全文获取类型
收费全文 | 1711篇 |
免费 | 62篇 |
国内免费 | 8篇 |
专业分类
化学 | 1358篇 |
晶体学 | 31篇 |
力学 | 23篇 |
数学 | 171篇 |
物理学 | 198篇 |
出版年
2023年 | 9篇 |
2022年 | 13篇 |
2021年 | 15篇 |
2020年 | 25篇 |
2019年 | 33篇 |
2018年 | 18篇 |
2017年 | 21篇 |
2016年 | 41篇 |
2015年 | 43篇 |
2014年 | 40篇 |
2013年 | 97篇 |
2012年 | 112篇 |
2011年 | 115篇 |
2010年 | 57篇 |
2009年 | 68篇 |
2008年 | 116篇 |
2007年 | 110篇 |
2006年 | 104篇 |
2005年 | 95篇 |
2004年 | 95篇 |
2003年 | 82篇 |
2002年 | 65篇 |
2001年 | 12篇 |
2000年 | 29篇 |
1999年 | 12篇 |
1998年 | 24篇 |
1997年 | 23篇 |
1996年 | 18篇 |
1995年 | 15篇 |
1994年 | 7篇 |
1993年 | 10篇 |
1992年 | 17篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 7篇 |
1987年 | 17篇 |
1986年 | 6篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 16篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 24篇 |
1979年 | 15篇 |
1978年 | 14篇 |
1976年 | 11篇 |
1975年 | 8篇 |
1974年 | 5篇 |
1973年 | 7篇 |
排序方式: 共有1781条查询结果,搜索用时 0 毫秒
41.
42.
Despite the fact that many transition-metal-catalyzed reactions of organosulfur compounds with internal alkynes are ineffective, cobalt carbonyl (Co2(CO)8) is an excellent catalyst for carbonylative cyclization of internal alkynes with carbon monoxide. When Co2(CO)8-catalyzed reactions of internal alkynes with organic thiols are conducted in acetonitrile under 4 MPa pressure of carbon monoxide, thiolative lactonization of internal alkynes successfully takes place with incorporation of two molecules of CO. This carbonylation provides a useful tool to prepare the corresponding α,β-unsaturated γ-thio-γ-lactones (butenolide derivatives) in good yields. In the cases of unsymmetrical alkynes, such as 2-octyne and 6-methyl-2-heptyne, the thiolative lactonization proceeds with moderate regioselectivity to give the butenolide derivatives on which the carbonyl group preferentially bonds to the less hindered acetylenic carbon. Mechanistic pathways about the present thiolative lactonization are also discussed. 相似文献
43.
Kiyofumi Katagiri Keiko Ohta Kunihito Koumoto Kei Kurosu Yoshihiro Sasaki Kazunari Akiyoshi 《Colloid and polymer science》2013,291(6):1375-1380
Novel organic–inorganic hybrid nanoparticles consisting of polymer–hydrogel nanoparticles (nanogels) and iron oxide were developed for potential biomedical applications. Hybrid nanoparticles were prepared by a simple procedure using polysaccharide nanogels as a reactive site for iron oxide formation. The hybrid nanoparticles have a narrow size distribution with a diameter of approximately 30 nm and show high colloidal stability. These nanohybrid particles could be used as a contrast medium for magnetic resonance imaging or for magnetic hyperthermia therapy. 相似文献
44.
Yoshihiro Shigemasa Kuninori Oogaki Nasuo Ueda Ruka Hakashima Ken-Ichi Harada Naohito Takeda 《Journal of carbohydrate chemistry》2013,32(3):325-330
Abstract The formose reaction, by which a complex mixture of sugars and sugar alcohols (the so-called formose) are produced by the base-catalyzed condensation of formaldehyde, has received much attention in connection with the prebiotic synthesis of carbohydrates2 and the microbial utilization of formose.3–5 Formose, however, has not been useful yet, because of the complexity of this product mixture (Fig. 1a). Therefore, it seemed desirable to make the reaction more selective. 相似文献
45.
Yoshihiro Shigemasa Takaaki Ueda Hiroyuki Saimoto 《Journal of carbohydrate chemistry》2013,32(4):669-673
Abstract The formose reactions2 in N,N-dimethylformamide (DMF) catalyzed by 2-(dimethylamino)ethanol and thiamine hydrochloride, have been found to give rise to dihydroxyacetone and DL-glycero-tetrulose selectively at 1.1 M and 3.0 M of formaldehyde concentration, respectively. In our consecutive study on the formose reaction in DMF, it has been fortunately found that the distribution of products is able to be controlled by the amount of water added to the reaction mixture. We describe herein the first example of the favored formation of DL-2-C-hydroxymethyl-3-pentu-lose (GP-191) in the formose reaction using DMF-H2O solvent, and it's isolation and structure elucidation. 相似文献
46.
Yoshihiro Kon Toshiyuki Yokoi Masato Yoshioka Shinji Tanaka Yumiko Uesaka Takehisa Mochizuki Kazuhiko Sato Takashi Tatsumi 《Tetrahedron》2014
Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions. 相似文献
47.
Rhodium(I)‐Catalyzed Cyclization of Allenynes with a Carbonyl Group through Unusual Insertion of a CO Bond into a Rhodacycle Intermediate 下载免费PDF全文
Dr. Yoshihiro Oonishi Takayuki Yokoe Akihito Hosotani Prof. Dr. Yoshihiro Sato 《Angewandte Chemie (International ed. in English)》2014,53(4):1135-1139
Rhodium(I)‐catalyzed cyclization of allenynes with a tethered carbonyl group was investigated. An unusual insertion of a C?O bond into the C(sp2)–rhodium bond of a rhodacycle intermediate occurs via a highly strained transition state. Direct reductive elimination from the obtained rhodacyle intermediate proceeds to give a tricyclic product containing an 8‐oxabicyclo[3.2.1]octane skeleton, while β‐hydride elimination from the same intermediate gives products that contain fused five‐ and seven‐membered rings in high yields. 相似文献
48.
Organic Dicarboxylate Negative Electrode Materials with Remarkably Small Strain for High‐Voltage Bipolar Batteries 下载免费PDF全文
Dr. Nobuhiro Ogihara Tomomi Yasuda Yoshihiro Kishida Dr. Tetsu Ohsuna Kaito Miyamoto Dr. Nobuko Ohba 《Angewandte Chemie (International ed. in English)》2014,53(43):11467-11472
As advanced negative electrodes for powerful and useful high‐voltage bipolar batteries, an intercalated metal–organic framework (iMOF), 2,6‐naphthalene dicarboxylate dilithium, is described which has an organic‐inorganic layered structure of π‐stacked naphthalene and tetrahedral LiO4 units. The material shows a reversible two‐electron‐transfer Li intercalation at a flat potential of 0.8 V with a small polarization. Detailed crystal structure analysis during Li intercalation shows the layered framework to be maintained and its volume change is only 0.33 %. The material possesses two‐dimensional pathways for efficient electron and Li+ transport formed by Li‐doped naphthalene packing and tetrahedral LiO3C network. A cell with a high potential operating LiNi0.5Mn1.5O4 spinel positive and the proposed negative electrodes exhibited favorable cycle performance (96 % capacity retention after 100 cycles), high specific energy (300 Wh kg?1), and high specific power (5 kW kg?1). An 8 V bipolar cell was also constructed by connecting only two cells in series. 相似文献
49.
Koji Yamamoto Kazuki Higuchi Masahiro Ogawa Hiromitsu Sogawa Shigeki Kuwata Yoshihiro Hayashi Susumu Kawauchi Toshikazu Takata 《化学:亚洲杂志》2020,15(3):356-359
We synthesised palladium and platinum complexes possessing cyclic and acyclic pincer‐type polyaromatic ligands and investigated their structural effect on the catalysis. The pincer‐type bis(6‐arylpyridin‐2‐yl)benzene skeleton was constructed via Kröhnke pyridine synthesis under transition metal‐free conditions on gram‐scale quantity. Ligand structure significantly influenced catalytic activity toward the platinum‐catalysed hydrosilylation of diphenyl acetylenes, despite the ligand‐independence of the conformations and electronic properties of these complexes. 相似文献
50.
Yoshihiro Itoh Masamitsu Inoue Akira Hachimori 《Journal of polymer science. Part A, Polymer chemistry》1996,34(1):89-93
Alternating and random copolymers of 2-(9-carbazolyl)ethyl methacrylate with aromatic vinyl monomers were synthesized and their fluorescence properties were compared in good and poor solvents. Contraction of the polymer coils induced the hypochromic effect, i.e., the mutual interaction of the ground-state chromophores, but caused little quenching of their excited state. This is sharp in contrast with the vinyl-type of polymers, exhibiting large interactions in both the ground and excited states. Introduction of bulky groups on the comonomers in the alternating copolymers further suppressed these interactions. © 1996 John Wiley & Sons, Inc. 相似文献