全文获取类型
收费全文 | 62198篇 |
免费 | 9802篇 |
国内免费 | 5523篇 |
专业分类
化学 | 41955篇 |
晶体学 | 604篇 |
力学 | 4015篇 |
综合类 | 249篇 |
数学 | 6655篇 |
物理学 | 24045篇 |
出版年
2024年 | 654篇 |
2023年 | 1460篇 |
2022年 | 2338篇 |
2021年 | 2747篇 |
2020年 | 3070篇 |
2019年 | 2835篇 |
2018年 | 2101篇 |
2017年 | 1866篇 |
2016年 | 2917篇 |
2015年 | 2805篇 |
2014年 | 3385篇 |
2013年 | 4170篇 |
2012年 | 5389篇 |
2011年 | 5408篇 |
2010年 | 3601篇 |
2009年 | 3411篇 |
2008年 | 3680篇 |
2007年 | 3295篇 |
2006年 | 2978篇 |
2005年 | 2524篇 |
2004年 | 1941篇 |
2003年 | 1539篇 |
2002年 | 1399篇 |
2001年 | 1191篇 |
2000年 | 1086篇 |
1999年 | 1237篇 |
1998年 | 1039篇 |
1997年 | 1023篇 |
1996年 | 1028篇 |
1995年 | 846篇 |
1994年 | 745篇 |
1993年 | 609篇 |
1992年 | 552篇 |
1991年 | 445篇 |
1990年 | 405篇 |
1989年 | 303篇 |
1988年 | 269篇 |
1987年 | 229篇 |
1986年 | 205篇 |
1985年 | 171篇 |
1984年 | 126篇 |
1983年 | 84篇 |
1982年 | 67篇 |
1981年 | 58篇 |
1980年 | 56篇 |
1979年 | 29篇 |
1978年 | 26篇 |
1977年 | 33篇 |
1976年 | 24篇 |
1975年 | 21篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
71.
Sheng-Rong Liao Yong Tang Liang Xu Xue-Feng Zhou Jun-Feng Wang Bin Yang Yong-Hong Liu 《Tetrahedron》2017,73(1):98-107
An unexpected ring-contraction from benzo[b]pyrazino[1,2-d][1,4]thiazine-1,4-diones (6) to benzo[4,5]thiazolo[3,2-a]pyrazine-1,4-diones (7) has been developed. The preliminary mechanistic studies showed the transformation contained two independent steps: the first step is the formation of a Michael adduct upon the addition of the protic solvent, in the presence of base, to the C-2-C-3 double bond of compound 6, and the second step is a ring-contraction induced by oxygen via the migration of sulfur atom from C-2 to C-3 position. And its scope is also studied. 相似文献
72.
The humulanolides are a series of sesquiterpene lactones, most of which have unique and challenging structure. The humulanolides have exhibited anticancer activity. The combinations of fascinating structural motifs and promising pharmacological properties have prompted significant interest in the synthetic community. In this review, we provide a summary of recent progress regarding the total synthesis of humulanolides. 相似文献
73.
Cuiling Wang Jiaxu Yan Mo Du Joseph A. Burlison Chi Li Yanni Sun Danqing Zhao Jianli Liu 《Tetrahedron》2017,73(19):2780-2785
One step synthesis of the natural product indirubin by reductive coupling of isatin with KBH4 is described and a possible mechanism for the reaction is proposed. Eleven indirubin derivatives were obtained easily from the corresponding substituted isatin. 相似文献
74.
A highly selective HBT-based “turn-on” fluorescent probe for hydrazine detection and its application
Zhen Chen Xinxin Zhong Wangbo Qu Ting Shi Heng Liu Hanping He Xiuhua Zhang Shengfu Wang 《Tetrahedron letters》2017,58(26):2596-2601
As one of the important industrial chemicals, hydrazine (N2H4) can be inhaled through the skin, leading to many serious health issues. In this paper, we constructed a novel turn-on fluorescent probe HBTM for N2H4 detection based on ESIPT and ICT mechanism by incorporating the methyl dicyanvinyl group to 2-(2′-hydroxylphenyl) benzothiazole (HBT) fluorophore. The probe showed the following advantages: high sensitivity with detection limit of 2.9 × 10?7 M, high selectivity over other related interfering species, wide linear range of 0–140 μM and pH value adaptation. Moreover, the probe could detect N2H4 on paper strips and image N2H4 in living cells. 相似文献
75.
Ming-Qi Wang Zi-Yu Wang Yi-Fan Yang Gui-Ying Ren Xiao-Ning Liu Shuo Li Jian-Wei Wei Lan Zhang 《Tetrahedron letters》2017,58(33):3296-3300
The development of small-molecule G-quadruplex DNA probes has attracted significant attention in recent years. However, G-quadruplexes can display a wide variety of topologies, which process different structures and functions. Therefore, selective discrimination one G-quadruplex structure over another is promising. Herein, we reported the design, synthesis and biological evaluation of a long-chain fatty amine functionalized triphenylamine-quinolinium conjugate 1b. Significant enhancement of the fluorescence intensity (over 180 fold) was observed when 1b bound with HRAS G-quadruplex DNA, while much weaker enhancements were presented in the presence of other G-quadruplexes (45–90-fold) and single/double-stranded DNAs (less than 20-fold), indicating 1b had an excellent selectivity to HRAS. The details of the interactions were investigated by UV–Vis, FID and CD analysis. The results show 1b could interact and stabilize HRAS structure mainly by π-π stacking binding mode. The introduced amine chain of the structure core was found to be better in the terms of inducing selectivity toward G-quadruplex structure. In addition, the application of 1b as a fluorescent agent for living cell imaging was also demonstrated. 相似文献
76.
Bijun Liu Yin Tian Qianhong Yu Qiang Li Wanjun Mu Zhaoyi Tan Fengchang Wu Dongqi Wang Xingliang Li 《Journal of solution chemistry》2017,46(12):2281-2292
O-Phospho-l-serine is one of the naturally occurring phosphorylated amino acids, having important pharmacological activity and bioactivity. The protonation constants of O-phospho-l-serine were determined by means of potentiometric titrations at 25 °C and ionic strength of 0.5 mol·L?1 (NaCl). The heat effects of the protonation reaction of the O-phospho-l-serine were measured by direct calorimetry. NMR spectroscopy has demonstrated that the first protonation site occurs at the nitrogen atom in the amino group, followed by one of the oxygen atoms in the phosphono group, and finally the carboxyl oxygen atom. This trend is in good agreement with the enthalpy of protonation and quantum chemical calculations. These data will help to predict the speciation of O-phospho-l-serine in physiological systems. 相似文献
77.
Yao-Yue Fan Shi-Xin Chen Qun-Fang Liu Li-She Gan Jian-Min Yue 《Tetrahedron letters》2017,58(50):4728-4730
Trigochinins A–C (1–3) are three highly oxygenated daphnane-type diterpenes isolated from Trigonostemon chinensis. Their structures with the absolute configurations were initially assigned by a combination of spectroscopic data, X-ray crystallography (Mo Kα radiation) study and CD analysis. In the current study, the absolute configurations of trigochinins A–C were confirmed by single crystal X-ray diffraction (Cu Kα radiation) study, CD spectral analogy, and theoretical ECD study by using quantum chemical TDDFT calculations. 相似文献
78.
Tao Wang Xinyu Zhang Hanzi Liu Yonghong Guo Yongsheng Zhang Yang Wang Baomin Sun 《Catalysis Surveys from Asia》2017,21(2):94-102
Manganese–copper bimetal oxide catalysts supported on ZSM5 and acid-treated multi-walled carbon nanotubes (MWCNTs) were produced by incipient wetness impregnation for selective catalytic reduction of NO with dielectric barrier discharge plasma. Plasma can activate molecules even at ambient temperature, generating active oxygen species such as O, O3, and HO2 radicals, which can oxidize NO to NO2 effectively. The SCR activity of Mn–Cu/MWCNTs was studied and compared to that of the Mn–Cu/ZSM5. The obtained samples were characterized by XRD, SEM, TEM, ICP, H2-TPR, Raman spectroscopy, and XPS. The results show that Mn–Cu/MWCNTs catalyst possesses NO removal activity superior to that of the Mn–Cu/ZSM5 catalyst. MWCNTs-based catalyst attains NO removal efficiency of 88% at 480 J/L, while the ZSM5-supported catalyst achieves NO removal efficiency of 82% at the same energy density. The oxygen content increased from 3.33 to 19.07% on the nanotube surface after introducing Mn and Cu, which almost remained unchanged on ZSM5. The oxygen-containing functionalities are important for NOx adsorption and removal. Moreover, the characterization revealed that CuO is the main phase of copper oxide, but copper dispersion decreases on Mn–Cu/ZSM5 surface because of the formation of copper dimer species. The manganese is well-dispersed on the catalysts, MnO2 and Mn2O3 contents of Mn–Cu/MWCNTs are larger than that of Mn–Cu/ZSM5, MnO2 is the predominant phase of manganese oxide. 相似文献
79.
The combination of gold nanoparticles and metal–organic frameworks is one of the new directions of current research. It has applications in many aspects, especially as a catalyst for a variety of reactions. Therefore, this paper describes recent progress of synthesis and application in Au@MOFs hybrid materials. 相似文献
80.
Shuai Zhang Zhi-Wei Zhao Zhen-Dong Fang Jie Liu 《Russian Journal of Applied Chemistry》2017,90(3):458-466
The effect of combined filtration efficiency on the performance of anthracite filtration?micro electrolysis?sand filtration (AMS) was investigated. Impact of different operating parameters, such as iron?carbon ratio of micro electrolytic units, filtration velocity of AMS, were studied. It was found that when iron?carbon ratio was 6: 4, the AMS’s average turbidity removal rate was 96.75% at the filtration velocity of 3 m h?1. The results showed that when the filtration rate was 3?9 m h?1 and iron?carbon ratio was 6: 4, the turbidity removal efficiency was over 94%, and the turbidity of the effluent was less than 1 NTU in effective filtration cycle. The effective filtration cycle can last for more than 5 h or longer. Meanwhile, the removal rate of UV254 was above 33%, and the concentration of iron ions in the effluent is less than 0.15 mg L?1. Turbidity and iron indicators have reached the national drinking water standards. It was also found the mechanism of iron?carbon micro electrolytic enhanced filtration by infrared spectroscopy and scanning electron microscopy. And It was also speculated the reasons for the reaction passivation. 相似文献