全文获取类型
收费全文 | 5412篇 |
免费 | 675篇 |
国内免费 | 581篇 |
专业分类
化学 | 4156篇 |
晶体学 | 79篇 |
力学 | 223篇 |
综合类 | 52篇 |
数学 | 641篇 |
物理学 | 1517篇 |
出版年
2024年 | 9篇 |
2023年 | 49篇 |
2022年 | 106篇 |
2021年 | 116篇 |
2020年 | 136篇 |
2019年 | 185篇 |
2018年 | 143篇 |
2017年 | 116篇 |
2016年 | 235篇 |
2015年 | 249篇 |
2014年 | 301篇 |
2013年 | 335篇 |
2012年 | 411篇 |
2011年 | 452篇 |
2010年 | 316篇 |
2009年 | 328篇 |
2008年 | 432篇 |
2007年 | 382篇 |
2006年 | 304篇 |
2005年 | 291篇 |
2004年 | 237篇 |
2003年 | 235篇 |
2002年 | 281篇 |
2001年 | 235篇 |
2000年 | 149篇 |
1999年 | 94篇 |
1998年 | 57篇 |
1997年 | 43篇 |
1996年 | 36篇 |
1995年 | 31篇 |
1994年 | 25篇 |
1993年 | 44篇 |
1992年 | 18篇 |
1991年 | 22篇 |
1990年 | 11篇 |
1989年 | 8篇 |
1988年 | 18篇 |
1987年 | 14篇 |
1986年 | 15篇 |
1985年 | 30篇 |
1984年 | 20篇 |
1983年 | 11篇 |
1982年 | 13篇 |
1980年 | 17篇 |
1979年 | 12篇 |
1978年 | 10篇 |
1977年 | 10篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1973年 | 10篇 |
排序方式: 共有6668条查询结果,搜索用时 15 毫秒
61.
Chemistry of Natural Compounds - A new seco-abietanoid, 12-hydroxy-6,7-seco-abieta-8,11,13-triene-6,7-dioic acid (1), was isolated from the methanol extract of the bark of Cryptomeria japonica. The... 相似文献
62.
Transition Metal Chemistry - A Cu(II) coordination polymer, [Cu2(pztrz)2(μ-CH3COO)(CH3COO)]·3H2O (1), derived from mono-substituted 1,2,4-triazole derivative 3-(pyrazinyl)-1,2,4-triazole... 相似文献
63.
(E)‐α,β‐Unsaturated pyrazoleamides undergo facile dienolization to furnish copper(I)‐(1Z,3Z)‐dienolates as the major in the presence of a copper(I)‐(R)‐DTBM‐SEGPHOS catalyst and Et3N, which react with aldimines to afford syn‐vinylogous products as the major diastereoisomers in high regio‐ and enantioselectivities. In some cases, the diastereoselectivity is low, possibly due to the low ratio of copper(I)‐(1Z,3Z)‐dienolates to copper(I)‐(1Z,3E)‐dienolates. (Z)‐Allylcopper(I) species is proposed as effective intermediates, which may form an equilibrium with copper(I)‐(1Z,3Z)‐dienolates. Interestingly, the present methodology is a nice complement to our previous report, in which (E)‐β,γ‐unsaturated pyrazoleamides were employed as the prenucleophiles in the copper(I)‐catalyzed asymmetric vinylogous Mannich‐Type reaction and anti‐vinylogous products were obtained. In the previous reaction, copper(I)‐ (1Z,3E)‐dienolates were generated through α‐deprotonation, which might form an equilibrium with (E)‐allylcopper(I) species. Therefore, it is realized in the presence of a copper(I) catalyst that (E)‐α,β‐unsaturated pyrazoleamides lead to syn‐products and (E)‐β,γ‐unsaturated pyrazoleamides lead to anti‐products. Finally, by use of (E)‐β,γ‐unsaturated pyrazoleamide, (E)‐α,β‐unsaturated pyrazoleamide, (R)‐DTBM‐SEGPHOS, and (S)‐DTBM‐SEGPHOS, the stereodivergent synthesis of all four stereoisomers is successfully carried out. Then by following a three‐step reaction sequence, all four stereoisomers of N‐Boc‐2‐Ph‐3‐Me‐piperidine are synthesized in good yields, which potentially serve as common structure units in pharmaceutically active compounds. 相似文献
64.
Wei Wang Hong Hai Shu-Hua Zhang Li Yang Chun-Lian Zhang Xiu-Ying Qin 《Journal of Cluster Science》2014,25(2):357-365
The reaction of Co(ClO4)2·6H2O with 2-hydroxy-3-methoxy-benzaldehyde and an aqueous solution of methylamine in acetonitrile/MeOH under microwave irradiation and controlled temperature/pressure leads to formation of heptanuclear cobalt cluster [Co7(mmp)6(CH3O)6]·(ClO4)2 (1) (mmp is 2-methoxy-6-methyliminomethyl-phenol anion) in only 20 min and also results in higher yields in contrast to other synthesis methods. Complex 1 displays dominant ferromagnetic interactions through μ 3-O and μ 2-O (oxidophenyl) binding modes. 相似文献
65.
Hongfei Cheng Kuo Li Qinfu Liu Shuai Zhang Xiaoguang Li Ray L. Frost 《Journal of Thermal Analysis and Calorimetry》2014,117(3):1231-1239
The thermal decomposition process of kaolinite–potassium acetate intercalation complex has been studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR-MS). The results showed that the thermal decomposition of the complex took place in four temperature ranges, namely 50–100, 260–320, 320–550, and 650–780 °C. The maximal mass losses rate for the thermal decomposition of the kaolinite–potassium acetate intercalation complex was observed at 81, 296, 378, 411, 486, and 733 °C, which was attributed to (a) loss of the adsorbed water, (b) thermal decomposition of surface-adsorbed potassium acetate (KAc), (c) the loss of the water coordinated to potassium acetate in the intercalated kaolinite, (d) the thermal decomposition of intercalated KAc in the interlayer of kaolinite and the removal of inner surface hydroxyls, (e) the loss of the inner hydroxyls, and (f) the thermal decomposition of carbonate derived from the decomposition of KAc. The thermal decomposition of intercalated potassium acetate started in the range 320–550 °C accompanied by the release of water, acetone, carbon dioxide, and acetic acid. The identification of pyrolysis fragment ions provided insight into the thermal decomposition mechanism. The results showed that the main decomposition fragment ions of the kaolinite–KAc intercalation complex were water, acetone, carbon dioxide, and acetic acid. TG-FTIR-MS was demonstrated to be a powerful tool for the investigation of kaolinite intercalation complexes. It delivers a detailed insight into the thermal decomposition processes of the kaolinite intercalation complexes characterized by mass loss and the evolved gases. 相似文献
66.
Jun-Wei Chen Yu-Yi Kuo Kuan-Ting Chen Chao-Ran Wang Chih-Yu Chao 《Molecular Crystals and Liquid Crystals》2015,611(1):139-145
We demonstrate that the supramolecular structure can be formed through the fibrous self-assembly of the polyfluorene-based polymer F8BT in liquid crystal (LC) 5CB. With the utility of alignment layer, the F8BT molecules can be aligned and formed oriented polymer network. We found that the presence of oriented polymer network makes twisted nematic LC exhibit excellent electro-optical properties (EO) of driving voltage reduction and EO bump peak elimination. The polyfluorene-based supramolecular structure provides the function of stabilizing LC molecules. We consider this functional self-assembled network has potential to apply in various devices for the ability of improving performance in operating property. 相似文献
67.
Concerted Asynchronous Hula‐Twist Photoisomerization in the S65T/H148D Mutant of Green Fluorescent Protein 下载免费PDF全文
Dr. Qiangqiang Zhang Prof. Xuebo Chen Dr. Ganglong Cui Prof. Wei‐Hai Fang Prof. Dr. Walter Thiel 《Angewandte Chemie (International ed. in English)》2014,53(33):8649-8653
Fluorescence emission of wild‐type green fluorescent protein (GFP) is lost in the S65T mutant, but partly recovered in the S65T/H148D double mutant. These experimental findings are rationalized by a combined quantum mechanics/molecular mechanics (QM/MM) study at the QM(CASPT2//CASSCF)/AMBER level. A barrierless excited‐state proton transfer, which is exclusively driven by the Asp148 residue introduced in the double mutant, is responsible for the ultrafast formation of the anionic fluorescent state, which can be deactivated through a concerted asynchronous hula‐twist photoisomerization. This causes the lower fluorescence quantum yield in S65T/H148D compared to wild‐type GFP. Hydrogen out‐of‐plane motion plays an important role in the deactivation of the S65T/H148D fluorescent state. 相似文献
68.
69.
Weidong Nie Guanghao Wu Jinfeng Zhang Li‐Li Huang Jingjing Ding Anqi Jiang Yahui Zhang Yanhong Liu Jingchao Li Kanyi Pu Hai‐Yan Xie 《Angewandte Chemie (International ed. in English)》2020,59(5):2018-2022
Exosomes hold great potential in therapeutic development. However, native exosomes usually induce insufficient effects in vivo and simply act as drug delivery vehicles. Herein, we synthesize responsive exosome nano‐bioconjugates for cancer therapy. Azide‐modified exosomes derived from M1 macrophages are conjugated with dibenzocyclooctyne‐modified antibodies of CD47 and SIRPα (aCD47 and aSIRPα) through pH‐sensitive linkers. After systemic administration, the nano‐bioconjugates can actively target tumors through the specific recognition between aCD47 and CD47 on the tumor cell surface. In the acidic tumor microenvironment, the benzoic‐imine bonds of the nano‐bioconjugates are cleaved to release aSIRPα and aCD47 that can, respectively, block SIRPα on macrophages and CD47, leading to abolished “don't eat me” signaling and improved phagocytosis of macrophages. Meanwhile, the native M1 exosomes effectively reprogram the macrophages from pro‐tumoral M2 to anti‐tumoral M1. 相似文献
70.
Hai‐Long Qian Fan‐Lin Meng Cheng‐Xiong Yang Xiu‐Ping Yan 《Angewandte Chemie (International ed. in English)》2020,59(40):17607-17613
Design of stable adsorbents for selective gold recovery with large capacity and fast adsorption kinetics is of great challenge, but significant for the economy and the environment. Herein, we show the design and preparation of an irreversible amide‐linked covalent organic framework (COF) JNU‐1 via a building block exchange strategy for efficient recovery of gold. JNU‐1 was synthesized through the exchange of 4,4′‐biphenyldicarboxaldehyde (BA) in mother COF TzBA consisting of 4,4′,4′′‐(1,3,5‐triazine‐2,4,6‐triyl)trianiline (Tz) and BA with terephthaloyl chloride. The irreversible amide linked JNU‐1 gave good stability, unprecedented fast kinetics, excellent selectivity and outstanding adsorption capacity for gold recovery. X‐ray photoelectron spectroscopy along with thermodynamic study and quantum mechanics calculation reveals that the excellent performance of JNU‐1 for gold recovery results from the formation of hydrogen bonds C(N)?H???Cl and coordinate interaction of O and Au. The rational design of irreversible bonds as both inherent linkage and functional groups in COFs is a promising way to prepare stable COFs for diverse applications. 相似文献