Graft copolymerization of ethyl acrylate onto cellulose using ceric ammonium nitrate as initiator in aqueous medium

Ceric ammonium nitrate (CAN) in the presence of nitric acid has been used as efficient initiator for graft copolymerization of the ethyl acrylate onto cellulose at 35.0 +/- 0.1 degrees C. Graft copolymerization of ethyl acrylate onto cellulose has taken place through the radical initiation process. The graft yield and other grafting parameters have been evaluated by varying concentration of ethyl acrylate from 2.5 x 10(-1) to 15.0 x 10(-1) mol dm(-3) and ceric ammonium nitrate from 5.0 x 10(-3) to 25.0 x 10(-3) mol dm(-3) at constant concentration of the nitric acid (8.0 x 10(-2) mol dm(-3)). The rate of graft copolymerization has shown 1.5 order with respect to the concentration of the ceric ammonium nitrate. The graft copolymerization data obtained at different temperatures were used to calculate the energy of activation, which has been found to be 28.9 kJ mol(-1) within the temperature range from 20 to 50 degrees C. The effect of addition of cationic and anionic surfactants on graft copolymerization has also been studied. On the basis of the experimental observations, reaction steps have been proposed and a suitable rate expression for graft copolymerization has been derived.     

Synthesis and properties of a water soluble graft (chitosan-g-2-acrylamidoglycolic acid) copolymer

The present paper reports the graft copolymerization of 2-acrylamidoglycolic acid onto chitosan by using potassium bromate/silver nitrate as an efficient redox initiator in an inert atmosphere. The effect of reaction conditions on grafting parameters i.e. grafting ratio, efficiency, conversion, add on, homopolymer and rate of grafting has been studied. Experimental results show that maximum grafting has been obtained at 0.4 g dm(-3) concentration of chitosan, 8.0×10(-2) mol dm(-3) concentration of 2-acrylamidoglycolic acid and 1.0×10(-3) mol dm(-3) concentration of hydrogen ion. It has also been observed that grafting ratio, add on, conversion, efficiency and rate of grafting increase up to 3.2×10(-3) mol dm(-3) of silver nitrate and 1.7×10(-2) mol dm(-3) of potassium bromate. Time (120 min) and temperature (40°C) were kept constant during reaction. The physicochemical properties of graft copolymer synthesized have been performed in terms of water swelling, metal ion sorption, flocculation and resistance to biodegradability with respect to the chitosan as a parent polymer. The graft copolymer has been characterized by Fourier transform infrared (FTIR) spectroscopy and thermogravimetric analysis.     

Surface-active and stimuli-responsive polymer--Si(100) hybrids from surface-initiated atom transfer radical polymerization for control of cell adhesion

A simple two-step method was developed for the covalent immobilization of atom-transfer radical polymerization (ATRP) initiators on the hydrogen-terminated Si(100) (Si-H) surface. Well-defined functional polymer-Si hybrids, consisting of covalently tethered brushes of poly(ethylene glycol) monomethacrylate (PEGMA) polymer, N-isopropylacrylamide (NIPAAm) polymer, and NIPAAm-PEGMA copolymers and block copolymers on Si-H surfaces, were prepared via surface-initiated ATRP. Kinetics study revealed that the chain growth from the silicon surface was consistent with a "controlled" process. Surface cultures of the cell line 3T3-Swiss albino on the hybrids were evaluated. The PEGMA graft-polymerized silicon [Si-g-P(PEGMA)] surface is very effective in preventing cell attachment and growth. At 37 degrees C [above the lower critical solution temperature (LCST, approximately 32 degrees C) of NIPAAm], the seeded cells adhered, spread, and proliferated on the NIPAAm graft polymerized silicon [Si-g-P(NIPAAm)] surface. Below the LCST, the cells detached from the Si-g-P(NIPAAm) surface spontaneously. Incorporation of PEGMA units into the NIPAAm chains of the Si-g-P(NIPAAm) surface via copolymerization resulted in more rapid cell detachment during the temperature transition. The "active" chain ends on the Si-g-P(PEGMA) and Si-g-P(NIPAAm) hybrids were also used as the macroinitiators for the synthesis of diblock copolymer brushes. Thus, not only are the hybrids potentially useful as stimuli-responsive adhesion modifiers for cells in silicon-based biomedical microdevices but also the active chain ends on the hybrid surfaces offer opportunities for further surface functionalization and molecular design.     

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.     

Swelling induced detachment of chondrocytes using RGD-modified poly(N-isopropylacrylamide) hydrogel beads

Thermally sensitive poly(N-isopropylacrylamide, NIPAAm) hydrogel beads conjugated with a cell adhesive motif, GRGDY, were prepared and utilized as cell culture substrate for chondrocytes. They were produced to be uniform in size and distribution by using calcium alginate as a temporal mold. The RGD moieties were introduced, in a spatially selective manner, to the surface of the beads by conjugating GRGDY under the precollapsed state at a higher temperature above the lower critical solution temperature (LCST). These RGD-conjugated polyNIPAAm beads demonstrated a reversible swelling and deswelling behavior around the LCST, which enabled the chondrocytes attached on the surface of collapsed beads at 37 degrees C to readily detach when the temperature was shifted below 37 degrees C. The cell detachment percentage was largely affected by the temperature-dependent reswelling extent of the collapsed RGD-modified beads.     

Synthesis and characterization of injectable poly(N-isopropylacrylamide-co-acrylic acid) hydrogels with proteolytically degradable cross-links

Hydrogels composed of N-isopropylacrylamide (NIPAAm) and acrylic acid (AAc) were prepared by redox polymerization with peptide cross-linkers to create an artificial extracellular matrix (ECM) amenable for testing hypotheses regarding cell proliferation and migration in three dimensions. Peptide degradable cross-linkers were synthesized by the acrylation of the amine groups of glutamine and lysine residues within peptide sequences potentially cleavable by matrix metalloproteinases synthesized by mammalian cells (e.g., osteoblasts). With the peptide cross-linker, loosely cross-linked poly(N-isopropylacrylamide-co-acrylic acid) [P(NIPAAm-co-AAc)] hydrogels were prepared, and their phase transition behavior, lower critical solution temperature (LCST), water content, and enzymatic degradation properties were investigated. The peptide-cross-linked P(NIPAAm-co-AAc) hydrogels were pliable and fluidlike at room temperature and could be injected through a small-diameter aperture. The LCST of peptide-cross-linked hydrogel was influenced by the monomer ratio of NIPAAm/AAc but not by cross-linking density within the polymer network. A peptide-cross-linked hydrogel with a 97/3 molar ratio of NIPAAm/AAc exhibited a LCST of approximately 34.5 degrees C. Swelling was influenced by NIPAAm/AAc monomer ratio, cross-linking density, and swelling media; however, all hydrogels maintained more than 90% water even at 37 degrees C. In enzymatic degradation studies, breakdown of the peptide-cross-linked P(NIPAAm-co-AAc) hydrogels was dependent on both the concentration of collagenase and the cross-linking density. These results suggest that peptide-cross-linked P(NIPAAm-co-AAc) hydrogels can be tailored to create environmentally-responsive artificial extracellular matrixes that are degraded by proteases.     

Rapid deswelling response of poly(N-isopropylacrylamide)/poly(2-alkyl-2-oxazoline)/poly(2-hydroxyethyl methacrylate) hydrogels

Ternary poly( N-isopropylacrylamide)/poly(2-alkyl-2-oxazoline)/poly(2-hydroxyethyl methacrylate) (PNIPAAm/PROZO/PHEMA) hydrogels were prepared by the free-radical copolymerization of N-isopropylacrylamide (NIPAAm), 2-hydroxyethyl methacrylate (HEMA), and poly(2-alkyl-2-oxazoline) (PROZO) multifunctional macromonomers. The resulting polymeric materials were characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM), as well as by equilibrium swelling experiments. All synthesized hydrogels display temperature sensitivity in the 28-38 degrees C range. A high rate of response was registered as compared to that of materials based only on PNIPAAm. The swelling-deswelling peculiar behavior was related to the chemical composition (hydrophile/hydrophobe balance), the length of the inserted PROZO sequence, and inner morphology, an aspect which points on its possible control by synthesis. It was evidenced that the architecture of the resulting porous materials has a high order degree, emerging from the self-assembling of the microgel particles, which provided numerous, nearly uniform, large water release channels.     

Formation and morphology of struvite and newberyite in aqueous solutions at 25 and 37 degrees C

The influence of the initial reactant concentrations (c(i)(Mg)tot = 5.0 x 10(6) to 5.0 x 10(-1) mol dm(-3), c(i)(P)tot = c(i)(NH4)tot = 1.0 x 10(-3) to 5.0 x 10(-1) mol dm(-3)) and temperature (25 and 37 degrees C) on the composition and morphology of the precipitates formed in the system MgCl2-NH4H2PO4-NaOH-H2O at initial pHi = 7.40 has been investigated. Precipitation diagrams are presented showing the concentration regions within which different morphologies of solid phase have been formed. The solid phases aged for 24 hours were characterized by means of optical microscopy, FT-IR spectrophotometry, X-ray diffractometry and thermogravimetry. It was found that struvite was a predominant phase formed within the concentration region examined and newberyite was obtained only in the region where pH(24h) < 6.5. The influence of the initial pH on the formation and transformation of these two compounds were studied in the region 5.0 < or = pHi < or = 9.0 and the results are discussed.     

Temperature-controlled properties of DNA complexes with poly(ethylenimine)-graft-poly(N-isopropylacrylamide)

End-functionalized poly(N-isopropylacrylamide) (PNIPA) was synthesized by living free radical polymerization and conventional free radical polymerization and was used to prepare graft copolymers with poly(ethylenimine) (PEI). The copolymers exhibited lower critical solution temperature (LCST) behavior between 30 and 32 degrees C and formed complexes with plasmid DNA. The LCST of the copolymers in the DNA complexes increased slightly to approximately 34-35 degrees C. Cytotoxicity of the copolymers was evaluated by measuring lactate dehydrogenase (LDH) release from cells. The copolymers exhibited temperature-dependent toxicity, with higher levels of LDH release observed at temperatures above the LCST. Cellular uptake and transfection activity of the DNA complexes with the PEI-g-PNIPA copolymers were lower than those of the control PEI/DNA complexes at temperature below the LCST but increased to the PEI/DNA levels at temperatures above the LCST.     

Preparation of a thermosensitive highly regioselective cellulose/N-isopropylacrylamide copolymer through atom transfer radical polymerization

Regioselective copolymerization of N-isopropylacrylamide (NIPAM) onto cellulose was achieved by atom transfer radical polymerization (ATRP) using a regioselectively modified 6- O-bromoisobutyryl-2,3-di- O-methyl cellulose macroinitiator. Varying the ratio of NIPAM to macroinitiator to ligand to transition metal in a Cu(I)Br/ N, N, N', N', N'-pentamethyldiethylenetriamine (PMDETA) catalyst system affected graft yield and degree of polymerization. ATRP proceeded to completion without any trace of the macroinitiator, and a degree of polymerization (DP) of polyNIPAM up to 46.3 was obtained. Increasing the DP of the NIPAM component increased both the thermal decomposition temperature and the glass transition temperature of the copolymer. The grafting of NIPAM also affected the solubility properties of the methylcellulose. The 6- O-polyNIPAM-2,3-di- O-methyl cellulose formed a stable suspension in water at room temperature and underwent a hydrophillic-to-hydrophobic transition and copolymer precipitation when the temperature was raised above 30 degrees C.     

Poly(N-isopropylacrylamide)-based semi-interpenetrating polymer networks for tissue engineering applications. 1. Effects of linear poly(acrylic acid) chains on phase behavior

Poly(N-isopropylacrylamide)-based [P(NIPAAm)-based] semi-interpenetrating polymer networks (semi-IPNs), consisting of P(NIPAAm)-based hydrogels and linear poly(acrylic acid) [P(AAc)] chains, were synthesized, and the effects of the P(AAc) chains on semi-IPN injectability and phase behavior were analyzed. In P(NIPAAm)- and P(NIPAAm-co-AAc)-based semi-IPN studies, numerous reaction conditions were varied, and the effects of these factors on semi-IPN injectability, transparency, phase transition, lower critical solution temperature (LCST), and volume change were examined. The P(AAc) chains did not significantly affect the LCST or volume change of the semi-IPNs, compared to control hydrogels. However, the P(AAc) chains affected the injectability, transparency, and phase transition of the matrices, and these effects were dependent on chain amount and molecular weight (MW) and on interactions between the P(AAc) chains and the solvent and/or copolymer chains in P(NIPAAm-co-AAc) hydrogels. These results can be used to design "tailored" P(NIPAAm)-based semi-IPNs that have the potential to serve as functional scaffolds in tissue engineering applications.     

Synthesis,structure and properties of new tung oil-styrene-divinylbenzene copolymers prepared by thermal polymerization

A variety of new polymers ranging from rubbery materials to tough and rigid plastics have been prepared by the thermal copolymerization of tung oil, styrene, and divinylbenzene. The thermal copolymerization is performed in the temperature range of 85-160 degrees C with variations in the stoichiometry, oxygen uptake, peroxides, and metallic catalysts used. Gelation of the reactants typically occurs at temperatures higher than 140 degrees C, and fully cured thermosets are obtained after post-curing at 160 degrees C. The fully cured thermosets are determined by Soxhlet extraction to contain approximately 90-100% cross-linked materials, and (1)H NMR and FTIR spectroscopy indicates that the cross-linked materials are random copolymers. The new bulk polymeric materials obtained are light yellow and transparent with glossy surfaces, and possess glass transition temperatures of -2 to +116 degrees C, cross-link densities of 1.0 x 10(3)-2.5 x 10(4) mol/m(3), coefficients of linear thermal expansion of 2.3 x 10(-4)-4.4 x 10(-4) per degrees C, compressive moduli of 0.02-1.12 GPa, and compressive strengths of 8-144 MPa. These materials are thermally stable below 300 degrees C and exhibit a major thermal degradation with a maximum degradation rate at 493-506 degrees C.     

Modulate the phase transition temperature of hydrogels with both thermosensitivity and biodegradability

The synthesis and characterization of thermoresponsive hydrogels on the basis of N-isoproplyarylamide (NIPAAm) and acrylamide (AAm) copolymers crosslinked with a novel biodegradable crosslinker (PEG-co-PLA) were carried out in this study. Swelling measurement results demonstrated that four gels of PNAM5, PNAM10, PNAM12 and PNAM15 are thermoresponsive. The equilibrium swelling ratio and degradation of the hydrogels strongly depend on hydrogels composition. The morphology of the hydrogels was observed by scanning electron microscopy (SEM), and their thermal property was characterized by differential scanning calorimetry (DSC). The results show that the proportion of AAm in the copolymer has notable effect on the low critical solution temperature (LCST) of the hydrogel. When the molar ratio of AAm to NIPAAm was increased from 1:10 to 3:10 the LCST of the copolymer increased from 39.7 to 64.2 °C. The compression modulus of PNAM15 is of the highest among other hydrogels, because PNAM15 hydrogel has a more compact structure.     

Intelligent dual-responsive cellulose surfaces via surface-initiated ATRP

Novel thermo-responsive cellulose (filter paper) surfaces of N-isopropylacrylamide (NIPAAm) and pH-responsive cellulose surfaces of 4-vinylpyridine (4VP) have been achieved via surface-initiated ATRP. Dual-responsive (pH and temperature) cellulose surfaces were also obtained through the synthesis of block-copolymer brushes of PNIPAAm and P4VP. With changes in pH and temperature, these "intelligent" surfaces showed a reversible response to both individual triggers, as indicated by the changes in wettability from highly hydrophilic to highly hydrophobic observed by water contact angle measurements. Adjusting the composition of the grafted block-copolymer brushes allowed for further tuning of the wettability of these "intelligent" cellulose surfaces.     

Photocrosslinkable biodegradable responsive hydrogels as drug delivery systems

Recently, controlled release from biocompatible materials has received much attention for biomedical applications. Due to their biocompatibility and biodegradability, glucopyranosides such as dextran appear as promising polymeric materials if one is able to regulate their rheological properties and the encapsulation/release efficiency. In this work graft polymer hydrogels from dextran and N-isopropylacrylamide (NIPAAm) were prepared and characterized.Dextran molecules were modified with 2-isocyanatoethylmethacrylate (IEMA) in order to obtain a polymer with carbon double bonds. Urethane linkages resulted from the reaction between hydroxyl groups (OH) of the dextran and isocyanate groups (NCO) of the IEMA. The obtained polymer was then crosslinked by UV irradiation in the presence of the photoinitiating agent Irgacure 2959 by CIBA^®. The drug Ondansetron^® was entrapped in the final system and its release profile was determined at 25 and 37 °C.The characterization of the materials was accomplished by: ATR-FTIR (Attenuated Total Reflectance-Fourier Transform Infrared) spectroscopy, elemental analysis, lower critical solution temperature (LCST) determination, swelling behaviour evaluation, determination of surface energy by contact angle measurement and drug delivery profile studies.     

Biodegradable thermoresponsive hydrogels for aqueous encapsulation and controlled release of hydrophilic model drugs

A series of hydrogels with both thermoresponsive and completely biodegradable properties was developed for aqueous encapsulation and controlled release of hydrophilic drugs in response to temperature change. The hydrogels were prepared in phosphate-buffered saline (pH 7.4) through free radical polymerization of N-isopropylacrylamide (NIPAAm) monomer and a dextran macromer containing multiple hydrolytically degradable oligolactate-2-hydroxyethyl methacrylate units (Dex-lactateHEMA). Swelling measurement results demonstrated that four gels with feeding weight ratios of NIPAAm:Dex-lactateHEMA = 7:2, 6:3, 5:4, and 4:5 (w/w) were thermoresponsive by showing a lower critical solution temperature at approximately 32 degrees C. The swelling and degradation of the hydrogels strongly depended on temperature and hydrogel composition. An empirical mathematical model was established to describe the fast water absorption at the early stage and deswelling at the late stage of the hydrogels at 37 degrees C. Two hydrophilic model drugs, methylene blue and bovine serum albumin, were loaded into the hydrogels during the synthesis process. The molecular size of the drugs, the hydrophilicity and degradation of the hydrogels, and temperature played important roles in controlling the drug release.     

Binding of the bovine and porcine pancreatic secretory trypsin inhibitor (Kazal) to human leukocyte elastase: a thermodynamic study.

The effect of pH and temperature on the apparent association equilibrium constant (Ka) for the binding of the bovine and porcine pancreatic secretory trypsin inhibitor (Kazal-type inhibitor, PSTI) to human leukocyte elastase has been investigated. At pH 8.0, values of the apparent thermodynamic parameters for human leukocyte elastase: Kazal-type inhibitor complex formation are: bovine PSTI--Ka = 6.3 x 10(4) M-1, delta G degree = -26.9 kJ/mol, delta H degree = +11.7 kJ/mol, and delta S degree = +1.3 x 10(2) entropy units; porcine PSTI--Ka = 7.0 x 10(3) M-1, delta G degree = -21.5 kJ/mol, delta H degree = +13.0 kJ/mol, and delta S degree = +1.2 x 10(2) entropy units (values of Ka, delta G degree and delta S degree were obtained at 21.0 degrees C; values of delta H degree were temperature independent over the range (between 5.0 degrees C and 45.0 degrees C) explored). On increasing the pH from 4.5 to 9.5, values of Ka for bovine and porcine PSTI binding to human leukocyte elastase increase thus reflecting the acidic pK-shift of the His57 catalytic residue from congruent to 7.0, in the free enzyme, to congruent to 5.1, in the serine proteinase: inhibitor complexes. Thermodynamics of bovine and porcine PSTI binding to human leukocyte elastase has been analyzed in parallel with that of related serine (pro)enzyme/Kazal-type inhibitor systems. Considering the known molecular models, the observed binding behaviour of bovine and porcine PSTI to human leukocyte elastase was related to the inferred stereochemistry of the serine proteinase/inhibitor contact region(s).     

Unique gelation behavior of cellulose in NaOH/urea aqueous solution

A transparent cellulose solution was prepared by mixing 7 wt % NaOH with 12 wt % urea aqueous solution which was precooled to below -10 degrees C and which was able to rapidly dissolve cellulose at ambient temperature. The rheological properties and behavior of the gel-formed cellulose solution were investigated by using dynamic viscoelastic measurement. The effects of temperature, time, cellulose molecular weight, and concentrations on both the shear storage modulus (G') and the loss modulus (G") were analyzed. The cellulose solution having a viscosity-average molecular weight (M(eta)) of 11.4 x 10(4) had its sol-gel transition temperature decreased from 60.3 to 30.5 degrees C with an increase of its concentration from 3 to 5 wt %. The gelation temperature of a 4 wt % cellulose solution dropped from 59.4 to 30.5 degrees C as the M(eta) value was increased from 4.5 x 10(4) to 11.4 x 10(4). Interestingly, at either higher temperature (above 30 degrees C), or lower temperature (below -3 degrees C), or for longer gelation time, gels could form in the cellulose solutions. However, the cellulose solution remains a liquid state for a long time at the temperature range from 0 to 5 degrees C. For the first time, we revealed an irreversible gelation in the cellulose solution system. The gel having been formed did not dissolve even when cooled to the temperature of -10 degrees C, at which it was dissolved previously. Therefore, this indicates that either heating or cooling treatment could not break such stable gels. A high apparent activation energy (E(a)) of the cellulose solution below 0 degrees C was obtained and was used to explain the gel formation under the cooling process.     

Control of the chemical cross-linking of gelatin by a thermosensitive polymer: example of switchable reactivity

Chemical cross-linking of gelatin is achieved using a thermosensitive reactive copolymer based on N-isopropylacrylamide (NIPAM). The copolymer bears 5 mol % acrylic acid units which form amide bonds with the amino groups of gelatin in the presence of a water-soluble carbodiimide. The cross-linking reaction occurs only below the LCST congruent with 34 degrees C (lower critical solution temperature), i.e., when the copolymer is in the coil conformation. Above the LCST the copolymer adopts a globule conformation and its ability to react with gelatin is drastically reduced. By setting the temperature above or below the LCST it is possible to switch off or on the reactivity of the system and control the gelation process. The switch temperature can be set at the desired value by adjusting the composition of the thermosensitive copolymer.     

The rate constants of the reaction of hydroxyl radicals (*OH) with alcohol dehydrogenase and Glyceraldehyde-3-phosphate dehydrogenase

The rate constants of the reactions of alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase with hydroxyl radicals were determined using the method of steady-state competitive reactions. Ethanol was used as a scavenger of hydroxyl radicals. The rate constants of the reactions of hydroxyl radicals with alcohol dehydrogenase and glyceraldehyde-3-phosphate dehydrogenase were found to be 2.8 x 10(12) dm(3) mol(-1) s(-1), and 1.6 x 10(12) dm(3) mol(-1) s(-1), respectively.