全文获取类型
收费全文 | 7170篇 |
免费 | 257篇 |
国内免费 | 44篇 |
专业分类
化学 | 4656篇 |
晶体学 | 47篇 |
力学 | 247篇 |
数学 | 1299篇 |
物理学 | 1222篇 |
出版年
2023年 | 36篇 |
2022年 | 85篇 |
2021年 | 121篇 |
2020年 | 125篇 |
2019年 | 144篇 |
2018年 | 136篇 |
2017年 | 138篇 |
2016年 | 216篇 |
2015年 | 218篇 |
2014年 | 220篇 |
2013年 | 425篇 |
2012年 | 505篇 |
2011年 | 528篇 |
2010年 | 328篇 |
2009年 | 293篇 |
2008年 | 402篇 |
2007年 | 394篇 |
2006年 | 395篇 |
2005年 | 358篇 |
2004年 | 289篇 |
2003年 | 252篇 |
2002年 | 207篇 |
2001年 | 117篇 |
2000年 | 100篇 |
1999年 | 76篇 |
1998年 | 60篇 |
1997年 | 54篇 |
1996年 | 60篇 |
1995年 | 42篇 |
1994年 | 60篇 |
1993年 | 33篇 |
1992年 | 43篇 |
1991年 | 56篇 |
1990年 | 57篇 |
1989年 | 52篇 |
1988年 | 47篇 |
1987年 | 39篇 |
1985年 | 46篇 |
1984年 | 68篇 |
1983年 | 34篇 |
1982年 | 48篇 |
1981年 | 39篇 |
1980年 | 40篇 |
1979年 | 31篇 |
1978年 | 33篇 |
1977年 | 46篇 |
1976年 | 32篇 |
1975年 | 32篇 |
1974年 | 32篇 |
1973年 | 30篇 |
排序方式: 共有7471条查询结果,搜索用时 468 毫秒
211.
Ion-molecule reactions between the O=P(OCH(3))(2) (+) phosphonium ions and five aliphatic esters (methyl acetate, methyl propionate, methyl 2-methylpropionate, methyl butyrate and ethyl acetate) were performed in a quadrupole ion trap mass spectrometer. The O=P(OCH(3))(2) (+) phosphonium ions, formed by electron ionization from neutral trimethyl phosphite, were found to react with aliphatic esters to give an adduct ion [RR'CHCOOR", O=P(OCH(3))(2)](+), which loses spontaneously a molecule of ketene CH(2)=CO or substituted ketenes RR'C=CO. Isotope-labeled methyl acetate was used to elucidate fragmentation mechanisms. The potential energy surface obtained from B3LYP/6-31G(d,p) calculations for the reaction between O=P(OCH(3))(2) (+) and methyl acetate is described. 相似文献
212.
The reaction of (R(2)PCH(2)SiMe(2))(2)NM (PNP(R)M; R = Cy; M = Li, Na, MgHal, Ag) with L(2)ReOX(3) [L(2) = (Ph(3)P)(2) or (Ph(3)PO)(Me(2)S); X = Cl, Br] gives (PNP(Cy))ReOX(2) as two isomers, mer,trans and mer,cis. These compounds undergo a double Si migration from N to O at 90 degrees C to form (POP(Cy))ReNX(2) as a mixture of mer,trans and fac,cis isomers. Additional thermolysis effects migration of CH(3) from Si to Re, along with compensating migration of halide from Re to Si. DFT calculations on various structural isomers support the greater thermodynamic stability of the POP/ReN isomer vs PNP/ReO and highlight the influence of the template effect on the reactivities of these species. 相似文献
213.
Aigars Vītiņš Ģirts Vītiņš Jānis Krastiņš Ints Šteins Ilmārs Zālīte Andrejs Lūsis 《Journal of Solid State Electrochemistry》1998,2(5):299-307
Ceramic specimens have been obtained from the powder of ZrO2-7.5 mol% Y2O3 having a specific surface area of 30 m2/g synthesized in air plasma. The novelty of this research lies in the fact that the plasma process makes it possible to prepare
so-called nanopowders with a particle size less than 100 nm, possessing specific physical, chemical and technological properties.
The sintered density of the specimens was 94–96% of the theoretical value, 6.001 g/cm3. The X-ray diffraction pattern of the specimens corresponded to a face-centered cubic lattice. Impedance in the frequency
range of 100 Hz–15 MHz and d.c. polarization curves in a potential range of −10 to 10 mV were measured in the temperature
range 200–850 °C in heating and cooling cycles. The intragrain, the grain boundary and the total bulk conductivities, the
electrode polarization resistance and their activation energies were determined. The thermal stability of the studied system
was proved in three measurement series up to 600–850 °C in heating and cooling cycles. The results obtained have shown that
the conductivity of ZrO2-7.5 mol% Y2O3 ceramics is not solely a function of temperature, but also depends on the previous thermal state of the ceramics.
Received: 16 October 1997 / Accepted: 19 January 1998 相似文献
214.
Ligand substitution of the mixed-metal clusters FeRu2(CO)12 and Fe2Ru(CO)12 with triphenylphosphine and trimethylphosphite has been studied. Mono- and di-substituted derivatives have been synthesized and characterized structurally. The following crystal and molecular structures are reported: Fe2Ru(CO)11PPh3: triclinic, space group P, a 9.203(2), b 11.903(3), c 15.117(4) Å, α 81.54(2), β 87.28(2), γ 66.72(2)°, Z = 2; Fe2Ru(CO)11P(OMe)3: orthorhombic, space group Pna21, a 17.220(5), b 14.572(4), c 8.708(6) Å, Z = 4, FeRu2(CO)11PPh3: monoclinic, space group P21/n, a 11.435(3), b 16.034(5), c 16.642(4) Å, β 93.35(2)°, Z = 4; FeRu2(CO)10(PPh3)2: orthorhombic, space group Pccm, a 14.854(4), b 17.180(7), c 16.786(12) Å, Z = 4.Ligand substitution is found to occur preferentially at the ruthenium centers of the FeRu2 and Fe2Ru clusters. Monosubstitution causes expansion of both of the clusters while the overall geometry is practically unchanged. Disubstitution of FeRu2(CO)12 causes contraction of the cluster and leads to a formation of carbonyl bridges. The structural trends have been interpreted in terms of electronic and packing effects of ligand substitution. The X-ray structures of Fe2Ru(CO)12 and FeRu2(CO)12 are not known; the ligand substitution studies indicate that Fe2Ru(CO)12 has the same structure as Fe3(CO)12, and that FeRu3(CO)12 does not have a Ru3(CO)12 structure as postulated previously from the IR studies. 相似文献
215.
In the present work
as well as HRO. radicals were generated in the photochemical interaction of 1,2-benzanthracene with -ethyl phenyl hydroperoxide /HROOH/ in C6H6 and CCl4 at 304 K.
radicals were trapped by C6H6. The main reaction of HRO. radicals is hydrogen abstraction from the hydroperoxide group of HROOH. Although OH radicals are less selective, the hydrogen abstraction is the main process during their interaction with aromatics in contrast to reactions in aqueous solutions, where addition to the benzene ring is the rate-determining process in CCl4:
相似文献
216.
217.
Marian Čerňanský Přemysl Vaněk Karel Král Radmila Krupková 《Monatshefte für Chemie / Chemical Monthly》2002,133(6):799-806
Summary. In this investigation the crystallization of PbTiO3 upon annealing of pure nanopowders and PbTiO3–SiO2 (1:1 v/v) nanocomposite powders prepared by the sol-gel technique was studied. Using X-ray diffraction phase analysis, the
start of PbTiO3 crystallization in pure PbTiO3 powders was detected at 400°C. Distinct crystallization of PbTiO3 in PbTiO3–SiO2 nanocomposites starts at 700°C, whereas SiO2 remains amorphous. There are indications that an interface interaction between the PbTiO3 and the SiO2 phase plays an important role in hindering the crystallization of PbTiO3. The particle size (size of coherently scattering regions) was estimated from the broadening of the X-ray diffraction line
profiles. The average size of PbTiO3 nanocrystallites increases with temperature and time of annealing, the influence of temperature being more significant than
that of the annealing time. Differential scanning calorimetry confirmed the results of the X-ray diffraction with respect
to the start of the crystallization. Laser beam scattering and scanning electron microscopy provided the statistical distribution
of the grain size and the morphology of the powder grains, showing that each grain of the powders contains several nanocrystallites
(coherently scattering regions).
Received October 4, 2001. Accepted (revised) December 14, 2001 相似文献
218.
Marchand C Nguyen CH Ward B Sun JS Bisagni E Garestier T Hélène C 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(9):1559-1563
Sequence-specific DNA recognition can be achieved by oligonucleotides that bind to the major groove of oligopyrimidine x oligopurine sequences. These intermolecular structures could be used to modulate gene expression and to create new tools for molecular biology. Here we report the synthesis and biochemical characterization of triple helix-specific DNA cleaving reagents. It is based on the previously reported triplex-specific ligands, benzo[e]pyridoindole (BePI) and benzo[g]pyridoindole (BgPI), covalently attached to ethylenediaminotetraacetic acid (EDTA). In the presence of iron, a reducing agent and molecular oxygen, BgPI-EDTA x FeII but not BePI-EDTA x FeII induced a double-stranded cut in a plasmid DNA at the single site where a triplex-forming oligonucleotide binds. At single nucleotide resolution, it was found that upon triplex formation BePI-EDTA x FeII led to cleavage of the pyrimidine strand and protection of the purine strand. BgPI-EDTA x FeII cleaved both strands with similar efficiency. The difference in cleavage efficiency between the two conjugates was rationalized by the location of the EDTA x FeII moiety with respect to the grooves of DNA (major groove: BePI-EDTA x FeII, minor groove: BgPI-EDTA x FeII). This work paves the way to the development of a new class of triple helix directed DNA cleaving reagents. Such molecules will be of interest for sequence-specific DNA cleavage and for investigating triple-helical structures, such as H-DNA, which could play an important role in the control of gene expression in vivo. 相似文献
219.
A novel transesterification reaction between acetylated maritime pine sapwood (Pinus pinaster Soland) and methyl benzoate (MB), in the presence of dibutyltin oxide (DBTO) as a catalyst, was performed. Reaction was confirmed by Fourier-transform infrared spectroscopy (FTIR) and 13C nuclear magnetic resonance cross-polarisation with magic-angle spinning (NMR CP MAS) analysis: signals corresponding to benzoylated wood were identified and, when transesterification was performed with ethyl trimethylsilylacetate (ETMSA), characteristic trimethylsilyl groups were detected. The acetyl/benzoyl exchange rate was found to increase with increasing amount of DBTO, temperature and reaction time and a concurrent deterioration of the woody material was evidenced. 相似文献
220.
Lilian F. J. Noël Ian A. Maxwell Willy J. M. Van Well Anton L. German 《Journal of polymer science. Part A, Polymer chemistry》1994,32(11):2161-2168
Recently a model has been developed capable of predicting absolute monomer concentrations and their ratios in the polymer, aqueous, and monomer droplet phases as a function of conversion in batch emulsion copolymerizations without using any adjustable parameters. In this article the sensitivity of model predictions of composition drift toward deviations of 10% in all model parameters (maximum swellabilities of monomer in the polymer phase, water solubilities, reactivity ratios, and monomer and polymer densities) was estimated using the monomer combination methyl methacrylate-styrene as an example. From the sensitivity analysis it can be concluded that the reactivity ratios are the most important parameters affecting composition drift. The effects of deviations in maximum swellabilities and monomer and polymer densities on composition drift can be neglected, while the water solubility is important only in those cases where the amount of monomer in the aqueous phase cannot be neglected as compared with the total monomer amount. © 1994 John Wiley & Sons, Inc. 相似文献
|