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971.
von Niessen Wolfgang Cederbaum Lorenz S. Kraemer Wolfgang P. 《Theoretical chemistry accounts》1977,44(1):85-93
The vertical valence ionization potentials of cyclopropane, ethylene oxide and ethylene imine are calculated by a many-body Green's function method. For C3H6 the ordering of the ionization potentials is 2e(), 1e(), 2a1(), 1a2(), 1e(). The assignment of the 2a1 and the 1a2 ionization potentials which has been controversial is thus clarified. The ordering is in agreement with the result obtained via Koopmans' theorem. For ethylene oxide and ethylene imine Koopmans' theorem fails in predicting the correct order of ionic states. For C2H4O the ordering of the ionization potentials is 2b
1(), 4a
1, 1a
2(), 2b
2,3a
1, 1b
1(), 1b
2, 2a
1 and for C2H5N 6a, 5a, 3a, 2a, 4a, 3a, 1a, 2a. The agreement of the computed ionization potentials with the experimental values is very satisfactory. 相似文献
972.
猴头菌寡糖的分离及其结构确定 总被引:2,自引:0,他引:2
报道了从猴头菌浸膏中分离出猴头菌二糖和三糖, 并确定了其化学结构. 相似文献
973.
去溶温度对微波诱导等离子体原子吸收光谱法分析性能影响的研究 总被引:1,自引:0,他引:1
本文研究了超声雾化微波诱导等离子体原子吸收光谱法(UN-MIP-AAS)中,去溶温度对选择载气流量、微波前向功率等因素的影响,并定量考察了去溶效果。通过改善去溶条件,提高了UN-MIP-AAS的分析性能。 相似文献
974.
Summary This paper deals for the first time with a direct method for analysis of the α and β anomers of bile acid esters of glucose
by capillary gas chromatography (CGC) without the need for a hydrolytic step. The bile acid esters were derivatized to their
trimethylsilyl (TMS) ethers, which in turn were chromatographed on a short (7m) metal capillary column chemically coated with
a thin (0.15 μm) film of thermostable, non-polar polydimethylsiloxane. Satisfactory CGC separation of the isomeric bile acid
esters was achieved on the column; the β anomers eluted before the corresponding α isomers. Particularly noteworthy is that
the α anomers are partially isomerized to the corresponding β anomers, and that both anomers are partially decomposed during
CGC analysis, demonstrating the chemical specificity and thermal instability of the bile acid esters. 相似文献
975.
Investigation of pyrolysis of chinese coals using thermal analysis/mass spectrometry 总被引:2,自引:0,他引:2
Li X. Matuschek G. Herrera M. Wang H. Kettrup A. 《Journal of Thermal Analysis and Calorimetry》2003,71(2):601-612
TA/MS (thermal analysis coupled with mass spectrometry) was applied to the pyrolysis of Chinese coals with different ranks.
A total of 13 Chinese coals were investigated. The samples were deliberately chosen to represent the 13 types of Chinese coals
according to the Chinese coal classification system. The experiments were carried out in an argon atmosphere with a flow rate
of 150 ml min-1. The samples were heated from 40 up to 1200°C with a constant heating rate of 10 k min-1. The main evolved pyrolysis products were identified through the on-line recorded mass spectra. The thermal and evolution
behavior was compared between the coals. The results showed a strong thermal and evaluation behavior dependence on the coal
rank. Different aliphatic fragments and also some aromatic substances, which are of environmental concern (BTX, PAHs), were
found to be released depending on the different types of coal.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
976.
The complexes Ln(NO3)3(OPCy3)3(EtOH)x (Cy = cyclohexyl, C6H11x = 0 for Ln = Eu, Er, x = 0.5 for Ln = La, Nd and x = 1 for Ln = Tm, Yb) have been prepared by reaction of lanthanide nitrates with Cy3PO in ethanol. The single crystal X-ray structures for Ln = La, Nd, Eu, Er, Tm and Yb are reported. The structures for Ln = La–Eu have two molecules in the unit cell in which the nitrates are all bound as bidentate ligands. The unit cell for Ln = Er contains two distinct molecules; one with three bidentate nitrates and one with two bidentate and one monodentate nitrate. The Tm and Yb complexes have one molecule in the unit cell with two bidentate and one monodentate nitrate ligands. The monodentate nitrates are hydrogen bonded to ethanol in the Tm and Yb structures but not in the Er complex. The infrared spectra of the three classes of complex do not readily permit identification of the monodentate nitrate groups. Electrospray mass spectrometry indicates that redistribution/ionisation reactions occur in solution. Ions formed by solvolysis reactions are attributed to gas phase processes associated with the electrospray technique. Tandem mass spectrometry for the La, Ho and Yb complexes shows that in the gas phase loss of Cy3PO is the sole fragmentation pathway for all but the Yb complex where the higher energy required for initial fragmentation leads to a more complex fragmentation pattern. 相似文献
977.
The behaviour of gold and elements impeding its x-ray fluorescence spectrometric (XRF) determination, namely zinc, lead and arsenic, was studied during their extraction from hydrochloric acid, nitric acid, and aqua regia solutions using tributyl phosphate as a solid extractant [SE(TBP)]. Extraction of gold from pulps after aqua regia leaching was found to be the most favourable approach for the quantitative and selective recovery of gold. The gold distribution ratio, DAu, is ca. 104 ml g?1. For extraction from hydrochloric acid solutions the DAu value also exceeds 104 in the whole range of gold concentrations studied (10?8?10?4 M), but it decreases substantially with increasing extraction temperature, from 5 × 105 ml g?1 at 20°C to 9 × 103 ml g?1 at 70°C. An anomalously high distribution ratio of lead, DPb ≈ 103 ml g?1, was observed during extraction from hydrochloric solutions in the presence of chlorine. This could be explained by the formation of the chloro complexes of lead(IV). An XRF method for the determination of gold in natural samples was developed, which includes back-extraction of gold from SE(TBP) using a hot 0.025 M thiourea solution, providing a thin sample layer for secondary XRF. For 25 g of sample material the limit of determination is 10 ng g?1 (10?6%). The accuracy of the technique was checked using different reference materials. The results agreed within 10%. 相似文献
978.
979.
980.
Yoshida N Ishizuka T Yofu K Murakami M Miyasaki H Okada T Nagata Y Itaya A Cho HS Kim D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(12):2854-2866
A series of zinc(II) porphyrin-imide dyads (ZP-Im), in which an electron donating ZP moiety is directly connected to an electron accepting imide moiety in the meso position, have been prepared for the examination of energy gap dependence of intramolecular electron transfer reactions with large electronic coupling. The nearly perpendicular conformation of the imide moiety towards the porphyrin plane has been revealed by Xray crystal structures. The energy gap for charge separation, 1ZP* - Im --> ZP+ - Im-, is varied by changing the electron accepting imide moiety to cover a range of about 0.8 eV in DMF. Definitive evidence for electron transfer has been obtained in three solvents (toluene, THF, and DMF) through picosecond-femtosecond transient absorption studies, which have allowed us to determine the rates of photoinduced charge separation, 1ZP* - Im --> ZP+ - Im-, and subsequent thermal charge recombination ZP+ - Im- --> ZP - Im. The free-energy gap dependence (energy gap law) has been probed from the normal to the nearly top region for the charge separation rate alone, and only the inverted region for the charge recombination rate. Although both of the energy gap dependencies can be approximately reproduced by means of the simplified semiclassical equation, when we take into consideration the effect of the high frequency vibrations replaced by one mode of averaged frequency, many features, including the effects of solvent polarity and the electron tunneling matrix element on the energy gap law, differ considerably from those of the previously studied porphyrin-quinone systems, which have weaker interchromophore electronic interactions. 相似文献