全文获取类型
收费全文 | 9664篇 |
免费 | 1327篇 |
国内免费 | 792篇 |
专业分类
化学 | 7025篇 |
晶体学 | 124篇 |
力学 | 464篇 |
综合类 | 54篇 |
数学 | 968篇 |
物理学 | 3148篇 |
出版年
2024年 | 28篇 |
2023年 | 185篇 |
2022年 | 279篇 |
2021年 | 319篇 |
2020年 | 365篇 |
2019年 | 336篇 |
2018年 | 263篇 |
2017年 | 247篇 |
2016年 | 456篇 |
2015年 | 389篇 |
2014年 | 475篇 |
2013年 | 683篇 |
2012年 | 869篇 |
2011年 | 883篇 |
2010年 | 539篇 |
2009年 | 536篇 |
2008年 | 622篇 |
2007年 | 601篇 |
2006年 | 526篇 |
2005年 | 491篇 |
2004年 | 317篇 |
2003年 | 218篇 |
2002年 | 235篇 |
2001年 | 202篇 |
2000年 | 191篇 |
1999年 | 169篇 |
1998年 | 162篇 |
1997年 | 131篇 |
1996年 | 126篇 |
1995年 | 149篇 |
1994年 | 132篇 |
1993年 | 94篇 |
1992年 | 89篇 |
1991年 | 72篇 |
1990年 | 70篇 |
1989年 | 37篇 |
1988年 | 46篇 |
1987年 | 37篇 |
1986年 | 35篇 |
1985年 | 31篇 |
1984年 | 24篇 |
1983年 | 9篇 |
1982年 | 20篇 |
1981年 | 14篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1978年 | 10篇 |
1977年 | 8篇 |
1976年 | 7篇 |
1975年 | 7篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
151.
在Polanyi吸附势理论基础上,结合程序升温脱附曲线的测定,建立了一个快速测定吸附热的新方法,详细讨论了该方法的原理,通过微机采样和数据处理,测定一条吸附热与覆盖度的曲线仅需1h左右。 相似文献
152.
Time-of-flight mass spectrum of C_nB~- has been recorded on a selfbuilt instrument with laser vaporization of tetraphenylboron sodium. By analysis of the com-position of the anions, it is found that number of the boron atoms in any of these ions equals to the number of the charges carried by the anion, and the sum of the numbers of the carbon and boron atoms in these species are always the odd numbers. The experimental results show that boron atom has a strong tendency to attract an electron so that those C_nB~- will have similar electronic structures as C_n, and carbon clusters with odd members are always more stable than their even neighbors. 相似文献
153.
The title compound has been synthesized under nitrogen atmosphere using V_2O_5 for the initiator by Schlenk techniques. It′s single crystal, which is very air and water-sensitive, was obtained and determined from three-dimensinal x-ray diffraction data collected by the four-circle diffractometer. The crystals are orth- orhombic with space group D_2~4-P_(212121) and unit cell constants a=0.909 nm, b=1.4909 nm, c=2.1635 nm and z=4. We derived first the positional parameters of V, Zn, Cland O atoms by direct method using SHELXTL program. The coordinates of other the non-hyleast-squares refinement for all atoms gave a final discrepency factor R=0.0945 and RW=0.0674.The result of structure analysis shows that the compound is composed of the octahedral cation [VCl_2·(THF)_4]~+ and the tetrahedral anion [ZnCl_3·THF]~-.The reaction mechanism was discussed. The title compound is reaction product of VCl_3 with ZnCl_2 in THF. 相似文献
154.
Double metal cyanide (DMC) complexes based on Zn3[Fe(CN)6]2 were synthesized using different molar ratios of ZnCl2 to K3[Fe(CN)6] and special complexing agents. IR spectroscopy, electron spectroscopy for chemical analysis, X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and other analytical techniques were employed to characterize these catalysts. The morphology and structure of these DMC catalysts were attributed to the different complexing agents as well as to the different molar ratios of ZnCl2 to K3[Fe(CN)6]. In addition, the catalytic activity was strongly correlated with the morphology and noncrystalline content of DMC catalysts. High-activity catalysts could be prepared by controlling the structure of DMC catalysts by incorporating complexing agents. The active species of DMC catalysts for ring-opening polymerization are Zn2+, [Fe(CN)6]3–, Cl–, and the compound of their ligands. 相似文献
155.
Xuejun Pan Dan Xie Neil Gilkes David J. Gregg Jack N. Saddler 《Applied biochemistry and biotechnology》2005,124(1-3):1069-1079
Pretreatment of Douglas-fir by steam explosion produces a substrate containing approx 43% lignin. Two strategies were investigated
for reducing the effect of this residual lignin on enzymatic hydrolysis of cellulose: mild alkali extraction and protein addition.
Extraction with cold 1% NaOH reduced the lignin content by only approx 7%, but cellulose to glucose conversion was enhanced
by about 30%. Before alkali extraction, addition of exogenous protein resulted in a significant improvement in cellulose hydrolysis,
but this protein effect was substantially diminished after alkali treatment. Lignin appears to reduce cellulose hydrolysis
by two distinct mechanisms: by forming a physical barrier that prevents enzyme access and by non-productively binding cellulolytic
enzymes. Cold alkali appears to selectively remove a fraction of lignin from steam-exploded Douglas-fir with high affinity
for protein. Corresponding data for mixed softwood pretreated by organosolv extraction indicates that the relative importance
of the two mechanisms by which residual lignin affects hydrolysis is different according to the pre- and post-treatment method
used. 相似文献
156.
A new bismaleimide (BMI) resin was synthesized to formulate epoxy(tetraglycidyl diaminodiphenyl methane; TGDDM) – bismaleimide thermoset blends for composite matrix applications. 4,4′-diaminodiphenyl methane (DDM) was used as an amine curing agent for the TGDDM. A Fourier transform infrared (FTIR) spectroscopy was employed to characterize the new BMI resin. Cure behavior of the epoxy–BMI blends was studied using a differential scanning calorimeter (DSC). DSC thermograms of the thermoset blends indicated two exothermic peaks. The glass transition temperature of the thermoset blends decreased with BMI content. Thermogravimetric analysis (TGA) was carried out to investigate thermal degradation behavior of the cured epoxy–BMI thermoset blends. The new BMI resin reacted partially with the DDM and weak intercrosslinking polymer networks were formed during cure of the thermoset blends. 相似文献
157.
Some photosensitive molecules, such as p-N,N′-dimethylaminobenzoic acid (DMABA), Nile Red, heteropolytungstic acid (H3PW12O40, HPA) and metalloporphyrins, have been entrapped onto nano-scale pores or channels of TiO2-modified Y-Zeolite (TiO2-Y-Zeolite) and MCM41 (TiO2-MCM41) and their excited-state intermediates have been characterized in terms of the excited-state dynamics by using laser spectroscopic techniques. Through these studies, it has been found that the photo-induced electrons are generated from the intramolecular charge transfer (ICT) state of DMABA, Nile Red or metalloporphyrin (MnTPP(Cl)), followed by transferring to the TiO2-Y-Zeolite or TiO2-MCM41 more efficiently as compared to the bulk TiO2, NaY-Zeolite or MCM41. The efficient photoinduced interfacial electron transfer causes the rapid formation of radicals of those photosensitive molecules (a few tens ps). It has been also found that these photophysical properties can be applied to develop the new photocatalyst as observed by the efficient photocatalytic activities of the DMABA or Nile Red-entrapped TiO2-Y-Zeolites for the photoreduction of an azo-dye such as Methyl Orange in water. On the other hand, in case of HPA-entrapped TiO2-Y-zeolite, the electron generated from the excited-state TiO2 is transferred to HPA, followed by formation of the reduction product, heteropoly blue (HPB) which is also generated by UV irradiation of HPA. This electron transfer is analogous to the Z-scheme mechanism of plant photosynthetic systems showing two photon reactions. Because of this photoelectron transfer mechanism, the HPA-entrapped TiO2-Y-zeolite has demonstrated the synergistic enhancement of the photocatalytic decomposition of Methyl Orange and hydrogen generation from photolysis of water. 相似文献
158.
Hong Su Yi‐Hang Wen Yun‐Long Feng 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):m208-m210
The title compound, [Mn(C10H8O5S)(H2O)4]n, a one‐dimensional manganese(II) complex comprising helical chains bridged by 4‐(carboxylatomethylsulfanyl)phenoxyacetate ligands has been characterized by single‐crystal X‐ray diffraction analysis. Hydrogen‐bonding interactions between adjacent chains extend the complex into a three‐dimensional supramolecular architecture. 相似文献
159.
Tsann-Long Su Yu-Kun Yang Jai-Tung Huang Wu-Yun Ren Kyoichi A. Watanabe Ting-Chao Chou 《Journal of heterocyclic chemistry》1993,30(5):1437-1443
This paper is dedicated to the memory of Professor Roland K. Robins The synthesis of 4-[(1,3-diaminopyrrolo[3′,4′:4,5]pyrido[2,3-d]pyrimidin-8-yl)benzoyl]-L-glutamic acid ( 18 ), a potential antifolate and anticancer agent, has been achieved starting from 1,4-dibromobutan-2-ol with alkyl p-aminobenzoic acids. Condensation of these two agents gave 1-(4-alkoxycarbonylphenyl)pyrrolidin-3-ols 7a,b , which were oxidized to the corresponding pyrrolidin-3-one derivatives 8a,b . Compounds 8a,b were converted into 1,3-diamino-8-(4-alkoxycarbonylphenyl)-7,8-dihydro-9H-pyrrolo[3′,4′:4,5]pyrido[2,3-d]pyrimidines 12a,b in 4 steps. Saponification of 12b the benzoate ester and coupling with di-tert-butyl glutamate afforded a mixture of 7,8-dihydro product 16 and its aromatized derivative 17 . Finally hydrolysis of esters 16 or 17 gave only the title compound 18 . The 7,8-dihydro tricyclic derivatives were easily air-oxidized to form their fully aromatized compounds. The title compound 18 was one tenth less active than MTX against HL-60 cells in culture. 相似文献
160.
Wanlong Xiao Yuhao Mo Jing Guo Zhishan Su Shunxi Dong Xiaoming Feng 《Chemical science》2021,12(8):2940
New types of C2-symmetric chiral macrodiolides are readily obtained via chiral N,N′-dioxide-scandium(iii) complex-promoted asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles. This protocol provides an array of enantioenriched macrodiolides with 16, 18 or 20-membered rings in moderate to good yields with high diastereoselectivities and excellent enantioselectivities through adjusting the length of the tether at the C3 position of indoles. Density functional theory calculations indicate that the formation of macrocycles is more favorable than that of 9-membered-ring lactones in terms of kinetics and thermodynamics. The potential utility of these intriguing chiral macrodiolide molecules is demonstrated in the enantiomeric recognition of aminols and chemical recognition of metal ions.An asymmetric tandem Friedel–Crafts alkylation/intermolecular macrolactonization of ortho-quinone methides with C3-substituted indoles was achieved by using a chiral N,N′-dioxide-scandium(iii) complex. 相似文献