全文获取类型
收费全文 | 2586篇 |
免费 | 87篇 |
国内免费 | 13篇 |
专业分类
化学 | 1962篇 |
晶体学 | 35篇 |
力学 | 33篇 |
数学 | 173篇 |
物理学 | 483篇 |
出版年
2021年 | 24篇 |
2020年 | 27篇 |
2019年 | 46篇 |
2018年 | 35篇 |
2017年 | 22篇 |
2016年 | 54篇 |
2015年 | 44篇 |
2014年 | 60篇 |
2013年 | 155篇 |
2012年 | 132篇 |
2011年 | 150篇 |
2010年 | 103篇 |
2009年 | 84篇 |
2008年 | 143篇 |
2007年 | 127篇 |
2006年 | 122篇 |
2005年 | 133篇 |
2004年 | 111篇 |
2003年 | 108篇 |
2002年 | 94篇 |
2001年 | 33篇 |
2000年 | 25篇 |
1999年 | 33篇 |
1998年 | 27篇 |
1997年 | 35篇 |
1996年 | 22篇 |
1995年 | 20篇 |
1994年 | 36篇 |
1993年 | 31篇 |
1992年 | 39篇 |
1991年 | 28篇 |
1990年 | 15篇 |
1989年 | 23篇 |
1988年 | 18篇 |
1987年 | 17篇 |
1986年 | 24篇 |
1985年 | 24篇 |
1984年 | 44篇 |
1983年 | 25篇 |
1982年 | 31篇 |
1981年 | 28篇 |
1980年 | 22篇 |
1979年 | 29篇 |
1977年 | 22篇 |
1976年 | 31篇 |
1975年 | 29篇 |
1974年 | 26篇 |
1973年 | 25篇 |
1972年 | 19篇 |
1969年 | 17篇 |
排序方式: 共有2686条查询结果,搜索用时 46 毫秒
11.
Prof. Dr. Tomoaki Tanase Dr. Kanako Nakamae Yume Okawa Mami Hamada Dr. Arimasa Matsumoto Prof. Dr. Takayuki Nakajima Prof. Dr. Takuya Nakashima Prof. Dr. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104060
A P-stereogenic linear tetraphosphine tetraoxide, (R,R)- or (S,S)-dpmppm(=O)4, was synthesized to prepare C2 dinuclear M(hfa)3 complexes (M=Eu, Tb, Y) as the first example of lanthanide(III) complexes with P-chiral multidentate phosphine oxides. The mononuclear M(hfa)3 complexes (M=Eu, Y) with a P-chiral diphosphine dioxide, tpdpb(=O)2, were also prepared, and comparison of their photophysical properties for the EuIII complexes revealed that significant chiral induction from the P-chiral centers arises on the achiral M(hfa)3 units through intramolecular π-π stacking constraint in the dinuclear system. 相似文献
12.
Dr. Hirokazu Tsukamoto Saki Nakamura Akito Tomida Prof. Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(55):12528-12532
Haouamines A, B, and their derivatives were synthesized via Suzuki–Miyaura coupling and three key cyclization reactions as follows: the newly developed palladium(0)-catalyzed arylative cyclization of phenylalanine-derived alkyne–aldehydes with 2-bromoarylboronic acid (an “anti-Wacker”-type cyclization); BF3 ⋅ OEt2-promoted Friedel–Crafts-type cyclization of symmetrical electron-rich aromatic rings adjacent to a tertiary allylic alcohol leading to the indeno-tetrahydropyridine skeleton; and (cyanomethyl)trimethylphosphonium iodide-mediated macrocyclization of amino alcohols to afford aza-paracyclophane precursors. The palladium-catalyzed reduction of mono- and di-triflate intermediates in the later stages enabled the alteration of both the position and number of hydroxyl groups on the C-ring. The instability of haouamine B was dramatically improved by salt formation with formic acid. An unambiguous evaluation of the cytotoxicity of the prepared haouamine derivative formates with and without hydroxyl groups at different positions on the C-ring indicated that the catechol structure in haouamine B produced weak cytotoxicity. 相似文献
13.
Prof. Takayuki Nakajima Mizuki Takubo Yurika Komura Yuki Maeda Miwa Sato Maki Zouda Prof. Tomoaki Tanase 《欧洲无机化学杂志》2023,26(9):e202200648
A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso-dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu ( 1 a ); M1=Pd, M2=Rh, R=tBu ( 2 a ), Xyl ( 2 b ); M1=Pt, M2=Rh, R=tBu ( 3 a ), Xyl ( 3 b ); M1=Pd, M2=Ir, R=tBu ( 4 a )), supported by a tetradentate phosphine ligand, meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), were synthesized by stepwise reactions of meso-dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso-dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso-dpmppp)(XylNC)] ( 5 ), was also prepared. The structures of 1 – 5 were determined by X-ray analyses to contain two square planar d8 metal centers with face-to-face arrangement, where meso-dpmppp supports M1 and M2 metal ions in cis/trans-P,P coordination mode, combining cis-{M1P2Cl2} and trans-{M2P2(CNR)2} units. Complexes 1 – 4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a – 4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1 – 5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo- and regioselectivity compared with 2 – 5 . 相似文献
14.
Ionic liquids (ILs) have a wide variety of applications in energy storage and material production. ILs are composed of only cations and anions, without any molecular solvents, and are generally known as “designer liquids (solvents)” because their physicochemical properties can be tuned by the combination of ionic species. In recent several decades, research and development activities of rechargeable batteries have garnered considerable attention because certain groups of ILs exhibit high electrochemical stability and moderate ionic conductivity, rendering them suitable for application in high-voltage batteries. ILs with amide anions are representative electrolytes and are extensively researched by many research groups, including our group. This paper focuses on amide-based ILs as electrolytes for alkali-metal-ion rechargeable batteries, introducing their history, characteristics, and existing challenges to be addressed. 相似文献
15.
Dr. Shinichiro Fuse Ayako Ikebe Kazuya Oosumi Tomoya Karasawa Keisuke Matsumura Dr. Miho Izumikawa Dr. Kohei Johmoto Dr. Hidehiro Uekusa Dr. Kazuo Shin‐ya Prof. Takayuki Doi Prof. Takashi Takahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9454-9460
An asymmetric total synthesis of ent‐pyripyropene A was achieved by a convergent synthetic route. We used our originally developed TiIII‐catalyzed radical cyclization to construct an AB‐ring portion that consisted of a trans‐decalin skeleton with five contiguous stereogenic centers. The coupling between the AB‐ring and the DE‐ring portions, and a subsequent C‐ring cyclization, led to the total synthesis of ent‐pyripyropene A. An evaluation of the insecticidal activity of ent‐pyripyropene A against two aphid species revealed that ent‐pyripyropene A was 35–175 times less active than naturally occurring pyripyropene A. This result indicated that the biological target of pyripyropene A recognizes the absolute configuration of pyripyropene A. 相似文献
16.
Fused Corrole Dimers Interconvert between Nonaromatic and Aromatic States through Two‐Electron Redox Reactions 下载免费PDF全文
Shota Ooi Dr. Takayuki Tanaka Kyu Hyung Park Sangsu Lee Prof. Dr. Dongho Kim Prof. Dr. Atsuhiro Osuka 《Angewandte Chemie (International ed. in English)》2015,54(10):3107-3111
A singly linked corrole dimer was synthesized by condensation of a dipyrromethane‐1‐carbinol with 1,1,2,2‐tetrapyrroethane. Oxidation of the dimer gave doubly linked corrole dimers 9 and 10 as the first examples of fused corrole dimers involving a meso–meso linkage. Dimers 9 and 10 exhibit characteristic 1H NMR spectra, absorption spectra, excited‐state dynamics, and two‐photon absorption (TPA) values, which indicate the nonaromatic nature of 9 and the aromatic nature of 10 . Interestingly, 9 is fairly stable despite its unusual 2H‐corrole structure, which has been ascribed to the presence of two direct connections between the individual corrole units. 相似文献
17.
Dr. Masahito Yoshida Yoshitaka Ishida Kenta Adachi Hayato Murase Dr. Hiroshi Nakagawa Prof.Dr. Takayuki Doi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(50):18417-18430
The solid‐phase combinatorial synthesis of cyclodepsipeptide destruxin E has been demonstrated. The combinatorial synthesis of cyclization precursors 8 was achieved by using a split and pool method on SynPhase Lanterns. The products were successfully macrolactonized in parallel in the solution phase by using 2‐methyl‐6‐nitrobenzoic anhydride and 4‐(dimethylamino)pyridine N‐oxide to afford macrolactones 9 , and the subsequent formation of an epoxide in the side chain gave 18 member destruxin E analogues 6 . Biological evaluation of analogues 6 indicated that the N‐MeAla residue was crucial to the induction of morphological changes in osteoclast‐like multinuclear cells (OCLs). Based on structure–activity relationships, azido‐containing analogues 15 were then designed for use as a molecular probe. The synthesis and biological evaluation of analogues 15 revealed that 15 b , in which the Ile residue was replaced with a Lys(N3) residue, induced morphological changes in OCLs at a sufficient concentration, and modification around the Ile residue would be tolerated for attachment of a chemical tag toward the target identification of destruxin E ( 1 ). 相似文献
18.
Crystal Structure of the Isopropylzinc Alkoxide of Pyrimidyl Alkanol: Mechanistic Insights for Asymmetric Autocatalysis with Amplification of Enantiomeric Excess 下载免费PDF全文
Dr. Arimasa Matsumoto Takaaki Abe Atsushi Hara Takayuki Tobita Taisuke Sasagawa Prof. Dr. Tsuneomi Kawasaki Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2015,54(50):15218-15221
Asymmetric amplification during self‐replication is a key feature that is used to explain the origin of homochirality. Asymmetric autocatalysis of pyrimidyl alkanol in the asymmetric addition of diisopropylzinc to pyrimidine‐5‐carbaldehyde is a unique example of this phenomenon. Crystallization of zinc alkoxides of this 5‐pyrimidyl alkanol and single‐crystal X‐ray diffraction analysis of the alkoxide crystals reveal the existence of tetramer or higher oligomer structures in this asymmetric autocatalytic system. 相似文献
19.
Supramolecular Polyelectrolyte Complexes of Bone Morphogenetic Protein‐2 with Sulfonated Polyrotaxanes to Induce Enhanced Osteogenic Differentiation 下载免费PDF全文
20.
Taku Hirama Takayuki Umemura Noriyuki Kogure Mariko Kitajima Hiromitsu Takayama 《Tetrahedron letters》2017,58(3):223-226
A new procedure for the asymmetric total synthesis of lythraceous alkaloids with a 4-arylquinolizidine skeleton was developed, which involved an organocatalyzed asymmetric intramolecular aza-Michael addition. 相似文献