全文获取类型
收费全文 | 5674篇 |
免费 | 633篇 |
国内免费 | 1021篇 |
学科分类
数理化 | 7328篇 |
出版年
2024年 | 12篇 |
2023年 | 78篇 |
2022年 | 144篇 |
2021年 | 235篇 |
2020年 | 257篇 |
2019年 | 241篇 |
2018年 | 205篇 |
2017年 | 217篇 |
2016年 | 237篇 |
2015年 | 235篇 |
2014年 | 299篇 |
2013年 | 490篇 |
2012年 | 356篇 |
2011年 | 347篇 |
2010年 | 254篇 |
2009年 | 331篇 |
2008年 | 384篇 |
2007年 | 359篇 |
2006年 | 328篇 |
2005年 | 280篇 |
2004年 | 289篇 |
2003年 | 218篇 |
2002年 | 466篇 |
2001年 | 158篇 |
2000年 | 130篇 |
1999年 | 109篇 |
1998年 | 106篇 |
1997年 | 74篇 |
1996年 | 78篇 |
1995年 | 78篇 |
1994年 | 74篇 |
1993年 | 48篇 |
1992年 | 48篇 |
1991年 | 39篇 |
1990年 | 22篇 |
1989年 | 14篇 |
1988年 | 13篇 |
1987年 | 10篇 |
1986年 | 14篇 |
1985年 | 14篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 6篇 |
1979年 | 2篇 |
1978年 | 2篇 |
1977年 | 6篇 |
1974年 | 4篇 |
1973年 | 3篇 |
1972年 | 1篇 |
排序方式: 共有7328条查询结果,搜索用时 15 毫秒
61.
62.
Jocelyn Jalbert Roland Gilbert Pierre Tétreault Brigitte Morin Denise Lessard-Déziel 《Cellulose (London, England)》2007,14(4):295-309
In this study, headspace gas chromatography/mass spectrometry has been used to assess the volatile by-products generated by
the ageing of oil-impregnated paper insulation of power transformers. Sealed-glass ampoules were used to age under oxidative
conditions 0.5-g specimens of insulating paper in 9 mL of inhibited mineral oil in a temperature range of 60–120 °C and moisture
of 0.5, 1 and 2% (w/w). A linear relationship between one of the oil-soluble degradation by-products, i.e. methanol, and the
number of ruptured 1,4-β-glycosidic bonds of cellulose, regardless of the type of paper (ordinary Kraft or thermally-upgraded
(TU) Kraft paper), was established for the first time in this field. Ageing at 130 °C of model compounds of the Kraft paper
constituents (α-cellulose, hemicellulose and lignin) and two cellulosic breakdown by-products (D-(+)-glucose and 1,6-anhydro-β-d-glucopyranose) confirmed that the α-cellulose degradation was mostly responsible for the presence of this molecule in the
system. Furthermore, additional 130 °C-tests with six different papers and pressboard samples under a tight control of initial
moisture indicated that at least one molecule of methanol is formed for each rupture of 1,4-β-glucosidic bond of the molecular
chains. Stability tests showed that the ageing indicator is stable under the oxygen and temperature conditions of open-breathing
transformers. The presence of methanol was detected in 94% of oil samples collected from over than 900 in-service pieces of
equipment, confirming the potential for this application. Lastly, the tests have shown that oil-oxidation by-products and
TU-nitrogenous agents modify the methanol partitioning coefficients in the paper/oil/air system, which makes their study essential
over a range of field conditions encountered by power transformers. Results are presented and discussed in comparison with
2-furfuraldehyde, which is the current reference in the domain. 相似文献
63.
A novel complex [Pb(qina)2(DMSO)]·H2O was synthesized, of which qina- is the quinaldic acid radical and DMSO the dimethyl sulfoxide. Elemental analysis, IR spectra, and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. This complex belongs to monoclinic system, space group P121/n1, with a = 7.1553(17), b = 17.543(2), c = 17.306(2)(A),β = 91.671(4)°, C22H20N2O6PbS, Mr = 647.65, Z = 4, V= 2171.5(6)(A)3, Dc= 1.981g/cm3,μ = 7.908 mm-1, F(000) = 1248, -9≤h≤6, -23≤k≤ 19, -22≤l≤22, R= 0.0221 and wR =0.0488. Weak coordinate bond is formed between oxygen atom in DMSO and Pb(Ⅱ ). There are also weak interactions, such as π-π interaction, hydrogen bonds and so on, among the complex molecules. 相似文献
64.
A novel coordination polymer [{Cd(hmbdc)(H2O)3}·2H2O]n (hmbdc=5-hydroxy- isophthalic acid) has been synthesized and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c, with a=9.599(3), b=18.699(5), c=7.557(2) (A), β= 108.198(4)°, V=1288.6(6) (A)3, Z=4, Mr=382.60, Dc=1.972 g/cm3, F(000)=760, μ=1.740, the final R=0.0555 and wR=0.0995 for 1732 observed reflections with Ⅰ > 2σ(Ⅰ). The structural analysis shows that the intermolecular hydrogen bonds and π-π interactions result in a three-dimensional supramolecular framework. 相似文献
65.
KEIKO TAKAHASHI HIDEKI YOKOMIZO KATSURO ISHIYAMA MASAHIKO KITSUTA MEGUMI OHASHI 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(1-2):95-99
Asymmetric reduction of indol-3-pyruvic acid (IPA) with NaBH4 in aqueous solution in the presence of various cyclodextrins (α-, β-, γ-, mono-6-amino-6-deoxy-β- and di-6ABamino-6AB-deoxy-β-cyclodextrin) was investigated. From the NMR and circular dichroism spectral studies, the conformation of the CyD–substrate complexes is suggested; the part of carboxylic group stay in the cavity of α-CyD, whole of IPA in β-CyD, two molecules in a γ-CyD cavity, and IPA(s) is/are on the rim of the cavity of mono-6-amino-6-deoxy-β- and di-6ABamino-6AB-deoxy-β-CyD (AβCyD, DAβCyD) with electrostatic interaction between amino group and carboxylic group. This conformational difference provides in the difference in the optical selectivity of reduction. 相似文献
66.
ZHU Jun ZHANG Yun CHEN Hao CHE Yun-Xia ZHENG Ji-Min ② 《结构化学》2006,25(8):1011-1013
1 INTRODUCTION Nonlinear optics (NLO) is at the forefront of cur- rent researches because of its importance in provi- ding the key functions of frequency shifting, optical modulation, optical switching, optical logic and op- tical memory for the emerging … 相似文献
67.
Bogumil Brzezinski Zbigniew Rozwadowski Teresa Dziembowska Georg Zundel 《Journal of Molecular Structure》1998,440(1-3):73-79
Three di-Schiff bases of 2-hydroxy-5-methyl-isophthalaldehyde with 4-R-anilines (R=H, CH3, OCH3) and their 1:1 complexes with HClO4 were studied by FT-IR, 1H, and 13C NMR spectroscopy in acetonitrile and [2H3]acetonitrile solutions, respectively. In di-Schiff bases intramolecular OH…N hydrogen bonds have been detected; however, they show no proton polarizability. Hydrogen-bonded systems with fast proton fluctuation and large proton polarizability have been found in the 1:1 complexes of di-Schiff bases with HClO4. 相似文献
68.
编写了普适性的多键表自洽场程序,该程序能对单电子轨道展开系数和键表系数同时优化,其中单电子轨道的展开空间可任意定义,实际计算建议采用“杂化”轨道形式,即每个单电子轨道只对一个原子的基函数展开。对H2、Li2及HLi采用不同基组进行计算,结果表明用3个键表自洽计算所得能量与MP2结果相近,且我们的计算对键的共价性和离子性分析非常直观。 相似文献
69.
The complexes between R3Tr (Tr = B, Al, and Ga; R = H, F, Cl, and Br) and H2X (X = O, S, and Se) were theoretically studied. The interaction energies of R3Al⋯H2X and R3Ga⋯H2X are consistent with the electronegativity of the halogen atom R (R ≠ H), but an opposite dependence is found for R3B⋯H2X. The triel bond of R3Tr⋯H2X is weaker for the heavier chalcogen donor. The dependence of triel bonding strength on the triel atom is complicated, depending on the nature of R and X. The methyl substitution of H2X causes a substantial increase in the interaction energy from −5.74 kcal/mol to −22.88 kcal/mol, and its effect is relevant to the nature of Tr, X, and R groups. For the S and Se donors, the increased percentage of interaction energy is almost the same due to the methyl substitution, which is larger than that of the O analogue. In most triel-bonded complexes, electrostatic dominates and polarization has comparable contribution. However, polarization plays a dominant role in R3B⋯ and R3B⋯ (R = Cl and Br; R′ = H and Me). 相似文献
70.
Extremely localized molecular orbitals (ELMOs), namely orbitals strictly localized on molecular fragments, are easily transferable from one molecule to another one. Hence, they provide a natural way to set up the electronic structure of large molecules using a data base of orbitals obtained from model molecules. However, this procedure obviously increases the energy with respect to a traditional MO calculation. To gain accuracy, it is important to introduce a partial electron delocalization. This can be carried out by defining proper optimal virtual orbitals that supply an efficient set for nonorthogonal configurations to be employed in VB-like expansions. 相似文献