The formation of hydroxyapatite–calcium polyacrylate composites

Tetracalcium phosphate (TetCP, Ca₄(PO₄)₂O) reacts rapidly with polyacrylic acid (PAA). Complete reaction results in the formation of hydroxyapatite (HAp) and calcium polyacrylate. Consequently, this combination of reactants can react to form a dental cement. However, reaction occurs so rapidly that it would be difficult to achieve a homogeneous mixture of reactants suitable for use in restorations. In order to explore extending the working time, the effects of prehydrating the TetCP to form surface layers of HAp on the TetCP particles was explored. Prehydration was found to be an effective means of allowing workability. Therefore, the effects of the proportions of TetCP and PAA, with and without HAp filler, on cement properties were investigated. The extents of the reactions were investigated by X-ray diffraction analysis; the extents of PAA neutralization were studied by Fourier transform infra-red spectroscopy (FTIR); pore structures were determined by mercury intrusion porosimetry; microstructures were observed by scanning microscopy, and compressive strengths were determined. After curing for 17 days at room temperature PAA neutralization was almost complete; however, residual TetCP could be detected by X-ray diffraction and PAA by FTIR. As expected, the compressive strengths of the cements showed a dependence on the liquid (water+polymer)-to-solid (TetCP+HAp filler) used. The presence of HAp filler caused a significant decrease in compressive strength and increasing the proportion of HAp filler resulted in a decrease in the compressive strength. The characteristics of the load–deflection curves showed a dependence on the presence of HAp filler. In the absence of filler, two slopes were observed in the curves whereas a linear curve, typical of a ceramic, was observed when HAp filler was present. Mercury intrusion porosimetry (MIP) indicated the majority of the porosity was present in pores larger than 0.1 m. Porosity increased with increasing liquid-to-solids ratio and with an increasing proportion of HAp filler at a constant liquid-to-solids ratio. Microstructural observations indicated the effect of HAp filler on increasing porosity was the result of porosity present in the filler itself. Thus, poorly consolidated HAp filler contributed to increased porosity and reduced compressive strength. © 1999 Kluwer Academic Publishers     

Introducing porosity into polyimide nanoparticles

Novel porous polyimides (PIs) having diameters of several hundred nanometers have been fabricated successfully from precursor poly(amic acid) (PAA) derivatives with poly(acrylic acid) (PAS) as the porogen, using a reprecipitation method and subsequent imidization. The superficial high porosity with deep pores was introduced when using a more compatible combination of PAA and the porogen, i.e., PI (BPDA-PDA) and PAS rather than PI (10FEDA-4FMPD and PAS); the pore sizes ranged from 20 to 100 nm. The resulting porous PI nanoparticles had thermally stabilities (determined from their 5% weight loss temperatures at 400 degrees C) similar to those of corresponding PI nanoparticles lacking porous structures. Microphase separation within the PAA nanoparticles after reprecipitation induced the porous surface structure, the properties of which were influenced by the molecular weight of PAS and the chemical structure of PAA. These unique porous PI nanoparticles have great potential for application as low-k materials in next-generation technologies.     

Surface Modification of an Alumina‐Based Bioceramic for Cement Application

Biograde zirconia toughened alumina (ZTA) has found wide application in load bearing endoprosthetic implants due to high strength, fracture toughness, and wear resistance. In order to enhance bonding to acrylic bone cement (BC) for implants, fixation modification of ZTA with a thin layer of porous anodic alumina (PAA) was investigated. An Al‐layer of approximately 500 nm was sputtered on the ZTA substrate which subsequently was electrochemically oxidized by anodic polarization in H₂C₂O₄ or H₃PO₄ solution. PAA layers with a total porosity ranging from 11 to 30%, mean pore spacing of 90–200 nm and pore diameters of 30–110 nm were prepared. Compared to unmodified ZTA/BC interface (≈ 30 MPa), the PAA modified specimens (ZTA/PAA/BC) achieved a significantly higher interface bonding strength (≈ 60 MPa) measured by four point bending on composite beam specimens. While crack propagation in the unmodified ZTA/BC specimen was found to proceed along the interface, fracture analysis on the ZTA/PAA/BC specimens showed a mixed mode fracture with part of the fracture propagation localized along the PAA/BC interface and part through BC. Thus, pore structure controlled mechanical interlocking is expected to offer a high potential for applying PAA surface modification to improve biomaterial to BC bonding.     

Development of an optical model for steady state porous anodic films on aluminium formed in phosphoric acid

Porous anodic oxide films on aluminium formed in phosphoric acid (PAA) have been characterized nondestructively by spectroscopic ellipsometry. Compared to previous studies on porous films formed in sulfuric acid, the optical behaviour of PAA films reveals new features which have been attributed to film-substrate interface roughness and optical anisotropy effects. On one hand relatively large interface roughness has been simulated by a graded index model. On the other hand, the implementation of uniaxial anisotropy in the optical model of the PAA film enables to interpret spectroscopic ellipsometry data acquired at multiple angles of incidence in terms of the morphology of the films. More specifically, accurate and physically realistic values are found for the porosity and porous film thickness. Although more difficult to interpret from the optical findings, the thickness of the barrier part of the porous film can also be estimated. The ellipsometry characterizations are confirmed by complementary TEM analysis of various films. Finally, the anisotropy exhibited by the PAA films is in line with recent theoretical predictions of the optical behaviour of arrays of parallel cylindrical capillaries in an isotropic medium proposed by other authors.     

多孔性聚酰亚胺纳米粒子的制备

介绍了用"再沉淀法"并经亚胺化成功制成PI(BPDA-PDA)多孔性粒子,粒径为几百nm;在此同时,加入与PAA(PI的先驱体)有较好相容性聚丙烯酸PAS为多孔源(porogen),而在其粒子表面生成较深的、较高空穴率的空穴,在20～100nm之间.这种多孔性PI纳米粒子可作为下一代低k值PI膜材料候选者之一.     

磷石膏/聚氨基酸医用多孔复合材料的制备与表征

用化学共沉淀法合成了钙磷原子比(Ca/P)为1.50和1.67的磷石膏(PG), 用熔融聚合法制备四元氨基酸共聚物(PAA4), 用挤出发泡法制备了两种磷石膏/四元氨基酸共聚物(PG/PAA4)多孔复合材料。通过TGA、SEM、XRD、IR、EDS等对两种复合材料的组成结构进行了表征, 并研究了复合材料在磷酸缓冲液(PBS)中的体外降解性能。结果表明: 无机组分PG在两种复合材料中分布均一, 质量分数均为60%左右; PG/PAA4复合材料的孔径为100~400 μm, 孔隙率在60%左右; 多孔复合材料的有机和无机相之间有化学作用。PG/PAA4复合材料具有良好的体外降解性能, 其失重率随PG钙磷比的增加而增加, 降解液的pH值维持在6.9~7.4之间。PG/PAA4复合材料降解后, 其表面沉积了片状钙磷化合物, 推测该复合材料可能具有生物活性。     

Development of a novel porous cryo-foam for potential wound healing applications

This body of work describes the development of a porous hydrogel for wound healing applications. In the present study poly (vinyl alcohol) (PVA) and poly (acrylic acid) (PAA) based hydrogels were prepared, and their properties were examined. Varying concentrations of the polymers and distilled water were used to prepare the hydrogels. The use of a high shear mixer, for foaming the PVA and PVA/PAA gels, and how this physical change can affect the structure and porosity of the hydrogel in question, represents a key feature of this work. The mechanical and thermal properties were determined by parallel plate rheometry and modulated differential scanning calorimetry (MDSC) respectively. The results indicated that the hydrogels containing low concentration of PVA and high volume of H₂O are significantly weaker than those synthesised with higher concentrations of PVA. The thermal analysis shows distinct endotherms and provides evidence of crystallisation. The chemical structure of the hydrogels was confirmed by means of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR).     

The fabrication of ordered nanoporous metal films based on high field anodic alumina and their selected transmission enhancement

A two-step high field anodization and a controllable barrier layer removing process have been used for the fabrication of porous anodic alumina (PAA) with different morphologies. Based on the PAAs, porous noble metal films with widely tunable pore size and inter-pore distance have been realized by a simple sputtering method. Their morphology and optical properties were studied with a field-emission scanning electron microscope, and ultraviolet and ultraviolet-visible spectrophotometers. An enhanced light transmission of the nanoporous metal films was detected. The transmissivity of a normal incidence light can be enhanced over ten times within a certain selected wavelength range. The intensity and position of the transmission peak depend on the morphology and porosity of the metal films.     

Synthesis and in vitro characterization of a novel PAA–ATP conjugate

The objective of this study was to improve the multifunctional properties of poly(acrylic acid) (PAA) by covalent attachment of 4-aminothiophenol (ATP) to its backbone. The permeation enhancing effect of PAA–ATP together with glutathione was evaluated in Ussing-type chambers using fluorescein isothiocyanate dextran as model compound. The mucoadhesive properties were evaluated in vitro on freshly excised porcine intestinal mucosa through the rotating cylinder method. The resulting conjugates PAA–ATP1 and PAA–ATP2 displayed 168 ± 35 and 426 ± 55 μmol immobilized free thiol groups per gram polymer, respectively. In addition, 279 ± 28 and 139 ± 22 μmol disulfide bonds per gram polymer, respectively, were identified on PAA–ATP1 and PAA–ATP2. Within disintegration studies in aqueous buffer solution, the modified polymers showed improved cohesive properties. Because of the immobilization of ATP, the swelling of PAA–ATP1 and PAA–ATP2 improved 12.0- and 17.8-fold, respectively. The adhesion times of the conjugates PAA–ATP1 and PAA–ATP2 were more than 20- and 30-fold increased in comparison to unmodified PAA. Furthermore, conjugates PAA–ATP1 and PAA–ATP2 exhibited a 1.86- and 2.07-fold higher permeation enhancing effect, respectively, over unmodified PAA. According to these results, PAA–ATP conjugates represent a very promising novel type of thiomer for the development of various mucoadhesive drug delivery systems.     

Effectiveness of a dispersant for the thickening of alumina slurries whilst retaining the fluidity

Concentrated alumina slurries were fluidized in an optimum amount of polyacrylates (PAA) in the content region where a good dispersion was obtained. Dispersion was necessary, but not sufficient for fluidization. The expected role of PAA in the thickening was retention of a water-reducing ability to retain the fluidity. Thickening of the alumina slurry to the limit of retaining the fluidity was achieved by the amount of PAA at which the flow point showed a minimum. The flow of alumina slurries around the limit was approximated by the Bingham model which was characterized by the yield stress and the Bingham viscosity. The flow curves of the slurries containing insufficient PAA had a yield stress which decreased with increasing amount of PAA and disappeared at an optimum amount of PAA to give a minimum flow point. The yield stress again increased retaining the low Bingham viscosity with increasing amount of PAA, to exceed the optimum amount for molecular weights smaller than 10 000. On the other hand, the Bingham viscosity increased without increasing the yield stress with increasing amount of PAA, to exceed the optimum amount for molecular weights larger than 20 000. The effect of PAA on the dispersion and flow behaviour could be explained by the electrostatic stabilization based on the Derjaguin-Landau, Verwey-Overbeek (DLVO) theory for the PAA with a molecular weight smaller than 10 000, and by the steric stabilization for the PAA with a molecular weight larger than 20 000.     

Extensions of polyacrylic acid ammonium salts in the adsorption layer to fluidize alumina slurries

An average shell volume occupied in the adsorption layer on alumina by a polyacrylic acid ammonium salts molecule (PAA) defined as the average area occupied by an adsorbed PAA on alumina multiplied by the average thickness of the water layer at the limit of thickening, has been calculated from the adsorbed amount of PAA and from the flow points of alumina in the presence of PAA of different molecular weights. A steric effect of the PAA dispersant on the dispersion of alumina resulted in a flow with no yield stress. This was due to the change of the extension of PAA in the adsorption shell from a sphere to an ellipsoid with a long axis which exceeded the effective distance that the van der Waals attraction force reaches at a molecular weight for the PAA of between 10 000–20 000.     

Healable and Mechanically Super‐Strong Polymeric Composites Derived from Hydrogen‐Bonded Polymeric Complexes

It is challenging to fabricate mechanically super‐strong polymer composites with excellent healing capacity because of the significantly limited mobility of polymer chains. The fabrication of mechanically super‐strong polymer composites with excellent healing capacity by complexing polyacrylic acid (PAA) with polyvinylpyrrolidone (PVPON) in aqueous solution followed by molding into desired shapes is presented. The coiled PVPON can complex with PAA in water via hydrogen‐bonding interactions to produce transparent PAA–PVPON composites homogenously dispersed with nanoparticles of PAA–PVPON complexes. As healable materials, the PAA–PVPON composite materials with a glass transition temperature of ≈107.9 °C exhibit a super‐high mechanical strength, with a tensile strength of ≈81 MPa and a Young's modulus of ≈4.5 GPa. The PAA–PVPON composites are stable in water because of the hydrophobic interactions among pyrrolidone groups. The super‐high mechanical strength of the PAA–PVPON composite materials originates from the highly dense hydrogen bonds between PAA and PVPON and the reinforcement of in situ formed PAA–PVPON nanoparticles. The reversibility of the relatively weak but dense hydrogen bonds enables convenient healing of the mechanically strong PAA–PVPON composite materials from physical damage to restore their original mechanical strength.     

The influence of poly(acrylic acid) molar mass and concentration on the properties of polyalkenoate cements Part III Fracture toughness and toughness

The influence of poly(acrylic acid), PAA molar mass and concentration on fracture toughness and toughness of glass polyalkenoate cements was investigated. Fracture toughness and toughness increased with both the molar mass of the PAA and its concentration. The fracture toughness and toughness increased dramatically with concentration for the highest molar mass PAA studied. However the increase in fracture toughness and toughness with PAA concentration was small for the lowest molar mass PAA. The influence of molar mass was greatest at the highest PAA concentration studied and least for the lowest PAA concentration. The toughness results were analysed with a reptation chain pull-out model. The greater dependance of toughness on PAA concentration for high molar mass cements can be explained by the critical molar mass for chain entanglements to form (M _e) being concentration dependant and M _e decreasing with increasing PAA concentration.     

Cationic liposomes-polyallylamine-plasmid nanocomplexes for gene delivery

The aim of the present study was to prepare, characterise and evaluate the transfection efficiency of ternary complexes (lipopolyplexes) composed of cationic liposome, polyallylamine (PAA), plasmid DNA (pDNA). PAA was reacted with a varying amount of a linker, 6-bromohexanoic acid (6-bromo-HA), to prepare a series of modified polymers. Lipopolyplexes consisting of cationic liposome, PAA (or modified PAA), pDNA were prepared. The nanoparticles, so formed, were characterised by their size and zeta potential and were subsequently evaluated for their cytotoxicity and transfection ability on Neuro2A cells. Mean size of prepared complexes ranged from 170 to 280 nm. All lipopolylexes showed a positive zeta potential. Highest transfection efficiency was for lipopolyplex containing PAA 15 kDa-modified polymer and liposome at C/P ratio of 0.5. High molecular weight PAA was more toxic than PAA 15 kDa for Neuro2A cells especially in higher C/P ratio. The results indicate that using the hydrophobic modified PAA in the structure of lipopolyplexes is an effective strategy for improving transfection efficiency.     

PVA-PAAIPN水凝胶的制备及其溶胀性质研究

利用化学交联和循环冰冻-解冻相结合的顺序逼近法，制备了由和聚乙烯醇（PVA）和聚丙烯酸（PAA）复合的具有互穿聚合物网络（IPN）结构的高分子水凝胶。研究了交联剂含量，PAA含量和温度对水凝胶溶胀性质的影响，实验结果表明，30℃时，交联剂含量为1.0mol%的凝胶溶胀度最大，凝胶中PAA含量越大，凝胶的溶胀度越大；具有IPN结构的凝胶具有温度敏感性质；调节凝胶中PAA和交联剂的含量，可以控制凝胶突变体系的大小。     

不同孔径纳米氧化铝膜的表征及其对U251细胞形态的影响

为了观察不同孔径的纳米多孔氧化铝膜对U251细胞形态的影响,采用电化学阳极氧化技术分别在硫酸、草酸、磷酸电解液中制备了3种不同孔径的氧化铝膜,用扫描电镜和X射线能谱仪(Energy dispersive X-ray spectroscopy,EDS)分别对氧化铝膜进行了微观结构与元素组成表征。使用倒置显微镜和扫描电镜观察U251细胞在不同孔径的氧化铝膜表面上的形态及生长粘附情况。结果表明,3种孔径的纳米氧化铝膜表面生长的U251细胞形态存在差异,生长情况不同。细胞在磷酸中制得的纳米氧化铝膜的突触生长情况优于草酸中制备的氧化铝膜,突触生长更牢固,硫酸中制得的氧化铝膜对U251细胞生长的支持作用最差。     

聚丙烯酸/活性炭复合凝胶的制备及溶胀行为

采用自由基溶液聚合的方法,以过硫酸铵(APS)为引发剂,N,N′-亚甲基双丙烯酰胺(NNMBA)为交联剂,制备了聚丙烯酸(PAA)复合活性炭凝胶(PAA/AC)。考察了凝胶在生理盐水和不同pH值缓冲溶液中的平衡溶胀比及溶胀动力学,结果表明,活性炭能有效提高PAA凝胶的平衡溶胀比。蒸馏水中PAA/AC凝胶的平衡溶胀比可达到303(g/g),约为PAA凝胶平衡溶胀比的2.3倍;生理盐水(0.9%g/mL NaCl水溶液)中PAA/AC凝胶的平衡溶胀比可达到60(g/g),约为PAA凝胶平衡溶胀比的2.4倍;在实验设计的pH范围内PAA/AC凝胶的平衡溶胀比比PAA凝胶更高,具有更好的pH值敏感特性。     

In vitro and in vivo biological characterizations of a new poly(amino acids)/calcium sulfate composite material for bone regeneration

A new poly(amino acids)/calcium sulfate (PAA/CS) composite was synthesized by melt polycondensation from a biodegradable PAA copolymer based on 6-aminocaproic acid and the bioactive CS. Its degradability, biocompatibility, bioactivity, and osteoconductivity were evaluated in vitro and in vivo, using phosphate buffer solution soaking test, MG63 adhesion test, and bone defect model repair test, respectively. The PAA/CS composite exhibited a much lower degradation rate than the CS, as 21.6 % of weight loss after immersing in phosphate buffer solution for 5 weeks. Moreover, the pH value of local environment restored to neutrality condition after a sharp drop in the first week. The MG63 cells adhered well on the surfaces of PAA and PAA/CS plates with their filopodium and lamellipodium, and displayed great osteogenic differentiation competence. The bone defect model repair test revealed that the composite could be intimately incorporated with the surrounding bone without causing any deleterious reaction. Radiological and histological evaluation indicated the PAA/CS granules were capable of guiding new bone formation and had a much slower degradation rate than the CS. In conclusion, the PAA/CS composite is expected to be a new bone graft material for its favorable bioactivity and biocompatibility and reasonable degradability.     

复合骨修复材料——聚氨基酸/硫酸钙的生物相容性研究

采用原位熔融缩聚法合成聚氨基酸/硫酸钙(poly(amino acids)/calcium sulfate,PAA/CS)复合材料.分别将PAA/CS圆片和其浸提液与L929细胞共培养后观察细胞形态变化,采用CCK-8试剂盒检测细胞增殖活性,流式细胞仪测定细胞周期.将致密圆柱状PAA/CS材料植入兔胫骨近端干骺端,进行...     

The influence of poly(acrylic acid) molar mass and concentration on the properties of polyalkenoate cements Part I Compressive strength

The influence of poly(acrylic acid), PAA molar mass, concentration and glass volume fraction were investigated on the compressive strength of polyalkenoate cements after ageing for 1, 7 and 28 days in water at 37°C. The compressive strength increased with the molar mass of the polyacid. The increase in compressive strength with molar mass was greater at higher PAA concentrations. Increasing the polyacid concentration generally increased the compressive strength, until PAA concentrations greater than 50% m/m were achieved. Increasing the glass volume fraction had little influence on the compressive strength of cements made with low PAA concentrations, however the compressive strength increased with glass volume fraction for cements that had a high PAA concentration. Increasing the ageing time of the cement prior to testing generally resulted in an increase in compressive strength. However the influence of ageing time was greater in cements made with high PAA concentrations.