Synthesis and characterization of perfluorohexylated poly(3,4-ethylenedioxythiophene)

The perfluorohexylated 3,4-ethylenedioxythiophene 5 was prepared via Mitsunobu reaction of perfluorohexylatyed diol 2 with diethyl 3,4-dihydroxythiophenedicarboxylate followed by decarboxylation. The polymerization of 5 was conducted with both oxidative chemical and electrochemical polymerizations. The polymers were characterized by cyclic voltammogram, UV, IR, TGA and DSC.     

Generalization of in-situ polymerization method for preparing core-shell polymeric nanospheres and hollow spheres

According to the new method of preparing core-shell nanospheres developed by our group, by using two monomers, 2-hydroxypropyl methacrylate(HPMA) and vinyl acetate(VAc), two kinds of core-shell nanospheres with poly(ɛ-caprolactone) (PCL) as the core and crosslinked poly(2-hydroxypropyl methacrylate) (PHPMA) or poly(vinyl acetate) (PVAc) as the shell were successfully prepared under similar conditions. After degrading the PCL cores of the two kinds of nanospheres by lipase, the corresponding crosslinked poly(methyl acrylic acid) hollow spheres and crosslinked poly(vinyl alcohol) hollow spheres were obtained. Results indicate that the new method we proposed for preparing core-shell polymeric nanospheres via in-situ polymerization can be generalized to a certain extent, and it is suitable for many systems provided the monomer used is soluble in water, while its corresponding polymer is insoluble in water. Translated from Chemical Journal of Chinese University, 2006, 27(9): 1762–1766 [译自: 高等学校化学学报]     

铟参与的4-溴-1，1，1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应：4，4，4-三氟-γ-羟基缬氨酸的合成

铟参与的4-溴-1,1,1-三氟-2-丁烯与α-烷氧基醛亚胺的烯丙化反应以中等的产率和高非对映选择性生成了高烯丙基胺3.从甘油醛亚胺和4-溴-1,1,1-三氟-2-丁烯反应制备的高烯丙基胺3g出发,以7步反应24%的总产率合成了4,4,4-三氟-γ-羟基缬氨酸11.     

NIR light-induced tumor phototherapy using ICG delivery system based on platelet-membrane-camouflaged hollow bismuth selenide nanoparticles

Near-infrared (NIR) light-triggered photothermal therapy (PTT) is a promising treatment strategy for treating cancer. The combination of nanotechnology and NIR has been widely applied. However, the therapeutic efficacy of the drug-delivery system depends on their ability to avoid phagocytosis of endothelial system, cross the biological barriers, prolong circulation life, localize and rapidly release the therapeutic at target sites. In this work, we designed a platelet membrane (PM)-camouflaged hollow mesoporous bismuth selenide nanoparticles (BS NPs) loading with indocyanine green (ICG) (PM@BS-ICG NPs) to achieve the above advantages. PM-coating has active tumor-targeting ability which could prevent drug leakage and provide drug long circulation, causing drug delivery systems to accumulate in tumor sites effectively. Moreover, as a type of the photothermal sensitizers, BS NPs are used as the inner cores to improve ICG stability and are served as scaffolds to enhance the hardness of this drug delivery system. For one hand, the thermal vibration of BS NPs under NIR laser irradiation causes tumor inhibition through hyperthermia. For another hand, this hyperthermia process could damage PM and let ICG rapid release from PM@BS-ICG NPs. The in vitro and in vivo results showed that this biomimetic nano-drug delivery system exhibits obvious antitumor activity which has good application prospect.     

The synthesis and application of fluorous boronates without perfluorinated solvents

The synthesis of a fluorous diol 4 bearing a perfluorodecyl chain was described. A series of boronic acid were attached to 4 by esterification. The purification of the products was fulfilled by facile filtration instead of expensive and environmental troublesome fluorous liquid-liquid extraction. The Suzuki cross-coupling reactions of the formed fluorous boronates 5 underwent smoothly and the fluorous diol 4 was recycled in good yields.     

Mechanical properties of BPDA-ODA polyimide fibers

An aromatic polyimide was synthesized via a one-step polycondensation reaction between biphenyltetracarboxylic dianhydride (BPDA) and 4,4′-oxydianiline (ODA) in p-chlorophenol. The polyimide (BPDA-ODA) solution dopes were spun into fibers by means of dry-jet wet spinning. The as-spun fibers were drawn and treated in heating tubes for improving the mechanical properties. The thermal treatment on the fibers resulted in a relatively high tensile strength and modulus. Thermal mechanical analysis (TMA) was employed to study the linear coefficient of thermal expansion (CTE). Thermal gravimetry analysis (TGA) spectra showed that the BPDA-ODA fibers possessed an excellent property of thermo-oxidative degradation resistance. The sonic modulus E_s of the polyimide fibers was measured.     

非合作博弈两阶段生产系统的效率评价——基于自由处置和管理处置的视角

为了识别被动适应环境和采取创新技术主动适应环境的生产系统的效率差异,基于主从非合作框架和决策者的期望需求,分别从自由处置和管理处置的视角建立了两阶段生产系统效率评价模型,应用模型对2017年中国24省市工业生产系统效率进行了分析。结果表明:两种环境适应策略下,中国24个省市工业生产的两个子系统的效率均值都较高,主要分布在中国东部。24省市在自由处置模式下的技术差距较小,管理处置模式下的技术差距较大。24省市技术创新的重点在于减少工业废水和工业废气的排放,但是对一般工业固体废物减量化的重视程度不足。各省市工业固体废物处理无效的根源包括固体废物减量化无效、固体废物再利用和固体废物处置同时无效,以及混合无效三种方式。     

Synthesis of a novel 18β-glycyrrhetinic acid derivative

A novel compound, biotinylated 18β-glycyrrhetinic acid (BGA), was synthesized. It is a compound of 18β-glycyrrhetinic acid linked with biotin. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 266–267, May–June, 2006. An erratum to this article is available at .     

Over 18% binary organic solar cells enabled by isomerization of non-fullerene acceptors with alkylthiophene side chains

Side-chain engineering has been demonstrated as an effective method for fine-tuning the optical, electrical, and morphological properties of organic semiconductors toward efficient organic solar cells (OSCs). In this work, three isomeric non-fullerene small molecule acceptors (SMAs), named BTP-4F-T2C8, BTP-4F-T2EH and BTP-4F-T3EH, with linear and branched alkyl chains substituted on the α or β positions of thiophene as the side chains, were synthesized and systematically investigated. The results demonstrate that the size and substitution position of alkyl side chains can greatly affect the electronic properties, molecular packing as well as crystallinity of the SMAs. After blending with donor polymer D18-Cl, the prominent device performance of 18.25% was achieved by the BTP-4F-T3EH-based solar cells, which is higher than those of the BTP-4F-T2EH-based (17.41%) and BTP-4F-T2C8-based (15.92%) ones. The enhanced performance of the BTP-4F-T3EH-based devices is attributed to its stronger crystallinity, higher electron mobility, suppressed biomolecular recombination, and the appropriate intermolecular interaction with the donor polymer. This work reveals that the side chain isomerization strategy can be a practical way in tuning the molecular packing and blend morphology for improving the performance of organic solar cells.

     

Interaction of –CClx (x=1–3) with Ru2 and RuSn dimers: a density functional study

Density functional calculation were performed on the Ru₂ and RuSn metal dimers and the species formed from their interaction with –CCl_x (x=1–3) fragments. The importance of these fragments in the hydrodechlorination of carbon tetrachloride has been motivated this study aiming to contribute to understand the effect of the tin in the performance of the noble metals based catalysts. We have observed that the carbon tetrachloride does not form a precursor with the metal dimers. The CCl₄ readily dissociates forming adsorbed chlorine and –CCl₃ complexes. The chlorine atoms prefer to adsorb on the bridge sites and the RuSn–Cl binding energy is about 5 kcal mol⁻¹ larger than the Ru₂–Cl binding energy. The Ru₂–CCl_x (x=1–3) binding energies are larger than the respective RuSn–CCl_x (x=1–3) binding energies. However, the reaction energy of the dechlorination of CCl₄ leading to adsorbed –CCl_x (x=1–3) and chlorine is thermodynamically more favorable for RuSn than the Ru₂. The differences between Ru₂ and RuSn systems have been discussed based on the different interaction mechanism due to the presence of the tin center and its affinity for the chlorine atoms.