micellar cores are designed to facilitate energy dissipation and nanoscale lubrication between the NFC domains under deformation. We show that the mechanical properties do not follow the rule of mixtures, and synergistic effects are observed with promoted work of fracture in one composition. As the concept allows wide possibilities for tuning, the work suggests pathways for nanocellulose-based biomimetic nanocomposites combining high toughness with stiffness and strength.     

Synthesis, characterization and applications of graft copolymer (κ-carrageenan-g-vinylsulfonic acid)

The synthesis of graft copolymer (κ-carrageenan-g-vinylsulfonic acid) is carried out in nitrogen atmosphere using potassium peroxymonosulfate (PMS) and malonic acid (MA) as redox system. The effect of reaction variables including the concentration of vinylsulfonic acid 1.3×10(-2) to 6.7×10(-2) mol dm(-3), PMS 4×10(-3) to 20×10(-3) mol dm(-3), MA 1.6×10(-3) to 4.8×10(-3) mol dm(-3), sulfuric acid 1×10(-3) to 8×10(-3) mol dm(-3), κ-carrageenan 0.4-1.8 g dm(-3) as well as time duration 60-180 min and temperature 25-45 °C has been studied. The water swelling capacity of graft copolymer is investigated. Flocculation property for both coking and non-coking coals is studied for the treatment of coal mine waste water. The graft copolymer has been characterized by FTIR and thermogravimetric analysis.     

Applications of minimum-order Wiener modeling to retinal ganglion cell spatiotemporal dynamics

In a previous paper (Marmarelis et al. 1986) we presented the concept of minimum-order Wiener (MOW) modeling of continuous-input/spike-output (CISO) systems. The associated MOW methodology aims at obtaining low-order Wiener models for CISO systems of practical interest. The assertion was made that many neurophysiological systems that fall in this class can be studied effectively by the use of this method. We have chosen a sensory system to demonstrate the efficacy of the method with actual experimental data. The response of retinal ganglion cells to spatiotemporal visual stimuli was studied with this approach and a second-order MOW model was obtained. The results appear to corroborate the adequacy of this model in terms of predicting the timing of the output spikes.     

Solidification/Stabilization of Cresol-Contaminated Soil: Mechanical and Leaching Behavior

In this research, the effects of a solidification/stabilization (S/S) technique on the remediation of cresol-contaminated soil were investigated. The soil samples were collected from the Tehran Oil Refinery (TOR) in Ray District, Iran. Cresols are hazardous chemicals whose exposure at high dosage results in irreparable damage to animal and human health. S/S process progresses through physicochemical reactions, reducing the leachability of a waste as well as changing its physical properties in order to encapsulate the contaminants and form a solid material. The samples were spiked by certain concentrations of cresols including meta-, ortho-, and para-isomers. The treatment process was conducted using Portland cement as the binder and modified bentonite as a stabilizer. The efficiency of the S/S technique was assessed by the unconfined compressive strength (UCS) test and toxicity characteristic leaching procedure (TCLP) test. The results of the tests showed that adding 20% and 30% Portland cement in combination with 15% and 30% modified bentonite to contaminated samples increased the 28-day compressive strength of S/S blocks to a range of 2.44 to 3.08 MPa. In fact, increasing the proportion of cement in the mix design resulted in enhanced compressive strength, while modified bentonite inversely affected samples’ strength. Regarding leaching behavior, adding organophilic clay to polluted samples noticeably declined cresol's concentrations in leachate. Overall efficiency of S/S in terms of leaching was about 70%, which was obtained by adding 20% cement and 30% modified clay. A logarithmic relationship between leaching percent and modified clay ratio was also detected with high logarithmic and linear correlation coefficients of 0.96 and 0.9, respectively, hence presenting the efficiency of S/S in stabilizing the cresols in the samples.     

Improved antifouling properties of PVDF membranes modified with oppositely charged copolymer

Biofouling resulting from the attachment of microorganisms communities to the membrane surface is the major obstacle for the widespread application of membrane technology. This work develops a feasible approach to prepare an anti-biofouling poly(vinylidene fluoride) (PVDF) membrane. A copolymer that possessed oppositely charged groups was first synthesized via radical copolymerization with methyl methacrylate, 2-methacryloxy ethyltrimethyl ammonium chloride and 2-acrylamide-2-methyl propane sulphonic acid as monomers. The copolymer was blended with the PVDF powder to prepare the antifouling membrane via the immersed phase inversion method. The antifouling properties of the modified PVDF membrane were studied by X-ray photoelectron spectroscopy, field emission scanning electron microscopy, water contact angle measurement, zeta-potential measurement, protein adsorption, microbial adhesion and filtration experiments. The modified PVDF membrane showed limited adsorption and adhesion of protein bovine serum albumin and microbes (Escherichia coli and Saccharomyces cerevisiae) with increasing copolymer concentration in the casting solution. The modified PVDF membrane exhibited excellent antibiofouling properties.