全文获取类型
收费全文 | 85篇 |
免费 | 12篇 |
国内免费 | 30篇 |
专业分类
化学 | 108篇 |
晶体学 | 1篇 |
力学 | 5篇 |
综合类 | 4篇 |
数学 | 6篇 |
物理学 | 3篇 |
出版年
2023年 | 5篇 |
2022年 | 3篇 |
2021年 | 5篇 |
2020年 | 4篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2017年 | 2篇 |
2016年 | 6篇 |
2015年 | 13篇 |
2014年 | 4篇 |
2013年 | 8篇 |
2012年 | 10篇 |
2011年 | 15篇 |
2010年 | 5篇 |
2008年 | 3篇 |
2007年 | 3篇 |
2006年 | 1篇 |
2005年 | 4篇 |
2004年 | 2篇 |
2003年 | 7篇 |
2002年 | 2篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1994年 | 3篇 |
1993年 | 5篇 |
1989年 | 1篇 |
1986年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有127条查询结果,搜索用时 93 毫秒
1.
Qintong Huang Ningyue Chen Lichen Liu Karen S. Arias Sara Iborra Xianfeng Yi Chao Ma Weichi Liang Anmin Zheng Chuanqi Zhang Jibo Hu Zilin Cai Yi Liu Jiuxing Jiang Avelino Corma 《Chemical science》2020,11(44):12221
Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds. The introduction of the costly and environmentally less benign phosphazene organic structure-directing agent is not required to grow the zeolite. Physicochemical characterization experiments show that Si/Al-BOG has good crystallinity, high surface area, tetrahedral Al3+ species, and acid sites. In order to test the catalytic performance of the zeolite, the synthesis of l,l-lactide from l-lactic acid was performed. Si/Al-BOG exhibits 88.2% conversion of l-lactic acid and 83.8% l,l-lactide selectivity, which are better than those of other zeolites studied up to now.Aluminosilicate boggsite (Si/Al-BOG) has been hydrothermally synthesized without adding organic structure-directing agents (OSDAs) in the synthesis gel using the borosilicogermanium ITQ-47 (Si/B-ITQ-47) zeolite as seeds. 相似文献
2.
A brief overview of our recent research results of thermoregulated liquid/liquid biphasic catalysis is presented. Emphasis is given to the general principles of thermoregulated phase-transfer catalysis (TRPTC) and thermoregulated phase-separable catalysis (TPSC). In addition, the applications of TRPTC and TPSC in biphasic catalysis are also discussed. The introduction of TRPTC to biphasic system is free from the shortcomings of classical aqueous/organic two-phase catalysis, in which the application scope is restrained by the water solubility of the substrate. Meanwhile, TPSC provides a very simple and reliable way to deal with the separation of catalyst in homogeneous catalysis. The common advantages of TRPTC and TPSC are characterized by homogeneous catalysis coupled with convenient biphasic separation. 相似文献
3.
用高效毛细管电泳前沿分析法研究了酸性药物那格列奈与人血浆白蛋白的结合常数、结合位点和结合率。使用未涂层的毛细管柱 (4 0cm× 5 0 μmi.d .;有效柱长 32cm) ,磷酸盐缓冲溶液 (pH 7.4 ,离子强度0 .17)为背景溶液 ,在紫外检测波长 2 14nm、运行电压 18kV和重力进样 10 0s的条件下 ,利用那格列奈谱峰的平台高度和游离药物浓度的良好线性关系 (r>0 .999,n =6 ) ,测定了那格列奈的游离药物浓度。固定药物浓度 (2 0 0 μmol L ,2 5 0 μmol L) ,考察不同的蛋白质浓度对结合的影响 ;固定蛋白质浓度 (10 0 μmol L) ,考察不同的药物浓度对结合的影响。实验数据采用非线性拟和程序进行处理 ,得到了那格列奈的蛋白质结合参数。高效毛细管电泳前沿分析法测定的数据重现性良好 (RSD <2 .5 % ,n =3) ,在药代动力学和药效学研究方面具有简便、准确的优点。 相似文献
4.
本文研究求解二维Fisher-Kolmogorov-Petrovsky-Piscounov (Fisher-KPP)方程的一类保正保界差分格式.运用能量分析法证明了当网格比满足$R_{x}+R_{y}+[b\tau (p-1)]/2\leq\frac{1}{2}$时差分解具有一系列数学性质,包括保正性、保界性和单调性,且在无穷范数意义下有$O (\tau+h_{x}^{2}+h_{y}^{2})$的收敛阶.然后通过发展Richardson外推法得到收敛阶为$O (\tau^{2}+h_{x}^{4}+h_{y}^{4})$的外推解.最后数值实验表明数值结果与理论结果相吻合.值得提及的是在运用本文构造的Richardson外推法时对时空网格比没有增加更严格的条件. 相似文献
5.
Alan P. Marchand Anna Hazlewood Zilin Huang Satish Kumar Vadlakonda John-David R. Rocha Trevor D. Power Kata Mlinarić-Majerski Lada Klaić Goran Kragol Jeffrey C. Bryan 《Structural chemistry》2003,14(3):279-288
Bis-cage-annulated 18-crown-6 and 20-crown-6 macrocyclic ethers (i.e., 1 and 2, respectively) have been synthesized, and their alkali metal picrate extraction profiles have been determined. Host system 1 proved to be a significantly more avid alkali metal cation complexant than 2 and somewhat more avid than 18-crown-6. Both 1 and 18-crown-6 display modest selectivity toward K+ and Rb+. A stable host–guest complex was prepared by slow evaporation of a CH2Cl2–hexane solution of an equimolar mixture of 2 and potassium picrate. The X-ray crystal structure of this complex reveals that picrate anion functions as a bidentate ligand therein. The gas-phase interaction energy between the 2 K+ complex and picrate anion was calculated to be ca. –64.9 kcal mol–1, thereby indicating that participation of picrate anion as an additional bidentate ligand results in significant stabilization of complex 10. 相似文献
6.
新型水溶性膦铑络合物催化烯烃的氢甲酰化反应研究 总被引:10,自引:1,他引:10
新型水溶性膦铑络合物催化烯烃的氢甲酰化反应研究燕远勇,左焕培,金子林(大连理工大学化工学院,大连116012)关键词烯烃,水溶性膦铑络合催化剂,氢甲酰化,醛.1.前言为克服催化剂的流失和与反应产物的分离困难,近年来均相催化的一个重要进展是开发了以磺化... 相似文献
7.
Electrospray ionization mass spectrometry (ESI-MS) is used to evaluate the metal binding selectivities of an array of novel caged macrocycles for silver, gold, copper, nickel, zinc, iron, lead, manganese and alkali metal ions. It is found that five of the new compounds display silver selectivity, and their relative affinities for various metals depend on the type, number, and arrangement of heteroatoms (N, O), the cavity size, and the presence of aromatic substituents. Alkali metal cation binding studies are used to evaluate the size-selectivities of the cavities of the macrocycles. Electronic structure calculation by B3LYP density function theory methods were used to model the metal complexes. The presence of nitrogen atoms in the macrocyclic ring is essential for silver selectivity over other transition metals and alkali metal ions, and the presence of aromatic groups also enhances silver avidity. Macrocycle 3, a triaza-18-crown-6 analog modified with two phenyl groups and a cage group, is capable of selective extraction of Ag+ from aqueous solutions in the presence of other transition metal ions and the most common alkali and alkaline earth metal ions. 相似文献
8.
An electrophoretically mediated microanalysis method with partial filling technique was developed for screening aromatase inhibitors in traditional Chinese medicine. The in‐capillary enzymatic reaction was performed in 20 mM sodium phosphate buffer (pH 7.4), and sodium phosphate buffer (20 mM, pH 8.0) was used as a background electrolyte. A long plug of coenzyme reduced β‐nicotinamide adenine dinucleotide 2′‐phosphate hydrate dissolved in the reaction buffer was hydrodynamically injected into a fused silica capillary followed by the injection of reaction buffer, enzyme, and substrate solution. The reaction was initiated with a voltage of 5 kV applied to the capillary for 40 s. The voltage was turned off for 20 min to increase the product amount and again turned on at a constant voltage of 20 kV to separate all the components. Direct detection was performed at 260 nm. The enzyme activity was directly assayed by measuring the peak area of the produced β‐nicotinamide adenine dinucleotide phosphate and the decreased peak area indicated the aromatase inhibition. Using the Lineweaver–Burk equation, the Michaelis–Menten constant was calculated to be 50 ± 4.5 nM. The method was applied to the screening of aromatase inhibitors from 15 natural products. Seven compounds were found to have potent AR inhibitory activity. 相似文献
9.
The Amaryllidaceae are widely distributed medical plants. Lycorine, lycoramine, lycoremine, and lycobetaine are the major active alkaloids in Amaryllidaceae plants. A nonaqueous CE ESI‐IT‐MS method for separation, identification, and quantification of the Amaryllidaceae alkaloids has been developed. The MS1–3 behavior has been studied and the fragmentation pathways of main fragment ions have been proposed. The effects of several factors such as composition and concentration of buffer, applied voltage, composition, and flow rate of the sheath liquid, nebulizing gas pressure, flow rate, and temperature of drying gas were investigated. Under the optimal conditions, the linear concentration range of these compounds was wide with the correlation coefficient (R2) >0.99. RSDs of migration time and peak areas were <10%. The LODs were <240 ng/mL. The proposed method can be successfully applied to the determination of the related alkaloids in the Lycoris radiata roots. 相似文献
10.
Zhiyun Chen Zilin Yang Xianlong Du Jihua Zhao 《Journal of Dispersion Science and Technology》2013,34(12):1756-1761
The kinetics for the reaction between potassium ferricyanide (K3Fe(CN)6) and cobalt chloride (CoCl2) in aqueous solution and water/bis(2-ethylhexyl) sodium sulfosuccianate (AOT)/isooctane microemulsions were studied by three-wavelength spectrophotometry at 298.2 K. The second-order rate constants (k2) were calculated from the time dependence of the concentration of reactant K3Fe(CN)6. The result showed that the reaction rates in water/AOT/isooctane microemulsions were slower than that in the aqueous solution, and k2 decreased with molar ratio (ω) of water to AOT in microemulsions, which was interpreted by the transition state theory and confirmed that the reaction took place at the interfaces of the microemulsion water pools. 相似文献