全文获取类型
收费全文 | 3816篇 |
免费 | 98篇 |
国内免费 | 21篇 |
专业分类
化学 | 2961篇 |
晶体学 | 44篇 |
力学 | 41篇 |
数学 | 249篇 |
物理学 | 640篇 |
出版年
2023年 | 20篇 |
2022年 | 26篇 |
2021年 | 32篇 |
2020年 | 48篇 |
2019年 | 45篇 |
2018年 | 30篇 |
2017年 | 27篇 |
2016年 | 73篇 |
2015年 | 66篇 |
2014年 | 96篇 |
2013年 | 224篇 |
2012年 | 186篇 |
2011年 | 215篇 |
2010年 | 152篇 |
2009年 | 129篇 |
2008年 | 219篇 |
2007年 | 217篇 |
2006年 | 239篇 |
2005年 | 259篇 |
2004年 | 216篇 |
2003年 | 182篇 |
2002年 | 182篇 |
2001年 | 76篇 |
2000年 | 64篇 |
1999年 | 39篇 |
1998年 | 42篇 |
1997年 | 37篇 |
1996年 | 33篇 |
1995年 | 23篇 |
1994年 | 32篇 |
1993年 | 22篇 |
1992年 | 35篇 |
1991年 | 26篇 |
1990年 | 25篇 |
1989年 | 23篇 |
1988年 | 22篇 |
1987年 | 14篇 |
1986年 | 28篇 |
1985年 | 44篇 |
1984年 | 58篇 |
1983年 | 33篇 |
1982年 | 50篇 |
1981年 | 53篇 |
1980年 | 39篇 |
1979年 | 35篇 |
1978年 | 23篇 |
1977年 | 32篇 |
1976年 | 24篇 |
1975年 | 23篇 |
1974年 | 23篇 |
排序方式: 共有3935条查询结果,搜索用时 0 毫秒
101.
Cp(2)Ti[P(OEt)(3)](2)-promoted reactions of 2-(alk-1-yn-1-yl)-2-(trialkylsilyl)-1,3-dithianes (RS)(2)C(Si)CCR with terminal olefins and carbonyl compounds produced (trialkylsilylethynyl)cyclopropanes and 1-(trialkylsilyl)alk-3-en-1-ynes, respectively. These compounds were suggest to be produced via the formation of intermediary titanium alpha-(trialkylsilylethynyl)carbene complexes Cp(2)Ti=C(R)CCSi in preference to their regioisomers, alpha-(trialkylsilyl)alkynylcarbene complexes Cp(2)Ti=C(Si)CCR. 相似文献
102.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献
103.
C. E. Parker J. R. Perkins K. B. Tomer Y. Shida K. O’Hara M. Kono 《Journal of the American Society for Mass Spectrometry》1992,3(5):563-574
Nanoscale separation techniques, nanoscale packed capillary columns (75 μm id), and capillary zone electrophoresis (CZE), on-line with electrospray mass spectrometry (ESI/MS), were applied to the separation of a series of ten macrolide antibiotics. Both techniques use sub-microliter-per-minute flow rates through the analytical column and therefore require an electrospray probe that incorporates coaxial sheath flow. Positive ion electrospray mass spectra of these compounds yielded mainly protonated molecules. Fragmentation to yield structurally significant fragment ions was achieved by collision-induced dissociation (CID) at increased skimmer voltages. Separations were achieved using both techniques, with CZE/ESI/MS showing improved peak shapes and detection limits combined with faster analysis times. Nanoscale packed capillary columns provided better chromatographic resolution and was less susceptible to peak broadening caused by overloading of the analytes. 相似文献
104.
105.
A simple method has been described for the Spectrophotometric determination of cobalt(II) with 2-(3′-sulfobenzoyl)pyridine benzoylhydrazone (SBPBH). In aqueous solution, cobalt(II) reacts with SBPBH to form a yellow complex, which is not destroyed even by the addition of 3.8 M perchloric acid. The absorption maximum of the complex in 1.5 M perchloric acid medium was found to be 400 nm; the molar absorptivity was 2.17 × 104 liters mol−1 cm−1. The proposed method is fairly selective and has been applied to the determination of cobalt in standard alloy steel samples. 相似文献
106.
Yoshio Iwakura Keikichi Uno Shigeyoshi Hara Shigeru Kurosawa 《Journal of polymer science. Part A, Polymer chemistry》1968,6(12):3381-3393
A new ring-opening reaction of 1,3,4-oxadiazole by methylating reagents was developed in fuming sulfuric acid or polyphosphoric acid and then, by applying this reaction to poly-p-phenylene-1,3,4-oxadiazole, a high molecular weight poly-N-methylterephthalylhydrazide was obtained. Various methylating reagents were investigated as ring-opening reagents. The degrees of ring-opening in polymers were estimated and related to the properties of the polymers. 相似文献
107.
Masahiko Ogura Norikazu Nakatani Norisuke Yamaji Makoto Imai Akio Itoh Nobutsugu Imanishi 《Radiation Physics and Chemistry》1997,49(6):645-649
We have studied effects of added elements as well as defects on trap-sites of hydrogen in metals. For the purpose, we observed depth profiles and thermal behaviors of hydrogen implanted into Al-1.5 at.% Si alloy samples in an implantation-temperature range of liquid nitrogen temperature (LNT) to 373 K at different doses. The results were compared with those for pure aluminum samples. It was found that hydrogen is trapped as molecules in grain boundaries of Al/Si. 相似文献
108.
Makoto Ojika Hideo Kigoshi Kiyotake Suenaga Yoshifumi Imamura Kohji Yoshikawa Takeshi Ishigaki Akira Sakakura Tsuyoshi Mutou Kiyoyuki Yamada 《Tetrahedron》2012,68(4):982-987
Five cytotoxic macrolides, aplyronines D–H (4–8), were isolated from the Japanese sea hare Aplysia kurodai. They are new congeners of the antitumor compound aplyronine A (1), which was previously isolated from the same organism. Their structures were determined by spectroscopic analysis (NMR and MS). The cytotoxicity of these new compounds was evaluated in comparison with that of aplyronines A–C (1–3), suggesting the importance of the 7-O-seryl ester group for mediating the potent cytotoxicity of aplyronines. 相似文献
109.
Tuning the Electronic Properties and Acid‐Response Behavior of N‐Heteroacene‐Based π‐Conjugated Liquids by Changing the Number of π‐Conjugated Substituents 下载免费PDF全文
Yuika Sato Dr. Yuichiro Mutoh Dr. Daisuke Matsukuma Makoto Nakagawa Prof. Takeshi Kawai Dr. Kyosuke Isoda 《化学:亚洲杂志》2018,13(18):2619-2625
We have designed and synthesized two room‐temperature‐fluorescent π‐conjugated liquids based on the N‐heteroacene framework ( 1 and 2 ). These two π‐conjugated liquids, which contained one and two thiophene rings, respectively, exhibited different electronic properties and rheology behaviors. Single‐crystal X‐ray analysis of dithiophene‐appended compound 4 revealed that two thiophene rings hindered the interactions of the imino N atoms with acids through the formation of interactions between the S atoms of the thiophene rings and the imino N atoms of the pyrazine group. On the other hand, monothiophene‐appended molecules 1 and 3 each contained an unhindered imino N atom on the opposite site to the thiophene ring. Upon dissolving various acids with different pKa values in compounds 1 and 2 , these slight structural differences gave rise to marked differences in their acid‐response behaviors, thereby resulting in the emission of variously colored fluorescence in the liquid state. Furthermore, when acids with lower pKa values was dissolved in compounds 1 and 2 , phase transition occurred from an isotropic liquid state to a self‐organized liquid‐crystalline phase. 相似文献
110.
Visualization of Heterogeneous Oxygen Storage Behavior in Platinum‐Supported Cerium‐Zirconium Oxide Three‐Way Catalyst Particles by Hard X‐ray Spectro‐Ptychography 下载免费PDF全文
Makoto Hirose Dr. Nozomu Ishiguro Kei Shimomura Dr. Nicolas Burdet Dr. Hirosuke Matsui Prof. Dr. Mizuki Tada Prof. Dr. Yukio Takahashi 《Angewandte Chemie (International ed. in English)》2018,57(6):1474-1479
The cerium density and valence in micrometer‐size platinum‐supported cerium–zirconium oxide Pt/Ce2Zr2Ox (x=7–8) three‐way catalyst particles were successfully mapped by hard X‐ray spectro‐ptychography (ptychographic‐X‐ray absorption fine structure, XAFS). The analysis of correlation between the Ce density and valence in ptychographic‐XAFS images suggested the existence of several oxidation behaviors in the oxygen storage process in the Ce2Zr2Ox particles. Ptychographic‐XAFS will open up the nanoscale chemical imaging and structural analysis of heterogeneous catalysts. 相似文献