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Surface modification of cellulose fibers: towards wood composites by biomimetics.

A biomimetic approach was taken for studying the adsorption of a model copolymer (pullulan abietate, DS 0.027), representing the lignin-carbohydrate complex, to a model surface for cellulose fibers (Langmuir-Blodgett thin films of regenerated cellulose). Adsorption results were assayed using surface plasmon resonance spectroscopy (SPR) and atomic force microscopy (AFM). Rapid, spontaneous, and desorption-resistant surface modification resulted. This effort is viewed as a critical first step towards the permanent surface modification of cellulose fibers with a layer of molecules amenable to either enzymatic crosslinking for improved wood composites or thermoplastic consolidation.

Biomimetics↗

Reduction of 2,4-dichlorophenol toxicity to Pseudomonas putida after oxidative incubation with humic substances and a biomimetic catalyst.

The effect of a synthetic iron(III)-porphyrin meso-tetra(2,6-dichloro-3-sulfonatophenyl)porphyrinate as a biomimetic catalyst in the oxidative treatment of 2,4-dichlorophenol (2,4-DCP) with humic substances and H(2)O(2) was evaluated in factorial design experiments conducted at different concentrations of 2,4-DCP (0-25 ppm) and different incubation treatment times (0, 24, 96, or 120 h). In the absence of this treatment, bioassays with the bacterium Pseudomonas putida (ATCC11250) showed decreasing specific growth rates mu (used here to quantify 2,4-DCP toxicity) with increasing concentrations of 2,4-DCP. However, when 2,4-DCP was treated as mentioned above the toxicity of the resulting 2,4-DCP solution was reduced significantly. At low 2,4-DCP concentrations (up to 5 ppm) and long incubation periods (as long as 120 h), the specific growth rate mu was comparable to that of cultures grown in the absence of 2,4-DCP. The reduction in toxicity was directly correlated to a decrease in the concentration of 2,4-DCP in the treated solutions, as measured by high-performance liquid chromatography. The reduced concentrations of 2,4-DCP in the treated solutions could be correctly predicted based on the relationship between the specific growth rates and the 2,4-DCP concentrations in untreated solutions. These results indicate that the oxidative coupling of 2,4-DCP to humic substances catalyzed by the synthetic iron(III)-porphyrin catalyst in the presence of H(2)O(2) is responsible for the removal of 2,4-DCP from solutions. This approach appears to be a promising alternative treatment to reduce 2,4-DCP bioavailability and thus toxicity in the environment.

Biomimetics↗

Linking organic pollutant (bio)availability with geosorbent properties and biomimetic methodology: a review of geosorbent characterisation and (bio)availability prediction.

The interdependent link between structure and physico-chemical properties of geosorbents and sorption activity of hydrophobic organic pollutants (HOC) upon interaction with solid matrices has been established. The conclusions derived from these investigations have not been actively incorporated into risk assessment and remediation protocols since legislators prefer to adopt a conservative approach when the potential of contaminants to be released from soil matrices are evaluated. With the advent of spectroscopic techniques, it is possible to determine the molecular properties of the geosorbent organic matter which play a pivotal role in HOC retention. Physical-chemical and biological methods are employed to predict the potential for HOC release from sorbent matrices. This article serves as a review discussing the literature and reports the progress that has been made in these particular areas. The implication of employing molecular descriptor factors correlated with a biomimetic method to assess availability and risk is also considered.

Adsorption↗

A biomimetic absorbent for removal of trace level persistent organic pollutants from water.

A novel biomimetic absorbent containing the lipid triolein was developed for removing persistent organic pollutants (POPs) from water. The structural characteristics of the absorbent were obtained by SEM and a photoluminescence method. Under optimum preparation conditions, triolein was perfectly embedded in the cellulose acetate (CA) spheres, the absorbent was stable and no triolein leaked into the water. Dieldrin, endrin, aldrin and heptachlor epoxide were effectively removed by the CA--triolein absorbent in laboratory batch experiments. This suggests that CA-triolein absorbent may serve as a good absorbent for those selected POPs. Triolein in the absorbent significantly increased the absorption capacity, and lower residual concentrations of POPs were achieved when compared to the use of cellulose acetate absorbent. The absorption rate for lipophilic pollutants was very fast and exhibited some relationship with the octanol--water partition coefficient of the analyte. The absorption mechanism is discussed in detail.

Absorption↗

A new route to the formation of biomimetic phosphate assemblies on gold: synthesis and characterization.

A biomimetic model system based on long-chain alkanethiols tailored with serine, threonine and tyrosine side-chain groups is created as a platform for the study of phosphorylated amino acids. The phosphorylated analogues are synthesized with protective tert-butyl groups that after assembly on thin polycrystalline gold films are removed in an acidic deprotection solution to form the corresponding phosphate self-assembled monolayers (SAMs). The SAMs are thoroughly characterized with null ellipsometry, contact angle goniometry, infrared reflection-absorption spectroscopy and X-ray photoelectron spectroscopy. The assembly and the subsequent deprotection process are optimized with respect to molecular orientation and chain conformation by varying the incubation time and the exposure time to the deprotection solution. The high quality of the generated SAMs suggests that the present assembly/deprotection approach is an attractive alternative when traditional synthetic routes become demanding because of solubility problems.

Amino Acids↗

Partially and fully beta-brominated Mn-porphyrins in P450 biomimetic systems: effects of the degree of bromination on electrochemical and catalytic properties.

Beta-hexabromo-5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrinatomanganese(III) chloride (Mn(III)(Br6TCMPP)Cl) was prepared by selective Br2-hexabromation of its parent non-brominated manganese complex (Mn(III)(TCMPP)Cl), whereas the octabrominated analogue beta-octabromo-5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrinatomanganese(III) chloride (Mn(III)(Br8TCMPP)Cl) was synthesized via metallation of the corresponding free-base. Beta-octabromo-5,10,15,20-tetrakis(4-carbomethoxyphenyl)porphyrin was obtained by demetallation of its brominated Cu(II) derivative, which, in its turn, was prepared by either a Br2 or an N-bromosuccinimide protocol. Relative to Mn(III)(TCMPP)Cl (E(1/2) = -0.16 V vs. normal hydrogen electrode, CH2Cl2), the Mn(III)/Mn(II) reduction potential of Mn(III)(Br8TCMPP)Cl and Mn(III)(Br6TCMPP)Cl showed anodic shifts of 0.43 and 0.33 V, respectively, which corresponded to a linear shift of 0.05 V per bromine added. These manganese complexes were evaluated as cytochrome P450 mimics in catalytic iodosylbenzene (PhIO)-oxidations of cyclohexane and cyclohexene. In aerobic PhIO-oxidation of cyclohexene, epoxidation and allylic autoxidation reactions were inversely related, competitive processes; the most efficient P450-mimics were the least effective autoxidation catalysts. Mn(III)(Br6TCMPP)Cl was more efficient as epoxidation or hydroxylation catalyst than both its fully and non-beta-brominated counterparts were. There was no linear relationship between the catalytic efficiency and both the number of bromine substituents and the Mn(III)/Mn(II) potential; these observations were compared to Lyons system literature data and discussed. Analogously to enzymatic optimum pH effects, an optimum redox potential effect is suggested as relevant in designing and understanding cytochrome P450 biomimetic catalysts.

Biomimetics↗

Biomimetic synthesis silver crystallite by peptide AYSSGAPPMPPF immobilized on PET film in vitro.

AG3 (AYSSGAPPMPPF) is an inorganic-binding peptide that specifically and selectively binds to silver demonstrated by phage display library according to the Stone group. In our experiment, synthesized silver-binding peptide AG3 was immobilized on the surface of protonated poly(ethylene terephthalate) (PET) film which was prepared for biomimetic synthesis silver particles in vitro. Silver crystallites formatted on the surface of AG3-PET film showed various shapes and was 1-4 microm in size. In addition to hexagonal and triangular crystallite, a silver crystallite presents a cubical shape that has seldom been reported in the literatures so far. With comparison of the control and silver nitrate salt, the surface energy of the silver particles on AG3-PET film surface XPS analysis suggested that Ag+ was being reduced to Ag0 in the reaction. Moreover, CD spectrum revealed that the secondary structure of AG3 peptide in solution had a little change before and after binding silver.

Amino Acid Sequence↗

Catalytic oxidation of cyclohexane by a binuclear Fe(III) complex biomimetic to methane monooxygenase.

A novel binuclear Fe(III) complex [Fe(III)(BPMP)Cl(mu-O)Fe(III)Cl3] (1) was prepared from the reaction between (bis(2-pyridylmethyl)-1,4-piperazine) and [Fe(OH2)6]Cl3, in acetonitrile. The title compound was characterized by spectroscopic, electrochemical and X-ray crystallography analysis. The catalytic activity of the complex was evaluated through cyclohexane oxidation, using hydrogen peroxide as the terminal oxidant. Reaction products were identified by gas chromatography. Conversions up to 19.2% were observed (12.6% and 6.6% yields for cyclohexanol and cyclohexanone, respectively). The catalytic activity exhibited by 1 suggests that it can be considered as a functional biomimetic analog to methane monooxygenase.

Biomimetic Materials↗

Biomimetic approaches to protein and gene delivery for tissue regeneration.

Novel therapeutic strategies that promote wound healing seek to mimic the response of the body to wounding, to regenerate rather than repair injured tissues. Many synthetic or natural biomaterials have been developed for this purpose and are used to deliver wound therapeutics in a controlled manner that prevents unwanted and potentially harmful side-effects. Here, we review the natural and synthetic biomaterials that have been developed for protein and gene delivery to enhance tissue regeneration. Particular emphasis is placed on novel biomimetic materials that respond to environmental stimuli or release their cargo according to cellular demand. Engineering biomaterials to release therapeutic agents in response to physiologic signals mimics the natural healing process and can promote faster tissue regeneration and reduce scarring in severe acute or chronic wounds.

Animals↗

The use of poly(ethylene glycol)-block-poly(lactic acid) derived copolymers for the rapid creation of biomimetic surfaces.

For many tissue engineering applications biomimetic or bioactive polymers would allow for a more precise control of cell behavior in growing tissues than has so far been possible. For this application recently developed amine reactive diblock copolymers (N-succinimidyl tartrate monoamine poly(ethylene glycol)-block-poly(D,L-lactic acid) [ST-NH-PEGxPLAy]) were investigated concerning their reactivity in binding model substances. Their ability to covalently immobilize proteins on their surfaces was examined using polymer films with amine reactive surfaces. Furthermore, thiol reactive polymers were obtained by attaching N-succinimidyl 3-maleinimido propionate, a thiol reactive linker to monoamine poly(ethylene glycol)-block-poly(D,L-lactic acid) [H2N-PEGxPLAy]. This allowed the immobilization of proteins carrying free thiol groups. The amine and thiol reactive polymers were characterized by 1H-NMR spectroscopy and gel permeation chromatography (GPC). Investigation of glass transitions temperatures using modulated differential scanning calorimetry proved suitability for the fabrication of polymeric scaffolds for tissue engineering applications. The functionality of the polymers was demonstrated by investigating their ability to bind model amines, like the fluorescent dye EDANS. Moreover, insulin and somatostatin were covalently attached to the active linker groups via amine and thiol groups. The polymers will permit covalently attaching different bioactive molecules, such as growth and differentiation factors, with fast and gentle procedures securing their biological activity.

Amino Acid Sequence↗

Biomimetic design in microparticulate vaccines.

Current efforts to improve the effectiveness of microparticle vaccines include incorporating biomimetic features into the particles. Many pathogens use surface molecules to target specific cell types in the gut for host invasion. This observation has inspired efforts to chemically conjugate cell-type targeting ligands to the surfaces of microparticles in order to increase the efficiency of uptake, and therefore the effectiveness, of orally administered microparticles. Bio-mimicry is not limited to the exterior surface of the microparticles. Anti-idiotypic antibodies, cytokines or other biological modifiers can be encapsulated for delivery to sites of interest as vaccines or other therapeutics. Direct mucosal delivery of microparticle vaccines or immunomodulatory agents may profoundly enhance mucosal and systemic immune responses compared to other delivery routes.

Animals↗

Biomimetic and electrolytic calcium phosphate coatings on titanium alloy: physicochemical characteristics and cell attachment.

Biomimetically deposited octacalcium phosphate (OCP) and carbonate apatite (BCA) as well as electrolytically deposited carbonate apatite (ECA) were considered as promising alternatives to conventional plasma spraying hydroxyapatite. This study compared their physicochemical characteristics and cell attachment behavior. The physicochemical characteristics included scanning electron microscopy observation, X-ray diffraction analysis, Fourier transform infrared spectroscopy analysis, surface roughness, coating thickness, dissolution test and scratch test. Cell attachment tests included morphology observation with stereomicroscopy and scanning electron microscopy as well as cell number count with DNA content assay. The OCP coating had 100% crystallinity and was about 40 microm thick, composed of large plate-like crystals of 30 microm, with the lowest surface roughness (R(a)=2.33 microm). The BCA coating had 60% crystallinity and was approximately 30 microm in thickness, composed of small crystals of 1-2 microm in size, with the highest surface roughness (R(a)=4.83 microm). The ECA coating had intermediate characteristics, with 78% crystallinity, 45 microm thickness, crystals of 5-6 microm and an average roughness of 3.87 microm. All coatings could be seen by eyes dissolving quickly and completely into acidic simulated body fluid (simulated physiological solutions-SPS, pH 3.0) but slowly and incompletely into neutral SPS (pH 7.3). It was suggested that the main factor determining coating dissolution in acidic SPS was the solubility isotherm, while some other factors including crystallinity and crystal size joined to determine coating dissolution in neutral SPS. In regard to adhesive strength, results of scratch test showed the critical load at the first crack of coating (L(c1)) was tightly related to crystal size as well as their arrangement, while the critical load at the total delamination of coating (L(c2)) was also related to the coating thickness. The ECA coating had the highest values. Owing to higher dissolution rate and globular appearance, BCA coating demonstrated the best goat bone marrow stromal cells attachment at 1 day or 3 days, followed by OCP and ECA coating.

Adsorption↗

Attachment, proliferation, and migration of marrow stromal osteoblasts cultured on biomimetic hydrogels modified with an osteopontin-derived peptide.

We prepared oligo(poly(ethylene glycol) fumarate) (OPF) hydrogels modified with a rat osteopontin-derived peptide (ODP), Asp-Val-Asp-Val-Pro-Asp-Gly-Arg-Gly-Asp-Ser-Leu-Ala-Try-Gly (DVDVPDGRGDSLAYG), as well as Gly-Arg-Gly-Asp-Ser (GRGDS) and investigated the modulation of marrow stromal osteoblast function on the peptide-modified hydrogels. Osteoblast attachment was competitively inhibited by a soluble peptide suggesting that the interaction of osteoblasts with the hydrogel was ligand specific. The proliferation index of osteoblasts relative to the initial seeding density was similar on the hydrogels modified with ODP (1.18+/-0.13) and GRGDS (1.27+/-0.12). However, fibroblasts proliferated faster on GRGDS-modified hydrogels than on ODP-modified hydrogels as evidenced by the proliferation indices of 4.89+/-0.03 and 2.42+/-0.16, respectively. A megacolony migration assay conducted for 3 days with a seeding density of 53,000 cells/cm(2) showed that osteoblasts migrated to a longer distance on ODP-modified hydrogels (0.23+/-0.06 mm/day) than on hydrogels modified with GRGDS (0.15+/-0.02 mm/day). In addition, osteoblasts migrated faster than fibroblasts seeded at the same density on ODP-modified hydrogels (0.15+/-0.11 mm/day). The migration of osteoblasts on the peptide-modified hydrogels was dependent on the peptide concentration of the hydrogels resulting in an increased migration distance with increasing the peptide concentration for the concentrations tested. These results show that OPF-based biomimetic hydrogels hold promise for modulating cell proliferation and migration for specific applications by altering the specific ligand and its concentration in the hydrogels.

Animals↗

Biomimetic approaches to tendon repair.

The linear organization of collagen fibers in tendons results in optimal stiffness and strength at low strains under tensile load. However, this organization makes repairing ruptured or lacerated tendons extremely difficult. Current suturing techniques to join split ends of tendons, while providing sufficient mechanical strength to prevent gapping, are inadequate to carry normal loads. Immobilization protocols necessary to restore tendon congruity result in scar formation at the repair site and peripheral adhesions that limit excursion. These problems are reviewed to emphasize the need for novel approaches to tendon repair, one of which is the development of biomimetic tendons. The objective of the empirical work described here was to produce biologically-based, biocompatible tendon replacements with appropriate mechanical properties to enable immediate mobilization following surgical repair. Nor-dihydroguaiaretic acid (NDGA), a di-catechol from creosote bush, caused a dose dependent increase in the material properties of reconstituted collagen fibers, achieving a 100-fold increase in strength and stiffness over untreated fibers. The maximum tensile strength of the optimized NDGA treated fibers averaged 90 MPa; the elastic modulus of these fibers averaged 580 MPa. These properties were independent of strain rates ranging from 0.60 to 600 mm/min. Fatigue tests established that neither strength nor stiffness were affected after 80 k cycles at 5% strain. Treated fibers were not cytotoxic to tendon fibroblasts. Fibroblasts attached and proliferated on NDGA treated collagen normally. NDGA-fibers did not elicit a foreign body response nor did they stimulate an immune reaction during six weeks in vivo. The fibers survived 6 weeks with little evidence of fragmentation or degradation. The polymerization scheme described here produces a fiber-reinforced NDGA-polymer with mechanical properties approaching an elastic solid. The strength, stiffness and fatigue properties of the NDGA-treated fibers are comparable to those of tendon. These fibers are biocompatible with tendon fibroblasts and elicit little rejection or antigenic response in vivo. These results indicate that NDGA polymerization may provide a viable approach for producing collagenous materials that can be used to bridge gaps in ruptured or lacerated tendons. The tendon-like properties of the NDGA-fiber would allow early mobilization after surgical repair. We predict that timely loading of parted tendons joined by this novel biomaterial will enhance mechanically driven production of neo-tendon by the colonizing fibroblasts and result in superior repair and rapid return to normal properties.

Animals↗

Mechanical properties of biomimetic tissue adhesive based on the microbial transglutaminase-catalyzed crosslinking of gelatin.

Fibrin sealants are a type of soft tissue adhesive that employs biochemical reactions from the late stages of the blood coagulation cascade. Intrinsic to these adhesives are a structural protein and a transglutaminase crosslinking enzyme. We are investigating an alternative biomimetic adhesive based on gelatin and a calcium-independent microbial transglutaminase (mTG). Rheological measurements show that mTG catalyzes the conversion of gelatin solutions into hydrogels, and gel times are on the order of minutes depending on the gelatin type and concentration. Tensile static and dynamic loading of the adhesive hydrogels in bulk form demonstrated that the Young's modulus ranged from 15 to 120 kPa, and these bulk properties were comparable to those reported for hydrogels obtained from fibrin-based sealants. Lap-shear adhesion tests of porcine tissue were performed using a newly published American Society for Testing and Materials (ASTM) standard for tissue adhesives. The gelatin-mTG adhesive bound the opposing tissues together with ultimate adhesive strengths of 12-23 kPa which were significantly higher than the strength observed for fibrin sealants. Even after failure, strands of the gelatin-mTG adhesive remained attached to both of the opposing tissues. These results suggest that gelatin-mTG adhesives may offer the benefits of fibrin sealants without the need for blood products.

Animals↗

pH controlled permeability of lipid/protein biomimetic microcapsules.

The permeability of lipid and protein microcapsules fabricated by alternating adsorption of human serum albumin (HSA) and L-alpha-dimyristoylphosphatidic acid (DMPA) on a template and subsequent removal of the core is studied as a function of pH value and supplementary layers. The capsules were permeable for macromolecules (FITC-labeled dextran, M(w) 40 kDa) at pH < 4.8 and impermeable at pH > 7.4. The assembly of supplementary DMPA bilayers rendered the capsules impermeable for small hydrophilic molecules such as 6-carboxyfluorescein (6-CF). Hence DMPA/HSA capsules can be resealed after fabrication by supplementary layers. This provides the opportunity of applying such biomimetic membrane capsules as drug carriers or model systems to study biological processes at membranes.

Adsorption↗

Biomimetic synthesis of water-soluble conducting copolymers/homopolymers of pyrrole and 3,4-ethylenedioxythiophene.

A novel biomimetic route for the synthesis of electrically conducting homopolymers/copolymers of pyrrole and 3,4-ethylenedioxythiophene (EDOT) in the presence of a polyelectrolyte, such as polystyrene sulfonate (SPS), is presented. A poly(ethylene glycol)-modified hematin (PEG-hematin) was used to catalyze the homopolymerization of pyrrole and EDOT as well as copolymerization of EDOT and pyrrole in the presence of SPS to yield homopolymers of polypyrrole/SPS and PEDOT/SPS as well as a polypyrrole-co-poly(3,4-ethylenedioxythiophene)/SPS complex. Spectroscopic characterization [UV-visible, Fourier transform infrared (FTIR), and X-ray photoelectron spectroscopy (XPS)], thermal analysis, (TGA), and electrical conductivity studies for these complexes indicated the presence of a stable and electrically conductive form of these polymers. Furthermore, the presence of SPS that serves as a charge-compensating dopant in this complex provides a unique combination of properties such as processability and water solubility.

Biomimetic Materials↗

Biomimetic nanofibrous scaffolds: preparation and characterization of PGA/chitin blend nanofibers.

Electrospinning of poly(glycolic acid) (PGA)/chitin blend solutions in 1,1,1,3,3,3-hexafluoro-2-propanol was investigated to fabricate biodegradable and biomimetic nanostructured scaffolds for tissue engineering. The morphology of the electrospun PGA/chitin blend nanofibers was investigated with a field emission scanning electron microscope. The PGA/chitin blend fibers have average diameters of around 140 nm, and their diameters have a distribution in the range 50-350 nm. The miscibility of PGA/chitin blend fibers was examined by differential scanning calorimetry. The PGA and chitin were immiscible in the as-spun nanofibrous structure. An in vitro degradation study of PGA/chitin blend nanofibers was conducted in phosphate-buffered saline, pH 7.2. It was found that the hydrolytic cleavage of PGA in the blend nanofibers was accelerated by the coexistence of hydrophilic chitin. To assay the cytocompatability and cell behavior on the PGA/chitin blend nanofibrous scaffolds, cell attachment and spreading of normal human epidermal fibroblasts seeded on the scaffolds were studied. Our results indicate that the PGA/chitin blend nanofibrous matrix, particularly the one that contained 25% PGA and 75% chitin with bovine serum albumin coating, could be a good candidate for tissue engineering scaffolds, because it has an excellent cell attachment and spreading for normal human fibroblasts.

Biomimetics↗