全文获取类型
收费全文 | 6425篇 |
免费 | 177篇 |
国内免费 | 25篇 |
专业分类
化学 | 4964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 | 87篇 |
2000年 | 78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 | 55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6627条查询结果,搜索用时 15 毫秒
81.
Hiroshi Sakurai Akira Tatematsu Hisao Nakata 《Journal of mass spectrometry : JMS》1973,7(9):1109-1110
A novel rearrangement reaction for a methyl group is found in doubly charged ion mass spectra of p-substituted acetophenone derivatives. The driving force for the reaction is discussed. 相似文献
82.
Mikio Hori Tadashi Kataoka Hiroshi Shimizu Eiji Imai Yukiharu Matsumoto Iwao Miura 《Tetrahedron letters》1981,22(13):1259-1262
The novel ring transformation reactions were found in the reactions of 1,3,7,9-tetra-alkyl-8,9-dihydroxanthines and acetylenic compounds. The reaction of the dihydroxanthine with DMAD gave a propellane type compound and with methyl propiolate afforded the similar type compound and a pyrimido[4,5-b]diazepine derivative. The mechanism of these reactions was also discussed. 相似文献
83.
Gas-phase ionization potentials of tetraphenylporphine and some metallotetraphenylporphines have been determined by the method of photocurrent measurements in nonpolar solvents reported previously [1]. The values obtained range from 5.9 to 6.3 eV, depending on the central metal ion, correlating well with the reported polarographic oxidation potentials. It has been concluded that photoelectron ejection from these complexes in isooctane occurs from the porphyrin π-system in all cases including Co(II) tetraphenylporphine, in which the electron is thought to be removed from the metal in polar solvents. 相似文献
84.
Kaoru Iwata Tsuneo Hagiwara Hiroshi Matsuzawa 《Journal of polymer science. Part A, Polymer chemistry》1986,24(5):1043-1051
The reciprocity effect under intense illumination was studied with photocrosslinkable polyesters of p-phenylenebis(α-cyanobutadiene carboxylic acid) (I), m-phenylenebis(α-cyanobutadiene carboxylic acid) (II), and p-phenylenebis(acrylic acid) (III), with an argon ion laser as a light source. The reciprocal sensitivities of I, II, and III were 5.0, 1800, and > 105 mJ/cm2, respectively. II and III required sensitization to enhance their sensitivities to a level at which reciprocity effects could be measured. I obeyed the reciprocity law over a wide range of exposure times from seconds to microseconds. Both II′, a copolyester of II, and III showed a dramatic decrease of sensitivity in high-intensity/short-time exposure when sensitized by 9,10-phenanthraquinone and pyrylium salts. 相似文献
85.
Tran QL Than MM Tezuka Y Banskota AH Kouda K Watanabe H Zhu S Komatsu K Thet MM Swe T Maruyama Y Kadota S 《Chemical & pharmaceutical bulletin》2003,51(6):679-682
Ginseng, the underground parts of plants of Panax species, has been used in oriental traditional medicine for centuries. Unfortunately, because of extensive exploitation over thousands of years, the natural source of these species has been almost exhausted. Recently, we have found a wild ginseng growing in Myanmar. Here, by a combination of chemical composition study and gene sequence analysis, we unambiguously demonstrate that the wild ginseng is actually P. zingiberensis, commonly known as ginger ginseng. This ginseng was an indigenous to the southwestern China. However, now it is seriously threatened to brink of extinction and is put on the highest level of protection in China. Therefore, an appropriate protection measure is highly recommended to preserve this valuable resource, since this Myanmar ginseng might turn out to be the last P. zingiberensis, which could ever be seen in the planet. 相似文献
86.
Yasuko Ishizuka Yoshinobu Nagawa Hiroshi Nakanishi Akira Kuboyama 《Journal of inclusion phenomena and macrocyclic chemistry》1990,9(3):219-225
Two aromatic rings of a phlorizin molecule form inclusion complexes with -CD and -CD. Induced circular dichroism spectra of these complexes have been measured to estimate the orientation of the two aromatic rings in the hydrophobic space of CDs. Apparent complex formation constants have been also estimated for each complex. It is concluded that phlorizin forms a stronger inclusion complex with -CD than with -CD. 相似文献
87.
A systematic investigation was performed to elucidate the cause of spontaneous ignition of Refuse Derived Fuel (RDF) and Meat Bone Meal (MBM). Heat generation in both RDF and MBM with addition of water liquid and vapor at room temperature was determined by isothermal calorimetry. Compared with water liquid, the heat of wetting by sorption of water vapor at 80% relative humidity and 25 °C was larger, which can raise the temperature of RDF and MBM more than 30 and 56 °C, respectively. Heat generation due to fermentation occurred and the temperature of RDF and MBM reached or exceeded 80 °C after 5 days for RDF and 4 days for MBM at 100% RH. The spontaneous ignition for RDF and MBM results from heat of wetting and fermentation at room temperature and a further exothermic reaction at higher temperature. 相似文献
88.
Summary The “chemical” relaxation of stress either in Amilan (6-Nylon) or polyvinyl alcohol caused by penetration of water vapor was
studied at 40% R. H. and temperatures 15, 30, and 50° C. A theory was presented of the chemical relaxation in a polymer which
comprises penetrant-sensitive bonds as the crosslinkages between the molecular chains. This theory assumes the diffusion coefficient
of penetrant in the polymer to he independent of concentration and any other factors. It was found that the system Amilan-water
behaves in exact conformity with the theory over the ranges of elongation and temperature studied. The diffusion coefficient,D, of water in Amilan could thus be evaluated from the chemical relaxation data, using the theory presented, as functions of
elongation and temperature. An ordinary sorption experiment was carried out for this system at 40% R. H. and 16.8° C and demonstrated
that the diffusion of water in Amilan was Fickian with a constant diffusion coefficient. Both diffusion coefficients from
the chemical relaxation data and the sorption. data were found to agree quite well when the former was extrapolated to zero-strain.
The chemical relaxation behavior in the system polyvinyl alcohol-water was markedly different from that expected from the
theory, suggesting primarily that the diffusion coefficient of water in this polymer was not constant. A parallel evidence
for this fact was obtained from sorption measurements on this system, which demonstrated the diffusion in this system to be
dependent both on concentration and time.
From these results it may be concluded that the chemical relaxation technique, when combined properly with an adequate theory,
can be used not only to evaluate the diffusion coefficient of penetrant in a given polymer solid but also to investigate,
at least qualitatively, the type of sorption behavior characteristic of the system under given experimental conditions.
Zusammenfassung Die chemische Spannungsrelaxation in Amilan (6-Nylon) und Polyvinylalkohol, verursacht durch Eindringen von Wasserdampf, wurde bei 40% r. F. und Temperaturen von 15, 30 und 50° C untersucht. Es wird eine Theorie der chemischen Relaxation von Polymeren vorgelegt, die als empfindliche Bindungen auf das eindringende Niedermolekulare die Vernetzungen zwischen den molekularen Ketten betrachtet. Diese Theorie setzt voraus, da? der Diffusionskoeffizient im Polymeren für die eindringende Substanz unabh?ngig von Konzentration und anderen Faktoren ist. Das System Amilan-Wasser benimmt sich vollkommen entsprechend dieser Theorie in den studierten Verstreckungs- und Temperaturbereiche. Der Diffusionskoeffizient von Wasser in Amilan konnte daher aus der chemischen Relaxation als Funktion von Dehnung und Temperatur ausgewertet werden. Ein normales Quellungsexperiment wurde für das System bei 40% r. F. und 16,8° C ausgeführt und zeigte, da? die Diffusion von Wasser in Amilan dem Fickschen Gesetz mit konstantem Diffusionskoeffizienten folgt. Beide Diffusionskoeffizienten, der aus chemischer Relaxation und der aus Quellungsdaten gewonnene, stimmten sehr gut überein, falls der erstere auf die Dehnung 0 extrapoliert wurde. Die chemische Relaxation des Systems Polyvinylalkohol-Wasser war merklich anders als nach der Theorie erwartet und lie? in erster Linie vermuten, da? der Diffusionskoeffizient von Wasser in diesem Polymeren nicht konstant ist. Eine entsprechende Andeutung wurde aus Quellungsmessungen an diesem System erhalten. Die Diffusion h?ngt von Konzentration und Zeit ab. Aus diesen Resultaten kann gefolgert werden, da? die Technik der Untersuchungen der chemischen Relaxation unter Verwendung einer geeigneten Theorie nicht nur dazu angewendet werden kann, Diffusionskoeffizienten von kleinen Molekülen in einem gegebenen festen Polymeren zu messen, sondern zumindest auch qualitativ den Typ des Quellungsverhaltens festzustellen, der das System unter den gegebenen experimentellen Bedingungen charakterisiert.相似文献
89.
A new force approach is reported in which we improve the wavefunction so that the Hellmann-Feynman theorem is satisfied. A sufficient condition for the Hellmann-Feynman theorem to be satisfied is that the basis set includes AO derivatives ?xr/?xrfor any basis xr. Here we test a procedure in which only the first derivative AOs are added to the “parent” AOs. The results are very encouraging. 相似文献
90.
Hidetake Sakuraba Hiroshi Maekawa 《Journal of inclusion phenomena and macrocyclic chemistry》2006,54(1-2):41-45
The two modified β-cyclodextrin (β-CD) derivatives having catechol-type ligand (2,3- and 3,4-dihydroxy groups on the benzoate
ring) were synthesized. The chiral catalytic activity of their MoV and CuII complexes was examined in the asymmetric oxidation of aromatic sulfides using hydrogen peroxide in water (pH 6.0). The oxidation
with the MoV complexes of two β-CD derivatives were more accelerated than that with the CuII complexes. The sign of the optical rotation of the sulfoxides obtained in the above two cases showed the opposite configuration
in the oxidation of the same sulfide. The difference of the enantioselectivity appeared also between the two complexes of
the 2,3- and 3,4-dihydroxybenzoate derivatives with the same metal ion. While the use of the MoV complexes with the catechol derivatives yielded the sulfoxides with 35–65% ee, the use of the CuII complexes gave the products with the␣opposite configuration at 26–52% ee. The chiral induction in the oxidation, observed
conversely between the␣catalysts, was reflected on the chiral conformation of the respective metal catalysts, showed in Induced
Circular Dichroism (ICD) spectra. The highest optical yield, 65%, was observed in the oxidation of butyl phenyl sulfide using
the catalytic amount (0.1 equiv) of the MoV complex with mono-6-O-(3,4-dihydroxybenzoyl)-β-CD. The reaction gave predominantly the (S)-sulfoxide in 95% chemical yield. 相似文献