Techniques to improve the shear strength of impacted bone graft: The effect of particle size and washing of the graft

Background: When fresh morselized graft is compacted, as in impaction bone-grafting for revision hip surgery, fat and marrow fluid is either exuded or trapped in the voids between particles. We hypothesized that the presence of incompressible fluid damps and resists compressive forces during impaction and prevents the graft particles from moving into a closer formation, thus reducing the graft strength. In addition, viscous fluid such as fat may act as an interparticle lubricant, thus reducing the interlocking of the particles. Methods: We performed mechanical shear testing in the laboratory with use of fresh-frozen human femoral-head allografts that had been passed through different orthopaedic bone mills to produce graft of differing particle-size distributions (grading). Results: After compaction of fresh graft, fat and marrow fluid continued to escape on application of normal loads. Washed graft, however, had little lubricating fluid and better contact between the particles, increasing the shear resistance. On mechanical testing, washed graft was significantly (p < 0.001) more resistant to shearing forces than fresh graft was. This feature was consistent for different bone mills that produced graft of different particle-size distributions and shear strengths. Conclusions: Removal of fat and marrow fluid from milled human allograft by washing the graft allows the production of stronger compacted graft that is more resistant to shear, which is the usual mode of failure. Further research into the optimum grading of particle sizes from bone mills is required. Clinical Relevance: Understanding the mechanical properties of milled human allograft is important when impaction grafting is used for mechanical support. A simple means of improving the mechanical strength of graft produced by currently available bone mills, including an intraoperative washing technique, is described.

The influence of variant PE-b-PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE-b-PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE-b-PEO (mPE-b-PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by H-1 NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T., and crystal growth rate.

Novel temperature- and pH-responsive graft copolymers composed of poly(L-glutamic acid) and poly(N-isopropylacrylamide)

A series of novel temperature- and pH-responsive graft copolymers, poly(L-glutamic acid)-g-poly(N-isopropylacrylamide), were synthesized by coupling amino-semitelechelic poly(N-isopropylacrylamide) with N-hydroxysuccinimide-activated poly(L-glutamic acid). The graft copolymers and their precursors were characterized, by ESI-FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (H-1 NMR). The phase-transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering.

In situ chlorinating-graft copolymerization on isotactic polypropylene in gas-solid phase

A novel method in situ chlorinating-graft copolymerization (ISCGC) of grafting maleic anhydride (MAH) on isotactic polypropylene (iPP) in gas-solid phase was investigated in this paper. Chlorine (Cl-2) was used as initiator, chlorinating agent and termination agent at the same time during the reaction. The iPP was chlorinated as well as grafted with MAH in the reaction process. The product with chlorine and MAH in the same molecule was named as PP-cg-MAH. Existence of PP-cg-MAH was identified by Fourier transform infrared. Thermal behavior and crystallinity of PP-cg-MAH were analyzed by differential scanning calorimetry, X-ray diffraction and polarizing microscope. Influencing factors for the value of graft degree were also discussed. Compared with conventional peroxide initiated graft method, ISCGC revealed higher MAH graft efficiency (33%), and particularly alleviated degradation of iPP. iPP could be grafted successfully and without changing physical properties dramatically through this method.

Multi-armed poly(L-glutamic acid)-graft-oligoethylenimine copolymers as efficient nonviral gene delivery vectors

Background The application of polyethylenimine (PEI) in gene delivery has been severely limited by significant cytotoxicity that results from a nondegradable methylene backbone and high cationic charge density. It is therefore necessary to develop novel biodegradable PEI derivates for low-toxic, highly efficient gene delivery.Methods A series of novel cationic copolymers with various charge density were designed and synthesized by grafting different kinds of oligoethylenimine (OEI) onto a determinate multi-armed poly(L-glutamic acid) backbone. The molecular structures of multi-armed poly(L-glutamic acid)-graft-OEI (MP-g-OEI) copolymers were characterized using nuclear magnetic resonance, viscosimetry and gel permeation chromatography. Moreover, the MP-g-OEI/DNA complexes were measured by a gel retardation assay, dynamic light scattering and atomic force microscopy to determine DNA binding ability, particle size, zeta potential, complex formation and shape, respectively. MP-g-OEI copolymers were also evaluated in Chinese hamster ovary and human embryonic kidney-293 cells for their cytotoxicity and transfection efficiency.

Monte Carlo simulation of the compatibility of graft copolymer compatibilized two incompatible homopolymer blends: Effect of graft structure

Compatibility of graft copolymer compatibilized two incompatible homopolymer A and B blends was simulated by using Monte Carlo method in a two-dimensional lattice model. The copolymers with various graft structures were introduced in order to study the effect of graft structure on the compatibility. Simulation results showed that incorporation of both A-g-B (A was backbone) and B-g-A (B was backbone) copolymers could much improve the compatibility of the blends. However, A-g-B copolymer was more effective to compatibilize the blend if homopolymer A formed dispersed phase. Furthermore, simulation results indicated that A-g-B copolymers tended to locate at the interface and anchor two immiscible components when the side chain is relatively long. However, most of A-g-B copolymers were likely to be dispersed into the dispersed homopolymer A phase domains if the side chains were relatively short. On the other hand, B-g-A copolymers tended to be dispersed into the matrix formed by homopolymer B. Moreover, it was found that more and more B-g-A copolymers were likely to form thin layers at the phase interface with decreasing the length of side chain.

A novel approach to synthesis of functional CPVC and CPE or graft copolymers - in situ chlorinating graft

A new process of graft copolymerization of poly(vinyl chloride) (PVC) and polyethylene (PE) with other monomers was developed. The grafted chlorinated poly(vinyl chloride) (CPVC) and chlorinated polyethylene (CPE) were synthesized by in situ chlorinating graft copolymerization (ISCGC) and were characterized. Convincing evidence for grafting and the structure of graft copolymers was obtained using FT-IR, H-1-NMR, gel permeation chromatography (GPC), and the vulcanized curves. Their mechanical properties were also measured. The results show that the products have different molecular structure from those prepared by other conventional graft processes. Their graft chains are short, being highly branched and chlorinated. The graft copolymers have no crosslinking structure. The unique molecular structure will make the materials equipped with special properties.

Preparation and chracaterization of novel graft copolymers of LLDPE

A series of novel fluorine surfactants, a, b, c, d, e and their acrylates, A, 13, C, D and E, were synthesized via poly( ethylene oxide) ( PEG) ( 200, 600, 1000, 2000, 5000) and perfluorooctane poly (ethylene oxide) ether as the main starting materials. Their chemical structures were characterized by means of FTIR and H-1 NMR. The surface activity and surface tension( y) of surfactants a, b, c, d and e were evaluated by maximum bubble pressure method. Surfactants A, 13, C, D and E were adopted as the grafting monomers of linear low density polyethere( LLDPE), and grafting reaction was carried out by melt reactive extrusion procedure. Their surface properties were characterized with measuring contact angle and XPS. It was found that the hydrophilic property of the graft copolymers was better than the palin LLDPE. Thermal properties of graft copolymers were studied by DSC. It was found that their crystalline temperatures of graft copolymers were faster than that of the plain LLDPE.

Poly(L-lysine)-graft-chitosan copolymers: Synthesis, characterization, and gene transfection effect

Polypeptide/polysaccharide graft copolymers poly(L-lysine)-graft-chitosan (PLL-g-Chi) were prepared by ring-opening polymerization (ROP) of epsilon-benzoxycarbonyl L-lysine N-carboxyanhydrides (Z-L-lysine NCA) in the presence of 6-O-triphenylmethyl chitosan. The PLL-g-Chi copolymers were thoroughly characterized by H-1 NMR, C-13 NMR, Fourier transform infrared (FT-IR), and gel permeation chromatography (GPC). The number-average degree of polymerization of PLL grafted onto the chitosan backbone could be adjusted by controlling the feed ratio of NCA to 6-O-triphenylmethyl chitosan. The particle size of the complexes formed from the copolymer and calf thymus DNA was measured by dynamic light scattering (DLS). It was found in the range of 120 similar to 340 nm. The gel retardation electrophoresis showed that the PLL-g-Chi copolymers possessed better plasmid DNA-binding ability than chitosan. The gene transfection effect in HEK 293T cells of the copolymers was evaluated, and the results showed that the gene transfection ability of the copolymer was better than that of chitosan and was dependent on the PLL grafting ratio. The PLL-g-Chi copolymers could be used as effective gene delivery vectors.

Polypeptide modification of multiwalled carbon nanotubes by a graft-from approach

Covalent surface functionalization of carbon nanotubes with polypeptides is promising for possible medical applications. This work presents a graft-from approach to perform the polypeptide modification of multiwalled carbon nanotubes (MWTNs). The raw MWNTs are first amine-functionalized. The amine-functionalized MWNTs are then used as the initiator to initiate the ring-opening polymerization of gamma-benzyl-L-glutamate N-carboxyanhydride (BLG- NCA), to results in the polypeptide-grafted MWNTs. FT-IR, XPS, and TGA data demonstrate that the functionalization is successful. The TEM images of the products show that the thickness of the polypeptide shell of the PBLG-MWNT is about 4.5-22 nm. Using the facile route developed here, carbon nanotubes functionalized with other types of polypeptides can be easily fabricated using the corresponding NCAs.

Graft chain propagation rate coefficients of acrylic acid in melt graft copolymerization with linear low density polyethylene

Graft chain propagation rate coefficients (k(p.g)) for grafting AA onto linear low density polyethylene (LLDPE) in the melt in ESR tubes have been measured via Fourier transform infrared (FTIR) spectroscopy and electron spin resonance (ESR) spectroscopy in the temperature range from 130 to 170 degrees C. To exclude the effect of homopolymerization on the grafting. the LLDPE was pre-irradiated in the air by electron beam to generate the peroxides and then treated with iodide solution to eliminating one kind of peroxides, hydroperoxide. The monomer conversion is determined by FTIR and the chain propagation free-radical concentration is deduced from the double integration of the well-resolved ESR spectra, consisting nine lines in the melt. The temperature dependence of k(p.g) is expressed:The magnitude of k(p.g) from FTIR and ESR analysis is in good agreement with the theoretical data deduced from ethylene-AA copolymerization, suggesting this method could reliably and directly provide the propagation rate coefficient. The comparison of k(p.g) with the data extrapolated from solution polymerization at modest temperature indicates that the extrapolated data might not be entirely fitting to discuss the kinetics behavior in the melt.

Synthesis and characterization of the biodegradable polycaprolactone-graft-chitosan amphiphilic copolymers

A novel synthetic approach to biodegradable amphiphilic copolymers based on poly (epsilon-caprolactone) (PCL) and chitosan was presented, and the prepared copolymers were used to prepare nanoparticles successfully. The PCL-graft-chitosan copolymers were synthesized by coupling the hydroxyl end-groups on preformed PCL chains and the amino groups present on 6-O-triphenylmethyl chitosan and by removing the protective 6-O-triphenylmethyl groups in acidic aqueous solution. The PCL content in the copolymers can be controlled in the range of 10-90 wt %. The graft copolymers were thoroughly characterized by H-1 NAM, C-13 NMR, FT-IR and DSC. The nanoparticles made from the graft copolymers were investigated by H-1 NMR, DLS, AFM and SEM measurements. It was found that the copolymers could form spherical or elliptic nanoparticles it? water. The amount of available primary amines on the surface of the prepared nanoparticles was evaluated by ninhydrin assail, and it can be controlled by the grafting degree of PCL.

Preparation of the HIPS/MA graft copolymer and its compatibilization in PA6/HIPS blends

The graft copolymer of high impact polystyrene (HIPS) grafted with malice anhydride (MA) (HIPS-g-MA) was prepared with melt mixing in the presence of a free-radical initiator. The grafting reaction was confirmed by IR analyses and the amount of MA grafted on HIPS was evaluated by a titration method. 1-5 wt% of MA can be grafted on HIPS. HIPS-g-MA is miscible with HIPS. Its anhydride group can react with the PA6 during melt mixing the two components. The compatibility of HIPS-g-MA in the HIPS/PA6 blends was evident. Evidence of reactions in the blends was confirmed in the morphology and mechanical properties of the blends. A significant reduction in domain size was observed because of the compatibilization of HIPS-g-MA in the blends of HIPS and PA6. The tensile mechanical properties of the prepared blends were investigated and the fracture surfaces of the blends were examined by means of the scanning electron microscope (SEM). The improved adhesion in a 16%HIPS/75%PA6 blend with 9%HIPS-g-MA copolymer was detected. The morphology of fibrillar ligaments formed by PA6 connecting HIPS particles was observed.

Synthesis of a novel graft-like copolymer of syndiotactic polystyrene with polybutadiene

A novel graft-like copolymer of syndiotactic polystyrene (sPS) with polybutadiene (PB) was synthesized by polymerization of styrene in a toluene solution of PB using the cyclopentadiene titanium trichloride (CpTiCl3)/methylaluminoxane (MAO) catalytic system. The effect of PB on the crystallization behavior of the copolymer was investigated by differential scanning calorimetry and wide angle X-ray diffraction. Hydrogenation of the sPS/PB copolymer with p-toluenesulfonyl hydrazide afforded a PE-like copolymer.

Self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine as an immobilization matrix for the construction of a tyrosinase-based amperometric biosensor

A tyrosinase-based amperometric biosensor using a self-gelatinizable graft copolymer of poly(vinyl alcohol) with 4-vinylpyridine (PVA-g-PVP) as an immobilization matrix was constructed. The 4-vinylpyridine component of PVA-g-PVP enhances the adherence to a glassy carbon electrode surface. The content of 4-vinylpyridine in this immobilization matrix plays a key role in retaining the activity of tyrosinase. A simple, milder method was adopted by simply syringing the copolymer-tyrosinase aqueous solution on to the electrode surface and allowing water to evaporate at 4 degrees C in a refrigerator. Several parameters, including copolymer composition; pH, applied potential and enzyme membrane composition, ware optimized. The enzyme membrane composition can be varied to obtain higher sensitivity or a wider linear detection range. The biosensor was used for the determination of phenol, p-cresol and catechol. The biosensor exhibited excellent reproducibility, stability and sensitive response and can be used in flow injection analysis. The biosensor showed an extended linear range in hydrophilic organic solvents and it can be used in monitoring organic reaction processes. The analytical performance demonstrated this immobilization matrix is suitable for the immobilization of tyrosinase.