全文获取类型
收费全文 | 2531篇 |
免费 | 195篇 |
国内免费 | 159篇 |
专业分类
化学 | 1784篇 |
晶体学 | 55篇 |
力学 | 83篇 |
综合类 | 12篇 |
数学 | 189篇 |
物理学 | 762篇 |
出版年
2023年 | 15篇 |
2022年 | 23篇 |
2021年 | 41篇 |
2020年 | 50篇 |
2019年 | 65篇 |
2018年 | 63篇 |
2017年 | 46篇 |
2016年 | 72篇 |
2015年 | 82篇 |
2014年 | 87篇 |
2013年 | 178篇 |
2012年 | 161篇 |
2011年 | 192篇 |
2010年 | 109篇 |
2009年 | 128篇 |
2008年 | 140篇 |
2007年 | 141篇 |
2006年 | 125篇 |
2005年 | 102篇 |
2004年 | 128篇 |
2003年 | 99篇 |
2002年 | 126篇 |
2001年 | 116篇 |
2000年 | 65篇 |
1999年 | 74篇 |
1998年 | 34篇 |
1997年 | 28篇 |
1996年 | 29篇 |
1995年 | 20篇 |
1994年 | 28篇 |
1993年 | 44篇 |
1992年 | 30篇 |
1991年 | 22篇 |
1990年 | 13篇 |
1989年 | 18篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 16篇 |
1985年 | 14篇 |
1984年 | 12篇 |
1983年 | 9篇 |
1981年 | 11篇 |
1980年 | 8篇 |
1979年 | 11篇 |
1978年 | 13篇 |
1976年 | 9篇 |
1975年 | 12篇 |
1974年 | 12篇 |
1973年 | 9篇 |
1972年 | 6篇 |
排序方式: 共有2885条查询结果,搜索用时 93 毫秒
91.
Minoru Yamaji Ai Suzuki Fuyuki Ito Shozo Tero-Kubota Seiji Tobita Bronislaw Marciniak 《Journal of photochemistry and photobiology. A, Chemistry》2005,170(3):253-259
Photodissociation of the carbon-X (X = Br and Cl) bonds in p-bromo- and p-chloromethylbenzophenone (BMBP and CMBP) in solution were investigated by time-resolved EPR and laser flash photolysis techniques. BMBP and CMBP were found to undergo ω-bond cleavage to yield the p-benzoylbenzyl radical (BBR) at 295 K, and the quantum yields (ΦBBR) were determined. The CIDEP signal originated from BBR formed upon decomposition of CMBP was obtained while that for BMBP was absent. By using triplet sensitization of acetone, the efficiencies (BBR) of the CX bond fission in the triplet states of BMBP and CMBP were determined. The agreement between the ΦBBR and BBR values for CMBP indicates that the CCl bond dissociation occurs only in the triplet state. In contrast to CMBP, the cleavage of the CBr bond in BMBP upon direct excitation was concluded to be the event only in the excited singlet state without triplet formation, whereas the triplet state was also reactive for ω-bond dissociation. The rate of CBr bond dissociation seemed to be greater than that of intersystem crossing from the S1 to the T1 state. Schematic energy diagrams of the excited states of BMBP and CMBP were shown, and the reaction profiles were discussed from the viewpoint of the CX bond enthalpies. 相似文献
92.
Masao Kato Takao Shiraga Tatsumi Kimura Takashi Fukuda Hiro Matsuda Hachiro Nakanishi 《先进技术聚合物》2002,13(2):120-126
We synthesized some novel rigid NLO‐active maleimide copolymers bearing DR‐1 moieties ( PMPD , PHSD and PHND ). All copolymers exhibited high Tg's (190~197 °C), good solubilities for common solvents and excellent film‐forming properties. Dependence of film thickness on the d33 value for the poled copolymer films induced by corona poling was investigated and it was demonstrated that in less than thickness of 0.3 µm decrease of the thickness gives rise to remarkable increase in the d33 value. The poled copolymer films exhibited large d33 values (270 × 10?9 esu (film thickness 0.13 µm) for PMPD , 290 × 10?9 esu (0.12 µm) for PHSD and 350 × 10?9 esu (0.08 µm) for PHND ) as well as large r33 values (51.0 pmV?1 for PMPD and 60.4 pmV?1 for PHND ) which are significantly large compared to the value of LiNbO3 (31 pmV?1) as a typical EO material. The d33 values of the poled copolymers were kept constant even after standing 1000h at 80 °C, although a small decrease was observed at an initial stage. Further, the d33 values did not change up to ca. 123 °C upon heating at the rate of 10 °C/min in all cases. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
93.
Rainer Telle Ai Momozawa Jochen M. Schneider 《Journal of solid state chemistry》2006,179(9):2850-2857
MAX-phases being usually composed of transition metals, group A elements and carbon/nitrogen are considered interesting materials for many applications because of their tremendous bulk modulus, “reversible” plasticity, and machinability. This is mainly due to their unique kind of bonding comprising covalent, ionic as well as metallic bonds providing “easy” planes of rupture and deformability due to the layered crystal structures.In transition metal boride systems, similar types of bonding are available. In particular the W2B5-structure type and its stacking variations allow the synthesis of strongly layered crystal structures exhibiting unique delamination phenomena.The paper presents ab initio calculations showing the similarities of bonding between the ternary carbides and the corresponding ternary or quaternary borides. Formation of boride-based nano-laminates from auxiliary liquid phases, from the melt as well as during sintering and precipitation from supersaturated solid solutions will be discussed by means of SEM and TEM studies. The role of impurities weakening the interlayer bonding will be addressed in particular. The pronounced cleavage parallel to the basal plane gives rise for crack deflection and pull-out mechanisms if the laminates are dispersed in brittle matrices such as boron carbide, silicon carbide or other transition metal borides. 相似文献
94.
95.
Mori M Oyama Y Suzuki A Takahashi K Yamada M Miyano K Miyata H Takei H Hirata KS Kajita T Kihara K Nakahata M Nakamura K Ohara S Sato N Suzuki Y Totsuka Y Yaginuma Y Koshiba M Suda T Tajima T Fukuda Y Nagashima Y Takita M Kaneyuki K Tanimori T Beier EW Frank ED Frati W Kim SB Mann AK Newcomer FM Van Berg R Zhang W 《Physical review D: Particles and fields》1991,43(9):2843-2846
96.
97.
Optically active sulfinylaziridines having a 4-methoxyphenyl group on their nitrogen atom were synthesized from optically active 1-chloroalkyl p-tolyl sulfoxide and an imine derived from benzaldehyde and p-anisidine stereoselectively in good overall yields. The sulfinylaziridines were treated with ethylmagnesium bromide or tert-butyllithium to afford aziridinylmagnesiums or aziridinyllithiums, respectively, in quantitative yields. Cross-coupling of the aziridinylmagnesiums with iodoalkanes in the presence of Cu(I) iodide gave tri-substituted aziridines in high yields from which enantiomerically pure β,β-disubstituted β-amino acid derivatives were synthesized. A β-amino acid derivative having deuterium at the stereogenic center was also realized by this method. On the other hand, from the aziridinyllithium, enantiomerically pure quaternary phenylalanine and quaternary aspartic acid derivatives were synthesized. 相似文献
98.
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
99.
H. Yamaguchi K. Ninomiya M. Fukuda S. Itô N. Kato Y. Fukazawa 《Chemical physics letters》1980,72(2):297-300
The electronic absorption spectra of syn-[2,2] (2,6) azulenophane (1) and anti-[2,2] (2,6)azulenophane (2) were investigated via magnetic circular dichroism spectra. The anomalous fluorescence spectra were also observed. From the assignment of the absorption spectra, it was concluded that molecules 1 and 2 emitted the fluorescence from the third excited singlet state. 相似文献
100.
Metal-ion-assisted hydrolysis of dipeptides involving a serine residue in a neutral aqueous solution
Yashiro M Sonobe Y Yamamura A Takarada T Komiyama M Fujii Y 《Organic & biomolecular chemistry》2003,1(4):629-632
Dipeptides having a serine residue at the C-terminus, X-Ser, where X is an appropriate amino acid residue, were efficiently hydrolyzed in the presence of ZnCl2 at pH 7.0. The rapid hydrolysis of X-Ser is due to an autocatalysis of the hydroxy group in the serine residue, and is found to be accelerated by a metal ion, in particular by ZnCl2. Roles of the metal ion in the hydrolysis of peptides involving a serine residue, in relation to the recently reported protein cleavages, are discussed. 相似文献