全文获取类型
收费全文 | 2198篇 |
免费 | 58篇 |
国内免费 | 18篇 |
专业分类
化学 | 1486篇 |
晶体学 | 27篇 |
力学 | 24篇 |
数学 | 261篇 |
物理学 | 476篇 |
出版年
2023年 | 15篇 |
2022年 | 18篇 |
2021年 | 22篇 |
2020年 | 28篇 |
2019年 | 28篇 |
2018年 | 19篇 |
2017年 | 12篇 |
2016年 | 30篇 |
2015年 | 37篇 |
2014年 | 46篇 |
2013年 | 117篇 |
2012年 | 95篇 |
2011年 | 107篇 |
2010年 | 66篇 |
2009年 | 65篇 |
2008年 | 126篇 |
2007年 | 122篇 |
2006年 | 126篇 |
2005年 | 125篇 |
2004年 | 130篇 |
2003年 | 113篇 |
2002年 | 113篇 |
2001年 | 41篇 |
2000年 | 37篇 |
1999年 | 36篇 |
1998年 | 29篇 |
1997年 | 23篇 |
1996年 | 27篇 |
1995年 | 20篇 |
1994年 | 17篇 |
1993年 | 20篇 |
1992年 | 21篇 |
1991年 | 20篇 |
1990年 | 26篇 |
1989年 | 16篇 |
1988年 | 25篇 |
1987年 | 19篇 |
1986年 | 22篇 |
1985年 | 23篇 |
1984年 | 28篇 |
1983年 | 23篇 |
1982年 | 20篇 |
1981年 | 27篇 |
1980年 | 33篇 |
1979年 | 39篇 |
1978年 | 15篇 |
1977年 | 11篇 |
1975年 | 14篇 |
1974年 | 23篇 |
1973年 | 13篇 |
排序方式: 共有2274条查询结果,搜索用时 10 毫秒
161.
Sato K Yamazoe S Yamamoto R Ohata S Tarui A Omote M Kumadaki I Ando A 《Organic letters》2008,10(12):2405-2408
1,3-Diketones were synthesized from alpha,beta-unsaturated ketones by treatment with acid chlorides and Et(2)Zn in the presence of RhCl(PPh(3))3. This is a very simple and extremely chemoselective reaction to give the adduct at the alpha-position of alpha,beta-unsaturated ketones. 相似文献
162.
Keiichi Kimura Ryoko Mizutani Tatsuya Suzuki Masaaki Yokohama 《Journal of inclusion phenomena and macrocyclic chemistry》1998,32(2-3):295-310
Design of two types of ion-conducting systems using photochromic crown ethers as the photocontrol agents is described; one type is based on the phase transition of azobenzene derivatives induced by their photoisomerization and the other based on the molecular control of metal ion complexation by crowned spirobenzopyrans. The photoresponsive ion-conducting systems are applicable to electrostatic imaging and photorefractive materials. 相似文献
163.
Yoshimura T Chen ZN Itasaka A Abe M Sasaki Y Ishizaka S Kitamura N Yarovoi SS Solodovnikov SF Fedorov VE 《Inorganic chemistry》2003,42(16):4857-4863
Hexarhenium(III) complexes with terminal isothiocyanate ligands, [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)(NCS)(6)] (1) and (L)(4)[Re(6)(mu(3)-Se)(8)(NCS)(6)] (L(+) = PPN(+) (2a), (n-C(4)H(9))(4)N(+) (2b)), have been prepared by three different methods. Complex 1 was prepared by the reaction of [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] with molten KSCN at 200 degrees C, while 2b was obtained by refluxing the chlorobenzene-DMF (2:1 v/v) solution of [Re(6)(mu(3)-Se)(8)(CH(3)CN)(6)](SbF(6))(2) and [(n-C(4)H(9))(4)N]SCN. The [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-) anion was also obtained from a mixture of Cs(2)[Re(6)(mu(3)-Se)(8)Br(4)] and KSCN in C(2)H(5)OH by a mechanochemical activation at room temperature for 20 h and isolated as 2a. The X-ray structures of 1 and 2a.4DMF have been determined (1, C(70)H(144)N(10)S(14)Re(6), monoclinic, space group P2(1)/n (No. 14), a = 14.464(7) A, b = 22.059(6) A, c = 16.642(8) A, beta = 113.62(3) degrees, V = 4864(3) A(3), Z = 2; 2a.4DMF, C(162)H(144)N(14)O(4)P(8)S(6)Se(8)Re(6), triclinic, space group P1 (No. 2), a = 15.263(2) A, b = 16.429(2) A, c = 17.111(3) A, alpha = 84.07(1) degrees, beta = 84.95(1) degrees, gamma = 74.21(1) degrees, V = 4098.3(8) A(3), Z = 1). All the NCS(-) ligands in both complexes are coordinated to the metal center via nitrogen site with the Re-N distances in the range of 2.07-2.13 A. The redox potentials of the reversible Re(III)(6)/Re(III)(5)Re(IV) process in acetonitrile are +0.84 and +0.70 V vs. Ag/AgCl for [Re(6)(mu(3)-S)(8)(NCS)(6)](4)(-) and [Re(6)(mu(3)-Se)(8)(NCS)(6)](4)(-), respectively, which are the most positive among the known hexarhenium complexes with six terminal anionic ligands. The complexes show strong red luminescence with the emission maxima (lambda(max)/nm), lifetimes (tau(em)/micros), and quantum yields (phi(em)) being 745 and 715, 10.4 and 11.8, and 0.091 and 0.15 for 1 and 2b, respectively, in acetonitrile. The data reasonably well fit in the energy-gap plots of other hexarhenium(III) complexes. The temperature dependence of the emission spectra and tau(em) of 1 and [(n-C(4)H(9))(4)N](4)[Re(6)(mu(3)-S)(8)Cl(6)] are also reported. 相似文献
164.
Platelet aggregation potentiators from cho-rei 总被引:4,自引:0,他引:4
W Lu I Adachi K Kano A Yasuta K Toriizuka M Ueno I Horikoshi 《Chemical & pharmaceutical bulletin》1985,33(11):5083-5087
165.
Adachi I Aihara H Dijkstra HB Enomoto R Fujii H Fujii K Fujii T Fujimoto J Fujiwara N Hayashii H Higashi S Iida N Imanishi A Ikeda H Ishii T Itoh R Iwasaki H Iwata S Kajikawa R Kamae T Kato S Kawabata S Kichimi H Kishida T Kobayashi M Kuroda S Kusuki N Maruyama A Maruyama K Masuda H Matsuda T Miyamoto A Morimoto T Nakamura K Nitoh O Noguchi S Ochiai F Okuno H Okusawa T Ohshima T Ozaki H Sato T Sai F Shimonaka J Shimozawa K Shirahashi A Sugahara R Sugiyama A Suzuki S Suwada T Takahashi K 《Physical review letters》1988,60(2):97-100
166.
Armentano A Riese M Taherkhani M Ben Yezzar M Müller-Dethlefs K Fujii M Dopfer O 《The journal of physical chemistry. A》2010,114(42):11139-11143
The various dissociation thresholds of phenol(+)···Ar(3) complexes for the consecutive loss of all three Ar ligands were measured in a molecular beam using resonant photoionization efficiency and mass analyzed threshold ionization spectroscopy via excitation of the first excited singlet state (S(1)). The adiabatic ionization energy is derived as 68077 ± 15 cm(-1). The analysis of the dissociation thresholds demonstrate that all three Ar ligands in the neutral phenol···Ar(3) tetramer are attached to the aromatic ring via π-bonding, denoted phenol···Ar(3)(3π). The value of the dissociation threshold for the loss of one Ar ligand from phenol(+)···Ar(3)(3π), ~190 cm(-1), is significantly lower than the binding energy measured for the π-bonded Ar ligand in the phenol(+)···Ar(π) dimer, D(0) = 535 ± 3 cm(-1). This difference is rationalized by an ionization-induced π → H isomerization process occurring prior to dissociation, that is, one Ar atom in phenol(+)···Ar(3)(3π) moves to the OH binding site, leading to a structure with one H-bonded and 2 π-bonded ligands, denoted phenol(+)···Ar(3)(H/2π). The dissociation thresholds for the loss of two and three Ar atoms are also reported as 860 and 1730 cm(-1). From these values, the binding energy of the H-bound Ar atom can be estimated as 870 cm(-1). 相似文献
167.
168.
169.
Uchida K Saito M Murakami A Kobayashi T Nakamura S Irie M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(2):534-542
A photochromic polymer film containing three different diarylethene derivatives, that is, 1,2-bis(3,5-dimethyl-2-thienyl)perfluorocyclopentene (1), 1,2-bis(2,5-dimethyl-3-thienyl)perfluorocyclopentene (2), and 1,2-bis(2-methyl-5-phenyl-3-thienyl)perfluorocyclopentene (3) was prepared. Upon UV irradiation, the three derivatives changed to their closed-ring isomers having different colors, yellow, red, and blue. They showed different spectra not only in UV/Vis region but also in the IR spectral region. Upon irradiation with visible light of appropriate wavelengths, each closed-ring isomer was selectively bleached, and three bits eight states recording was performed. The eight states could be read out nondestructively by using IR light of appropriate wavenumbers. 相似文献
170.
Shintaro Kohata Prof. Hajime Nakanotani Prof. Youhei Chitose Prof. Takuma Yasuda Prof. Youichi Tsuchiya Prof. Chihaya Adachi 《Angewandte Chemie (International ed. in English)》2023,62(44):e202312326
Photon-upconversion in organic molecular systems is one of the promising technologies for future energy harvesting systems because these systems can generate excitons that possess higher energy than excitation energy. The photon-upconversion caused by absorbing ambient heat as additional energy is particularly interesting because it could ideally provide a light-driving cooling system. However, only a few organic molecular systems have been reported. Here, we report the anti-Stokes photoluminescence (ASPL) derived from hot-band absorption in a series of multi-resonance-type thermally-activated delayed fluorescence (MR-TADF) molecules. The MR-TADF molecules exhibited an anti-Stokes shift of approximately 0.1 eV with a high PL quantum yield in the solution state. The anti-Stokes shift corresponded well to the 1–0 vibration transition from the ground state to the excited singlet state, and we further evaluated a correlation between the activation energy for the ASPL intensity and the TADF process. Our demonstration underlines that MR-TADF molecules have become a novel class of ASPL materials for various future applications, such as light-driving cooling systems. 相似文献