全文获取类型
收费全文 | 2081篇 |
免费 | 410篇 |
国内免费 | 202篇 |
专业分类
化学 | 1403篇 |
晶体学 | 22篇 |
力学 | 115篇 |
综合类 | 12篇 |
数学 | 286篇 |
物理学 | 855篇 |
出版年
2023年 | 55篇 |
2022年 | 53篇 |
2021年 | 95篇 |
2020年 | 104篇 |
2019年 | 85篇 |
2018年 | 71篇 |
2017年 | 78篇 |
2016年 | 128篇 |
2015年 | 121篇 |
2014年 | 134篇 |
2013年 | 163篇 |
2012年 | 202篇 |
2011年 | 217篇 |
2010年 | 149篇 |
2009年 | 147篇 |
2008年 | 123篇 |
2007年 | 108篇 |
2006年 | 96篇 |
2005年 | 88篇 |
2004年 | 68篇 |
2003年 | 55篇 |
2002年 | 49篇 |
2001年 | 45篇 |
2000年 | 31篇 |
1999年 | 27篇 |
1998年 | 22篇 |
1997年 | 24篇 |
1996年 | 25篇 |
1995年 | 20篇 |
1994年 | 18篇 |
1993年 | 10篇 |
1992年 | 15篇 |
1991年 | 14篇 |
1990年 | 20篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 1篇 |
1984年 | 2篇 |
1983年 | 1篇 |
1981年 | 3篇 |
1974年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有2693条查询结果,搜索用时 546 毫秒
51.
以硝酸铽、苯乙酮酸(HL), 2, 2'-联吡啶(dipy)、 1, 10-菲啰啉(phen)和三苯基氧膦(TPPO)合成了TbL3dipy(H2O)2, TbL3phen(H2O)2和TbL2(TPPO)2NO3 3种新型固态配合物. 用元素分析、电导率、红外光谱和核磁共振谱对其进行了表征, 确定了配合物的组成. IR表明, 配合物中羧酸根可能以单齿方式配位. 1HNMR显示, 苯乙酮酸根配位后苯环上5个氢原子的化学位移移向高场. 室温下测定了配合物的荧光激发光谱, TbL3dipy(H2O)2, TbL3phen(H2O)2和TbL2(TPPO)2NO3最佳激发波长分别为361.0, 359.0和367.0 nm;分别以最佳激发波长测定了配合物的发射光谱, 配合物TbL3dipy(H2O)2, TbL3phen(H2O)2 和TbL2(TPPO)2NO3显示Tb3+离子的特征发射光谱, TbL3dipy(H2O)2和TbL3phen(H2O)2均产生四条谱带, 分别归属于^5D4-^7Fj(j= 6, 5,4,3)能级跃迁(TbL3dipy(H2O)2: 489.0, 545.0, 584.0, 620.0 nm;TbL3phen(H2O)2: 490.0, 544.0, 583.0, 620.0 nm);但在相同测定条件下, TbL2(TPPO)2NO3仅显示5D4-7F5(544.0 nm)能级跃迁光谱. 3种配合物中TbL3dipy(H2O)2发光强度最高. 相似文献
52.
Isolation and purification of honokiol and magnolol from cortex Magnoliae officinalis by high-speed counter-current chromatography 总被引:5,自引:0,他引:5
High-speed counter-current chromatography was used to isolate and purify honokiol and magnolol from cortex Magnoliae Officinalis (Magnolia officinalis Rehd. et Wils.), a plant used in the traditional Chinese medicine. A crude sample, 150 mg, was successfully separated with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:0.4:1:0.4, v/v), and the fractions were analyzed by high-performance liquid chromatography. The separation produced 80 and 45 mg of honokiol and magnolol with purities of 99.2 and 98.2%, respectively, in 2.5 h. 相似文献
53.
提出了测量气相色谱中吸附等温线的新方法,用不同进样量下测定的容量因子计算平衡时气-固两相组分浓度。利用建立的方法分别测量了正-己烷、正-壬烷和正-十一烷在邻苯二甲酸二辛酯(DOP)、阿皮松-L(Apiezon)和β,β′-氧二丙腈(ODPN)柱上的吸附等温线,讨论了色谱峰形状与吸附等温线的对应关系。研究了气相色谱中进样量对保留值的影响,利用佛伦德利希(Freundlich)吸附等温式导出了描述保留值与进样量关系的数学表达式。理论和实验证明,保留值与进样量具有良好的对数线性关系。 相似文献
54.
SynthesisandMagnetismof2┐Hydroxy┐1,3┐propylene┐bis(oxamato)┐bridgedCoⅡCuⅡCoⅡComplexesMIAOMing-ming,CHENGPeng,LIAODai-zhengJIA... 相似文献
55.
偶合反应化学发光法测定痕量银的研究 总被引:6,自引:0,他引:6
本将Ag(Ⅰ)催化S2O^2-8氧化Mn(Ⅱ)生成MnO^-4的催化反应与LuminolMnO^-4-OH^-的化学发光反应相偶合,建立起一种新的灵敏测定痕量银的化学发光分析法,在所研究的优化条件下,该法测定银的选择性较好,检测限达到3.2×10^-12g/mLAg线性浓度范围为1.0×10^-11-1.0×10^-5g/mLAg,用于水样分析,结果较为满意。 相似文献
56.
Ji-Lai Li Cai-Yun Geng Xu-Ri Huang Chia-Chung Sun 《Theoretical chemistry accounts》2007,117(3):417-429
The reaction of atomic radical F with propyne has been studied theoretically using ab initio quantum chemistry methods and
transition state theory. The potential energy surface was calculated at the CCSD(T)/aug-cc-pVDZ (single-point) level using
the UMP2/6-311++G(d,p) optimized structures. Two reaction mechanisms including the addition–isomerization–elimination reaction
mechanism and the directed hydrogen abstraction reaction mechanism are considered. For the hydrogen abstraction reactions,
i.e., the most probable evolution pathway in the title reaction, the HF formation occurs via direct abstraction mechanism
dominantly and the H atom picked up by the atomic radical F should come mostly from the methyl group of normal propyne. On
the other hand, for the addition–isomerization–elimination mechanism, the most feasible pathway should be the atomic radical
F attacking on the C≡C triple bond in propyne (CH3C≡CH) to form a weakly-bound adduct A1 with no barrier, followed by F addition to the C≡C triple bond to form the low-lying
intermediate isomer 5. Subsequently, isomer 5 directly dissociates to P3 H2CCCHF + H via transition state TS5/P3. The other reaction pathways on the doublet PES are less competitive due to thermodynamical or kinetic factors. Furthermore,
based on the analysis of the kinetics of all channels through which the addition and abstraction reaction proceed, we expect
that the competitive power of reaction channels may vary with experimental conditions for the title reaction. The present
work will provide useful information for understanding the processes of atomic radical F reaction with other unsaturated hydrocarbons.
This material is available from author via E-mail. 相似文献
57.
Paulus UA Wang Y Kim SH Geng P Wintterlin J Jacobi K Ertl G 《The Journal of chemical physics》2004,121(22):11301-11308
Catalytic CO oxidation on the RuO(2)(110) surface was studied at 300 K by scanning tunneling microscopy (STM), high-resolution electron-energy-loss spectroscopy (HREELS), and thermal desorption spectroscopy (TDS). Upon repeatedly exposing the surface to several 10 L of CO and O(2) at 300 K, STM shows that unreactive features accumulate with each CO and O(2) titration run. HREELS and TDS show formation of increasing amounts of H(2)O, retarded formation of O-cus atoms and incomplete removal of CO-bridge molecules during O(2) dosing, and a changing ratio of single- and double-bonded CO-bridge molecules. It is concluded that H(2)O (presumably from the residual gas) is accumulating at the Ru-cus sites thus blocking them, so that the dissociative adsorption of oxygen is prevented and the CO oxidation reaction is suppressed. Some 10% CO- bridge remains on the surface even during oxygen exposure. Consistent with this interpretation, deactivation of the surface is suppressed at 350 K, at the onset of H(2)O desorption. 相似文献
58.
N. Kent Dalley Weiming Jiang Krzysztof E. Krakowiak Geng Wu D. Wade Walke Jerald S. Bradshaw Reed M. Izatt 《Journal of inclusion phenomena and macrocyclic chemistry》1990,8(3):299-308
Hydrazino-crown ethers have been synthesized in only 3 or 4 steps starting from 1,2-diacetylhydrazine. The X-ray crystal structure of protonated hydrazino-19-crown-7 (2) showed that one of the hydrazino nitrogen atoms was directed outside the ring cavity. A solvent methanol molecule is held in the cavity of the host ligand by three hydrogen bonds involving two hydrogen atoms bonded to nitrogens of the ligand and the alcohol hydrogen of the methanol. The logK values for the interaction of2 with CH3NH
+
3
, Ag+, Pb2+, and Cd2+ were much less than those for the interaction of symmetrical triaza-l8-crown-6 (5) with the same cations. Hydrazino-crown2 reduced silver ions to silver metal when a solution of2 and silver ions in DMSO was allowed to stand for several days. 相似文献
59.
Geng ZhiYuan Yao Kun Wang YongCheng Fang Ran Zhang XingHui Jia BaoLi 《中国科学B辑(英文版)》2007,50(3):335-344
The mechanisms of theion reaction of alkylidenegermylene with oxirane and thiirane have been characterized detail in using density functional theory, as well as ab initio method, including geometry optimization and vibrational analysis for the involved stationary points on the potential energy surface. Energies were calculated by CCSD(T)/6-311G(d)//B3LYP/6-311G(d,p) method for the involved conformations. The results show that the reaction pathways for both reactions consist of two ways: (1) the reactants can yield bent products (P1; P4) by syn-isomers; (2) the reactants can also yield three-membered products (P2; P5) by anti-isomers, which then further react with oxirane and thiirane to form the ultimate products (P3-1, P3-2; P6). Furthermore, a comparison with alkylidenecarbene, oxirane, and thiirane was done. 相似文献
60.