全文获取类型
收费全文 | 846篇 |
免费 | 21篇 |
国内免费 | 1篇 |
专业分类
化学 | 568篇 |
晶体学 | 8篇 |
力学 | 2篇 |
数学 | 15篇 |
物理学 | 275篇 |
出版年
2022年 | 7篇 |
2021年 | 9篇 |
2020年 | 14篇 |
2019年 | 14篇 |
2018年 | 12篇 |
2017年 | 7篇 |
2016年 | 10篇 |
2015年 | 8篇 |
2014年 | 16篇 |
2013年 | 34篇 |
2012年 | 37篇 |
2011年 | 38篇 |
2010年 | 19篇 |
2009年 | 10篇 |
2008年 | 50篇 |
2007年 | 34篇 |
2006年 | 37篇 |
2005年 | 35篇 |
2004年 | 40篇 |
2003年 | 24篇 |
2002年 | 32篇 |
2001年 | 17篇 |
2000年 | 23篇 |
1999年 | 6篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 11篇 |
1995年 | 13篇 |
1994年 | 15篇 |
1993年 | 22篇 |
1992年 | 22篇 |
1991年 | 21篇 |
1990年 | 23篇 |
1989年 | 19篇 |
1988年 | 11篇 |
1987年 | 12篇 |
1986年 | 14篇 |
1985年 | 18篇 |
1984年 | 10篇 |
1983年 | 10篇 |
1982年 | 9篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 5篇 |
1978年 | 10篇 |
1977年 | 14篇 |
1976年 | 8篇 |
1975年 | 10篇 |
1974年 | 10篇 |
1968年 | 5篇 |
排序方式: 共有868条查询结果,搜索用时 15 毫秒
61.
Hitoshi Tamiaki Shun Koizumi Kazuki Tsuji Yusuke Kinoshita Tomohiro Miyatake 《Tetrahedron letters》2014
Chlorophyll-a derivatives possessing an un/mono/disubstituted methylene moiety at the 131-position were prepared by (un)substituted methylation of the 13-carbonyl group and successive dehydration. Substitution of the 131-oxo to the methylene group slightly blue-shifted electronic absorption and emission bands in a solution and decreased chemical stability to give an oxidation product cleaved at the E-ring. Further mono/disubstitution at the methylene terminal increased wavelengths of absorption and emission maxima as well as oxidative tolerance. 相似文献
62.
YoungSook Yun Mariko Shioura Yukio Hitotsuyanagi Satoshi Yotsumoto Yuji Takahashi Yutaka Aoyagi Takeshi Kinoshita Koichi Takeya Hideshi Inoue 《Molecules (Basel, Switzerland)》2021,26(9)
Cytotoxicity and apoptosis-inducing properties of compounds isolated from Garcinia subelliptica leaves were investigated. The hexane-soluble portion of MeOH extracts of G. subelliptica leaves that showed cytotoxic activity was separated to yield seven compounds 1–7. Chemical structure analysis using NMR spectroscopy and mass spectrometry confirmed that compound 1 was canophyllol, and compounds 2–7 were garcinielliptones N, O, J, G, F, and garcinielliptin oxide, respectively. Among them, garcinielliptone G (5) showed growth inhibition by causing apoptosis in THP-1 and Jurkat cells derived from human acute monocytic leukemia and T lymphocyte cells, respectively. Apoptosis induced by garcinielliptone G (5) was demonstrated by the detection of early apoptotic cells with fluorescein-labeled Annexin V and increases in cleaved caspase-3 and cleaved PARP protein levels. However, the addition of caspase inhibitor Z-VAD-FMK did not affect growth arrest or apoptosis induction. These results suggest that garcinielliptone G (5) can induce both caspase-3 activation and caspase-independent apoptosis. Therefore, garcinielliptone G (5) may be a potential candidate for acute leukemia treatment. 相似文献
63.
Wang XL Yuan CZ Shen CP Wang P Adachi I Aihara H Arinstein K Aushev T Bakich AM Barberio E Bedny I Bhardwaj V Bitenc U Blyth S Bondar A Bozek A Bracko M Brodzicka J Browder TE Chang P Chen A Chen KF Cheon BG Chiang CC Chistov R Cho IS Choi SK Choi Y Dalseno J Danilov M Dash M Drutskoy A Eidelman S Epifanov D Gabyshev N Go A Gokhroo G Ha H Hayasaka K Hayashii H Hazumi M Heffernan D Hoshi Y Hou WS Hyun HJ Iijima T Inami K Ishikawa A Ishino H Itoh R Iwasaki Y Kah DH Kang JH Kawai H Kawasaki T 《Physical review letters》2007,99(14):142002
The cross section for e+ e- --> pi+ pi- psi(2S) between threshold and sqrt[s]=5.5 GeV is measured using 673 fb(-1) of data on and off the Upsilon(4S) resonance collected with the Belle detector at KEKB. Two resonant structures are observed in the pi+ pi- psi(2S) invariant-mass distribution, one at 4361 +/- 9 +/- 9 MeV/c2 with a width of 74 +/- 15 +/- 10 MeV/c2, and another at 4664 +/- 11 +/- 5 MeV/c2 with a width of 48 +/- 15 +/- 3 MeV/c2, if the mass spectrum is parametrized with the coherent sum of two Breit-Wigner functions. These values do not match those of any of the known charmonium states. 相似文献
64.
Abe K Adachi I Aihara H Arinstein K Asano Y Aulchenko V Aushev T Aziz T Bakich AM Balagura V Barbero M Bedny I Bitenc U Bizjak I Bondar A Bracko M Brodzicka J Browder TE Chao Y Chen A Cheon BG Chistov R Choi SK Choi Y Choi YK Chuvikov A Cole S Dalseno J Danilov M Dash M Drutskoy A Eidelman S Epifanov D Fratina S Gabyshev N Gershon T Gokhroo G Golob B Ha HC Haba J Hasegawa Y Hayasaka K Hayashii H Hazumi M Hinz L Hoshi Y Hou S Hou WS Hsiung YB Iijima T Ishikawa A Iwasaki M Iwasaki Y Kapusta P 《Physical review letters》2007,98(8):082001
We report the first observation of a charmoniumlike state recoiling from the J/psi in the inclusive process e+e- -->J/psi+anything at a mass of (3.943+/-0.006+/-0.006) GeV/c{2}. We also observe the decay of this state into D*D[over ] and determine its intrinsic width to be less than 52 MeV/c{2} at the 90% C.L. These results are obtained from a 357 fb{-1} data sample collected with the Belle detector near the Upsilon(4S) resonance, at the KEKB asymmetric-energy e+e- collider. 相似文献
65.
Design of Ratiometric Fluorescent Probes Based on Arene–Metal‐Ion Interactions and Their Application to CdII and Hydrogen Sulfide Imaging in Living Cells
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Ippei Takashima Miyuki Kinoshita Ryosuke Kawagoe Saika Nakagawa Prof. Dr. Manabu Sugimoto Prof. Dr. Itaru Hamachi Prof. Dr. Akio Ojida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(8):2184-2192
Non‐coordinative interactions between a metal ion and the aromatic ring of a fluorophore can act as a versatile sensing mechanism for the detection of metal ions with a large emission change of fluorophores. We report the design of fluorescent probes based on arene–metal‐ion interactions and their biological applications. This study found that various probes having different fluorophores and metal binding units displayed significant emission redshift upon complexation with metal ions, such as AgI, CdII, HgII, and PbII. X‐ray crystallography of the complexes confirmed that the metal ions were held in close proximity to the fluorophore to form an arene–metal‐ion interaction. Electronic structure calculations based on TDDFT offered a theoretical basis for the sensing mechanism, thus showing that metal ions electrostatically modulate the energy levels of the molecular orbitals of the fluorophore. A fluorescent probe was successfully applied to the ratiometric detection of the uptake of CdII ions and hydrogen sulfide (H2S) in living cells. These results highlight the utility of interactions between arene groups and metal ions in biological analyses. 相似文献
66.
Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Tsuneomi Kawasaki Mai Nakaoda Yutaro Takahashi Yusuke Kanto Nanako Kuruhara Kenji Hosoi Prof. Dr. Itaru Sato Arimasa Matsumoto Prof. Dr. Kenso Soai 《Angewandte Chemie (International ed. in English)》2014,53(42):11199-11202
Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction. 相似文献
67.
Suzuka Kinoshita Ryota Yamano Dr. Yu Shibata Yusuke Tanaka Kyoichi Hanada Dr. Takashi Matsumoto Prof. Dr. Kazunori Miyamoto Dr. Atsuya Muranaka Prof. Dr. Masanobu Uchiyama Prof. Dr. Ken Tanaka 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(27):11113-11120
An S-shaped double helicene-like molecule (>99 % ee), possessing stable helical chirality, has been synthesized by the rhodium(I)/difluorphos complex-catalyzed highly diastereo- and enantioselective intramolecular double [2+2+2] cycloaddition of a 2-naphthol- and benzene-linked hexayne. The collision between two terminal naphthalene rings destabilizes the helical chirality of the S-shaped double helicene-like molecule, but the introduction of two additional fused benzene rings significantly increases the configurational stability. Thus, no epimerization and racemization were observed even at 100 °C. The enantiopure S-shaped double helicene-like molecule forms a trimer through the multiple C−H⋅⋅⋅π and C−H⋅⋅⋅O interactions in the solid-state. The trimers stack to form columnar packing structures, in which neighboring stacks have opposite dipole directions. The accumulation of helical structures in the same direction in the S-shaped double helicene-like molecule enhanced the chiroptical properties. 相似文献
68.
69.
Adachi I Aihara H Arinstein K Asner DM Aushev T Aziz T Bakich AM Barberio E Belous K Bhardwaj V Bhuyan B Bondar A Bračko M Brodzicka J Browder TE Chang P Chen A Chen P Cheon BG Chilikin K Chistov R Cho IS Cho K Choi Y Dalseno J Danilov M Drásal Z Drutskoy A Eidelman S Epifanov D Esen S Fast JE Feindt M Gaur V Gabyshev N Garmash A Goh YM Golob B Hara T Hayasaka K Hayashii H Hoshi Y Hou WS Hsiung YB Hyun HJ Iijima T Ishikawa A Iwabuchi M Iwasaki Y Jaegle I Julius T Kang JH Katayama N Kawasaki T 《Physical review letters》2012,108(3):032001
We report the first observations of the spin-singlet bottomonium states h(b)(1P) and h(b)(2P). The states are produced in the reaction e(+)e(-)→h(b)(nP)π(+)π(-) using a 121.4 fb(-1) data sample collected at energies near the Υ(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. We determine M[h(b)(1P)]=(9898.2(-1.0-1.1)(+1.1+1.0)) MeV/c(2) and M[h(b)(2P)]=(10,259.8±0.6(-1.0)(+1.4)) MeV/c(2), which correspond to P-wave hyperfine splittings ΔM(HF)=(+1.7±1.5) and (+0.5(-1.2)(+1.6)) MeV/c(2), respectively. The significances of the h(b)(1P) and h(b)(2P) are 5.5σ and 11.2σ, respectively. We find that the production of the h(b)(1P) and h(b)(2P) is not suppressed relative to the production of the Υ(1S), Υ(2S), and Υ(3S). 相似文献
70.