全文获取类型
收费全文 | 6401篇 |
免费 | 205篇 |
国内免费 | 25篇 |
专业分类
化学 | 4968篇 |
晶体学 | 77篇 |
力学 | 114篇 |
数学 | 499篇 |
物理学 | 973篇 |
出版年
2022年 | 57篇 |
2021年 | 56篇 |
2020年 | 75篇 |
2019年 | 94篇 |
2018年 | 57篇 |
2017年 | 43篇 |
2016年 | 112篇 |
2015年 | 107篇 |
2014年 | 146篇 |
2013年 | 307篇 |
2012年 | 349篇 |
2011年 | 381篇 |
2010年 | 210篇 |
2009年 | 203篇 |
2008年 | 395篇 |
2007年 | 412篇 |
2006年 | 427篇 |
2005年 | 360篇 |
2004年 | 321篇 |
2003年 | 296篇 |
2002年 | 269篇 |
2001年 | 89篇 |
2000年 | 79篇 |
1999年 | 75篇 |
1998年 | 55篇 |
1997年 | 87篇 |
1996年 | 86篇 |
1995年 | 45篇 |
1994年 | 62篇 |
1993年 | 56篇 |
1992年 | 49篇 |
1991年 | 52篇 |
1990年 | 34篇 |
1989年 | 32篇 |
1988年 | 43篇 |
1987年 | 42篇 |
1986年 | 38篇 |
1985年 | 84篇 |
1984年 | 90篇 |
1983年 | 41篇 |
1982年 | 85篇 |
1981年 | 80篇 |
1980年 | 75篇 |
1979年 | 74篇 |
1978年 | 69篇 |
1977年 | 55篇 |
1976年 | 63篇 |
1975年 | 42篇 |
1974年 | 44篇 |
1973年 | 64篇 |
排序方式: 共有6631条查询结果,搜索用时 80 毫秒
81.
Minimal contracted Gaussian basis sets are presented for Ga through Cd. Characteristically these Gaussian-based minimal sets give far better d orbital energies than those by minimal STO basis sets. These new basis sets were tested on Br2 for which a new benchmark calculation was also performed. The test result is satisfactory in that these basis sets produce good general agreement with the near Hartree–Fock calculation with respect to the molecular spectroscopic constants. 相似文献
82.
Mariko Kusabe Hiromitsu Kozuka Satoru Abe Hiroshi Suzuki 《Journal of Sol-Gel Science and Technology》2007,44(2):111-118
Hydroxypropylcellulose (HPC)–titania hybrid thin films were prepared by sol–gel method where titanium tetraisopropoxide Ti(OC3H7
i
)4 was hydrolyzed under acidic conditions in the presence of HPC, followed by dip-coating and drying at 120 °C for 24 h. The
viscosity average molecular weight of HPC was 55,000–70,000 or 110,000–150,000, and the TiO2/(HPC + TiO2) mass ratio ranged from 0 to 1, which was calculated on the assumption that all Ti(OC3H7
i
)4 is converted into TiO2. The films were 0.35–1.0 μm thick, transparent in visible region and opaque in ultraviolet (UV) region, where the optical
absorption coefficient in UV region increased with increasing titania content. The refractive index increased with increasing
titania content, ranging from 1.6 to 1.8 for the hybrid thin films. The pencil hardness increased from 6B to 5H, the durability
in hot water significantly increased and the contact angle of water on films increased from 35° to 89° with increasing titania
content. Crack-free films could be deposited on organic polymer substrates irrespective of titania or HPC contents, where
cracking did not occur at higher HPC contents even when the substrate was bent. 相似文献
83.
Yohei Hashimoto Masataka Moriyasu Eiko Kato Masaru Endo Naohiko Miyamoto Hiroshi Uchida 《Mikrochimica acta》1978,70(1-2):159-167
Summary A new type of detector for high-pressure liquid chromatography has been designed. This detector is equipped with a RC resonance circuit, and is similar to the capacitance detector previously reported. It is operated as a capacitance detector with nonpolar eluents; while with polar solvents, it behaves as a conductance detector. Electrolytes such as salts, acids and bases are sensitively detected. The detector was successfully used for the detection of fatty acids and alkaloids.
Zusammenfassung Ein neuartiger Detektor für die Hochdruck-Flüssigchromatographie wurde entwickelt. Dieser ist mit einem Resonanzstromkreis ausgestattet und ähnelt dem kürzlich beschriebenen Kapazitanz-Detektor. Als solcher funktioniert er mit nichtpolaren Eluenten, während er sich mit polaren Lösungsmitteln wie ein Leitfähigkeitsdetektor verhält. Salze, Säuren und Basen werden empfindlich nachgewiesen. Das Gerät wurde zum Nachweis von Fettsäuren und Alkaloiden verwendet.相似文献
84.
The H2 and CH4 chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H2O or elimination of CO2, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]+ involve loss of H2O or CH2O, analogous to the CO2 elimination reaction for the benzoic acids. It is shown that the CO2 and CH2O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]+ is an enhancement of the H2O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H2O elimination. Apparently, this route is favoured over the direct elimination of H2O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions. 相似文献
85.
Tanaka K Ding MY Helaleh MI Taoda H Takahashi H Hu W Hasebe K Haddad PR Fritz JS Sarzanini C 《Journal of chromatography. A》2002,956(1-2):209-214
In this preliminary study, a new approach to ion-exclusion chromatography is proposed to overcome the relatively poor conductivity detection response which occurs in ion-exclusion chromatography when acids are added to the eluent in order to improve peak shape. This approach, termed vacancy ion-exclusion chromatography, requires the sample to be used as eluent and a sample of water to be injected onto a weakly acidic cation-exchange column (TSKgel OApak-A). Vacancy peaks for each of the analytes appear at the retention times of these analytes. Highly sensitive conductivity detection is possible and sharp, well-shaped peaks are produced, leading to efficient separations. Retention times were found to be affected by the concentration of the analytes in the eluent, and also by the presence of an organic modifier such as methanol in the eluent. Detection limits for oxalic, formic, acetic, propionic, butyric and valeric acids were 0.1, 0.2, 0.3, 0.3, 0.4 and 0.5 microM, respectively, and linear ranges for some acids extended over two orders of magnitude. Precision values for retention times were 0.21% and for peak areas were <1.90%. The vacancy ion-exclusion chromatography method was found to give detection responses four to 10 times higher than conventional ion-exclusion chromatography using sulfuric acid eluent and two to five times higher than conventional ion-exclusion chromatography using benzoic acid eluent. 相似文献
86.
Hasegawa JY Takata K Miyahara T Neya S Frisch MJ Nakatsuji H 《The journal of physical chemistry. A》2005,109(14):3187-3200
Excited states of free-base porphyrin isomers, porphycene (Pc), corrphycene (Cor), and hemiporphycene (hPc), were studied by the Symmetry-Adapted Cluster (SAC)/SAC-Configuration Interaction (CI) method. The absorption peaks of the porphyrin isomers were assigned on the basis of the SAC-CI spectra. The X, Y, X', and Y' bands of the porphyrin isomers, which have weak intensities, are identified. The differences in the Q-band absorptions among the isomers were clearly explained by the four-orbital model. In Cor and hPc, the wave function of the B-band corresponds to the mixture of the four-orbital excitations and the optically forbidden excitation of free-base porphin (P), due to the molecular symmetry lowering in the isomers. The B-band character is described by the five-orbital model in Pc and the six-orbital model in Cor and hPc. Two tetrazaporphycenes and two ring-extended (dibenzo) porphycenes were designed, and the Q-band transition moment was successfully controlled. These examples show that the control of the four-orbital energy levels is the guiding principle for pigment design in porphyrin compounds. 相似文献
87.
γ-Radiolysis of 5-fluorouracil and 5-fluorouridine derivatives having sulfur-containing substituents
Tokuyuki Kuroda Koji Hisamura Hiroshi Nishikawa Nobuhiro Nakamizo Yoshio Otsuji 《Journal of heterocyclic chemistry》1994,31(2):335-339
γ-Radiolysis reactions of eight 5-fluorouracil (5-FU) derivatives having sulfonyl group-containing substituents at the 1-position and five 5-fluorouridine (5-FUR) derivatives having thioureido group-containing substituents were studied under the conditions where hydrated electron (eaq?) and hydroxyl radical (HO·) become the principal reactive species. The 5-FU and 5-FUR derivatives were radiolyzed to give 5-FU and 5-FUR, respectively. The efficiency of the reactions depended upon the nature of reactive species and also upon the nature of substituents. The reactivity features of the γ-radiolysis reactions are discussed. 相似文献
88.
Chisuzu Tokoh Keiji Takabe Minoru Fujita Hiroshi Saiki 《Cellulose (London, England)》1998,5(4):249-261
Acetobacter xylinum was cultured in Hestrin-Schramm medium (control medium) and Hestrin-Schramm medium containing acetyl glucomannan (mannan medium). Loose bundles of the cellulose microfibrils are formed in the mannan medium in contrast to the normal ribbons being produced in the control medium. Rapid-freeze and substitution method followed by metal-shadowing revealed the droplet-like structures around the microfibril synthesized in the mannan medium. The cellulose synthesized in the mannan medium was stained heavily by the periodic acid-thiocarbohydrazide-silver proteinate (PATAg) method, while the cellulose synthesized in the control medium was not stained. X-ray diffractometry and FT-IR spectroscopy indicated that the addition of mannan induced a change in the crystal structure from the algal-bacterial type to the cotton-ramie type. Thus the presence of acetyl glucomannan in the medium prevents the assembly of cellulose microfibrils and changes the crystal structure of cellulose. 相似文献
89.
Acetophenone photo-sensitized addition of indene to cyclic fluoro-olefins (1,2-dichlorohexafluorocyclopentene-1, 1,2-dichlorotetrafluorocyclobutene-1 and hexafluorocyclobutene) gave the corresponding cycloadducts in satisfactory yields. The cycloadducts obtained predominantly had exo configuration.Some reactions such as reduction, oxidation, dechlorination and halogenation, of the cycloadducts were also studied. 相似文献
90.
Itsuki Shindachi Hiroshi Hanaki Ryo Sasai Tetsuya Shichi Tatsuto Yui Katsuhiko Takagi 《Research on Chemical Intermediates》2007,33(1-2):143-153
Diarylethene derivatives (DE) covalently bonded to silanol oxygens of layered silicate surfaces, i.e., magadiite (Mag), were synthesized and investigated for their photochromic behavior. The DE-Mag layered hybrids were found to undergo reversible color change by alternating UV and visible light irradiation. A more highly efficient, reproducible photochromic behavior was realized with DE-Mag than with a corresponding DE-Si possessing silyl substituents on DE in place of the Mag surface. Moreover, the present covalently bonded DE exhibited an improvement over DE hybrids incorporated in layered double hydroxide (LDH) clays, in which the repetitive photochromic behavior decreased during alternating irradiation, due to the accumulation of the photochemically inert parallel isomers of DE. 相似文献