Preparation of chitosan/hydroxyapatite guided membrane used for periodontal tissue regeneration

<正>In an effort to develop biomaterials to meet guided tissue regeneration(GTR) standards for periodontal tissue recovery,a homogeneous and transparent chitosan(CS)/hydroxyapatite(HA) membrane with potential applications as GTR barrier in periodontal therapy has been prepared via in situ compositing.The membrane has been designed to have a smoothrough asymmetric structure that meets the demand for GTR.Component and morphology of the membrane are characterized by XRD and SEM.It can be indicated that HA was in situ synthesized uniformly in the CS membrane.Mechanical experiments of the membranes with various HA contents show that their tensile strengths are adequate for periodontal therapy.Biological properties of the membrane have been performed by cell toxicity assays,hemolysis tests and animal experiments.Results indicate that the membrane has good biocompatibility and inductive effect for cell growth.Therefore this membrane can be potentially applied as GTR barrier membrane for periodontal tissue regeneration.     

Fabrication and characterization of low-cost freeze-gelated chitosan/collagen/hydroxyapatite hydrogel nanocomposite scaffold

In the present research, chitosan/collagen and chitosan/collagen/nano-hydroxyapatite (nHAP) hydrogel nanocomposites were prepared using naturally extracted chitosan from Persian Gulf shrimp wastes and rat tail-tendon collagen. Freeze-gelation method was used to prepare highly porous scaffolds. The morphology, chemical structure, water retainability, and thermal properties were characterized using SEM, FTIR, water content experiment, simultaneous thermal analysis (STA), respectively. Atomic force microscopy (AFM) nanoindentation and unconfined compression test were used to assess different feature of the mechanical properties of the hydrogels. The obtained results were so promising that the prepared nanocomposites can be considered as a potential candidate for cartilage tissue engineering.     

Preparation and characterization of novel hydroxyapatite/copper assemblies with well-defined morphologies

Micrometer-sized powders with small crystallite sizes, high dispersion, and high copper contents, like Cu and/or Cu₂O assembled on core particles would find potential applications in fields of catalysts, transparent conducting films and plasmonic-based technologies. Novel hydroxyapatite (HA)/copper assemblies were synthesized via a facile glucose reduction route. During hydrothermal treatment, copper ions were firstly released after dissolution of copper-modified HA, then reduced by glucose and finally assembled as shell on HA aggregates. After 12 h, cuprous oxide grew with truncated-octahedron morphology. When the reduction time was prolonged to 24 and 36 h, Cu phase was formed in situ via glucose reduction of Cu₂O. Interestingly, HA/copper assemblies with well-defined morphologies were prepared under different reaction conditions. With presence of more Na₂CO₃, the reduction of copper ion occurred at a fast rate, which resulted in formation of spherical assemblies. Contrastingly, reduction reaction hardly occurred without Na₂CO₃ addition and assemblies with irregular morphology were prepared. Additionally, copper fibers with length of millimeters were prepared without Na₃Cit addition. The UV–Vis absorbance peak of assemblies showed a blue or red shift due to the effect of crystalline size and/or hollowing process.     

Degradation of poly(lactide-co-glycolide) and its composites with carbon fibres and hydroxyapatite in rabbit femoral bone

The aim of the present work was to analyse the degradation rate of PGLA copolymer depending on a modifier (hydroxyapatite, carbon fibres) under in vivo conditions (rabbit femoral bone). Also, the influence of the implantation site on the degradation rate of a copolymer (rabbit mandible and femoral bone) was analyzed as a continuation of our previous research.The structural and phase changes of poly(lactide-co-glycolide) and its composite with hydroxyapatite and carbon fibres were determined on the basis of IR and NMR spectroscopy. Additionally, microscopic observations with elemental analyses were performed (SEM, EDS).The addition of a modifying phase accelerates implant degradation. However, modifying additives promote regeneration of the treated bone tissue simultaneously with faster polymer degradation. The compositions of a copolymer and composites are variable during degradation.The process of copolymer degradation in the femoral bone is much faster in comparison with previous studies on mandibles. This may be caused by higher activity of osteoblasts, differences in blood supply and oxygenation of tissue as well as different anatomical structure of these two kinds of bones.FTIR and NMR methods allow for following the changes occurring in the resorbable copolymer structure with time and they are very useful tools in analyzing the degradation mechanism and rate of aliphatic polyesters and their composites.     

A study of adsorption behavior of human serum albumin and ovalbumin on hydroxyapatite/chitosan composite

In situ adsorption of human serum albumin (HSA) and ovalbumin (OVA) was real-time monitored by piezoelectric quartz crystal impedance (PQCI) technique to fully understand the initial cellular response on hydroxyapatite/chitosan (HAP/CS) composite. The PQCI parameters, such as resonant frequency (f), static capacitance (C_s), and motional resistance (R_m) were measured for investigating the kinetic adsorption behaviors of both proteins. The change in frequency shifts (Δf) depends on the amount of the adsorbed protein, and the change in motional resistance (ΔR_m) results from the microporosity variation of HAP/CS coating. The results show that the amount of the absorbed HSA is much greater than that of OVA on HAP/CS coating because of the unique construction of HSA as well as a flexible protein. Furthermore, Δf and ΔR_m data were fitted according to the kinetic exponential decay equations. It can be seen that there is only one adsorption process for OVA, but the absorption process for HSA is followed by a rearrangement process, and the former process is faster than the rearrangement process. Subsequently, the composite binding with proteins were demonstrated by the Fourier transform infrared (FTIR), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS).     

Au/FeOx-羟基磷灰石催化CO氧化反应中羟基磷灰石和FeOx的作用

近期我们报道了Au/FeO_x-羟基磷灰石(HAP, Ca₁₀(PO₄)₆(OH)₂)催化剂应用于CO氧化反应的研究结果,该催化剂不仅具有很高的低温CO氧化活性和反应稳定性, 同时也具有很好的高温抗烧结性能, 即使600℃焙烧后依然能够维持很好的CO氧化反应活性. 为了进一步研究Au/FeO_x-HAP催化CO氧化反应中HAP和FeO_x的作用, 本文对该催化剂进行了更加深入的表征. X射线光电子能谱结果表明, HAP能与Au和FeO_x形成强相互作用, 进而在高温条件下稳定Au和FeO_x纳米粒子. 根据原位漫反射红外结果, FeO_x则主要通过改变反应路径和中间产物的方式起到促进催化剂CO氧化活性的作用. 结合透射电镜, 穆斯堡尔谱和原位漫反射红外结果可知, Au/FeO_x-HAP催化剂良好的反应稳定性源于其优异的抗碳酸盐累积能力.     

Design of Ag3PO4 for highly enhanced photocatalyst using hydroxyapatite as a source of phosphate ion

The effect of hydroxyapatite on structure, particle size, and band gap energy of silver orthophosphate (Ag₃PO₄) have been investigated. The hydroxyapatite as a source of phosphate ion was prepared using the coprecipitation of CaCl₂ and KH₂PO₄. To produce the product of Ag₃PO₄, the as-synthesized hydroxyapatite was suspended in water and quickly added to a silver nitrate solution. The obtained photocatalysts were characterized using XRD, SEM, DRS, and XPS. The high crystallinity of single phase Ag₃PO₄ was easily produced using the hydroxyapatite. Photocatalytic activities of the product were evaluated using RhB decomposition under blue light irradiation. The hydroxyapatite as a source of phosphate ion dramatically decreases the particle size and increases the absorption in the visible region. This obtained photocatalyst significantly improves the photocatalytic activity. The mechanism of reaction works in the following order: holes > superoxide radical > hydroxyl radical.     

Optimizing the mechanical and surface topography of hydroxyapatite/Gd2O3/graphene oxide nanocomposites for medical applications

A ternary nanocomposite (TNC) was fabricated for introducing multifunctional properties for various biomedical applications. The nanocomposites consist of hydroxyapatite (HAP) combined with/without graphene oxide (GO) and gadolinium oxide (Gd₂O₃). The lattice constants of HAP were around 9.4285 and 6.7476 Å, while for Gd₂O₃ was around 10.8441 Å. The morphological investigation detected the nanosheets of GO, and nanorods of HAP/Gd₂O₃ with length of 27 nm. Moreover, the topological study based on a field emission scanning electron microscope (FESEM) showed that HAP/GO had average roughness (R_a) of 4.8 nm, and the root mean square value (R_q) with a value of 7 nm. Furthermore, the average pore size reached 7.99 nm for the NC of HAP/GO. In addition, the cumulative surface area using the density functional theory (DFT) method was calculated at around 44.61 m²/g for TNC. The cell viability in vitro of osteoblast cell line improved from 95.6 ± 0.6% to 96.7 ± 0.5% which indicates the biocompatibility of the implants to be used in biomedical applications.     

In vitro and in vivo evaluations of nanofibrous nanocomposite based on carboxymethyl cellulose/polycaprolactone/cobalt-doped hydroxyapatite as the wound dressing materials

These days, Ophthalmic wound treatment is a major problem; due to its nature, bio/materials are the best choices as wound dressing materials. The main objective of the current survey is to develop and investigate effective wound dressing materials for skin care applications. In these ways, we combined the good biological properties of Cobalt-doped hydroxyapatite particles (CoHAp) with the structural properties of Polycaprolactone (PCL)/ carboxymethyl cellulose (CMC) nanofibers. Electrospinning and co-precipitation methods were used to synthesize nanofibers and CoHAp particles, respectively. Nanocomposites were synthesized in the absence and different percentages of CoHAp. The PCL/CMC, PCL/CMC/CoHA 5 %, PCL/CMC/CoHA 10 %, and PCL/CMC/CoHA 15 % formulated nanocomposites have the diameter of 383 ± 50, 391 ± 84, 441 ± 65, and 495 ± 99 nm, respectively. The synthesized nanofibrous wound dressing porosity and water absorption capacity were in the range of 40 to 60 % and 32 to 63 %, respectively. Hemo and cytocompatibility of the nanofibrous wound dressing were analyzed by in vitro evaluation, and the results were satisfactory and the structures were fully biocompatible. The PCL/CMC/CoHA 10 % wound dressing, were selected as the best nanocomposites for wound healing based on our animal studies on the healing outcomes. The results showed that the PCL/CMC nanofibers-Cobalt-doped HAp wound dressing is an effective bioactive nano-biomaterials for the wound healing process.     

Preparation of 3D fibroin/chitosan blend porous scaffold for tissue engineering via a simplified method

In this work, we developed a simple and flexible method to manufacture a 3D porous scaffold based on the blend of regenerated silk fibroin (RSF) and chitosan (CS). No crosslinker or other toxic reagents were used in this method. The pores of resulted 3D scaffolds were connected with each other, and their sizes could be easily controlled by the concentration of the mixed solution. Compared with pure RSF scaffolds, the water absorptivities of these RSF/CS blend scaffolds with significantly enhanced mechanical properties were greatly increased. The results of MTT and RT-PCR tests indicated that the chondrocytes grew very well in these blend RSF/CS porous scaffolds. This suggested that the RSF/CS blend scaffold prepared by this new method could be a promising candidate for applications in tissue engineering.     

掺氮介孔炭作为双功能材料用于氧还原与超级电容器

以壳聚糖为含氮碳源,正硅酸乙酯为软模板,硝酸镍为催化剂,通过简单的低温水热法及后续炭化,成功合成出掺氮介孔炭材料（NMC-1）.NMC-1含有多孔结构以及氮氧等杂原子,能提高其电催化性能、双电层电容与赝电容.由于NMC-1在碱液中表现出显著的催化氧还原反应活性和具有较高的超级电容器比电容（在0.2A/g时为252F/g）及好的循环稳定性,因此,它有可能作为一种可再生、环保的双功能材料同时应用于燃料电池与超级电容器领域.     

固相微萃取新型活性炭涂层萃取头的研究

利用合成的有机硅树脂胶粘剂和活性炭微粉首次制成活性涂层萃取头。通过苯系物(BTEX)表征了涂层表观结构、厚度及萃取性能。对苯、甲苯、乙苯、对二甲苯、邻二甲苯等进行固相微萃取,结果表明:该萃取头热稳定性好,最高使用温度可达290℃;使用寿命长,250℃解吸条件下反复使用140余次以后,膜层没有脱落或性能下降的现象。该涂层对苯系物的最低检出质量浓度在0 21～0 94μg L之间。与100μm的商品聚二甲基硅氧烷(PDMS)涂层相比,对苯系物的富集能力整体上相当。     

Fabrication and characterization of chitosan-gelatin/single-walled carbon nanotubes electrospun composite scaffolds for cartilage tissue engineering applications

Cartilage is a connective tissue with a slow healing rate due to lack in blood circulation and slow metabolism. Designing tissue engineering scaffolds modified based on its specific features can assist its natural regeneration process. In this study, the chitosan-gelatin/single-walled carbon nanotubes functionalized by COOH (SWNTs-COOH) nanocomposite scaffolds were fabricated through electrospinning. The effect of each component and different duration of cross-linking were assessed in terms of morphology, porosity, chemical structure, thermal behavior, mechanical properties, wettability, biodegradability, and in vitro cell culture study. Adding SWNTs-COOH decreased fiber diameter, water contact angle and degradation rate while increased tensile strength, hydrophilicity, stability and cell viability, due to their high intrinsic electrical conductivity, and mechanical properties and the presence of COOH functional groups in its structure. All the sample presented a porosity percentage of more than 80%, which is essential for tissue engineering scaffolds. The presence SWNTs-COOH did not have any adverse effect on cytocompatibility. The optimal cross-linking time increased the stability of the scaffolds in PBS. It can be concluded that the chitosan-gelatin/1wt% SWNTs-COOH scaffold can be appropriate for cartilage tissue engineering applications.     

A novel approach to massive preparation of LiV3O8 as a cathode material for lithium rechargeable battery

The layered cathode materials of LiV₃O₈ were successfully prepared for the lithium rechargeable battery via a wet-chemistry synthesis method. The as-synthesized materials were characterized by XRD (powder X-ray diffraction), SEM (scanning electron microscope) and galvanostatic charge-discharge test. The results indicate that this soft-synthesis technique offers reduced calcinations temperature, preferred surface morphology and better electrochemical performance. Among the thus-prepared materials, the material obtained at 350 °C demonstrates the first discharge capacity as high as 308 mAh g^-1 in the range of 4.0 ～1.7 V at a current rate of 30 mA g^-1 and remains at a stable discharge capacity of 250 mAh g^-1 within 30 cycles.     

Preparation and Characterization of a Novel Drug Delivery System: Biodegradable Nanoparticles in Thermosensitive Chitosan/Gelatin Blend Hydrogels

A novel injectable in situ gelling drug delivery system (DDS) consisting of biodegradable N-(2-hydroxyl) propyl-3-trimethyl ammonium chitosan chloride (HTCC) nanoparticles and thermosensitive chitosan/gelatin blend hydrogels was developed for prolonged and sustained controlled drug release. Four different HTCC nanoparticles, prepared based on ionic process of HTCC and oppositely charged molecules such as sodium tripolyphosphate, sodium alginate and carboxymethyl chitosan, were incorporated physically into thermosensitive chitosan/gelatin blend solutions to form the novel DDSs. Resulting DDSs interior morphology was evaluated by scanning electron microscopy. The effect of nanoparticles composition on both the gel process and the gel strength was investigated from which possible hydrogel formation mechanisms were inferred. Finally, bovine serum albumin (BSA), used as a model protein drug, was loaded into four different HTCC nanoparticles to examine and compare the effects of controlled release of these novel DDSs. The results showed that BSA could be sustained and released from these novel DDSs and the release rate was affected by the properties of nanoparticle: the slower BSA release rate was observed from DDS containing nanoparticles with a positive charge than with a negative charge. The described injectable drug delivery systems might have great potential application for local and sustained delivery of protein drugs.     

Preparation and applications of a variety of fluoroalkyl end-capped oligomer/hydroxyapatite composites

A variety of fluoroalkyl end-capped oligomers were applied to the preparation of fluorinated oligomer/hydroxyapatite (HAp) composites (particle size: 38-356 nm), which exhibit a good dispersibility in water and traditional organic solvents. These fluoroalkyl end-capped oligomer/HAp composites were easily prepared by the reactions of disodium hydrogen phosphate and calcium chloride in the presence of self-assembled molecular aggregates formed by fluoroalkyl end-capped oligomers in aqueous solutions. In these fluorinated HAp composites thus obtained, fluoroalkyl end-capped acrylic acid oligomers and 2-methacryloyloxyethanesulfonic acid oligomer/HAp nanocomposites afforded transparent colorless solutions toward water; however, fluoroalkyl end-capped N,N-dimethylacrylamide oligomer and acryloylmorpholine oligomer were found to afford transparent colorless solutions with trace amounts of white-colored HAp precipitants under similar conditions. HAp could be encapsulated more effectively into fluorinated 2-methacryloyloxyethanesulfonic acid oligomeric aggregate cores to afford colloidal stable fluorinated oligomer/HAp composites, compared to that of fluorinated acrylic acid oligomers. These fluorinated oligomer/HAp composites were applied to the surface modification of glass and PVA to exhibit a good oleophobicity imparted by fluorine. HAp formation was newly observed on the modified polyethylene terephthalate film surface treated with fluorinated 2-methacryloyloxyethanesulfonic acid oligomers and acrylic acid oligomer/HAp composites by soaking these films into the simulated body fluid.     

新型介孔羟基磷灰石/壳聚糖-万古霉素药物释放系统复合材料的制备及体外抗菌和成骨能力

采用冷冻干燥法合成了介孔羟基磷灰石(HA)/壳聚糖(CS)-万古霉素(VCM)药物释放系统复合材料, 利用SEM, XRD和FTIR等方法对材料进行了表征. 结果证实CS与HA混合复合材料具有良好的孔径和孔隙率, 万古霉素吸附于复合材料的表面和内部. 细胞毒性实验[噻唑蓝(MTT)比色法]结果表明, 材料可以促进成骨细胞增殖且具有良好的细胞相容性. 体外抑菌实验结果证实此材料可长时间抑制耐甲氧西林金葡菌(MRSA)的生长, 具有良好的抑菌和杀菌能力. 细胞黏附实验结果表明, 成骨细胞附着于材料表面增殖并通过孔道延伸. 实时聚合酶链式反应(RT-PCR)实验结果表明, 在成骨相关标志产物胶原蛋白-1(COL-1)及骨形态发生蛋白-2(BMP-2)基因上均有较高的表达, 表明材料在体外可以促进成骨细胞生长, 具有良好的成骨能力.     

1,4-dicyanobenzene as a scaffold for the preparation of bimetallic actinide complexes exhibiting metal-metal communication

Reaction of two equivalents of [(C(5)Me(4)Et)(2)U(CH(3))(Cl)] (6) or [(C(5)Me(5))(2)Th(CH(3))(Br)] (7) with 1,4-dicyanobenzene leads to the formation of the novel 1,4-phenylenediketimide-bridged bimetallic organoactinide complexes [{(C(5)Me(4)Et)(2)(Cl)U}(2)(mu-{N==C(CH(3))-C(6)H(4)-(CH(3))C==N})] (8) and [{(C(5)Me(5))(2)(Br)Th}(2)(mu-{N==C(CH(3))-C(6)H(4)- (CH(3))C==N})] (9), respectively. These complexes were structurally characterized by single-crystal X-ray diffraction and NMR spectroscopy. Metal-metal interactions in these isovalent bimetallic systems were assessed by means of cyclic voltammetry, UV-visible/NIR absorption spectroscopy, and variable-temperature magnetic susceptibility. Although evidence for magnetic coupling between metal centers in the bimetallic U(IV)/U(IV) (5f(2)-5f(2)) complex is ambiguous, the complex displays appreciable electronic communication between the metal centers through the pi system of the dianionic diketimide bridging ligand, as judged by voltammetry. The transition intensities of the f-f bands for the bimetallic U(IV)/U(IV) system decrease substantially compared to the related monometallic ketimide chloride complex, [(C(5)Me(5))(2)U(Cl){-N==C(CH(3))-(3,4,5-F(3)-C(6)H(2))}] (11). Also reported herein are new synthetic routes to the actinide starting materials [(C(5)Me(4)Et)(2)U(CH(3))(Cl)] (6) and [(C(5)Me(5))(2)Th(CH(3))(Br)] (7) in addition to the syntheses and structures of the monometallic uranium complexes [(C(5)Me(4)Et)(2)UCl(2)] (3), [(C(5)Me(4)Et)(2)U(CH(3))(2)] (4), [(C(5)Me(4)Et)(2)U{-N==C(CH(3))-C(6)H(4)-C==N}(2)] (10), and 11.     

Mesoporous porphyrinic metal-organic framework nanoparticles/3D nanofibrous scaffold as a versatile platform for bone tumor therapy

Removal of residual tumor cells and regeneration of large bone defects are urgently required after surgical resection of bone tumors. To address these issues, a bifunctional scaffold with high photothermal effect and osteogenesis was developed for bone tumor therapy. Sintered mesoporous imidazolate framework 8 (ZIF8) nanoparticles with porphyrin-like macrocycles were synthesized by calcination of ZIF8 precursors under an N₂ atmosphere. The prepared ZIF8 possesses good photothermal efficacy and drug loading capability. Phenamil (Phe), an activator of bone morphogenetic protein pathways, was encapsulated into ZIF8 before loading onto gelatin nanofibrous (GF) scaffolds. The loaded Phe exhibited sustained and near-infrared triggered release profiles, which is capable of promoting bone morphogenetic protein 2 induced osteogenic differentiation even under near-infrared treatment. Moreover, our studies revealed that the photothermal effect of GF/ZIF8-Phe scaffolds can kill MG-63 cells in vitro and inhibit subcutaneous tumor growth in vivo. Therefore, the GF/ZIF8-Phe scaffold represents a novel bifunctional platform for tumor therapy and bone regeneration.     

LiNb3O8 as a novel anode material for lithium-ion batteries

A novel anode material, LiNb₃O₈, whose theoretical capacity is 389 mAh/g assuming two-electron transfers (Nb⁵⁺ → Nb³⁺), was prepared by a solid state reaction. It was found that only 3.8 Li per unit formula can be inserted into the as-prepared micro-sized sample. However, when the sample was ball-milled with acetylene black to form a mixed conducting network, 5.4 Li can be inserted in the same voltage range and 2.8 Li (180 mAh/g) can be reversibly extracted after 50 cycles.