全文获取类型
收费全文 | 9439篇 |
免费 | 1313篇 |
国内免费 | 2679篇 |
专业分类
化学 | 6599篇 |
晶体学 | 148篇 |
力学 | 736篇 |
综合类 | 134篇 |
数学 | 384篇 |
物理学 | 2291篇 |
无线电 | 3139篇 |
出版年
2024年 | 90篇 |
2023年 | 316篇 |
2022年 | 562篇 |
2021年 | 546篇 |
2020年 | 524篇 |
2019年 | 377篇 |
2018年 | 295篇 |
2017年 | 405篇 |
2016年 | 509篇 |
2015年 | 454篇 |
2014年 | 546篇 |
2013年 | 691篇 |
2012年 | 609篇 |
2011年 | 628篇 |
2010年 | 534篇 |
2009年 | 583篇 |
2008年 | 647篇 |
2007年 | 616篇 |
2006年 | 538篇 |
2005年 | 507篇 |
2004年 | 476篇 |
2003年 | 412篇 |
2002年 | 340篇 |
2001年 | 270篇 |
2000年 | 317篇 |
1999年 | 213篇 |
1998年 | 241篇 |
1997年 | 193篇 |
1996年 | 163篇 |
1995年 | 155篇 |
1994年 | 145篇 |
1993年 | 123篇 |
1992年 | 111篇 |
1991年 | 59篇 |
1990年 | 48篇 |
1989年 | 38篇 |
1988年 | 42篇 |
1987年 | 22篇 |
1986年 | 9篇 |
1985年 | 17篇 |
1984年 | 14篇 |
1983年 | 15篇 |
1982年 | 11篇 |
1981年 | 5篇 |
1979年 | 4篇 |
1977年 | 2篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1971年 | 2篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
111.
Dongmei He Li Zeng Guiqing Zhang Qinggang Li Wenjuan Guan Zuoying Cao Shengxi Wu 《应用有机金属化学》2019,33(9)
A new compound, α‐aminophosphonate derivative containing pyridine ring (PPDE), was designed and synthesized as an extractant for the separation of nickel from metal impurities. Over 94.5% of Ni (II) extraction from sulfuric acid solution was achieved by using PPDE with an equilibrium pH of 4.02. Meanwhile, high separation coefficients of 23.8 for Ni to Co, 84.9 for Ni to Mn, 254.1 for Ni to Ca and 696.7 for Ni to Mg, respectively, were obtained. It was noted that PPDE exhibited an excellent regenerability, and the extraction of Ni with the recycled organic phase ranged from 92.5% to 93.9% during six circulations. The extracted nickel complex was determined as [Ni (PPDE)2(DNNSA?)2(H2O)4], which was supported by the data obtained from Fourier transform‐infrared, UV–Vis and electrospray ionization‐mass spectrometry spectra. 相似文献
112.
乙烯醇锂的从头算研究 总被引:1,自引:1,他引:1
用限制的HF/3-21G和HF/6-31G*优化乙烯醇锂的几种可能构型,比较了它们的稳定性.用限制的HF/3-1G,从乙醛开始,探讨了气相反应生成乙烯醇锂的机理,并在MP2水平上用6-31G*基组计算了反应热. 相似文献
113.
Huakuan Lin Shourong Zhu Appolin Bave Kondiano Xuncheng Su Fuping Kou Yunti Chen 《Polyhedron》1998,17(25-26)
The kinetics of the acid dissociation of copper(II) complexes of novel C-functionalized macrocyclic dioxotetraamines has been studied by means of a stopped-flow spectrophotometer. The acid dissociation rate follows the law Vd = CcomkK1K2H 2/(1+K1H+K1K2H 2). From the experimental facts we have obtained, the dissociation kinetics are interpreted by a mechanism involving the negatively charged carbonyl oxygen of the complex being rapidly protonated in a pre-equilibrium step, the rate-determining step being intramolecular hydrogen (enolic tautomer) migration (to imine nitrogen). The dissociation rate reached a plateau in the strongly acidic solution. By means of temperature coefficient method, ΔH φ, ΔS φ of the pre-equilibrium step and ΔH ≠, ΔS≠ of the rate-determining step were obtained. The results of 13-membered macrocyclic dioxotetraamines have been discussed. The influence of the substituents to the acid dissociation rates has also been discussed. The Bronsted type linear free energy relationships do also exist in these C-functionalized dioxotetraamine copper(II) complexes. 相似文献
114.
We have used combined quantum mechanical and molecular mechanical (QM/MM) calculations to study the reaction mechanism of nitrogenase, assuming that none of the sulfide ligands dissociates. To avoid the problem that there is no consensus regarding the structure and protonation of the E4 state, we start from a state where N2 is bound to the cluster and is protonated to N2H2, after dissociation of H2. We show that the reaction follows an alternating mechanism with HNNH (possibly protonated to HNNH2) and H2NNH2 as intermediates and the two NH3 products dissociate at the E7 and E8 levels. For all intermediates, coordination to Fe6 is preferred, but for the E4 and E8 intermediates, binding to Fe2 is competitive. For the E4, E5 and E7 intermediates we find that the substrate may abstract a proton from the hydroxy group of the homocitrate ligand of the FeMo cluster, thereby forming HNNH2, H2NNH2 and NH3 intermediates. This may explain why homocitrate is a mandatory component of nitrogenase. All steps in the suggested reaction mechanism are thermodynamically favourable compared to protonation of the nearby His-195 group and in all cases, protonation of the NE2 atom of the latter group is preferred. 相似文献
115.
Four Fe—CO states with 3dσ-4s, 3dδ-3dδ electrons spin-paired or spinunpaired were examined to investigate the influences of pairing versus unpairing mechanisms upon the bonding, interaction in Fe—CO. The calculation results show that the Fe—CO bonding, interaction are determined by a balance between the bonding stabilization, the exchange stabilization with 3dσ-4s electron spinpairing or without it. The 3dδ-3dδ electron spinpairing versus unpairing has a surprised effect on the Fe—CO bonding properties even though the 3dδ orbitals are usually considered as non bonding ones. 相似文献
116.
《Journal of computational chemistry》2017,38(7):438-445
DFT calculations were conducted to pursue deeper understandings on the mechanism and the explicit role of trace water in the DBU‐catalyzed β‐amination of NBS to chalcone. Being different from previously proposed by Liang et al., a cooperative participation of both DBU and water is noticed in the preferred mechanism. The preferential mechanistic scenario assisted by water undergoes three major steps: the formation of succinimide and HBrO, concerted nucleophilic addition and H‐shift, and keto‐enol tautomerization. Moreover, we found that DBU‐HBrO is unnecessary in the third step and three‐water‐cluster assisted keto‐enol tautomerization is the most advantageous case. It is further noted that the catalytic position of the third water molecule and the proton shift orientation to some extent affect step 3 via O···H O and O H···π interactions, which is confirmed by AIM analysis. The computational results suggest that water molecules play pivotal roles as reactant, catalyst, and stabilizer to promote the reaction of chalcone and NBS. The origin of the more stable transition state structure in the rate‐determining step of DBU‐water catalyzed mechanism is ascribed to noncovalent interactions, halogen bond, and electrostatic interactions than DBU only ones. © 2017 Wiley Periodicals, Inc. 相似文献
117.
118.
V. V. Kuznetsov 《Chemistry of Heterocyclic Compounds》2006,42(5):559-569
New examples of the borylation of a series of five-and six-membered saturated 1,3-and 1,3,2-heterocycles with the formation
of cyclic boric esters are described. The probable mechanism of the reaction is discussed.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 643–654, May, 2006. 相似文献
119.
由溶剂热法合成了 2 个锰的超分子配合物[Mn2(2,2''-bipy)4(H2O)Cl3](L1)·6H2O (1)和[Mn(2,2''-bipy)2(H2O)Cl](L2)·3H2O (2)(L1-=对甲基苯磺酸根,L2-=间硝基苯磺酸根,2,2''-bipy=2,2''-联吡啶),并用单晶X射线衍射、红外光谱、热重分析和氮气吸附-脱附测试对其进行了表征。以Mannich反应为探针,研究了2种配合物的催化性能,并通过对比2种配合物的扫描电镜和粉末X射线衍射表征结果,分析了配合物结构对其催化性能的影响。最后通过密度泛函理论预测了配合物的活性位点,利用X射线光电子能谱证明了活性位点的活化作用,进而阐述了配合物催化Mannich反应的机理。 相似文献
120.
《中国科学B辑(英文版)》2008,(4)
The impact of TiO2 nanoparticles on DNA synthesis in vitro in the dark and the molecular mechanism of such impact were studied. The impact of TiO2 nanoparticles on DNA synthesis was investigated by adding TiO2 nanoparticles in different sizes and at various concentrations into the polymerase chain reaction (PCR) system. TiO2 nanoparticles were premixed with the DNA polymerase, the primer or the template, respectively and then the supernatant and the precipitation of each mixture were added into the PCR system separately to observe the impact on DNA synthesis. Sequentially the interaction be- tween TiO2 nanoparticles and the DNA polymerase, the primer or the template was further analyzed by using UV-visible spectroscopy and polyacrylamide gel electrophoresis (PAGE). The results suggest that TiO2 nanoparticles inhibit DNA synthesis in the PCR system in the dark more severely than mi- croscale TiO2 particles at the equivalent concentration and the inhibition effect of TiO2 nanoparticles is concentration dependent. The molecular mechanism of such inhibition is that in the dark, TiO2 nanoparticles interact with the DNA polymerase through physical adsorption while TiO2 nanoparticles do with the primer or the template in a chemical adsorption manner. The disfunction levels of the bio-molecules under the impact of TiO2 nanoparticles are in the following order: the primer > the tem- plate > the DNA polymerase. 相似文献