Perfectly alternating segmented polyimide-polydimethyl siloxane copolymers via transimidization

New strategies for the synthesis of perfectly alternating segmented polyimide-polydimethyl siloxane copolymers were developed by utilizing a transimidization method. Imide oligomers endcapped with 2-aminopyrimidine were reacted with aminopropyl terminated (dimethyl siloxane) oligomers to afford perfectly alternating segmented imide siloxane copolymers. The polymerization was conducted in solvents such as chlorobenzene and chlorofrom. High molecular weight, fully imidized perfectly alternating segmented imide siloxane copolymers were obtained within 2 h at temperatures of 60-110°C. The mechanism of the reaction was further elucidated via model compounds and NMR characterization. The block copolymers exhibited two T_gs due to the microphase separation of the polyimide and polysiloxane phases. The T_g of the polyimide phase was a function of the length of the polyimide block. However, partial phase mixing was also evident from the DSC results on the imide siloxane copolymers prepared with low molecular weight polyimide segments. Thermooxidative stability and tensile properties of the perfectly alternating segmented imide siloxane copolymers were found to be principally dependent on the amount of poly (dimethyl siloxane) incorporated in the copolymer and did not correlate with the poly (dimethyl siloxane) or polyimide block lengths. The stress-strain behavior of both solvent cast films or molded films is also reported. © 1994 John Wiley & Sons, Inc.     

Diisocyanate route as a convenient method for the preparation of novel optically active poly(amide-imide)s based on N-trimellitylimido-S-valine

A new class of optically active poly(amide-imide)s based on an α-amino acid was synthesized via direct polycondensation reaction of different diisocyanates with a chiral diacid monomer. The step-growth polymerization reactions of N-trimellitylimido-S-valine (TISV) (1) with 4,4′-methylene-bis(4-phenylisocyanate) (MDI) (2) was performed under microwave irradiation, as well as solution polymerization under graduate heating and reflux conditions. The optimized polymerization conditions for each method were performed with tolylene-2,4-diisocyanate (TDI) (3), hexamethylene diisocyanate (HDI) (4), and isophorone diisocyanate (IPDI) (5) to produce optically active poly(amide-imide)s via diisocyanate route. The resulting polymers have inherent viscosities in the range of 0.02-1.10 dL/g. Decomposition temperatures for 5% weight loss (T₅) occurred above 300 °C (by TGA) in nitrogen atmospheres. These polymers are optically active, thermally stable and soluble in amide-type solvents. Some structural characterization and physical properties of this new optically active poly(amide-imide)s are reported.     

Study on surfactant coating of polymeric nanoparticles for controlled delivery of anticancer drug

Biodegradable nanoparticles loaded with anticancer drug paclitaxel and appropriately coated with polyvinyl alcohol (PVA), polyethylene glycol (PEG) as well as d--tocopheryl polyethylene glycol 1000 succinate (TPGS) were produced and characterised by various analysis techniques such as laser light scattering (LLS) for particle size and size distribution, scanning electron microscopy (SEM) and atomic force microscopy (AFM) for particle morphology, X-ray photoelectron spectroscopy (XPS) and Fourier Transform Infrared-Photoacoustic Spectroscopy (FTIR-PAS) for surface chemistry, and high performance liquid chromatography (HPLC) for drug encapsulation efficiency (EE) and in vitro release kinetics. The emphasis was given to the possible effects of surface coating on the physicochemical and pharmaceutical properties of paclitaxel loaded nanoparticles. It was found that the type and amount of the surfactant could significantly affect the drug EE in the nanoparticles, the particles characteristics and their in vitro release behaviour. The surfactants dominated on the nanoparticles surface and the coated nanoparticles displayed in spherical shape with relative smooth surface within the resolution scope of the equipment. The particle size and size distribution showed close relation to the surface coating, which may also be responsible for the drug encapsulation efficiency and the in vitro release kinetics. A favourable formulation of drug loaded nanoparticles of desired properties could be obtained by optimising the fabrication parameters.     

北海航道班轮运输排班模型的构建与求解

首先,以拟开通的大连港至鹿特丹港北海航道班轮航线为研究对象,以油耗和运营成本最小化为优化目标,将官方已有记载的北海航道通过的货船航速数据输入Eureqa软件,得到航行最高速度f(x)与进入北海航道时间t的拟合度最好的函数公式.在此基础上,构建了北海航道班轮运输排班的数学模型;其次,在仿真实例分析中,选用了5000TEU的集装箱船作为计算参数,将捕食搜索算法运用到数学模型求解之中,并且运用MATLAB软件进行求解,在最快航速受限的前提下,得到单艘班轮最佳往返时间和相同型号班轮的最低配置数目以及在服务周期内班轮公司所要付出的最低运营成本;最后,通过比较研究,得出结论是:最快航速的提高,对于降低北海航线班轮运输的运营成本将起较大作用.     

Electrical Conduction Mechanisms of MxPS3, M1−xM'xPS3 and their Intercalation Compounds

Abstract

In the M_xPS₃ and M_1?xM'_xPS₃ systems, the P₂S₆ cluster contributes to the poor electrical conductivity for the compounds in which the energy level of the metal 3d orbital is deeper than those of the P, S 3p orbitals. For the compounds in which metal 3d orbital is closed to P and S 3p orbitals and has mixed valency, the induced mixed valency of P₂S₆, cluster and/or hopping mechanism contribute to the electrical conductivity. In the organic electron donor intercalation into M_xPS₃ and M_1?xM'_xPS₃ compounds, the new intercalation reaction is discovered, in which formation of tris-complexes of metal ions with guest molecules occurs in the host interlayer.     

Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc–gallium oxynitrides and zinc–gallium–indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m² g⁻¹). X-ray diffraction studies show that the final material is not a mixture of single oxides but a distinctive compound. The photocatalytic properties of the oxynitrides have been tested towards the decomposition of an organic dye (as a model reaction for the decomposition of air pollutants), showing better photocatalytic performances than the corresponding pure phases (reaction constant 0.22 h⁻¹), whereas almost no reaction was observed in absence of catalyst or in the dark. The photocatalysts have been also tested for H₂ evolution (semi-reaction of the water splitting process) with results comparable to the best literature values but leaving room for further improvement.     

Observation of unusual Griffith’s phase behavior in quadruple perovskite oxide CaCu3Mn4O12 (CCMO) synthesized through chemical route

The CaCu₃Mn₄O₁₂ (CCMO) ceramic was successfully synthesized through the chemical route. The phase formation was confirmed by the X-ray diffraction pattern. Thermogravimetric (TGA), FT-IR, SEM, TEM, EDX, and XPS analysis were performed for investigation of the thermal behavior, phase identification, microstructural analysis, elemental analysis and oxidation state of the CCMO ceramic respectively. FT-IR spectra confirmed the existence of MnO₆ octahedral in body-centered cubic (BCC) complex perovskite oxide that resembles the CaCu₃Ti₄O₁₂ structure. The average particle size was observed by TEM in the range between 100 and 200 nm. AFM shows the average roughness of the surface was found to be in the range of 30 ± 5 nm. XPS and EDX studies confirmed the purity and oxidation state of the CCMO ceramic. The synthesized material shows very interesting unique Griffith’s phase (T_G) results that arise disorder in magnetic susceptibility in which ferromagnetic transition was to be observed in the paramagnetic region.     

基于不同条件的旅游路线规划问题研究

运用2015年全国研究生数学建模竞赛F题的数据资料,针对旅游路线合理规划问题的第一问展开研究.以F题的问题一为起点进行了分析研究,是因为第一问的完成是解决后续问题的关键.首先通过地图搜集并补全了缺失数据并对数据进行合理的处理,然后采用将旅游年数最少目标转化为该最小生成树的"最少圈覆盖"方法来进行对问题一的求解,也可以理解为一个广义的多旅行商问题,以旅行商的人数(即年数)最少为目标.采用Dijkstra算法、最少圈覆盖法、智能算法和图论聚类等方法,通过这些方法建立了单目标优化模型,并运用旅行商问题和模型之间的转换来对问题进行分析与求解.     

Amorphous Calcium Phosphates: Solvent-Controlled Growth and Stabilization through the Epoxide Route

Calcium phosphates stand among the most promising nanobiomaterials in key biomedical applications, such as bone repairment, signalling or drug/gene delivery. Their intrinsic properties as crystalline structure, composition, particle shape and size define their successful use. Among these compounds, metastable amorphous calcium phosphate (ACP) is currently gaining particular attention due to its inherently high reactivity in solution, which is crucial in bone development mechanisms. However, the preparation of this highly desired (bio)material with control over its shape, size and phase purity remains as a synthetic challenge. In this work, the epoxide route was adapted for the synthesis of pure and stable ACP colloids. By using biocompatible solvents, such as ethylene glycol and/or glycerine, it was possible to avoid the natural tendency of ACP to maturate into more stable and crystalline apatites. Moreover, this procedure offers size control, ranging from small nanoparticles (60 nm) to micrometric spheroids (>500 nm). The eventual fractalization of the internal mesostructured can be tuned, by simply adjusting the composition of the ethylene glycol:glycerine solvent mixture. These findings introduce the use of green solvents as a new tool to control crystallinity and/or particle size in the synthesis of nanomaterials, avoiding the use of capping agents and preserving the natural chemical reactivity of the pristine surface.     

Novel Route for Preparation of 7‐Methyl‐camptothecin and Its Possible Mechanism

A novel route for preparation of 7‐methyl‐camptothecin is described. Its possible mechanism is discussed.