全文获取类型
收费全文 | 5340篇 |
免费 | 1149篇 |
国内免费 | 797篇 |
专业分类
化学 | 3862篇 |
晶体学 | 54篇 |
力学 | 205篇 |
综合类 | 71篇 |
数学 | 515篇 |
物理学 | 2579篇 |
出版年
2024年 | 14篇 |
2023年 | 109篇 |
2022年 | 129篇 |
2021年 | 166篇 |
2020年 | 190篇 |
2019年 | 183篇 |
2018年 | 191篇 |
2017年 | 153篇 |
2016年 | 266篇 |
2015年 | 266篇 |
2014年 | 293篇 |
2013年 | 396篇 |
2012年 | 537篇 |
2011年 | 625篇 |
2010年 | 381篇 |
2009年 | 374篇 |
2008年 | 412篇 |
2007年 | 348篇 |
2006年 | 300篇 |
2005年 | 238篇 |
2004年 | 213篇 |
2003年 | 140篇 |
2002年 | 160篇 |
2001年 | 120篇 |
2000年 | 137篇 |
1999年 | 120篇 |
1998年 | 110篇 |
1997年 | 115篇 |
1996年 | 87篇 |
1995年 | 87篇 |
1994年 | 66篇 |
1993年 | 75篇 |
1992年 | 46篇 |
1991年 | 64篇 |
1990年 | 42篇 |
1989年 | 36篇 |
1988年 | 16篇 |
1987年 | 15篇 |
1986年 | 18篇 |
1985年 | 15篇 |
1984年 | 11篇 |
1983年 | 11篇 |
1982年 | 7篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有7286条查询结果,搜索用时 438 毫秒
981.
以单分散亲水性交联聚甲基丙烯酸环氧丙酯-甲基丙烯酸乙二醇双酯(PGMA/EDMA)树脂为载体,制备新型L-羟脯氨酸聚合物键合高效手性配体交换固定相。该固定相在配体交换分离模式下,以0.2mol/LNaAc和0.1mmol/LCu(Ac)2水溶液(pH5.2)为流动相,柱温为30℃~50℃,对衍生和非衍生的D,L-氨基酸和α-羟基酸等9种手性化合物进行了高效液相色谱拆分。详细考察了流动相pH值、温度、流速和进样量对手性分离的影响,选择了合适的色谱分离条件。结果表明,所拆分的9种手性化合物,有5种手性化合物能得到基线分离,最好的分离因子α=2.32。 相似文献
982.
LI Zhi-Qiang BU Yu-Xiang ZHAO Xian 《结构化学》2008,27(12):1475-1486
The proton transfer isomerization of pyrazole and the water assisting effect by looping 1 to 4 water molecules on the singlet state potential energy surface have been investigated by using hybrid density functional theory method (B3PW91) with a 6-311++G^** basis set. Two mechanisms were proposed to explain the mono- and multi-water assisting effects, respectively. The reactants and products of all groups have been characterized on their potential energy surfaces. For the isomerizafion of monomolecule pyrazole, the isomeriz'ation energy barrier is 46.4 kcal·mol^-1. For the monohydration assisting mechanism, the reactant complex is connected to the product complex via two saddle points. The corresponding isomerization barriers are 46.7and 23.0 kcal·mol^-1, respectively. As to the multihydration assisting mechanism, the isomerization barriers are 12.0, 10.9 and 13.14 kcal·mol^-1 accordingly, when the number of water molecules is 2, 3 and 4, respectively. The multihydration assisting isomerization can occur in water-dominated environments, for example, in the organism, and thereby is crucial to energy transference. The deproton and dehydrogen energies of monomolecule pyrazole and various hydrated pyrazoles were calculated and then found much bigger than the isomerization barriers of their relative complexes, suggesting the impossibility of deprotonation or dehydrogenation. The isomerization of pyrazole is a proton-coupling-electron-migration process, but two different mechanisms are noticed, viz. σ- and π-type mechanisms. The π-bond of pyrazole participates in isomerization in the π-type mechanism, whereas only o-electron takes part in isomerization in the σ-type mechanism. 相似文献
983.
Park MS Lim TH Jeon YM Kim JG Joo SW Gong MS 《Journal of colloid and interface science》2008,321(1):60-66
We developed a simple method for the preparation of polyelectrolyte/silver nanocomposites, where silver nanoparticles were dispersed in a polyelectrolyte. Copoly(TEAMPS/VP)/silver (w/w=100/0, 100/1, 100/2, 100/3 and 100/4) nanocomposites were obtained by a thermal decomposition reaction of silver carbamate complex at 130 degrees C, and well-dispersed silver colloids were stabilized by copolymer of tetraethylammonium 2-acrylamido-2-methyl-1-propanesulfonate (TEAMPS) and N-vinylpyrrolidone (VP). A dark brown solution in its UV-vis absorption spectrum showed surface plasmon resonance absorption bands at 420 nm in solution. The silver precursor and the resulting polyelectrolyte/Ag nanocomposite was characterized by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), X-ray diffraction (XRD), infrared (IR), transmission electron microscopy (TEM). In addition the humidity-sensing properties using copoly(TEAMPS/VP)/Ag nanocomposite films were examined. 相似文献
984.
Zhang L Wang XC Gong QT Zhang L Luo L Zhao S Yu JY 《Journal of colloid and interface science》2008,327(2):451-458
The dilational rheological properties of absorbed film of three pairs of structural isomers, tri-substituted alkyl benzene sulfonates, at the air-water and decane-water interfaces have been investigated by drop shape analysis method. The influences of bulk concentration on dilational elasticity and viscosity were expounded. Interfacial tension relaxation method was employed to obtain dilational parameters in a reasonably broad frequency range. The experimental results showed that the meta-alkyl to sulfonate group plays a crucial role in the interfacial dilational properties: the longer meta-alkyl will lead to higher dilational parameters for air-water interface and lower ones for decane-water interface when the total alkyl carbon numbers are equal. For alkyl benzene sulfonates with shorter meta-alkyl, the surface dilational properties are similar to interfacial dilational properties, whereas the surface dilational parameters are obviously higher than the interfacial dilational parameters for alkyl benzene sulfonates with longer meta-alkyl in general. The possible mechanism has been proposed and ensured by Cole-Cole plots. 相似文献
985.
Clements M Pullela SR Mejia AF Shen J Gong T Cheng Z 《Journal of colloid and interface science》2008,317(1):96-100
We demonstrate an extension of a UV-Vis spectroscopy method to determine the phase boundaries for thermosensitive colloids as an alternative to the time-consuming sedimentation method. The Bragg attenuation peak from colloidal crystallites was monitored during the quasi-equilibrium colloidal crystal melting. The melting and freezing boundaries of the coexistence region were determined via a blue shift of Bragg's peak and the disappearance of peak area. We confirm this method using poly(N-isopropylacrylamide) (PNIPAM) particles at different charge densities and temperatures far below the lower critical solution temperature. At low pH, the particles behave as thermosensitive hard spheres. 相似文献
986.
987.
Bang-Sen Wang Dr. Qi Zhang Dr. Zhi-Qiang Wang Chen-Yu Shi Prof. Xue-Qing Gong Prof. He Tian Prof. Da-Hui Qu 《Angewandte Chemie (International ed. in English)》2023,62(11):e202300984
Poly(1,2-dithiolane)s are a family of intrinsically recyclable polymers due to their dynamic covalent disulfide linkages. Despite the common use of thiolate-initiated anionic ring-opening polymerization (ROP) under basic condition, cationic ROP is still not exploited. Here we report that disulfide bond can act as a proton acceptor, being protonated by acids to form sulfonium cations, which can efficiently initiate the ROP of 1,2-dithiolanes and result in high-molecular-weight (over 1000 kDa) poly(disulfide)s. The reaction can be triggered by adding catalytic amounts of acids and non-coordinating anion salts, and completed in few minutes at room temperature. The acidic conditions allow the applicability for acidic monomers. Importantly, the reaction condition can be under open air without inert protection, enabling the nearly quantitative chemical recycling from bulk materials to original monomers. 相似文献
988.
Cong Yu Zhengdong Guo Lifeng Yang Jiyu Cui Sen Chen Yawen Bo Xian Suo Qihan Gong Shang Zhang Prof. Xili Cui Shengbao He Prof. Huabin Xing 《Angewandte Chemie (International ed. in English)》2023,62(16):e202218027
Adsorptive separation is an energy-efficient alternative, but its advancement has been hindered by the challenge of industrially potential adsorbents development. Herein, a novel ultra-microporous metal-organic framework ZU-901 is designed that satisfies the basic criteria raised by ethylene/ethane (C2H4/C2H6) pressure swing adsorption (PSA). ZU-901 exhibits an “S” shaped C2H4 curve with high sorbent selection parameter (65) and could be mildly regenerated. Through green aqueous-phase synthesis, ZU-901 is easily scalable with 99 % yield, and it is stable in water, acid, basic solutions and cycling breakthrough experiments. Polymer-grade C2H4 (99.51 %) could be obtained via a simulating two-bed PSA process, and the corresponding energy consumption is only 1/10 of that of simulating cryogenic distillation. Our work has demonstrated the great potential of pore engineering in designing porous materials with desired adsorption and desorption behavior to implement an efficient PSA process. 相似文献
989.
Dr. Yuxuan Hu Dr. Jingsheng Miao Dr. Cheng Zhong Yang Zeng Prof. Shaolong Gong Dr. Xiaosong Cao Xue Zhou Dr. Yu Gu Prof. Chuluo Yang 《Angewandte Chemie (International ed. in English)》2023,62(19):e202302478
Heavy-atom integration into thermally activated delayed fluorescence (TADF) molecule could significantly promote the reverse intersystem crossing (RISC) process. However, simultaneously achieving high efficiency, small roll-off, narrowband emission and good operational lifetime remains a big challenge for the corresponding organic light-emitting diodes (OLEDs). Herein, we report a pure green multi-resonance TADF molecule BN-STO by introducing a peripheral heavy atom selenium onto the parent BN-Cz molecule. The organic light-emitting diode device based on BN-STO exhibited state-of-the-art performance with a maximum external quantum efficiency (EQE) of 40.1 %, power efficiency (PE) of 176.9 lm W−1, well-suppressed efficiency roll-off and pure green gamut. This work reveals a feasible strategy to reach a balance between fast RISC process and narrow full width at half maximum (FWHM) of MR-TADF by heavy atom effect. 相似文献
990.
在酸性离子液体催化下,通过吲哚及其衍生物和吲哚甲醛反应合成了一系列三吲哚甲烷化合物。[hmim]HSO4/EtOH 对于该反应来说,是一个高效、绿色的催化体系。 相似文献