Hydrophilic Prepolymer Research Articles

Preparation and characterization of amphiphilic, biodegradable, waterborne polyurethanes without using organic solvent and catalyst.

Traditionally, waterborne polyurethanes (WPUs) are prepared using toxic organic solvents and catalysts. These WPUs are non-biodegradable and are buried or incinerated after the expiration date. This has adverse effects on the environment and human health, which limits the applications of WPUs. Herein, a special synthetic method was developed for biodegradable waterborne polyurethane (BWPU) by adding hydrophilic prepolymers into WPU prepolymers without using organic solvents and catalysts. Different proportions of polyethylene glycol (PEG) were introduced into polycaprolactone (PCL)-based BWPUs to improve the comprehensive properties. Results showed that as the PEG content was increased from 0 to 16 wt%, the solid content of BWPU increased from 34.8 wt% to 53.1 wt%, while the tensile strength and Young's modulus of BWPU films increased from 21.81 MPa to 56.83 MPa and 8.08 MPa to 19.4 MPa, respectively. However, the elongation at break did not decrease significantly, but still reached 827.17%. With an increase in PEG content, the crystallinity and phase separation decreased, while the hydrophilicity and surface energy increased for BWPU films. In addition, the prepared BWPUs had good biodegradability in PBS/lipase solution. The mass loss of BWPU without PEG reached 6.3 wt% after 4 weeks of degradation, whereas the mass losses of BWPUs with PEG reached 2.3-4.3 wt%. Obviously, the introduction of PEG did not increase biodegradability. Thus, the higher the PCL content, the faster the biodegradation rate. This work would provide an effective method for the preparation of ecofriendly biodegradable BWPU with excellent comprehensive properties.

Thermoresponsive DNA hydrogels through hydrophilic pre-polymer cross-linker and self-assembly

Denatured DNA molecules were used as building blocks to fabricate thermoresponsive hydrogels by cross-linking DNA strands with an isocyanate (NCO) end-capped star-shaped poly(EO-stat-PO) cross-linker. The NCO groups reacted with the amine groups of DNA’s bases through urea links while base pairing between the matching strands of DNA led to the self-assembly of DNA into a three-dimensional hydrogel network. Analysis of the ultrastructure by scanning force microscopy (SFM) revealed the temperature-mediated transition from the rod-to-coil structure as a result of the destabilization of double-stranded DNA (dsDNA) to form a single-stranded DNA (ssDNA), which eventually resulted in a DNA network due to base pairing, along with hairpin loops due to mismatches between nucleotides. Dynamic oscillatory and large deformation creep tests, as well as stress relaxation tests, revealed the formation of robust cross-linked gels: A ten-fold rise in the elastic modulus was observed for the covalent DNA gel compared to the physical gel at the identical DNA concentration. The thermoresponsiveness of the hydrogels was confirmed by a heating–cooling cycle while the non-porous internal morphology of the hydrogel was demonstrated through scanning electron microscopic analysis. Overall, this is the first study showing the fabrication of covalent DNA hydrogels using an NCO-end-capped hydrophilic prepolymer. Such gels have a high potential to be exploited in many fields to benefit from the structural properties of DNA molecules.

Development of bio-inspired multi-functional polymeric-based fibers (BioFiber) for advanced delivery of bacterial-based self-healing agent in concrete

The goal of this research is to develop innovative damage-responsive bacterial-based self-healing fibers (hereafter called BioFiber) that can be incorporated into concrete to enable two functionalities simultaneously: (1) crack bridging functionality to control crack growth and (2) crack healing functionality when a crack occurs. The BioFiber is comprised of a load-bearing core fiber, a sheath of bacteria-laden hydrogel, and an outer impermeable strain-responsive shell coating. An instant soaking manufacturing process was used with multiple reservoirs containing bacteria-laden, hydrophilic prepolymer and crosslinking reagents to develop BioFiber. Sodium-alginate was used as a prepolymer to produce calcium-alginate hydrogel via ionic crosslinking on the core fiber. The dormant bacteria (spore) of Lysinibacillus sphaericus was incorporated in hydrogel as a self-healing agent. Then, an impermeable polymeric coating was applied to the hydrogel-coated core fibers. The impermeable strain-responsive shell coating material was manufactured using the polymer blend of polystyrene and polylactic acid. The high swelling capacity of calcium-alginate provides the water required for the microbially induced calcium carbonate precipitation (MICP) chemical pathway, i.e., ureolysis in this study. The strain-responsive impermeable coating provides adequate flexibility during concrete casting to protect the spores and alginate before cracking and sufficient stress-strain behavior to grant damage-responsiveness upon crack occurrence to activate MICP. To evaluate the behavior of developed BioFiber, the swelling capacity of the hydrogel, the impermeability of shell coating, the spore casting survivability, and MICP activities were investigated.

Star-shaped polyester-based elastomers as an implantable delivery system for insulin: Development, pharmacokinetics, pharmacodynamics, and biocompatibility

Elastomers are largely developed for biomedical applications; however, little is reported on them although they are an effective and controllable delivery system for proteins. In the present study, we investigated the pharmacokinetics, biosecurity, and hypoglycemic effect of an insulin-loaded elastomer formulation in diabetic rats. Cylindrical insulin-loaded elastomers were fabricated using a UV cross-linking process based on methyl-acrylic-star-poly(ε-caprolactone-co-D,L-lactide) cyclic ester and methyl-bi-acrylic-poly(ε-caprolactone-b-polyethylene glycol-b-ε-caprolactone) (CLPEGCLMA). The encapsulated insulin was well protected during the formulation. An in vitro pharmacokinetic study revealed that the rate of insulin release from the elastomers was affected by the hydrophilicity/hydrophobicity of the system and controlled by the CLPEGCLMA (hydrophilic prepolymer) composition. It was observed that insulin release followed the Higuchi model. In addition, the more hydrophilic elastomers showed higher degradation rates in vivo. Furthermore, in the pharmacodynamic study, all the elastomers, except those that contained star-poly(ε-caprolactone-co-D,L-lactide) (number-average molecular weight, Mn), polyethylene glycol (PEG) (kMn), ε-caprolactone/PEG (mol/mol), and CLPEGCLMA (weight, %) at a ratio of 3432:10:20:30, respectively, decreased blood glucose concentration and maintained it at a stable level. It was observed that the hypoglycemic effect of the drug-loaded elastomers was directly proportional to the rate of in vitro insulin release; however, emaciation was not observed. Moreover, elastomers play a positive role in biosecurity. Therefore, the elastomers might be effective carriers for the delivery of peptide drugs in the form of implants.

Poly(arylene ether sulfone) multi-block copolymers bearing perfluoroalkylsulfonic acid groups

Poly(arylene ether sulfone) (PAES) multi-block copolymers bearing perfluoroalkylsulfonic acid moieties were prepared from hydrophilic and hydrophobic prepolymers. The latter were synthesized by reaction of N, N-diisopropylethylammonium 2,2-bis( p-hydroxyphenyl)pentafluoropropanesulfonate (HPPS) with bis-(4-fluorophenyl) sulfone (FPS), and biphenol (BP) with FPS, respectively. Prepolymers and multi-block copolymers were prepared at 180 °C in N, N-dimethylacetamide in the presence of K 2CO 3. The prepolymers were reacted overnight; the multi-block copolymers were reacted only 80 min to minimize transetherification. Prepolymers and multi-block copolymers were characterized using 1H and 13C NMR. 19F NMR provided molecular weight of hydrophilic prepolymers bearing aryl fluoride end groups. GPC was used to characterize the multi-block copolymers. Copolymer block lengths were determined by quantifying 13C NMR peak areas of quaternary carbon atoms adjacent to sulfur in FPS moieties. Hydrophilic and hydrophobic block lengths were in the range 9.4–23.4 and 4.4–11.8 repeating units, respectively. AFM showed phase separation for all block lengths. Conductivity at 80 °C and 100% relative humidity ranged from 6.2 to 34.3 mS/cm, with the best value obtained for hydrophilic/hydrophobic block lengths of 13.3/6.0.

Tailored hyaluronic acid hydrogels through hydrophilic prepolymer cross-linkers

Despite its enormous biological importance, a lack of mechanical stability and fast degradability often hampers more intense application of hyaluronic acid (HA) for biomedical applications. We present a method to prepare hyaluronic acid based hydrogels with tailored stability, degradability and porosity by cross-linking with functional 18 kDa six arm star shaped poly(ethylene oxide-stat-propylene oxide) (sP(EO-stat-PO)) prepoylmers in aqueous solutions. In the case of NCO groups at the distal ends of the arms, cross-linking occurs through reaction with OH groups of the HA resulting in urethane bridges between star molecules and HA. In parallel, slow hydrolysis of isocyanates to amines that subsequently rapidly aminolyze other isocyanate groups and lead to urea bridges between prepolymers occurs as a side reaction. Overall, this process leads to cross-linking within 5 to 15 min depending on the molar ratios of NCO-sP(EO-stat-PO) to HA. A chemically orthogonal way of cross-linking can be achieved with acrylate functional prepolymers and thiolated HA where cross-linking exclusively results from Michael-type addition of the thiol to the acrylate groups. This process also results in gelation times of 5 to 15 min. The two mechanisms are compared and the resulting gels are analyzed regarding chemical composition, equilibrium water content, degree of sol-content, porosity, mechanical stability and resistance towards enzymatic degradation by hyaluronidase.

Self-positioning microlens arrays prepared using ink-jet printing

We have employed ink-jet printing (IJP) technology to fabricate self-positioning microlens arrays (MLAs). The glass substrates were first prepatterned through microcontact printing (µCP) hydrophobic self-assembled monolayers (SAMs) to divide the surface into hydrophobic and hydrophilic regions. After IJP of the hydrophilic prepolymer liquids, the lenses were effectively repelled by the patterned SAMs. We obtained high-quality MLAs having diameters of 75 and 100 µm after polymerization of the prepolymers. The lenses' shapes could be controlled by varying the number of printed droplets.

Fabrication of hydrogel microstructures using polymerization controlled by microcontact printing (PCμCP)

Hydrogels are widely applied as functional biomaterials in the diagnostic and therapeutic fields. For example, intelligent hydrogels containing ionic groups (pH responsive) and poly(ethylene glycol) have promising applications as pH responsive materials in the biomedical and pharmaceutical fields. For potential use of hydrogels in micro- and nano devices, methods are needed to fabricate structures of various geometries at the micro- and nano scale. In this work, polymerization controlled by microcontact printing (PCmicroCP) is utilized, which is a method that uses microcontact printing to spatially define polymerization zones. Specifically, gold surfaces were modified by a hydrophobic thiol self assembled monolayer via microcontact printing and then a hydrophilic prepolymer solution was applied and only spatially occupied the regions confined by the hydrophobic thiol. Subsequently, polymerization reactions were carried out to create hydrogel microstructures. The patterned hydrogel produced using these methods are highly uniform in size and shape, having potential application in the field of biomedical microdevices.

Entrapment of microbial cells within polyurethane hydrogel beads with the advantage of low toxicity

A new method is described for the entrapment of microbial cells in polyurethane (PUR) hydrogel beads. This hydrogel is produced from a hydrophilic pre-polymer blocked with bisulphite by adjusting the pH between 4 and 6.5. Bisulphite-blocked isocyanate has a substantially lower toxicity against living cells than unblocked (conventional) isocyanates. The poly(carbamoylsulfonate) (PCS) hydrogels have optimal elastic properties and therefore can be used for a matrix of biocatalysts in an agitated reactor as well as in a fluid-bed reactor. The results of ethanol fermentation ofSaccharomyces cerevisiae entrapped in PCS hydrogel beads, and of the denitrification activity of immobilizedParacoccus denitrificans are promising. In contrast, entrapped cells in conventional PUR hydrogels didn’t show any activity.

Immobilization of amyloglucosidase using two forms of polyurethane polymer

Amyloglucosidase was covalently immobilized using two hydrophilic prepolymers: Hypol FHP 2002 (creates foams) and Hypol FHP 8190H (creates gels). The foamable prepolymer was superior as a support for enzyme immobilization. The percent activity immobilized in the polyurethane foams was 25 +/- 1.5%. Large substrates (greater than 200,000 daltons in mol wt) were hydrolyzed as effectively as smaller ones by the immobilized enzyme. The Km value of the foam-immobilized enzyme increased from 0.76 mg/mL (free) to 0.86 mg/mL (immobilized), whereas the Vmax dropped from 90.9 (free) to 12.4 nmol glucose/min/mL (immobilized). The long-term (2 mo) storage stability of amyloglucosidase was enhanced by immobilization in foams (70% activity retained; free enzyme only retained 50%). Immobilization also improved the enzyme stability to various denaturing agents (sodium chloride, urea, and ethanol). The immobilized enzyme exhibited increased stability compared to the free enzyme at high temperatures (95 degrees C). Both glycogen and starch could be utilized by the immobilized enzyme, indicating that this technique could prove useful for starch hydrolysis.

Establishment of a neovascular bed in a collagen-impregnated polyurethane sponge.

A technique for promoting vascularization of a polyurethane sponge is demonstrated in the present study. Collagen-impregnated polyurethane sponges (Hypol, 2002) Foamable Hydrophilic Prepolymer (FHP) were implanted in the femoral fossa of rats for 1 day to 6 weeks. The ligated femoral artery/vein was pulled through the sponges to facilitate more complete neovascularization. Light-microscopic evaluation of the implanted sponges revealed that significant vascularization had occurred by the seventh day of implantation, and was maximal by the fourth to sixth week. Sponges containing collagen had a more thorough vascularization process than sponges without collagen, perhaps due to a more uniform pore size as demonstrated by scanning EM. Time course studies suggested that the artery/vein pull-through enhanced the development of the neovascularization process in the center of the sponges. We conclude that significant vascular tissue in-growth can be developed in polyurethane sponges and that both collagen and centrally placed blood vessels help promote the vascularization process. Potential applications could extend to a variety of bioartificial systems including endocrine or hepatic transplantation, soft-tissue prosthetic materials, bone grafts, or drug delivery systems. Further studies would be useful in providing additional information on the factors promoting neovascularization, and on the potential applications of this methodology using the present or similar biomaterials.

Continuous production of oxytetracycline by immobilized growing Streptomyces rimosus cells

Streptomyces rimosus cells were immobilized with urethane prepolymers and used in the production of oxytetracycline. Based on the criteria for oxytetracycline productivity, cell growth in gels, cell leakage from gels and mechanical strength of gel, a hydrophilic prepolymer, PU-1, the main chain of which was polyethylene glycol (molecular weight, approximately 1500) was employed as gel material among 11 kinds of urethane prepolymers. Use of glucose-free medium for cultivation of PU-1-entrapped cells increased the production rate of oxytetracycline and minimized cell leakage from the gels. When the gel-entrapped cells lost activity, treatment of the cell-entrapping gels with saline or 70% ethanol resulted in recovery of the oxytetracycline productivity. Continuous oxytetracycline fermentation using PU-1-entrapped growing cells was successfully achieved in air-bubbled reactor for at least 35 days with reactivation of the cells.

Application of photo-crosslinkable resin prepolymers to entrap microbial cells. Effects of increased cell-entrapping gel hydrophobicity on the hydrocortisone ?1-Dehydrogenation

Acetone-dried cells of Arthrobacter simplex, whose steroid Δ1 activity had been previously induced, were entrapped by the use of photo-crosslinkable resin prepolymers. When the hydrophobicity of the cell-entrapping gel was increased by mixing a hydrophobic prepolymer (main chain component; polypropyleneglycol) with a hydrophilic prepolymer (main chain component; polypropyleneglycol) with a hydrophilic prepolymer (main chain component; polyethyleneglycol) (up to 30%), the hydrocortisone to prednisolone conversion rate of the immobilized cells increased significantly, attaining approximately 20% of that of the free cells. A 10% addition of organic solvents, such as methanol, to the aqueous reaction mixture enhanced the solubility of the substrate greatly and to a lesser degree the reaction rate of the immobilized cells. The presence of an electron acceptor, phenazine methosulfate or 2,6-dichlorophenolindophenol, stimulated the steroid conversion of the entrapped as well as the free cells. The stability of the entrapped cells over repeated reactions was improved by immobilization.