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81.
Mian Fu Xiaomei Zhuang Tianhong Zhang Ying Guan Qingbin Meng Yongjun Zhang 《Macromolecular bioscience》2020,20(9)
Leuprolide has been widely used in androgen deprivation therapy for the treatment of advanced prostate cancer, but its use is still limited due to its short half‐life. Herein, hydrogen‐bonded layer‐by‐layer films are fabricated from PEGylated leuprolide (PEG‐LEU) and tannic acid (TA). Because of its dynamic nature, the film disintegrates gradually in water and releases PEG‐LEU and TA. The in vitro release profile indicated perfect zero‐order kinetics, which is explained by the unique release mechanism. When implanted subcutaneously in male rats, the films maintain a constant serum drug level. For a 60‐bilayer film, the serum drug level is maintained constant for ≈24 days. No initial burst release is observed, suggesting that the in vivo release also follows zero‐order kinetics. Initially, an increase in the level of serum testosterone is induced by the released drug, followed by testosterone suppression to a constant level below the castrate level, which could be maintained as long as a constant serum drug level is maintained. Since the new drug carriers avoid an initial burst release of the drug and maintain a constant serum drug level and hence a constant serum testosterone level below the castrate level, these carriers are highly promising for androgen deprivation therapy. 相似文献
82.
Xiao Jun-An Cheng Xiu-Liang Peng Hai Li Jin-Lian Xie Zhen-Zhen Chen Wen-Qiang Liu Zhi-Ping Xiao Qi Su Wei Yang Hua 《中国科学:化学(英文版)》2020,63(6):785-791
A diastereoselectivity-controllable formal [3+2]-cycloaddition of arylvinyl oxirane 2,2-diesters with cyclic N-sulfonyl imines is developed, affording the corresponding tricyclic oxazolidine derivatives in moderate to excellent yields with excellent diastereoselectivities in the presence of palladium(0) or scandium(III) triflate. This protocol allows selective synthesis of diastereomers of tricyclic oxazolidine derivatives under switchable and mild conditions. Further transformations of the obtained products were conducted by removing ester groups and arylvinyl moieties. 相似文献
83.
工业催化:选择性提升策略 总被引:1,自引:0,他引:1
工业催化直接或间接贡献了世界GDP的20%-30%,推动了产业变革和社会进步.对于工业催化,开发高活性、高选择性和高稳定性的多相催化剂至关重要,而选择性是最主要的挑战.因为实现催化选择性的精确控制是绿色化学的重要概念之一,更是工业催化可持续发展的重要驱动力;而且,选择性不仅决定了催化过程的原子经济性,也影响到后续分离过程的能耗.针对多数工业催化反应存在'活性越高、选择性越低'的相互制约与矛盾问题,本文以若干能源化工催化反应为例,试图总结催化选择性提升的一般策略,以期为有关工业应用的催化新过程提供科学参考.多相催化一般经历与反应物有关的步骤(反应物的外扩散、内扩散和化学吸附)、与反应有关的步骤(活化和表面反应)、以及与产物相关的步骤(产物脱附、内扩散和外扩散).本文依此归纳并举例说明提高选择性的一般策略.在汽油催化吸附脱硫中,主要利用了催化剂中零价镍-氧化锌耦合活性中心的选择吸附策略,使零价镍优先吸附含硫化合物,从而实现选择性脱硫而不饱和烯烃.在甲苯和甲醇侧链烷基化反应中,主要利用了特定空间分布的酸碱吸附位,实现吸附甲苯和稳定甲醛中间体的协同匹配.在乙苯脱乙基型二甲苯异构化反应中,主要利用了双床层对催化剂功能的分离策略,在不同的择形催化剂床层中分别进行乙苯脱乙基反应和二甲苯异构化反应,从而提高对二甲苯的产量.在苯选择加氢制环己烯反应中,主要利用强化产品脱附的策略,促进环己烯产品从亲水改性的催化剂表面脱附,实现环己烯选择性的提升.这些炼油与化工研究案例中同时存在多个连串-平行反应,主要是利用吸附中心、反应中心在时间或空间上的耦合、解耦或限域策略,调控不同途径的扩散能垒、反应能垒,实现了催化剂选择性的提升.多相催化多是复杂过程,基于提高选择性的初步认识,还要结合具体复杂催化过程,系统研究单策略以及多策略组合作用下的选择催化过程,实现在合理时间尺度、空间尺度上设计高选择性的催化剂,而这本质上是一种介尺度催化. 相似文献
84.
Dong-Liang Zhang Cheng-Long Deng Bin Xie Yu-Long Li Chuan Lai Wen-Yu Mou Lin-Xin He Xiao-Xue Bai Tao Li Jia-Xi Cao Jun Wang 《应用有机金属化学》2020,34(1):e5261
Six new O-alkyldithiophosphate nickel complexes with dcpf ligand, [(dcpf)Ni(S2P{O}OR)] (dcpf = 1,1′-bis (dicyclohexylphosphino)ferrocene, R = CH3 ( 1 ), CH3CH2 ( 2 ), Ph ( 3 ), 4-MeC6H4 ( 4 ), PhCH2 ( 5 ) and PhCH2CH2 ( 6 )), have been synthesized by the treatment of dcpf with ((RO)2PS2)2Ni in satisfactory yields. These complexes were characterized by elemental analysis, spectroscopy (FTIR, UV–vis, 1H, 13C, and 31P NMR), thermogravimetric analysis and single crystal X-ray diffraction. The nickel atom in 1 , 2 ·CH2Cl2, 3 ·CH2Cl2, 4 ·2CH2Cl2·THF, and 2( 5 )·hexane adopts a slightly distorted square-planar coordination environment finished by two phosphorus atoms of dcpf ligand and two sulfur atoms of O-alkyldithiophosphate ligand. Furthermore, the electrochemical properties for complexes 1 – 6 were also investigated by cyclic voltammetry. With the addition of 120 mM trifluoroacetic acid (TFA), the turnover frequency (TOF) values for 1 – 6 are estimated to be 1243.83, 1046.54, 1331.71, 2545.29, 1899.03, and 1191.37 s−1, with the overpotential (η) values of 0.62, 0.58, 0.71, 0.67, 0.60, and 0.56 V, respectively. The result of electrochemical studies indicates that all complexes can be used as efficient molecular eletrocatalysts for the reduction of protons to hydrogen in the presence of TFA in MeCN. 相似文献
85.
We describe an effective and novel method to prepare N-aryl imidazoles via the copper quinolate-catalyzed N-arylation of aryl halides and imidazoles. A wide range of products were obtained in moderate to excellent yields under the optimal reaction conditions. Applying standard conditions, the model reaction could be performed on a gram scale. This method also presents a new avenue to the “click” reaction of terminal alkynes, benzyl bromide, and sodium azide and to the construction of C–C bonds by homocoupling of phenylboronic acid or phenylacetylene derivatives with the aid of copper quinolate. 相似文献
86.
土地利用信息是国土资源管理的基础和重要依据,随着高分辨率遥感图像数据的日益增多,迫切需要快速准确的土地利用分类方法。目前应用较广的面向对象的分类方法对空间特征的利用尚不够充分,在特征选择上存在一定的局限性。为此,提出一种基于多尺度学习与深度卷积神经网络(deep convolutional neural network,DCNN)的多尺度神经网络(multi-scale neural network,MSNet)模型,基于残差网络构建了100层编码网络,通过并行输入实现输入图像的多尺度学习,利用膨胀卷积实现特征图像的多尺度学习,设计了一种端到端的分类网络。以浙江省0.5 m分辨率的光学航空遥感图像为数据源进行了实验,总体分类精度达91.97%,并将其与传统全卷积网络(fully convolutional networks,FCN)方法和基于支持向量机(support vector machine,SVM)的面向对象方法进行了对比,结果表明,本文所提方法分类精度更高,分类结果整体性更强。 相似文献
87.
Cheng Sheng Dr. Zheng Ling Dr. Tanveer Ahmad Prof. Dr. Fang Xie Prof. Dr. Wanbin Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(23):e202200128
Regioselective [3+3] annulation of alkynyl ketimines with α-cyano ketones for the synthesis of polysubstituted 4H-pyran derivatives with a quaternary CF3-containing center has been realized by using Cu(OAc)2 as the catalyst. The novel strategy tolerates a wide range of α-CF3 alkynyl ketimines and α-cyano ketones with both aryl and alkyl substitutents. A preliminary asymmetric synthesis of chiral product 3 has been attempted by using copper and chiral thiourea as the cocatalyst with excellent yields (86-99 %) and good enantioselectivities (71–78 % ee). Furthermore, product 3 aa could be obtained on a gram-scale reaction with 75 % yield and 99 % ee after recrystallization. Several products were also transformed readily. Control experiments indicate that the reaction involves a process with a base-catalyzed or chiral thiourea-catalyzed Mannich-type reaction followed by a highly regioselective copper-catalyzed ring-closing reaction on the alkynyl moiety in a 6-endo-dig fashion. 相似文献
88.
Yao Chen Wenchuan Wang Dong Xie Lili Wu Chaocan Zhang 《Journal of polymer science. Part A, Polymer chemistry》2021,59(14):1528-1539
TPPAlCl-PPN+Cl− binary catalyst (where TPPAlCl is 5,10,15,20-tetraphenylporphyrin aluminum chloride, PPN+Cl− is bis[triphenylphosphine] iminium chloride, the molar ratio of TPPAlCl to PPN+Cl− is 1 to 0.5) can initiate the effective one-pot/one-step ternary copolymerization of CO2, lactide and 4-vinyl-1-cyclohexene-1,2-epoxide, and the quaternary copolymerization of CO2, propylene oxide, lactide, 4-vinyl-1-cyclohexene-1,2-epoxide, to form multiblock poly(carbonate-co-lactide) products with pendant vinyl group. The ternary copolymerization product composes of polylactide (PLA) block and poy(vinylcyclohexylene carbonate) (PVCHC) block, and the quaternary copolymerization product composes of poy(propylene carbonate) (PPC) block, PLA block and PVCHC block, which are verified by 1H NMR, 13C NMR, 1H-1H cosy, hetero-nuclear multiple bond correlation, DTG, and Gel permeation chromatography analysis. The functionality and glass-transition temperature of the products can be easily adjusted by the copolymerization variables, such as the molar ratio of comonomers, copolymerization temperature, pressure of CO2, the concentration of the catalyst. 相似文献
89.
Colloidal lithography is an efficient and low-cost method to prepare an ordered nanostructure array with new shapes and properties. In this study, square-shaped and cone-shaped Au nanostructures were obtained by 70° angle deposition onto polystyrene bead array with the diameter of 500 nm when a space of 120 nm is created between the neighbor beads by plasma etching. The gaps between the units decrease when the Au deposition time increases, which leads to the polarized enhanced local field, in agreement with the surface-enhanced Raman scattering spectra (SERS) observations and finite-difference time-domain (FDTD) simulations. When the Au deposition time increased to 5 min, 5 nm gaps form between the neighbor units, which gave an enhancement factor of 5 × 109. The SERS chip was decorated for the detection of the liver cancer cell marker Alpha-fetoprotein (AFP) with the detection limit down to 5 pg/mL. 相似文献
90.
Dr. Liang Bao Qinyu Bao Dr. Huaiwei Zhang Prof. Dr. Yongjun Yuan 《Chemphyschem》2021,22(21):2168-2171
A feasible tuning method for oxygen vacancies was realized by annealing under 3 atm H2 with (001)-exposed TiO2 nanosheets. The colored TiO2 sample exhibits an excellent N2 photo-fixation rate owing to the abundant oxygen vacancies (OVs) thus demonstrating that annealing with high pressure H2 is exceedingly efficient for tuning surface OVs. 相似文献