药物缓释材料聚磷酸酯-聚乳酸的直接熔融聚合法合成工艺研究

以外消旋乳酸(D,L-LA)、乙二醇和二氯磷酸苯酯为原料,通过熔融聚合法直接合成生物降解材料聚磷酸酯-聚乳酸,用凝胶渗透色谱测定产物的相对分子质量,探讨了预聚方式、催化剂种类和用量,以及熔融聚合反应时间、反应温度对共聚物相对分子质量的影响.在160℃、70Pa、催化剂ZnO的用量0.5%的条件下熔融聚合8h,共聚物的重均分子量可达9200,可以用于药物缓释微球.新合成方法有利于降低聚磷酸酯-聚乳酸作为药物缓释载体材料的合成成本.     

溶液缩聚法直接合成聚乳酸的研究

本研究采用溶液缩聚法直接合成聚乳酸,探索了催化剂用量、单体浓度、反应温度及反应时间对聚乳酸分子量的影响.结果表明:选用辛酸亚锡作为催化剂,用量为0.8%;甲苯作为溶剂,甲苯与乳酸单体的比例为2:1,聚合温度控制在170℃,反应24h,可得到粘均分子量为12320的聚乳酸.     

熔融缩聚合成聚L-乳酸的研究

以L-乳酸为原料,通过熔融缩聚法合成了聚乳酸(PLLA).考察了预聚条件、催化剂种类和用量、催化剂溶解程度、聚合温度及时间对聚乳酸分子量的影响.采用FTIR和1H-NMR分析聚合物结构,GPC测定分子量分布.研究表明,等摩尔量的氯化亚锡(SnCl2)和对甲苯磺酸(TSA)组成的复合催化剂效果最好,SnCl2的用量为预聚物(OLLA)的0.4%为宜;预聚过程和催化剂在OLLA中的充分溶解对提高聚合物分子量具有重要意义;合适的聚合温度约为165 ℃;在发生爬杆现象前,随反应时间的增加,聚乳酸分子量增加.在优化的工艺条件下,可以在较短时间(8 h)内获得分子量为65000左右的聚乳酸.     

Catalyst-free synthesis of macro-scale ZnO nanonail arrays on Si substrate by simple physical vapor deposition

Macro-scale ZnO nanonail arrays have been synthesized on silicon wafer by a simple physical vapor deposition approach without any catalyst. These synthesized ZnO nanonails grow vertically on the substrate with their caps upside. This probably results from the crowding effect. Each ZnO nanonail has a large hexagonal cap and a thinner shaft of several microns in length. Most of the nanonails are perfect single crystals with wurtzite structure and their preferred growth orientation is along [001] direction. The growth mechanism is VS mechanism and the detailed growth process is also proposed. The macro-scale nanonail arrays on Si substrate could offer novel opportunities for both fundamental research and technological applications.     

Catalyst-free synthesis of carbon and boron nitride nanoflakes using RF-magnetron sputtering

Catalyst-free boron nitride (BN) and carbon (C) nanoflakes have been produced by direct radio frequency (RF)-magnetron sputtering on molybdenum and tungsten substrates at or above temperatures of 1000 °C and 800 °C, respectively. Selected-area electron diffraction (SAED) shows that the films are polycrystalline and contain disordered graphite and hexagonal BN. Transmission electron microscopy (TEM) reveals curved or twisted flakes up to several hundred nanometres in length. High resolution transmission electron microscopy (HRTEM) confirms the nanoflake structure to be turbostratic, which is intermediate between an amorphous phase and the ordered layered phases of hexagonal BN or graphite.     

Catalyst-free synthesis of ZnO nanorod arrays on InP (001) substrate by pulsed laser deposition

High-density well-aligned ZnO nanorod arrays were successfully fabricated on ZnO a seed-layer coated InP (001) substrate by using pulsed laser deposition (PLD) technique without metal catalyst. SEM image showed that uniformly distributed droplet-like ZnO seed-layer was formed on the InP wafer. Well-oriented ZnO nanorods were formed perpendicular to the seed-layer coated substrate and well-separated from each other. X-ray diffraction θ-2θ scanning measurements demonstrated that the ZnO nanorods exhibited a strong c-axis orientation with high crystalline quality. The photoluminescence (PL) spectrum measurement illuminated that the ZnO nanorods produced in this work had well optical quality. The well-aligned and separated ZnO nanorods fabricated by this comparatively simple technique shed light on further applications for nanodevices.     

溶液缩聚法制备聚酰亚胺绝缘膜及性能研究

以联苯四酸二酐(BPDA)和4,4’-二氨基二苯醚(ODA)为单体原料,利用溶液缩聚法制备聚酰亚胺(PI)绝缘膜,采用XRD、SEM、FT-IR对不同热亚胺化温度合成的PI薄膜结构和表面形貌进行了表征,利用超高阻微电流测试仪测试了热亚胺化温度和粉体含量对PI绝缘膜击穿场强的影响。结果表明,在真空度为1.0×10-2Pa条件下,300℃热亚胺化1h,聚酰亚胺酸(PAA)薄膜完全被热亚胺化,制备的PI绝缘膜内部结构致密;当BPDA和ODA的粉体含量为5%时,PI绝缘膜击穿场强高达2.15MV/cm,表明PI薄膜具有良好的电学性能。     

酶法合成脂肪族聚酯的研究进展

酶法合成的脂肪族聚酯不仅是具有生物可降解性的高聚物,而且具有良好的生物吸收性,保证了其作为医用材料的安全性.酶法合成脂肪族聚酯的方法是一种新型的环境友好绿色化学技术,合成条件温和,产物易于分离,可以弥补传统合成方法的不足.本文评价了酶法合成脂肪族聚酯的发展现状和最新研究进展,介绍了酶催化合成脂肪族聚酯的方法及影响因素.     

热致性液晶聚芳酯的相对分子质量控制与性能

用对苯二甲酸(TPA)作为相对分子质量调节剂,将6-乙酰氧基-2-萘甲酸和对乙酰氧基苯甲酸通过熔融酯交换和固相缩聚两步法,合成了数均相对分子质量约为5619~12264的热致液晶聚芳酯(PAT)。采用傅里叶变换红外光谱、核磁共振波谱仪、偏光显微镜、热失重分析和差示扫描量热分析等手段对单体和聚合物进行了结构与性能表征。结果表明,所制备的聚合物结构与实验设计相符,其热稳定性随着聚合物相对分子质量的增加而提高,在高温下保持向列型液晶相,因此在高温下可以与其他聚合物复合加工。当聚合物发生固相缩聚以后,聚合物的相对分子质量变大,结晶性能变好,热稳定性也明显提高。     

Microbial synthesis and enzymatic degradation of renewable poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate]

This paper reports our recent progress on a microbial system for efficient production of biodegradable copolyester of poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyhexanoate], P(3HB-co-3HHx), with desirable copolymer compositions using genetically engineered bacteria. We have developed a fermentation technique to achieve high cell density cultivation of a recombinant Ralstonia eutropha using inexpensive soybean oil as a sole carbon source. In addition, we demonstrate that the use of polyhydroxyalkanoate (PHA) synthase (PhaC) mutants having an amino acid substitutions is able to vary the copolymer composition of P(3HB-co-3HHx) synthesized from soybean oil by the recombinant bacteria. On the other hand, it is also important to understand the enzymatic degradation process of PHA materials for establishing a method to regulate the rate of biodegradation. The enzymatic degradation process of P(3HB-co-3HHx) thin film using an extracellular PHB depolymerase has been studied by in situ atomic force microscopy in buffer solution. We demonstrate that the PHA depolymerase predominantly degrades the less-ordered molecular chain-packing regions along the crystallographic a-axis.     

Synthesis of porous Mg-doped CeO2 powders via self-propagating high-temperature synthesis route

The aim of this study was synthesis of Mg-doped porous cerium oxide powder by self-propagating high-temperature synthesis reaction of Mg-xCeO₂-O₂ system. Results indicated that doping Mg in the CeO₂ crystal structure increased its lattice parameter slightly, and shifted the Ce-O band in the FTIR spectra from 490 to 574 cm⁻¹. Moreover, the EDS results revealed the distribution of Mg in the CeO₂ microstructure. There were a high volume fraction of interconnected macro-pores in the microstructure of cerium oxide after the synthesis process. Increase in the x-value from 0.05 to 0.25 mol decreased the mean size and volume fraction of pores from 2.4 to 1 µm and 50 to 30 vol%, respectively. In addition, the BET surface area of porous CeO₂ varied between 0.3 and 1.57 m²/g. Finally, it was inferred that the SHS technique can be introduced as a rapid and novel method for synthesis of Mg-doped porous CeO₂ powders.     

Templated synthesis of metal nanotubes via electroless deposition

A simple route that utilizes carbon nanofibers as templates for preparing metal or alloy nanotubes via electroless deposition is developed. SEM and TEM images of the prepared Ni-Ni₃P nanotubes are presented. In this method, it is easy to control the size or the shape of the prepared metal nanotubes by using different carbon or other nanofibers as templates.     

Hydrothermal synthesis of cuboidal PbSe microcrystals via an EDTA reduction route

Cuboidal lead selenide (PbSe) microcrystals have been successfully synthesized via a novel EDTA reduction route in which EDTA molecules serve as both chelating reagent and reductant. Hereafter EDTA is the abbreviation for ethylenediaminetetraacetic acid tetrasodium salt dihydrate (C₁₀H₁₂N₂Na₄O₈·2H₂O). The unique cuboidal PbSe microcrystals have eight symmetric arms along the < 111> directions. The edge of a cuboidal PbSe microcrystal extends outwards from its core with a tiny cubic center leaving step-like faces. The whole synthetic system provides an appropriate crystal growth environment for the formation of these microcrystals. Furthermore cuboidal PbSe microcrystals with different concave faces can be obtained at different reaction stages.     

Direct synthesis of highly crystalline single-phase hexagonal tungsten oxide nanorods by spray pyrolysis

The metastable state hexagonal-tungsten oxide (h-WO₃) has been attracting attention over the past decade because of its high reactivity that arises from the hexagonal channels in its crystal structure. Simplification of the process used to synthesize h-WO₃ is an important step to facilitate the industrial applications of this material. In this study, we addressed this challenge by developing a spray pyrolysis process to synthesize highly crystalline h-WO₃. The ratio of the monoclinic to the hexagonal phase was controlled by adjusting the segregation time. Single-phase h-WO₃ nanorods were synthesized using a carrier gas flow rate of 1?L/min, which was equivalent to a segregation time of 18.4?s. The ability of the h-WO₃ nanorods to adsorb nitrogen and carbon dioxide was evaluated to confirm the presence of hexagonal channels in the crystal structure.     

Morphological control of mesoporous alumina nanostructures via template-free solvothermal synthesis

Mesoporous alumina nanostructures with tunable morphologies have been synthesized using different solvents through the template-free solvothermal approach. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), and nitrogen adsorption/desorption were used to characterize the samples. By manipulating the volume ratio and the composition of the reaction solvent, various morphologies of mesoporous alumina with crystalline-framework walls, i.e. nanotubes, nanofibers, nanorods, nanolaths, and nanosheets were synthesized. The specific surface area and the pore size correlated with the morphologies of γ-alumina nanocrystals. In comparison with conventional surfactant-templating methods, the new approach is simple and more suitable for industrial scale production.     

Surfactant-assisted synthesis of Sn nanoparticles via solution plasma technique

We have adopted a solution plasma synthesis for preparing Sn nanoparticles (Sn-NPs) directly from metallic Sn electrode. The Sn-NPs were synthesized in the presence of the surfactant, cetyltrimethylammonium bromide (CTAB), and the effect of the concentration of CTAB on the Sn-NPs was investigated. Without CTAB addition, SnO plates were precipitated. Sn-NPs with less than 200 nm were synthesized at a high concentration of 200 × 10⁻⁶ g ml⁻¹ of CTAB. Electrochemical properties of SnO plates and Sn-NPs were analyzed for use as an anode material in Li-ion batteries. A composite of Sn-NPs and graphite enhanced the cyclic stability owing to the buffer space provided by the graphite for volume expansion. In the case of the 30 wt% loaded Sn-NPs, the capacity was measured to be 414 mA h g⁻¹ after 20 cycles.     

Simulation and shape synthesis of kinematic pairs via small-scale interference detection

We present a shape representation and algorithms for the simulation and shape synthesis of kinematic higher pairs. The shape of a kinematic member is represented as an arrangement of small contiguous nondirected circles, which we call molecules. Given the shapes of the two members, a valid initial configuration, and the motion of one of the members (known as the driver), the motion of the other member (known as the driven) is determined. This simulation is based upon finding the points of contact between the member shapes. Contact is defined by interference of the molecules. As output, the simulation produces the functional relationship between the members and a record of the molecules of each member shape that came into contact during the process. Two procedures for shape synthesis are described. Given the shape of one member and the functional kinematic relationship between the member pair, the first procedure generates the shape of the second member from a blank of material. The second procedure modifies the shapes of two interacting members in order to change their contact characteristics during a kinematic interaction. Several examples from an implementation are provided.Work was performed at: Massachusetts Institute of Technology, Department of Mechanical Engineering, Computer-Aided Design Laboratory, Cambridge, MA 02139, USA [rakesh@mimsy.mit.edu]     

Morphology-controlled synthesis of ZnS nanostructures via single-source approaches

ZnS nanoparticles of various morphologies, including hollow or solid spherical, and polyhedral shape, were synthesized from single-source precursor Zn(S₂COC₂H₅)₂ without using a surfactant or template. The as-prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy. The results indicate that ZnS hollow and solid spheres assembled by nanoparticles can be easily generated by the solution phase thermalysis of Zn(S₂COC₂H₅)₂ at 80 °C using N, N-dimethylformamide (DMF) and ethylene glycol (EG) or water as solvents, respectively, whereas solvothermal process of the same precursor led to ZnS nanoparticles of polyhedral shape with an average size of 120 nm. The optical properties of these ZnS nanostructures were investigated by room-temperature luminescence and UV-vis diffuse reflectance spectra.     

A general synthesis of high-quality inorganic nanocrystals via a two-phase method

A two-phase method is exploited to prepare many kinds of nearly monodisperse, highly crystalline, size- and shape-controlled, surface-property-tunable inorganic nanocrystals, such as metal, semiconducting, magnetic, dielectric, and rare earth nanocrystals. The reaction of the two-phase system happens at the interface between the oil (nonpolar) and water (polar) phases and the interface is an exclusive site for both nucleation and growth. Interestingly, many solvent pairs with a clear interface can be applied to synthesize inorganic nanocrystals successfully. Generally, as-prepared nanocrystals with organic ligands are soluble in nonpolar solvents. Furthermore, exchange of ligands can also be realized readily and the final nanocrystals can be soluble in polar solvents. This two-phase method is a simple, reproducible, and general route and is becoming as powerful an approach as other solution-based synthetic approaches to high-quality inorganic nanocrystals.     

短时间室温合成介孔分子筛MCM-48

以正硅酸乙酯（TEOS）为硅源、十六烷基三甲基溴化铵（CTAB）为模板剂在碱性介质中室温合成了介孔分子筛MCM-48，考察了模板剂用量、pH值、乙醇以及水的用量等条件对分子筛合成的影响。利用IR、XRD、SEM等手段对产物进行了表征。结果表明：在室温条件下pH=11．8，20min合成孔道结构规整的介孔分子筛MCM-48，其最佳配比为：n（TEOS）：n（CTAB）：n（EG）：n（H2O）=1：0．3：27：261。