全文获取类型
收费全文 | 21457篇 |
免费 | 3838篇 |
国内免费 | 3490篇 |
专业分类
化学 | 16998篇 |
晶体学 | 293篇 |
力学 | 1060篇 |
综合类 | 314篇 |
数学 | 2336篇 |
物理学 | 7784篇 |
出版年
2024年 | 53篇 |
2023年 | 414篇 |
2022年 | 626篇 |
2021年 | 708篇 |
2020年 | 925篇 |
2019年 | 890篇 |
2018年 | 748篇 |
2017年 | 695篇 |
2016年 | 1069篇 |
2015年 | 1104篇 |
2014年 | 1211篇 |
2013年 | 1599篇 |
2012年 | 1851篇 |
2011年 | 1960篇 |
2010年 | 1460篇 |
2009年 | 1502篇 |
2008年 | 1575篇 |
2007年 | 1431篇 |
2006年 | 1363篇 |
2005年 | 1191篇 |
2004年 | 913篇 |
2003年 | 806篇 |
2002年 | 858篇 |
2001年 | 666篇 |
2000年 | 552篇 |
1999年 | 469篇 |
1998年 | 319篇 |
1997年 | 277篇 |
1996年 | 254篇 |
1995年 | 251篇 |
1994年 | 206篇 |
1993年 | 164篇 |
1992年 | 149篇 |
1991年 | 120篇 |
1990年 | 100篇 |
1989年 | 70篇 |
1988年 | 42篇 |
1987年 | 48篇 |
1986年 | 35篇 |
1985年 | 34篇 |
1984年 | 12篇 |
1983年 | 10篇 |
1982年 | 8篇 |
1981年 | 7篇 |
1980年 | 5篇 |
1979年 | 5篇 |
1977年 | 5篇 |
1973年 | 4篇 |
1957年 | 6篇 |
1936年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 417 毫秒
971.
972.
973.
在水热条件下,以N-氧化-2-吡啶膦酸(H2L)为主配体,4,4'-联吡啶(bpy)为桥联配体,合成了3个铜有机膦酸配合物: {[CuL(bpy)0.5(H2O)]·2H2O}n(1), {[Cu(HL)2(bpy)]·4H2O}n(2)和{[Cu2(L)2(bpy)]·3H2O}n(3)。配合物1中,相邻的铜离子由2个膦酸根连成二聚体,二聚体之间通过bpy桥联成一维链。配合物2中,单核[Cu(HL)2]被bpy连接成一维链。配合物3中,四聚体[Cu2(L)2]2被bpy连接成“砖块状”结构的二维层。磁性研究表明,配合物1和3中铜离子之间存在反铁磁性耦合。 相似文献
974.
选择具有强给电子能力的1,2,4-三唑为配体,成功合成了银基金属有机骨架材料(Ag-MOF)并用于电催化还原CO2反应(CO2RR)。借助粉末X射线衍射、透射电子显微镜、扫描电子显微镜、计时电流法等表征手段对材料的晶体结构、形貌和电催化CO2RR性能进行了系统的研究。与商品化的纳米Ag颗粒对比,Ag-MOF展现出更优异的电催化CO2RR产物选择性、催化活性和稳定性,在-0.9 V (vs RHE)时,CO的法拉第效率高达96.1%。当电压为-1.1 V (vs RHE)时,电流密度可达17 mA·cm-2,且电极可以稳定运行300 min。这说明通过选择合适的配体结构,可以改变催化位点周围的化学环境,从而高效将CO2转化为目标产物。 相似文献
975.
A direct and efficient approach to 1‐aminoindolizines through three‐component one‐pot reaction of heteroaryl aldehydes, secondary amines and terminal alkynes catalyzed by CuI under solvent‐free conditions has been developed. This methodology provides a rapid access to substituted aminoindolizines with good yields (up to 97%). 相似文献
976.
You-An Xiao Zhi-Qiang Wang Xue-Min Wang Yi Hui Yong Ling Xin-Yang Wang Li-Qin He 《中国化学快报》2013,24(8):727-730
Novel 2-aminoimidazolone derivatives were synthesized.Most compounds displayed strong anticancer activities against human carcinoma cells in vitro.Compounds 8a,8b and 8j exhibited optimal activity superior to 5-FU in most cancer cells tested.Especially,the lC50s of 8b(12.6-21.5μmol/L) against five tumor cells were 1 -4 fold less than those of 5-FU(18.4-56.1μmol/L) in vitro.Furthermore,comp以ound 8b could induce SMMC-7721 cell apoptosis in a dose-dependent manner.Therefore,our novel findings may provide a new framework for the design of new 2-aminoimidazolone derivatives for the treatment of cancer. 相似文献
977.
Yi Chen Chan Abdussalam Salhin Mohamed Ali Melati Khairuddean Kooi Yeong Khaw Vikneswaran Murugaiyah Alireza Basiri 《中国化学快报》2013,24(7):609-612
Thiosemicarbazones of 2-amino-5-chlorobenzophenone and 3-aminobenzophenone(L1-L4) have been synthesized and their Cu(Ⅱ) complexes(1-4) were afforded via coordination with cupric chloride.All these compounds were characterized by UV-vis and IR spectroscopy together with CHN elemental analysis.NMR spectroscopy was also applied to characterize the ligands.In vitro chohnesterase inhibitory assays for the complexes(1-4) showed IC50 values less than 10μmol/L,with complex 1 exhibiting the most activity,IC50=2.15μmol/L and 2.16μmol/L for AChE and BuChE,respectively. Molecular modeling simulation revealed the binding interaction template for complex 1 with the AChE and BuChE receptors.In DPPH assay,the complexes also showed more in vitro antioxidant activities in comparison to their parent ligands. 相似文献
978.
A Cu(I) generated in situ from CuSO4·5H2O/sodium ascorbate catalyzed cross‐coupling reaction of aryl halides with aqueous ammonia for the synthesis of primary aromatic amines has been developed. Key to the success included the application of aqueous ammonia under a homogeneous condition. 相似文献
979.
Addition of nitroalkanes into n‐alkanes can lower the activation barriers of free‐radical production and accelerate the decomposition of n‐alkanes at relatively low temperatures. Four initial decomposition mechanisms of the n‐butane/nitroethane binary mixture were proposed for the promoting effect and considered theoretically at the B3LYP, BB1K, BMK, MPW1K, and M06‐2X levels with MG3S basis set. Energetics above was compared to high‐level CBS‐QB3 and G4 calculations. Calculated results confirm the feasibility of the four initial decomposition pathways: (I) the C? NO2 bond rupture of nitroethane to produce ethyl and ·NO2, (II) HONO elimination from nitroethane followed by decomposition to ·OH and ·NO, (III) rearrangement of nitroethane to ethyl nitrite which further dissociates into CH3CH2O· and ·NO, and (IV) direct hydrogen‐abstraction of nitroethane with n‐butane. 相似文献
980.
An efficient strategy for the synthesis of a variety of 3‐methyleneisoindolin‐1‐ones has been developed. The reaction proceeded from coupling of 2‐iodobenzamides (or 2‐bromobenzamides) and terminal alkynes via Cu(OAc)2·H2O/2,2′‐biimidazole catalyzed in DMF at 60°C and subsequent additive cyclization produced substituted 3‐methyleneisoindolin‐1‐ones in good to excellent yields. 相似文献