全文获取类型
收费全文 | 2245篇 |
免费 | 87篇 |
国内免费 | 12篇 |
专业分类
化学 | 1642篇 |
晶体学 | 23篇 |
力学 | 55篇 |
综合类 | 1篇 |
数学 | 181篇 |
物理学 | 442篇 |
出版年
2022年 | 12篇 |
2021年 | 24篇 |
2020年 | 31篇 |
2019年 | 33篇 |
2018年 | 37篇 |
2017年 | 30篇 |
2016年 | 62篇 |
2015年 | 55篇 |
2014年 | 55篇 |
2013年 | 101篇 |
2012年 | 127篇 |
2011年 | 113篇 |
2010年 | 83篇 |
2009年 | 66篇 |
2008年 | 144篇 |
2007年 | 132篇 |
2006年 | 117篇 |
2005年 | 134篇 |
2004年 | 109篇 |
2003年 | 90篇 |
2002年 | 90篇 |
2001年 | 40篇 |
2000年 | 41篇 |
1999年 | 29篇 |
1998年 | 30篇 |
1997年 | 16篇 |
1996年 | 30篇 |
1995年 | 34篇 |
1994年 | 17篇 |
1993年 | 18篇 |
1992年 | 21篇 |
1991年 | 19篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 21篇 |
1987年 | 15篇 |
1986年 | 17篇 |
1985年 | 26篇 |
1984年 | 24篇 |
1983年 | 11篇 |
1982年 | 29篇 |
1981年 | 18篇 |
1980年 | 19篇 |
1979年 | 32篇 |
1978年 | 19篇 |
1977年 | 21篇 |
1976年 | 21篇 |
1975年 | 18篇 |
1974年 | 11篇 |
1967年 | 11篇 |
排序方式: 共有2344条查询结果,搜索用时 15 毫秒
61.
Ihara M Katsumata A Setsu F Tokunaga Y Fukumoto K 《The Journal of organic chemistry》1996,61(2):677-684
[Ni(cyclam)](ClO(4))(2)-catalyzed indirect electroreduction of olefinic bromides produced six-membered compounds in low to high yields. The synthetic intermediate 49 of Ipecac and Corynanthe alkaloids was obtained in 88% yield in a highly stereoselective manner. Lactam 66, the synthetic precursor of tacamonine, was prepared in 49% yield as a mixture of two diastereoisomers. The electrolysis of the bromoacetates gave the debrominated compounds in good yields. 相似文献
62.
63.
64.
The cyclopropane ring can be used effectively in restricting the conformation of biologically active compounds to improve activity and also to investigate bioactive conformations. We designed (1S,2R)- and (1R,2R)-2-aminomethyl-1-(1H-imidazol-4-yl)cyclopropanes (1 and 2, respectively) and their enantiomers (ent-1 and ent-2) as conformationally restricted analogues of histamine. The four types of chiral cyclopropanes bearing two differentially functionalized carbon substituents in a cis or trans relationship on a cyclopropane ring, (1S,2R)-2-(tert-butyldiphenylsilyloxy)methyl-1-formylcyclopropane (7) and (1R,2R)-2-(tert-butyldiphenylsilyloxy)methyl-1-formylcyclopropane (8) and their enantiomers (ent-7 and ent-8), were developed as the key intermediates for synthesizing 1, 2, ent-1, and ent-2. The reaction between (R)-epichlorohydrin [(R)-12] and phenylsulfonylacetonitrile (13a) in the presence of NaOEt in EtOH followed by treatment with acid gave the chiral cyclopropane lactone 11a with 98% ee in 82% yield. Compound 11a was converted into both the cis- and trans-chiral cyclopropane units 7 and 8, respectively, via reductive desulfonylation with Mg/MeOH as the key step. The corresponding enantiomers, the cis-substituted ent-7 and the trans-substituted ent-8, were also prepared starting from (S)-epichlorohydrin [(S)-12]. The four conformationally restricted target histamine analogues 1, 2, ent-1, and ent-2 were successfully synthesized from 7, 8, ent-7, and ent-8, respectively. The chiral cyclopropane units 7, 8, ent-7, and ent-8 should be useful as versatile intermediates for synthesizing various compounds having an asymmetric cyclopropane structure. 相似文献
65.
Yuji Naruse Atsushi Takamori Itsuki Nagasawa 《Phosphorus, sulfur, and silicon and the related elements》2020,195(7):523-525
AbstractWe previously designed and prepared the first molecules to exhibit observable CD spectra by n-σ* excitation, 2,6-dithiaspiro[3.3]heptane 2,6-dioxide. Spiro[3.3]heptane frameworks possess axial asymmetry due to puckering of 2 four-membered rings; the ring bonds are rich in p-character due to acute bond angles, which lowers the σ* energy levels. In contrast, the lone pairs are rich in s-character, which results in a good donor with conformational fixation. We expected that, instead of lone pairs as donating orbitals, the use of σ-electron-donating Si-Si bonds should result in UV absorption in the observable range (>180?nm), so that the Cotton effect could appear, at least partially, in that range. We designed 2,6-disilyl-2,6-disilaspiro[3.3]heptanes as models, and performed theoretical calculations to confirm our idea. 相似文献
66.
M. Ueshima K. Sano M. Ikeda K. Yoshino J. Okamura 《Research on Chemical Intermediates》1998,24(2):133-141
The selective catalytic oxidation (SCO) of ammonia to N2 was studied by using a series of noble metal-V2O5-WO3 catalysts supported on titania-silica (TS) prepared by coprecipitation method. In the V2O5-WO3 catalyst system, the use of TS as a support was very effective to enhance catalytic activity compared with TiO2 or SiO2 alone. The addition of a slight amount of Pd and Ir to V2O5-WO3/TS catalyst caused also remarkable enhancement of the catalytic activity without decreasing the selectivity to N2. The present catalysts provide remarkably high catalytic performance for SCO of ammonia to N2 under the practical reaction conditions for an industrial application. 相似文献
67.
The origin of Cotton effect shown by o-nitrobenzoyl esters is discussed. The Cotton effect observed for 1-(?)-methyl ester of 3-nitrophalic acid and 4-nitrohemimellitic acid (6 and 12), indicated that the favoured twisting direction of the nitrobenzene moiety is determined by the asymmetric menthyl group through the intervening carboxyl groups. This provides a new concept in conformational analysis of aromatic compounds. Extending the concept of conformational transmission to 2,2′-dinitrobipenhyl derivatives with known ab twisted nitrobenzene was related to the sign of the Cotton effect at 330 nm in accordance with the result of X-ray crystal analysis 1-(?)-menthyl 4-bromo-2-nitrobenzoate (1) 相似文献
68.
Aggregation factor, the macromolecular complex which mediates species-specific aggregation of dissociated sponge cells, was isolated from several species, partially characterized, and visualized by electron microscopy. All factors were large fibrous complexes with a backbone and side chains or arms. In some factors, the backbone is linear. In others it is circular and the complex appears as a sunburst with arms extending like rays from the circle. The size and location of the polysaccharide chains have been studied using purified preparations of Microciona prolifera. "Sunbursts" treated with ethylenediaminetraacetate (EDTA) for 4 weeks at 0 degrees C dissociate into 3 protein- and polysaccharide-containing components. Sodium dodecyl sulfate does not cause the sunburst to dissociate nor does it inhibit dissociation in the presence of EDTA suggesting that dissociation is not due to hydrolytic enzymes. The dissociation products were fractionated on a 977-A pore size micropore glass column. Fifteen percent of the material is excluded and appears in the electron microscope as the central circle of the sunburst. Digestion of the circles with 10(-3) M dithiothreitol (DTT) and 0.5 mg/ml proteinase K for 72 h at 37 degrees C produces 2 polysaccharide chains of 65,000 and 6,000 daltons as fractionated and sized on a 233-A pore size micropore glass column using Pharmacia dextrans as standards. The included fractions of the EDTA-treated material are subunits of the arms which contain 70% of the polysaccharide. A single polysaccharide of 6,000 daltons as measured on 233-A size glass beads and Sephadex G-75 is released from these subunits by proteinase digestion. Pharmacia dextrans are used as standard on both columns. We calculate that there would be four 65,000-dalton chains and one hundred 6,000-dalton chains per circle and fifty 6,000-dalton chains per arm. The third component of the EDTA-treated preparation is partially included on the column. It appears as linear fibrils in the electron microscope and contains polydisperse polysaccharides of several-hundred-thousand daltons. It may be an impurity since there is apparently less than 1 of the large polysaccharide chains per sunburst. 相似文献
69.
Shinji Toyota Takashi Nakagawa Masashi Kotani Michinori
ki Hidehiro Uekusa Yuji Ohashi 《Tetrahedron》2002,58(52):10345-10351
All the three possible rotamers of the title compound were separated by chromatography, and unambiguously identified by NMR and X-ray analysis. One of the isomers was optically inactive Ci conformation. The other optical active forms were resolved to give a pair of enantiomers, which were characterized by optical rotation and CD spectra. Thus the optical inactivity of a compound such as meso-tartaric acid that can take Ci conformation in solution, is now ascribed to that the molecule has an optically inactive Ci conformer and equal amounts of optically active conformers, that are enantiomers, in solution. 相似文献
70.
Takumi Taninaka Yuji Minoura 《Journal of polymer science. Part A, Polymer chemistry》1976,14(3):685-692
Polymerization of vinyl monomers having large negative e values in the presence of phosphorus compounds containing halogens was studied in order to examine the cationic initiation ability of phosphorus compounds. N-Vinylcarbazole was effectively polymerized by phosphorus compounds such as PCI3, PBr3, PCI2C6H5, PCI(C6H5)2, POCI3, and POCI2C6H5 even in benzene. The initiation ability of phosphorus compounds decreased in the order; PCI2 ? PBr3 > PCI2C6H5 > PCI(C6H5)2, and also POCI3 > POCI265. On the other hand, PCI3 and PBr3, which were less effective than POCI3, showed initiation ability for the polymerizations of styrene and α-methylstyrene in nitrobenzene as a solvent. The results of the copolymerization of styrene with methyl methacrylate by PCI3 in nitrobenzene, the result of solvent dielectric constant effect, and the effect of additives such as water, tert-butyl chloride, triethylamine, and hydroquinone, indicate the polymerization of styrene by PCI3 to proceed by a cationic mechanism. 相似文献