全文获取类型
收费全文 | 4380篇 |
免费 | 137篇 |
国内免费 | 19篇 |
专业分类
化学 | 3141篇 |
晶体学 | 43篇 |
力学 | 104篇 |
数学 | 199篇 |
物理学 | 1049篇 |
出版年
2022年 | 35篇 |
2021年 | 49篇 |
2020年 | 56篇 |
2019年 | 66篇 |
2018年 | 37篇 |
2017年 | 36篇 |
2016年 | 87篇 |
2015年 | 77篇 |
2014年 | 96篇 |
2013年 | 207篇 |
2012年 | 237篇 |
2011年 | 270篇 |
2010年 | 131篇 |
2009年 | 120篇 |
2008年 | 214篇 |
2007年 | 203篇 |
2006年 | 219篇 |
2005年 | 195篇 |
2004年 | 198篇 |
2003年 | 176篇 |
2002年 | 188篇 |
2001年 | 133篇 |
2000年 | 110篇 |
1999年 | 73篇 |
1998年 | 53篇 |
1997年 | 54篇 |
1996年 | 57篇 |
1995年 | 46篇 |
1994年 | 57篇 |
1993年 | 57篇 |
1992年 | 64篇 |
1991年 | 40篇 |
1990年 | 43篇 |
1989年 | 50篇 |
1988年 | 41篇 |
1987年 | 42篇 |
1986年 | 42篇 |
1985年 | 82篇 |
1984年 | 77篇 |
1983年 | 26篇 |
1982年 | 38篇 |
1981年 | 34篇 |
1980年 | 39篇 |
1979年 | 65篇 |
1978年 | 46篇 |
1977年 | 53篇 |
1976年 | 47篇 |
1975年 | 31篇 |
1974年 | 24篇 |
1973年 | 18篇 |
排序方式: 共有4536条查询结果,搜索用时 15 毫秒
41.
Ivanova SM Nolan BG Kobayashi Y Miller SM Anderson OP Strauss SH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2001,7(2):503-510
The relative Lewis basicities of six Al(ORF)4- ions, Al[OC(CH3)(CF3)2]4-, Al(OC(CF3)3]4-, Al(OCPh(CF3)2]4-, Al[OC[4-C6H4(tBu)](CF3)2]4-, Al(OC(Cy)(CF3)2]4-, and Al(OCPh2(CF3)]4-, have been determined by measuring their relative coordinating abilities towards Li+ in dichloromethane. The relative Li- Lewis basicities of the Al(ORF)4- ions are linearly related to the aqueous pKa values of the corresponding parent HORF fluoroalcohols. The Lewis basicity of Al[OCH(CF3)2]4- could not be measured because two of these anions can coordinate to one Li+ cation. The structures of LiAl[OCH(CF3)2]4 and [1-Et-3-Me-1,3-C3H3N2][Li[Al[OCH(CF3)2)4]2] were determined. 相似文献
42.
Matsuda R Kitaura R Kitagawa S Kubota Y Kobayashi TC Horike S Takata M 《Journal of the American Chemical Society》2004,126(43):14063-14070
In situ synchrotron X-ray powder diffraction patterns of porous coordination polymers [[Cu(2)(pzdc)(2)(bpy)].G] have been measured (pzdc = pyrazine-2,3-dicarboxylate, bpy = 4,4'-bipyridine) (where G = H(2)O for CPL-2 superset H(2)()O, G = benzene for CPL-2 superset benzene, and G = void for the apohost). The structures of apohost and CPL-2 superset benzene were determined from Rietveld analysis. Adsorption of benzene in the channels induced a remarkable contraction in the crystal (b axis; 6.8%, volume; 4.9%), although the channels were occupied by the benzene molecules. This crystal transformation provides a new pore structure that is well suited for benzene molecules, and we denote it as a "shape-responsive fitting" transformation. This type of pore gives rise to a new guideline: frameworks can be composed of flexible motifs that are linked via strong bond and/or stiff motifs that are connected via weaker bonds. 相似文献
43.
T. Kobayashi I. Endo A. Fukumi T. Horiguchi Y. Ishida T. Kondo T. Kuwamoto N. Minamoto T. Nakamura T. Takahasi 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,39(3):209-216
Atomic-beam laser spectroscopy with fluorescence detection is applied to investigate the hyperfine structure (hfs), Stark and Zeeman effects of the electric dipole transitions of Sm i. The measurements are performed for the four transitions of 0 → 15650.55, 292.58 → 15650.55, 292.58 → 15567.32, and 1489.55 → 16890.59 cm-1. The hfs constants of the upper and lower levels and the isotope shifts of the transitions are determined. The tensor polarizability of the 15650.55 cm-1 level is found to be α2 = -556.2 ± 11.8 kHz/(kV/cm)2. Thanks to the accurate g values of the lower levels [Childs, W.J., Goodman, L.S.: Phys. Rev. A 6, 2011 (1972)], the g values of the upper levels are obtained from the observed Zeeman splittings. The values are found to be -0.115907(79), 2.22259(20) and 1.599968(51) for the 15650.55 cm-1 .1, 15567.32 cm-1 and 16890.59.cm-1 levels, respectively. 相似文献
44.
Thermolysis of 2,5-diphenyl-1,4-dithiin-1-oxide afforded 2-formyl-2,4-diphenyl-1,3-dithiole, which was obtained also in photolysis along with another rearranged product, 2-benzoyl-4-phenyl-1,3-dithiole. 相似文献
45.
Hamao Umezawa Tomohisa Takita Yukio Sugiura Masami Otsuka Susumu Kobayashi Masaji Ohno 《Tetrahedron》1984,40(3):501-509
Biosynthetic intermediates and synthetic analogues of bleomycin (BLM) have been investigated for their metal binding, dioxygen activation, and DNA cleavage. Molecular O2 was activated by the Fe(II) complex of a synthetic model ligand. Nucleotide sequence specificities in DNA cleavage by the BLM-Fe(II) and deglyco-BLM-Fe(II) complexes were almost identical. It has been shown that (1) the β-aminoalanine-pyrimidine-β-hydroxyhistidine portion of BLM is essential for the metal binding and dioxygen activation and (2) the bithiazole moiety contributes to the specific binding to guanine base of DNA. 相似文献
46.
A method of rapid determination for indium, nickel and copper in Spinach (NBS; SRM-1570) by substoichiometric radioactivation
analysis is described. The method is based on the principle that an equal amount of non-irradiated test sample is added to
the irradiated standard sample and subsequent substoichiometric extraction for the irradiated test and standard samples is
carried out. Indium is extracted as diethyldithiocarbamate into carbon tetrachloride, nickel as dimethylglyoximate into chloroform
and copper as dithizonate into carbon tetrachloride. The radioactivities of these extracts are measured by NaI(Tl) or Ge(Li)
detector coupled with pulse-height analyser. The analytical results obtained by the method were in good agreement with our
published values and certified values by NBS. 相似文献
47.
Ito S Nomura A Morita N Kabuto C Kobayashi H Maejima S Fujimori K Yasunami M 《The Journal of organic chemistry》2002,67(21):7295-7302
The Diels-Alder reaction of di-2-azulenylacetylene with tetraphenylcyclopentadienone afforded 7,8,9,10-tetraphenyldiazuleno[2,1-a:1,2-c]naphthalene in one pot via autoxidation of the presumed 1,2-di-2-azulenylbenzene derivative. In contrast, a similar reaction of bis(1-methoxycarbonyl-2-azulenyl)acetylene with tetraphenylcyclopentadienone gave the 1,2-di-2-azulenylbenzene derivative. The following cyclodehydrogenation reaction of the benzene derivative with iron(III) chloride afforded diazuleno[2,1-a:1,2-c]naphthalene 6,11-bismethoxycarbonyl derivative. The redox behavior of these novel diazuleno[2,1-a:1,2-c]naphthalenes was examined by cyclic voltammetry (CV). These compounds exhibited two-step oxidation waves at +0.22 to +0.71 V upon CV, which revealed the formation of a radical cation and dication stabilized by the fused two azulene rings under the electrochemical oxidation conditions. Since the 1,2-di-2-azulenylbenzene derivative was oxidized at higher oxidation potentials (+0.83 and +1.86 V), the fusion of the two azulene rings to naphthalene increased electron-donating properties because of the formation of a closed-shell dicationic structure. Formation of the radical cation was characterized by UV-vis spectroscopy under the electrochemical oxidation conditions, although no evidence was obtained for the presumed dication under the conditions of the UV-vis spectroscopy measurement. 相似文献
48.
49.
Kobayashi Y Kumar GB Kurachi T Acharya HP Yamazaki T Kitazume T 《The Journal of organic chemistry》2001,66(6):2011-2018
By using the convenient protocol for conversion of 2-substituted furans into 4-oxo-2-alkenoic acids ((i) NBS, (ii) NaClO(2)), macrosphelide B (2) was synthesized from furyl alcohol 5 (>98% ee) and acid 6 (99% ee). The protocol was first applied to the PMB ether of 5 to afford acid 13b. On the other hand, DCC condensation of acid 6 with 5 gave 16 after deprotection of the TBS group. Condensation was again carried out between 13b and 16 to furnish the key ketone 17, which upon reduction with Zn(BH(4))(2) afforded anti alcohol 18 stereoselectively (15:1). After protection/deprotection steps, the furan 18 was converted to seco acid 3 by using the furan oxidation protocol mentioned above, and lactonization of 3 with Cl(3)C(6)H(2)COCl, Et(3)N, and DMAP afforded 22 (MOM ether of 2), which upon deprotection with TFA produced 2. Transformation of 22 to macrosphelide A (1) was then investigated. Although the chelation-controlled reduction of 22 should afford the desired anti alcohol 24, Zn(BH(4))(2) at <-90 degrees C gave a 2 approximately 1:1 mixture of anti/syn alcohols. On the contrary, reduction with NaBH(4) in MeOH at -15 degrees C produced the syn isomer 23 with >10:1 diastereoselectivity. Mitsunobu inversion of the resulting C(14)-hydroxyl group and deprotection of the MOM group with TFA afforded 1. Similarly, reduction of 2 with NaBH(4) afforded the C(14)-epimer of 1 stereoselectively. The observed stereoselectivity in the reductions of 22 and 2 could be explained on the basis of computer-assisted calculation, which showed presence of the low-energy conformers responsible for the stereoselective reduction. In addition, conversion of 2 to 1 was established, for the first time. 相似文献
50.
Masayoshi Watanabe Tadashi Iida Kohei Sanui Naoya Ogata Tadahiko Kobayashi Zentaro Ohtaki 《Journal of polymer science. Part A, Polymer chemistry》1984,22(6):1299-1307
Novel polyamides that contain tetrathiafulvalene (TTF) moieties were synthesized by direct polycondensation of Δ2,2′ -bi-1,3-dithiole-4,4′(5′)-dicarboxylic acid with aromatic diamines in the presence of triphenylphosphine, hexachloroethane, and pyridine. Complexes of these polyamides with bromine were TTF cation radical () salts which resulted from the charge transfer of TTF moieties to bromine. The electrical conductivity of undoped polyamides increased with a decrease in diamine length. By doping the bromine the conductivity of the polyamides was enhanced by 3–5 orders of magnitude and reached 10?5–;10?9S cm?1. Maximum conductivity was observed at the doping ratio of [Br]/[repeat unit] < 1. The electrical conduction in the bromine complexes may be attributed to the hopping of odd electrons of between TTF moieties. 相似文献