全文获取类型
收费全文 | 11545篇 |
免费 | 1598篇 |
国内免费 | 1349篇 |
专业分类
化学 | 8212篇 |
晶体学 | 137篇 |
力学 | 744篇 |
综合类 | 90篇 |
数学 | 1380篇 |
物理学 | 3929篇 |
出版年
2024年 | 61篇 |
2023年 | 291篇 |
2022年 | 439篇 |
2021年 | 455篇 |
2020年 | 471篇 |
2019年 | 490篇 |
2018年 | 420篇 |
2017年 | 395篇 |
2016年 | 568篇 |
2015年 | 548篇 |
2014年 | 644篇 |
2013年 | 857篇 |
2012年 | 958篇 |
2011年 | 993篇 |
2010年 | 696篇 |
2009年 | 637篇 |
2008年 | 767篇 |
2007年 | 639篇 |
2006年 | 586篇 |
2005年 | 426篇 |
2004年 | 387篇 |
2003年 | 299篇 |
2002年 | 329篇 |
2001年 | 233篇 |
2000年 | 216篇 |
1999年 | 274篇 |
1998年 | 197篇 |
1997年 | 145篇 |
1996年 | 152篇 |
1995年 | 150篇 |
1994年 | 103篇 |
1993年 | 113篇 |
1992年 | 98篇 |
1991年 | 88篇 |
1990年 | 83篇 |
1989年 | 68篇 |
1988年 | 45篇 |
1987年 | 36篇 |
1986年 | 23篇 |
1985年 | 31篇 |
1984年 | 21篇 |
1983年 | 14篇 |
1982年 | 12篇 |
1981年 | 6篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 20 毫秒
991.
A pressurized gradient capillary electrochromatography (pCEC) instrument was developed to separate 18 amino acid derivatives. A reversed-phase C18 column (3 microm, 130 mm x 75 microm I.D.) and an acetate buffer (50 mmol/l NaAc, pH 6.4) with an ion-pair reagent (1% N,N-dimethylformamide) were used to separate derivatized amino acids from a standard solution (2 microg/ml), and the wavelength of the UV-Vis detector was 360 nm. The pressure on the capillary column was kept at approx. 70 Pa and 3 kV positive voltage was added on the outlet end of column. The effect of voltage on the eluting order of amino acids and the resolution of separation were studied, and it was found that when the voltage was higher than 3 kV, the adsorption of amino acids in the porous C18 column occurred. The effect of salt concentration, injection volume, and column length on the separation of amino acids was determined. The amino acid sample was separated by pCEC, and RSDs of the migration times of each amino acid were all less than 2.5%. 相似文献
992.
993.
994.
A new study of the enzymatic hydrolysis of carboxymethyl cellulose with a bulk acoustic wave sensor 总被引:4,自引:0,他引:4
A new bulk acoustic wave (BAW) cellulase sensing technique, which is based on the enzymatic hydrolysis process of sodium carboxymethylcellulose (CMC) by cellulase, was established. The frequency shift curves of BAW sensor indicated that the viscosity of the tested solutions decreased during the hydrolysis process. The hydrolysis rate of CMC by cellulase was calculated from the frequency shift curves. The hydrolysis rate of CMC under different pH conditions at 30°C showed that cellulase had high hydrolysis ability approximately at pH 5.0. Kinetic parameters (the Michaelis constant Km and the maximum rate Vmax) of the process were estimated by using a linear method of Lineweaver–Burk plot. Km is 1.95±0.25 mg ml−1 and Vmax is −(4.25±0.58)×10−3 g1/2 cm−3/2 cP1/2 min−1. Also the activation energy (Ea) of the enzymatic hydrolysis, with a value of 51.99±1.26 kJ mol−1, was estimated in this work. 相似文献
995.
为了更好地利用太阳光和提高二氧化钛的光催化性能,以钛酸四正丁酯、正硅酸乙酯、六水合硝酸镍为原料,在高压釜中140℃非水溶剂热反应,所得材料经400℃焙烧制得镍硅共掺杂的二氧化钛光催化剂.所得材料用X射线衍射、氮吸附、透射电镜、X射线光电子能谱、傅里叶变换红外光谱、紫外漫反射等测试手段分析,结果显示所有样品均为锐钛矿型二氧化钛,Si和Ni均掺杂到TiO2体相中,样品具有较大的比表面积,其最大达303.3m2·g-1.在可见光照射下,以降解罗丹明-B为探针反应研究其可见光催化性能,与未掺杂和镍掺杂的二氧化钛相比较,共掺杂的二氧化钛具有更高的可见光催化性能,当Ni/Ti和Si/Ti的物质的量的比分别为0.01和0.20时,可见光催化性能最好.可见光催化性能的提高归因于镍和硅的协同作用. 相似文献
996.
Yong Mei Hu Guang Hai Su Stephen Cho‐Wing Sze Wencai Ye Yao Tong 《Biomedical chromatography : BMC》2010,24(4):438-453
A simple method based on liquid chromatography coupled with diode array detection and electrospray ionization mass spectrometry (LC‐DAD‐ESI‐MS) was developed for the quality assessment of Cortex Phellodendri (CP), which was mainly derived from two species of Phellodendron chinense Schneid and Phellodendron amurense Rupr. Total 41 compounds, including 14 phenols, 24 alkaloids and three liminoidal triterpenes were identified or tentatively characterized from the 75% methanol extract of CP samples by online ESI‐MSn fragmentation and UV spectra analysis. Among them, two phenols and six alkaloids were simultaneously quantified using HPLC‐DAD method. The validated HPLC‐DAD method showed a good linearity, precision, repeatability and accuracy for the quantification of eight marker compounds. Furthermore, the plausible fragmentation pathway of the representative compounds were proposed in the present study. The differences of the chemical constituents content and the comprehensive HPLC profiles between the two CP species using LC‐DAD‐ESI‐MS method are reported for the first time, indicating that the CP drugs from different resources should be used separately in the clinic. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
997.
998.
Wenjun Tang Dr. Andrew G. Capacci Xudong Wei Dr. Wenjie Li Dr. Andre White Dr. Nitinchandra D. Patel Jolaine Savoie Joe J. Gao Sonia Rodriguez Dr. Bo Qu Dr. Nizar Haddad Dr. Bruce Z. Lu Dr. Dhileepkumar Krishnamurthy Dr. Nathan K. Yee Dr. Chris H. Senanayake Dr. 《Angewandte Chemie (International ed. in English)》2010,49(34):5879-5883
999.
The syntheses and reactivity of the two N‐heterocyclic carbene (NHC)→ silylene complexes 2 and 4 have been investigated. The latter are easily accessible by reaction of the zwitterionic, N‐heterocyclic silylene LSi: 1 [L=Ar‐N‐C(=CH2)CH?C(Me)‐N‐Ar, Ar=2,6‐iPr2C6H3] with 1,3,4,5‐tetramethylimidazol‐2‐ylidene and 1,3‐diisopropyl‐4,5‐dimethylimidazol‐2‐ylidene, respectively. While compound 2 undergoes facile rearrangement above ?20 °C to give the unsymmetrical N‐heterocyclic silylcarbene 3 , the derivative 4 remains unchanged even after boiling in benzene. The remarkable reactivity of 3 and 4 towards cyclohexylisocyanide has been examined which leads in a unique series of C? H, Si? H, and C? N bond activations to the new triaminosilanes 5 and 6 , respectively. The novel compounds 3 , 4 , 5 , and 6 were fully characterized by 1H, 13C, and 29Si NMR spectroscopy, EI‐MS, elemental analysis, and single‐crystal X‐ray diffraction. 相似文献
1000.
Pingping Yao Yunfeng Qiu Dr. Penglei Chen Dr. Yanping Ma Dr. Shenggui He Prof. Dr. Jian‐Yu Zheng Prof. Dr. Minghua Liu Prof. Dr. 《Chemphyschem》2010,11(3):722-729
Molecular assemblies of metalloporphyrins trans‐dichloro(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (SnCl2TPPMe) and trans‐dihydroxo(5,10,15,20‐tetra‐p‐tolylporphyrinato)tin(IV) (Sn(OH)2TPPMe), which have two trans axial ligands, as well 5,10,15,20‐tetrakis(4‐methoxyphenyl)‐21H,23H‐porphine iron(III) chloride (FeClTPPOMe) and 5,10,15,20‐tetraphenyl‐21H,23H‐porphine manganese(III) chloride (MnClTPP), which have one axial ligand, are interfacially organized by Langmuir and Langmuir–Blodgett (LB) techniques. SnCl2TPPMe and Sn(OH)2TPPMe form nanofibrous structures which can display distinct supramolecular chirality, although the molecular units themselves are achiral, while FeClTPPOMe and MnClTPP form irregular nanoparticles that display negligible supramolecular chirality. An interpretation in terms of the effects of the axial ligands is proposed for this interesting phenomenon. Moreover, compared with assemblies of the diprotonated free‐base porphyrins, which are fabricated by interfacial (air/2.4 M HCl) organization of free‐base porphyrin, those of SnCl2TPPMe and Sn(OH)2TPPMe display higher stability in terms of supramolecular chirality. These results indicate that the assembly properties of metalloporphyrins can essentially be affected by the axial ligands that are attached to their chromophores, and that stable chiral porphyrin supramolecular associations can be easily produced by using achiral metalloporphyrins bearing two trans axial ligands. 相似文献