Current Strategies of Surface Modifications to Polyurethane Biomaterials for Vascular Grafts

As the number of patients suffering from cardiovascular diseases and peripheral vascular diseases rises,the constraints of autologous transplantation remain unavoidable.As a result,artificial vascular grafts must be developed.Adhesion of proteins,platelets and bacteria on implants can result in stenosis,thrombus formation,and postoperative infection,which can be fatal for an implantation.Polyurethane,as a commonly used biomaterial,has been modified in various ways to deal with the adhesions of proteins,platelets,and bacteria and to stimulate endothelium adhesion.In this review,we briefly summarize the mechanisms behind adhesions,overview the current strategies of surface modifications of polyurethane biomaterials used in vascular grafts,and highlight the challenges that need to be addressed in future studies,aiming to gain a more profound understanding of how to develop artificial polyurethane vascular grafts with an enhanced implantation success rate and reduced side effect.

Graft modification of ZnO nanoparticles with silane coupling agent KH570 in mixed solvent

The reaction of ZnO nanoparticles grafted with KH570 silane coupling agent was carried out in water-alcohol mixed solvent. Several characterization methods were applied to analyzing the results of surface modification such as Soxhlet extraction, Fourier transform infrared spectroscopy （FT-IR）, transmission electron microscopy （TEM）, thermogravimetry （TG）, differential scanning calorimetry （DSC） and zeta potential （ζ）. The results of FT-IR and TG-DSC show that the desired reaction chains have been covalently bonded on the surface of ZnO nanoparticles. Zetasizer results reveal that the maximal absolute value of ζ of the modified ZnO particles in acetone medium was 67.0 mV, which was much higher than that of the unmodified ZnO particles. So the surface of nanosized ZnO changed from hydrophilicity to hydrophobicity and the dispersity of ZnO nanoparticles were improved simultaneously. Finally, the mechanism of graft modification was discussed.

UV-induced Self-initiated Graft Polymerization of Acrylamide onto Poly(ether ether ketone)

Photo-grafting of hydrophilic monomer was used to enhance the hydrophilicity of poly（ether ether ketone） （PEEK） with the aim of extending its applications to biological fields. PEEK sheets were surface modified by grafting of acrylamide（AAm） with ultraviolet（UV） irradiation in the presence or absence of benzophenone（BP）. The effects of BP, irradiation time and monomer concentration on the surface wettability of PEEK were investigated. Characteriza tion of modified PEEK using scanning electron microscopy（SEM）, energy-disperse spectrometer（EDS） and water contact angle measurements shows that AAm was successfully grafted on PEEK surface both in presence and absence of BP. With the increase in irradiation time and monomer concentration, contact angles decrease to as low as 30°, demonstrating a significant improvement of surface hydrophilicity. In agreement with the decrease in contact angle, under identical conditions, the nitrogen concentration increases, suggesting the increase in grafting degree of the grafting polymerization. This investigation demonstrates a self-initiation of PEEK due to its BP-like structure in the backbone of the polymer. Though the graft polymerization proceeds more readily in the presence of BP, the self-initiated graft polymerization is clearly observed.

SURFACE MODIFICATION OF MICROPOROUS POLYPROPYLENE MEMBRANES BY GRAFT POLYMERIZATION OF N,N-DIMETHYLAMINOETHYL METHACRYLATE

Surface modification of microporous polypropylene hollow fiber membranes was performed by radical-induced graft polymerization of N,N-dimethylaminoethyl methacrylate (DMAEMA). The influences of temperature, monomer concentration and pre-adsorbed amount of benzoyl peroxide on grafting degree were studied respectively. It was found that the appropriate graft temperature was 75 'C, at which the grafting degree was the highest and the hydrolytic decomposition of DMAEMA the lowest. Scanning electron photomicrography and the average pore diameters of the modified membranes demonstrated that part of the micropores on the membrane surface was plugged by the grafted polyDMAEMA chains, especially at high grafting degree. Contact angle and water swelling experiments showed that a moderate grafting degree could improve the hydrophilicity of the membranes. In the range of 11.3%-12.0% grafting degree, the water swelling percentage reached its maximum (51.1%) and the contact angle reached its minimum (74 degrees). The bovine serum albumin (BSA) adsorption experiment indicated that the grafted polyDMAEMA had a dual effect on protein adsorption. At the first stage, the BSA adsorption decreased with increasing of DMAEMA grafting degree. As the interaction between BSA and polyDMAEMA on membrane surface increased, the BSA adsorption increased with increasing of DMAEMA grafting degree.

Polymer grafting modification of the surface of nano silicon dioxide

Based on the composite modification technology of the surface of nano Silicondioxide by non-soap emulsion polymerization, it is verified that there are polymer grafted on thesurface of nano silicon dioxide. The modification mechanism and the bonding status on the surface ofnano silicon dioxide after modification were suggested via the results of the infrared spectrum,transmission electronic microscope photograph and X-ray photoelectron spectrum. The hydroxyl formedby hydrolyzing of silane coupling agent reacts with hydroxyl on the surface of nano silicon dioxideto form Si-O-Si bonds by losing water molecules and hence the double bonds are introduced onto thesurface of nano silicon dioxide. The surface of nano silicon dioxide is grafted with polymer throughfree radical polymerization between the double bonds on the surface of nano silicon dioxide andstyrene under the action of initiating agent. The dispersibility of nano silicon dioxide and thecontrollability of surface modification of nano silicon dioxide can be greatly improved by themodification process.

MODIFICATION OF SILK FIBER via EMULSION GRAFT COPOLYMERIZATION WITH FLUOROACRYLATE

2,2,3,3,4,4,5,5-Octafluoropentyl acrylate was grafted onto silk fiber in a two-step heterogeneous system through the vinyl bonds of acryloyloxyethyl isocyanate modified on the silk.The grafted copolylner was analyzed by FTIR and WAXD,and the results revealed that the fluoroacrylate was successfully grafted onto silk fiber and the crystalline structure of silk fibroin withβ-sheet structure was not changed after graft copolymerization.The FT-IR corrected method was used to simulate the grafting yield onto sil...

Graft Modification of N,N'-methylene- bisacrylamide onto Silk in the Presence of Air

The graft modification of N, N'-methylene-bisacrylamide (NNMBAA) onto silk using eerie ammonium sulfate, potassium persulfate, ammonium persulfate and 2, 2-azobis (isobutyronitrile) as the initiators has been studied in the presence of air. To establish reaction conditions for the graft modification of NNMBAA onto silk, the effect of different variables such as the initiator concentration, monomer concentration, acetic acid concentration, time of polymerization, reaction temperature and liquor ratio (fabric: liq.) have been studied. The optimum grafting conditions were found. As evidence of grafting, analyses of amino acid composition and alkali solubility have been carried out. Grafting caused changes in amino acid composition and alkali solubility of silk. The observation has been explained in relation to structural changes in the grafted silk.

Chemical Modification of Scraped Tires through Grafting with 2-Acrylamido-2-methylpropansulfonic Acid

Scrap vulcanized rubber is amongst a bigger waste polymers. It does not decompose easily owing to its cross linked structure. Modification of scrap tires powder by the grafting with 2-acrylamido-2-methylpropanesulfonic acid (AMPS) is described. The grafting is achieved through free radical initiation. The effects of different amount of monomer and initiator were examined. Also the influence of reaction time and temperature were investigated. The grafted waste rubber was characterized by FT/IR, SEM and DSC measurements. The proposed mechanism of the grafting reaction is discussed. From DSC and SEM studies of WR-g-AMPS compared with PAMPS and WR, the results show that the particle size and crystallinity were enhanced for the grafted copolymers. The obtained modified scraped tires will used as an ion exchanger for the future applications.

MODIFICATION OF MULTI-WALLED CARBON NANOTUBES WITH POLY(NITRILOETHYLENENITRILOVINYLENE)“GRAFTING TO”THE SURFACE

A mild and facile way was used to prepare poly(nitriloethylenenitrilovinylene)-grafted multi-walled carbon nanotubes(MWCNTs-g-PNENV)nanocomposites via the"grafting to"method.The MWCNTs-g-PNENV nanocomposites are well dispersible in polar solvents such as water,tetrahydrofuran and ethanol.Chemical structure of the resulting product was characterized by Fourier transform infrared(FTIR)spectroscopy,transmission electron microscopy(TEM)and thermal gravimetric analysis(TGA).FTIR showed that the"grafting to"process belonged to covalent attachment mechanisms.TEM observations indicated that the MWCNTs were coated with a uniform PNENV layer,and the MWCNTs existed as a hard backbone.TGA data also showed that the PNENV shell was successfully grafted to the side wall of MWCNTs.

Grafting modification on the surface of titanium dioxide by polystyrene

Based on the technology of titanium dioxide grafting modification withpolystyrene (PS), the modification mechanisms are studied and the polystyrene-grafting states on thesurface of titanium dioxide have been set up. Under the synergistic actions of mechanical force,chemistry and heat, macromolecular free radicals of PS are created, at the same time, the O-O bondsof titanium dioxide are broken and the oxide free radicals produced, and the numbers of oxygen atomare increased and crystal lattice defects rich electrons are formed on the surface of titaniumdioxide. The radical polymerization is the main reaction between PS and titanium dioxide and C-Obonds form in the process of modification. Multi-sites chemical adsorption also exists besidesgrafting between PS and titanium dioxide.

Synthesis and Characterization of Lignin Grafting Modification-based Aliphatic Superplasticizer

Lignin as the main component of black liquor is generally employed to modify aliphatic superplasticizer（AFS）. However, the modification effect is hard to evaluate correctly due to the uncertain molecular structure of lignin and the disturbance from the complexity of black liquor compositions. In this paper, the purified lignin via acid precipitation from straw black liquor is used to modify AFS. The modified AFS named as LAFS for short presents lower molecular mass than AFS. It is assumed that it is due to the single active site of guaiacol segments in lignin by which lignin graft modifies AFS in virtue of methylolation reaction. In order to verify this assumption, guaiacol and dihydro eugenol as the typical segments of lignin macromolecule were selected, respectively, as the simplified model compounds of lignin to modify AFS, and corresponding products are abbreviated in GAFS and DAFS. Both GAFS and DAFS show the lower molecular mass than unmodified AFS. FTIR and TG-DTG analyses prove that lignin is successfully grafted onto AFS. The graft modification of lignin results in a decrease in electrostatic epulsion, but an enhanced steric hindrance. Therefore, although the replacement rate of lignin in LAFS was about 23.3%, the dispersion performance was only slightly affected.

Plasma Surface Modification of Kevlar Fibers

Cold plasma techniques were used to treat the surface of Kevlar-49 fibers. The dynamic parameters of wetting, contact-angles and surface energy of the fiber before and alter the treatment were compared to see the changes in the wetting property. ESCA and electron spin resonance were utilized to examine the chemical composition and the attached free radicals of the fiber surface. The results, together with changes in the magnitude of the contact-angle and the number of free radicals with time after the plasma treatment do not show any ageing effect. Single filament test revealed that the tensile strength was not impaired but even improved somewhat after the plasma treatment. The experiment shows that the interlaminar shear strength of Kevlar fiber reinforced epoxy resin compo- site is increased for more than 60％% after the treatment.

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANE BY TETHERING POLYPEPTIDES

Two kinds of polypeptides were tethered onto the surface of polypropylene microporous membrane （PPMM） through a ring opening polymerization of L-glutamate N-carboxyanhydride initiated by amino groups which were introduced by ammonia plasma and y-aminopropyl triethanoxysilane treatments. X-ray photoelectron spectroscopy （XPS）, attenuated total reflectance Fourier transform infrared spectroscopy （FT-IR/ATR）, scanning electron microscopy （SEM）, together with water contact angle measurements were used to characterize the modified membranes. XPS analyses and FT-IR/ATR spectra demonstrated that polypeptides are actually grafted onto the membrane surface. The wettability of the membrane surface increases at first and then decreases with the increase in grafting degrees of polypeptide. Platelet adhesion and murine macrophage attachment experiments reveal an enhanced hemocompatibility for the polypeptide modified PPMMs. All these results give evidence that polypeptide grafting can simultaneously improve the hemocompatibility as well as reserve the hydrophobicity for the membrane, which will provide a potential approach to improve the performance of polypropylene hollow fiber microporous membrane used in artificial oxygenator.

CHEMICAL MODIFICATION OF THE SURFACE OF CALCIUM ALGINATE GEL BEADS

The chemical modification of the surface of calcium alginate gel beads (CAGB) via grafting copolymerization with vinyl acetate (VAc) was studied. The optimum reaction conditions with activation and graft copolymerization two steps were explored. First, 5 grams CAGB with 2.5 mm initial diameter was initiated with 0.0493 mol/L K2S2O8 at 51 °C for 30 min in 15 mL 1 % PVA/H2O. Then 4.34 moi/L VAc was added dropwise and the reaction was allowed to proce at 48 °C for 3 h. The grafting efficiency could come up to 30%. It was found the stability of modified CAGB in the air and in electrolyte solutions was greatly improved.

Surface Modification of Polyethylene by Heparin for Improvement of Antithrombogenicity

The purpose of this paper was to enhance blood compatibility of polyethylene （PE） film. PE film pretreated by argon plasma was subjected to ultraviolet （UV） -induced graft polymerization with Acrylic acid（AAc） （AAc-grafted PE films, PE-g-PAAc） without photo-initiator, then heparin was covalently immobilized on the PE surface （PE-g-HPAAc）. The surface properties and microstructure of PE-g-PAAc and PE-g-HPAAc were studied by static contact angle measurement, atomic force microscope （AFM）, X-ray photoelectron spectroscopy （XPS） and Attenuated total reflectance Fourier transfer infrared spectroscopy （ATR-FTIR）. It was confirmed that AAc and heparin were successfully immobilized onto the surface of PE film. Results of platelet adhesion experiments indicated that the antithrombogenicity of the modified PE film was remarkably improved.

Study on the Surface Modification of Hydrophobic Polyacrylate Intraocular Lens

In this study, the polyacrylate intraocularr lens is irradiated by argon ion which can produce free radicals. In order to obtain better hydrophilic and lower platelets adhesion, monomer vinyl pyrrolidone (NVP) is grafted onto the hydrophobic polyacrylate intraocular lens surface in a certain reaction conditions. Specific changes in intraocular lens are detected by static contact angle (CA), scanning electron microscope (SEM) and light transmittance. The results show that this surface modification can greatly improve its hydrophilic character and surface formation.

Myringoplasty Modification Adopted to Overcome Some Long and Short Term Surgical Issues

Objective/Hypothesis: We have tried to present some of our concerns regarding the usually adopted surgical techniques of Myringoplasty with their possible solutions. Also we have tried to present digital recordings of pre and post-operative findings in reference cases, which have been provided rarely in available literature. Pre- and post-operative pictures and videos of two representative cases are attached. Study design: This prospective study was carried out in MMABM hospital. Forty six (46) ears, 37 patients underwent tympanoplasty by the modified dual grafting technique and the results were analysed. Results: Objectives of tympanic membrane repair, dry ear, closure of AB gap, and stoppage of tinnitus if any, were achieved in all cases. Small residual perforations which healed over time were seen in two cases in cartilage deficient areas. Conclusion: Dual graft modified techniques served as an effective alternative myringoplasty technique.

Surface Modification of Barium Sulfate Particles

In this study, surface modification of barium sulfate was investigated using several model molecules for chemical treatment: ethanesulfonic acid, butyric acid, trimethoxy(propyl) silane and phosphoric acid 2-hydroxyethyl methacrylate. Samples were characterized by FT-IR and TGA to check the capability of these model molecules to interact with BaSO4 surface. The results pointed out the presence of an organic layer around the surface after the chemical treatment even after several washings to remove all species in excess. Model molecules were grafted onto BaSO4 surface and grafted density was determined. It reveals that phosphoric acid and carboxylic acid are the best candidates for the modification of BaSO4 surface. Both can be used as anchoring groups to modify the hydrophilic balance of barium sulfate surface in order to avoid the formation of aggregates and to improve the compatibility of this filler within hydrophobic polymer matrix.

极性分子的结构异同性对接枝改性交联聚乙烯材料直流电性能的影响

为改善高压直流电缆运行过程中绝缘层材料的电导率对温度与电场强度敏感性所导致的电场反转问题,以及直流高压长时间作用下的空间电荷积聚现象,该文采用极性基团接枝改性的方式提升交联聚乙烯(XLPE)材料的直流电性能。由于接枝单体一般为沸点较低的极性小分子化合物,为避免材料在接枝过程中单体的气化损失,首先通过平行双螺杆挤出机配合低温高压计量泵装置实现熔融接枝反应。将丙烯酸酯类小分子化合物(丙烯酸甲酯(MA)、丙烯酸丁酯(BA)、甲基丙烯酸甲酯(MMA))分别预先接枝到低密度聚乙烯(LDPE)大分子链上制备接枝材料,通过红外光谱测试分析得出接枝单体皆成功接枝到LDPE大分子链上,熔融指数与凝胶含量测定表明材料的流变性能并未发生显著改变,X射线衍射测试与扫描电子显微镜观测发现接枝改性材料的结晶特性保持与基础树脂相似。进一步对三种接枝母料按一定比例稀释并完成交联过程,通过变温直流电导测试发现三种接枝改性材料的电导率-温度敏感性均出现不同程度的下降,综合高温空间电荷测试可以得出,接枝MA的XLPE材料电导率-温度敏感性下降幅度最大、空间电荷分布特性优异;结合第一性原理仿真计算可以进一步得到,三种接枝单体改性XLPE模型的陷阱能级较为一致,其直流电性能的改善效果与接枝单体的静电势分布存在显著关联。

蔬菜嫁接砧穗互作分子机制研究进展

嫁接技术是园艺作物增产、改良品质和增强抗逆性最经济有效的手段之一,其应用范围仍在不断扩大。除了要求嫁接技术不断提高外,还需进一步探索嫁接亲和性与砧穗互作的机制。嫁接成活包括一系列的生理、生化过程,嫁接激活、激素通路或参与维管束形成相关基因都有可能参与嫁接组织的再生重建,明确其调控机制具有重要意义。嫁接是砧木/接穗相互识别与作用的过程,砧穗间长距离信号传导是理解嫁接生理的基础。不同基因型的砧木/接穗嫁接组合,嫁接植株在生长发育、表型、产量及胁迫抗性方面表现不同。本文就蔬菜嫁接砧穗互作分子机制的研究进展进行综述,如嫁接成活、砧穗间遗传信号传递、嫁接与表观遗传变化及嫁接与基因表达,以期为深入研究蔬菜嫁接分子机制提供理论参考,为砧木选择和蔬菜种质材料创新提供指导。