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PubMed2006

Hybrids of colloidal silica and waterborne polyurethane.

Waterborne polyurethane (WPU) was synthesized and followed by adding colloidal silica to prepare WPU-silica hybrids. The silica content in the hybrid thin films was varied from 0 to 50 wt%. The experimental results revealed that the viscosity of these hybrid solutions increased with increasing silica content and resulted in the aggregation of silica particle in the hybrid films. The latter result was evidenced by SEM examination. The effect of interaction between silica particle and urethane polymer chains is more significant with increasing silica content. The prepared hybrid films show much better thermal stability and mechanical properties than pure WPU. The optical transparence did not linearly decrease with increasing the silica fraction in the hybrid thin film. At below 20% silica content, the film transparence decreased with increasing silica content; the converse is true at above 20% silica content. These results showed that the prepared hybrid films demonstrated tunable transparence with the silica fraction in the films.

Journal Article↗

PubMed2006

A comparison of the properties of polyurethane immobilised Sphagnum moss, seaweed, sunflower waste and maize for the biosorption of Cu, Pb, Zn and Ni in continuous flow packed columns.

The biosorption of Cu, Pb, Zn and Ni from a mixed solution of the metals was investigated in continuous flow packed columns containing polyurethane immobilised biomass. The characteristics and biosorption properties of Sphagnum moss, the brown seaweed Ascophyllum nodosum, waste biomass from the preparation of sunflower oil, and whole plant maize were compared. All the biomass types showed a preference for the sequestration of Pb followed by Cu, with Ni and Zn having roughly equal affinity. With continuous metal loading to the column there was an initial binding of all metals and then a displacement of the lower affinity metals by those with a high affinity. This led to a chromatographic effect in the column with breakthrough concentrations for low-affinity metals higher than the concentration in the feed. A similar phenomenon was found on desorption using acidic solutions where low-affinity metals were desorbed preferentially. The results also indicated that despite competitive displacement of one metal species by another the biomass appeared to succeed in retaining some low-affinity metal species indicating that there may be selective sites present with different affinity characteristics. When using a multi-metal solution with Cu, Pb, Zn and Ni at equal 10 mgl(-1) concentrations as column influent, the total quantities of metal sequestered were: seaweed, 117.3 mg g(-1); sunflower waste, 33.2 mg g(-1); Sphagnum moss, 32.5 mg g(-1); and maize, 2.3 mg g(-1). The use of an acid base potentiometric titration showed a relationship between the number of acid functional groups and biosorption capacity, although this was not proportional for the biomass types studied. It can, however, be used in conjunction with a simple classification of metals into high and low-affinity bands to make a preliminary assessment of a biosorption system.

Adsorption↗

PubMed2003

Properties of amphoteric polyurethane waterborne dispersions. II. Macromolecular self-assembly behavior.

Amphoteric polyurethane (APU) samples used in this paper were composed of hydrophobic soft segments and pendent -COOH and -CH(2)N(CH(3))(2) groups on the hard segments, which present the properties of both amphoteric polyelectrolytes and amphiphilic block copolymers. APU macromolecules can self-assemble into micelles in acidic and basic aqueous media by hydrophobic/hydrophilic interaction. The self-assembly behavior of APU in acidic and basic media was studied by transmission electron microscopy and light scattering methods. The spherical and hollow micelles of APU were observed respectively in acidic and basic aqueous media. The results indicate that the size and size distribution of APU self-assembly micelles largely depend on the ratio of -COOH to -CH(2)N(CH(3))(2) groups, density of ionizable groups, concentration of APU, and types of acid and base in the media.

Journal Article↗

PubMed2001

Calcite precipitation induced by polyurethane-immobilized Bacillus pasteurii.

Polyurethane (PU) foam was used to immobilize the whole cell of Bacillus pasteurii. The immobilized cells exhibited the rates of calcite precipitation and ammonia production as high as those of the free cells. Scanning electron micrographs identified the cells embedded in calcite crystals throughout PU matrices. Calcite in PU showed little effect on the elastic modulus and tensile strength of the polymer, but increased the compressive strengths of concrete cubes, whose cracks were remediated with PU-immobilized cells. These observations led us to believe that the calcite might remain as a form of precipitation, not as a bonding material within the matrices.

Journal Article↗

PubMed2000

Morphology of and release behavior from porous polyurethane microspheres.

A novel biomaterial application of porous microspheres is for sustained delivery of biologically active agents. Recent studies have pointed out the importance of biomaterial porosity in promoting biocompatibility and controlling release rate of active agents. The objective of this research was to investigate the effect of chain-extending agent on the porosity and release behavior of polyurethane (PU) microspheres prepared using a two-step suspension polycondensation method with methylene diphenyl diisocyanate (MDI) as the isocyanate, polyethylene glycol (PEG400) as the diol, and 1,4-butanediol as the chain-extending agent. Chain-extending agent was used to increase the ratio of hard to soft segments of the PU network, and its effect on microsphere morphology was studied with scanning electron microscopy. According to the results, porosity was significantly affected by the amount of chain-extending agent. The pore size decreased as the concentration of chain-extending agent increased from zero to 50 mole%. With further increase of chain-extending agent to 60 and 67%, PU chains became stiffer and formation of pores was inhibited. Therefore, pore morphology was significantly affected by variations in the amount of chain-extending agent. The release behavior of microspheres was investigated with diazinon as the active agent. After an initial burst, corresponding to 3% of the incorporated amount of active agent, the release rate was zero order.

Drug Carriers↗

PubMed2001

Coating of Dacron vascular grafts with an ionic polyurethane: a novel sealant with protein binding properties.

The purpose of this study was to develop a novel sealant that would seal prosthetic vascular graft interstices and be accessible for protein binding. Crimped knitted Dacron vascular grafts were cleaned (CNTRL) and hydrolyzed in boiling sodium hydroxide (HYD). These HYD grafts were sealed using an 11% solids solution of a polyether-based urethane with carboxylic acid groups (PEU-D) via a novel technique that employs both trans-wall and luminal perfusion. Carboxylic acid content, determined via methylene blue dye uptake, was 2.3- and 4.2-fold greater in PEU-D segments (1.0+/-0.27 nmol/mg) as compared to HYD and CNTRL segments, respectively. Water permeation through PEU-D graft (1.1+/-2 ml/cm2 min(-1)) was comparable to collagen-impregnated Dacron (9.8+/-10 ml/cm2 min(-1)). Non-specific 125I-albumin (125I-Alb) binding to PEU-D segments (18+/-3 ng/mg) was significantly lower than HYD and CNTRL segments. 125I-Alb linkage to PEU-D using the crosslinker EDC resulted in 5.7-fold greater binding (103+/-2 ng/mg) than non-specific PEU-D controls. However, covalent linkage of 125I-Alb to PEU-D was 4.9- and 5.9-fold less than CNTRL and HYD segments with EDC, respectively. Thus, ionic polyurethane can be applied to a pre-formed vascular graft, seal the interstices and create "anchor" sites for protein attachment.

Biocompatible Materials↗

PubMed1997

Vasoactive intestinal peptide supports induced migration of human keratinocytes and their colonization of an artificial polyurethane matrix.

We investigated the effect of the neuropeptides vasoactive intestinal peptide (VIP), (D-Phe2)-VIP, (Lys-Pro-Arg-Tyr)-VIP and the VIP fragment (1-12) on induced migration and colonization in vitro. In confluent keratinocyte cultures "wounded" with a razor blade, the VIP-treated samples disclosed a more rapid migration from the wound margins into the wound bed, starting within the first 4 h. Almost 80% of the wounded area was covered within 24 h. In contrast, VIP-derivatives were not significantly different from controls, covering 10 to 18% of the wounded area (p < 0.02). Colonization has been assessed with an artificial non-toxic polyurethane matrix. In controls, we were able to observe migration of keratinocytes on the matrix within the first 24 h. The cells, however, were not able to migrate further and to survive. After 48 h, VIP-treated cultures showed a complete colonization of the matrix by keratinocytes vs. less than 10% of the total area in controls (p < 0.001). The induction of migration and of colonization was VIP-dose-dependent. The data indicate that induced migration is stimulated by VIP, when the N-terminal ending is intact, but loss of the C-terminus abrogates both migration and colonization. Our investigations have implications for wound healing but also for bioengineering of skin.

Cell Movement↗

PubMed2003

Effect of amphiphilic polyurethane nanoparticles on sorption-desorption of phenanthrene in aquifer material.

Micelle-like amphiphilic nano-sized polyurethane (APU) nanoparticles were synthesized via chemical cross-linking reaction of nano-aggregates of urethane acrylate nonionomer (UAN) chain and were tested for extraction efficiency of sorbed phenanthrene from aquifer material. Even though the solubilizing performance and interfacial activity of APU nanoparticles were inferior to that of Triton X-100, in the low concentration region, APU nanoparticles could effectively reduce phenanthrene sorption on the aquifer material and extracted sorbed phenanthrene from the aquifer material, whereas Triton X-100 could not extract sorbed phenanthrene and rather increased phenanthrene sorption onto the aquifer materials. At higher concentrations, APU nanoparticles and Triton X-100 had almost the same soil washing effectiveness. This interesting result is mainly due to a lower degree of sorption of APU nanoparticles onto the aquifer material. The sorption of APU nanoparticles onto aquifer sand is largely hindered by their chemically cross-linked nature, resulting in better soil-washing performance of APU nanoparticles than Triton X-100.

Adsorption↗

PubMed2000

Proliferation of endothelial cells on the plasma-treated segmented-polyurethane surface: attempt of construction of a small caliber hybrid vascular graft and antithrombogenicity.

To prepare a porous segmented-polyurethane (SPU) tube, a solution of SPU containing different concentrations of NaCl was coated on a glass rod and the coated SPU was immediately immersed in water. When the surface of the porous SPU, where bovine aortic endothelial cells are not normally capable of adhering and proliferating, was modified by plasma treatment, the proliferation of endothelial cells could be drastically improved. The cells proliferated confluently on the porous SPU surface prepared at low concentrations of NaCl below 10 g per 100 ml, but poorly on the porous surface prepared at high concentrations of NaCl. The construction of a hybrid vascular graft consisting of a porous SPU tube (2 mm in inner diameter, 5 cm in length) and endothelial cells was attempted. The cells cultured on the inner surface of the tube proliferated to confluency everywhere. From an in vitro antithrombogenic evaluation test, which involved the use of human blood, the present hybrid graft can be considered to provide an inert surface against thrombus formation and blood coagulation. Negligible changes in shape of human leukocytes in contact with bovine aortic endothelial cell surface occurred, suggesting that the bovine aortic endothelial cells used are immunologically less active against human blood.

Journal Article↗

PubMed1999

Purification and properties of culture-broth-secreted esterase from the polyurethane degrader Comamonas acidovorans TB-35.

The polyester-polyurethane (PUR)-degrading bacterium Comamonas acidovorans TB-35 produces two kinds of esterases, one cell-bound esterase (PUR esterase) and the other secreted in the culture broth (CBS esterase). In this study, the CBS esterase and the two recombinant esterases were purified. Identification of the physical and biochemical properties of the CBS and PUR esterases revealed that they have the same polypeptide from one gene. This finding was supported by the observation that Escherichia coli harboring the PUR esterase gene also produced two kinds of esterases. Though the PUR esterase degraded PUR and poly(diethylene glycol adipate), the soft segment of the PUR, the CBS esterase degraded only poly(diethylene glycol adipate). Furthermore, the hydrophobicity of the CBS esterase was lower than that of the PUR esterase. As the PUR esterase has been previously indicated to possess a PUR-binding domain, it was assumed that structural change around the PUR-binding domain of the CBS esterase was responsible for its inability to degrade PUR.

Journal Article↗

PubMed1999

Lignin-degrading enzyme production by Bjerkandera adusta immobilized on polyurethane foam.

Production of the lignin-degrading enzymes lignin peroxidase (Lip), manganese peroxidase (MnP), and laccase (Lac) by the white-rot fungus Bjerkandera adusta was investigated experimentally using polyurethane foam (PUF) as a carrier of immobilized fungal mycelia. An immobilized cell culture with a low-nitrogen medium yielded significantly greater LiP, MnP, and Lac activities in comparison with those obtained in a liquid culture. The maximum activities of the three enzymes were 450, 370, and 100 U/ml, respectively, under the following incubation condition: glucose concentration, 20 g/l; temperature, 30 degrees C; pH 4.5. The activities of MnP and Lac were significantly higher than those reported using other incubation methods. Lignin was degraded to the extent of 40% and its decolorization ratio was about 70% at an incubation time of 40 h using lignin-degrading enzymes from B. adusta. Six different isozymes of MnP were synthesized by B. adusta, two of which exhibited high MnP activity. Our preliminary finding that extracellular enzymes from B. adusta are capable of degrading and decoloring lignin makes these enzymes attractive for further research aimed at their large-scale application in lignin depolymerization, pulp biobleaching, and the degradation of toxic pollutants.

Journal Article↗

PubMed2003

Sum frequency generation studies on the surface structures of plasticized and unplasticized polyurethane in air and in water.

This study characterizes the molecular surface structures of polyurethane (PU) and plasticized PU films in air, in water, and in albumin solution in situ using a nonlinear optical technique, sum frequency generation (SFG) vibrational spectroscopy. Two different plasticizers are investigated: dioctyl sebacate (DOS) and o-nitrophenyl octyl ether (NPOE). Plasticization of PU is common for biosensors to achieve better adhesion, malleability, elasticity, and permeability; however, this can adversely affect biocompatibility. Our research indicates that plasticizers can segregate to the PU surface not only in air but also in water. In addition, plasticizer content can affect protein adsorption behaviors of PU surfaces. This is the first time surface-sensitive SFG has been applied to deduce plasticizer surface behavior in situ. More specifically, we found that DOS dominates the surface of the film with DOS surface concentrations higher than DOS bulk concentrations both in air and in contact with an aqueous environment. NPOE has a reduced effect at the surface compared to DOS in both air and aqueous environments. Addition of either DOS or NPOE to PU was also found to cause a change in albumin adsorption.

Journal Article↗

PubMed2002

Synthesis and characterization of an isocyanate functionalized polyhedral oligosilsesquioxane and the subsequent formation of an organic-inorganic hybrid polyurethane.

Organic-inorganic hybrids are an important class of new materials that offer improved thermal and mechanical properties over normal polymers. They may be produced by either the sol-gel route or through the use of inorganic compounds possessing reactive functional groups. Polyhedral oligosilsesquioxanes (POSS) are completely defined molecules of nanoscale dimensions that may be functionalized with reactive groups suitable for the synthesis of new organic-inorganic hybrids. Here we report the synthesis and characterization of a novel POSS possessing eight isocyanate groups via the hydrosilylation of octakis(hydridodimethylsiloxy)octasilsesquioxane (Q8M8H) and m-isopropenyl-alpha,alpha'-dimethylbenzyl isocyanate (m-TMI). The suitability of this new macromer to the synthesis of a organic-hybrids has been explored by forming a new type of highly cross-linked polyurethane elastomer via reaction of the macromer with poly(ethylene glycol) using dibutyltin dilaurate catalyst.

Journal Article↗

PubMed2003

[60]Fullerene-containing polyurethane films with large ultrafast nonresonant third-order nonlinearity at telecommunication wavelengths.

A significantly enhanced, ultrafast third-order optical nonlinearity at the wavelengths of 1150-1600 nm was demonstrated with cross-linked C60-containing polyurethane films using the Z-scan technique. Good-quality polymer films with a high loading of C60 derivative were obtained by cross-linking of the hydroxyl-containing C60 derivative and a triisocyanate. The positive Kerr coefficient with nonresonant nonlinear refractive index n2 falls in the range of (3.7 +/- 0.80) x 10-4 to (2.0 +/- 0.6) x 10-3 cm2/GW, and the calculated chi(3) and gamma values are up to 9.7 x 10-11 and 9.6 x 10-32 esu at 1550 nm, which are several orders of enhancement in third-order optical nonlinearity over pristine C60 in solution and 1-2 orders of enhancement over recently reported C60 derivatives and conjugated polymers.

Journal Article↗

PubMed2007

From controllable attached isolation moieties to possibly highly efficient nonlinear optical main-chain polyurethanes containing indole-based chromophores.

For the first time, the indole-based NLO chromophores were embedded into the polymer main chain, and different isolation groups were attached to their donor side with the efforts of adjusting the NLO properties of the resultant main-chain polyurethanes, according to the site isolation principle. Thanks to the main-chain structure and the advantages of the indole-based chromophores, all the polymers show excellent transparency, good processability, thermal stability, and relatively good NLO effects. The tested NLO properties of the polymers demonstrate that there is a suitable isolation group present for the sulfonyl-based chromophore to boost its microscopic beta value to a possibly higher macroscopic NLO property efficiently.

Journal Article↗

PubMed2005

Film formation from aqueous polyurethane dispersions of reactive hydrophobic and hydrophilic components; spectroscopic studies and Monte Carlo simulations.

Film formation of waterborne two-component polyurethanes is exceedingly complex due to the heterogeneous nature along with simultaneous progression of several parallel physicochemical processes which include water evaporation, cross-linking reactions, phase separation, and droplet coalescence, to name a few. While internal reflection infrared imaging (IRIRI) spectroscopy clearly facilitates analysis of chemical changes resulting from film formation, the complexity of processes leading to formation of specific surface/interfacial entities is a major experimental challenge. For this reason, we combined a spectrum of surface/interfacial analytical approaches including IRIRI, atomic force microscopy, and attenuated total reflectance Fourier transform infrared spectroscopy with Monte Carlo computer simulations to advance the limited knowledge of how temperature, stoichiometry, concentration levels, and reactivities of individual components affect the development of surface morphologies and compositional gradients across the film thickness. These studies show that in heterogeneous systems having both hydrophobic and hydrophilic components stratification of individual components to the film-air (F-A) interface is ultimately responsible for formation of rough surface topographies. These studies show that simultaneous stratification of hydrophobic components along with water evaporation to the F-A interface results in metastable interfacial layers, leading to surface dewetting. Subsequently, surface roughness is enhanced by higher concentrations of water in the cross-linking film.

Journal Article↗

PubMed2006

Luminescence techniques and characterization of the morphology of polymer latices. 3. An investigation of the microenvironments within stabilized aqueous latex dispersions of poly(n-butyl methacrylate) and polyurethane.

Fluorescence techniques (including time-resolved anisotropy measurements, TRAMS) have been used to probe differences in morphology between two stabilized aqueous latex dispersions (poly(n-butyl methacrylate), PBMA, and polyurethane, PU). Use of the emission characteristics of probes such as pyrene and phenanthrene dispersed within particles reveals that the PU latices are more heterogeneous in nature: evidence exists, particularly from quenching measurements and TRAMS, that voids and channels of water permeate the PU structure, resulting in a relatively soft, open particle, swollen by ingress of the bulk aqueous phase. Fluorescence measurements indicate that PBMA colloids, however, are composed of relatively hard, hydrophobic particles. In addition, TRAMS are considered to be a valuable tool both for probing the morphological characteristics of such dispersions and in estimating the average particle size.

Journal Article↗

PubMed2007

Synthesis of nanocrystal-polymer transparent hybrids via polyurethane matrix grafted onto functionalized CdS nanocrystals.

We reported the first synthesis of CdS nanocrystal-polymer transparent hybrids by using polyurethane (PU) grafted onto quantum dots (QDs) CdS nanocrystals. In a typical run, the appropriate amounts of cadmium chloride (CdCl2) and sodium sulfide (Na2S) in the presence of 2-mercaptoethanol (ME) as the organic ligand are well dispersed in H2O/DMF solution without any aggregation. From a combination of transmission electron microscopy (TEM) and a computing method of Brus's model according to UV-vis absorption spectra, the particle size of as-prepared hydroxyl-coated CdS nanocrystals is about 5 nm. Then, PU-CdS transparent nanocomposites hybrids were synthesized by a two-step reaction. The effect of the different ratios of ME/Cd2+ and H2O/DMF on the resulting particle size of CdS nanocrystals was investigated by UV-vis absorption measurements. FT-IR and TGA characterizations indicate the formation of robust bonding between CdS nanocrystals and the organic ligand. The fluorescence measurement shows that CdS-PU hybrids exhibit good optical properties.

Journal Article↗