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961.
This paper describes the determination of Henry's law coefficients by means of the EPICS (equilibrium partitioning in closed systems) technique in combination with SPME (solid-phase microextraction). The use of solid-phase microextraction-sampling allowed us to extend the possibilities of the equilibrium partitioning in closed systems technique with respect to the range of Henry's law coefficients which can be measured. Whereas the equilibrium partitioning in closed systems technique is limited to determine air–water equilibrium partitioning of volatile compounds with Henry's law coefficients of at least 0.06 (dimensionless), the current method allowed to measure coefficients between 0.0023 and 13.5. In this way Henry's law coefficients of 20 compounds, being in a range covering five orders of magnitude, were measured with relative standard deviations between 1.0 and 19.8% (mean standard deviation: 5.7%; median of standard deviations: 4.8%, n=99). Several types of compounds were examined i.e. aliphatic hydrocarbons, monocyclic and polycyclic aromatic hydrocarbons, chlorinated and fluorinated compounds, ethers and esters, biphenyl and N-containing compounds, including compounds for which availability of experimental Henry's law coefficients is limited. Measurement of the equilibrium partitioning in the 2 to 25°C range allowed to establish relations of Henry's law coefficient as a function of temperature. 相似文献
962.
Sincetheearlyl980sinterestin0rganicpoIyvalentiodinec0mp0undshasexperiencedaresurgence'.Afewexamplesofhomo-couplingreacti0nsviathesec0mpoundshavebeenrep0rted-.Wef0undthatl-aIkyneswereeasytoc0upleinthepresenceofPhI(OAc)=orPhI(OH)OTs,catalyticCulandbase,t0aff0rdc0njugateddiynes.l,3-Diyneplaysanimportantr0leinstudiesofm0lecularrec0ngnition',innaturalpr0ducts',andinsynthesis.AlthoughEglintonreaction',Cadi0t-Chalkiewiczc0upling'andGlaserreaction5haveprovidedc0nvenientmeth0dst0synthesizeconjug… 相似文献
963.
I. V. Kostyuchenko G. P. Okonnishnikova E. V. Shulishov Yu. V. Tomilov 《Russian Chemical Bulletin》2004,53(10):2257-2261
3-Cyano- and 3-(alkoxycarbonyl)spiro[2-pyrazoline-5,1’-cyclopropane] and 5-phenylspiro[1-pyrazoline-3,1’-cyclopropane] undergo unusual transformations into 3(5)-substituted 5(3)-(2-hydroperoxyethyl)pyrazoles in the presence of atmospheric oxygen. The conditions for the formation of hydroperoxides (e.g., in oxygen-saturated solutions of spiro[2-pyrazoline-5,1’-cyclopropanes] in CHCl3) and their conversion into (2-hydroxyethyl)pyrazoles or the corresponding nitrates under the action of nitrosating reagents were considered.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2160–2164, October, 2004. 相似文献
964.
In the presence of low molecular weight organic acids (formic, acetic, propionic and malonic), inorganic selenium(IV) is converted by UV irradiation to volatile selenium carbonyl, dimethylselenide and diethylselenide, depending on the acid used. Gas chromatography–mass spectrometry analysis of the volatile products shows that, in 0.7 M formic acid solution, approximately 60–70% (v/v) SeH2 and 30–40% (v/v) SeCO are formed. The presence of nitrate ion appears to increase threefold the formation of SeCO while completely suppressing formation of SeH2. Copyright © 2003 Crown in the right of Canada. Published by John Wiley & Sons, Ltd. 相似文献
965.
MNA/PMMA有机薄膜光波导 总被引:2,自引:0,他引:2
研究出MNA/PMMA有机薄膜光波导。用棱镜耦合器进行了波导参数的测量,发现薄膜呈现各向异性,有较大的双折射。 相似文献
966.
Fuping He Yiwang Chen Xiaohui He Muqing Chen Weihua Zhou Qing Wu 《Journal of polymer science. Part A, Polymer chemistry》2009,47(16):3990-4000
Vinyl‐type copolymerization of norbornene (NBE) and 5‐NBE‐2‐yl‐acetate (NBE‐OCOMe) in toluene were investigated using a novel homogeneous catalyst system based on bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3. The copolymerization behavior as well as the copolymerization conditions, such as the levels of B(C6F5)3 and AlEt3, temperature, and monomer feed ratios, which influence on the copolymerization were examined. Without combination of AlEt3, the catalytic bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3 exhibited very high catalyst activity for polymerization of NBE. Combination of AlEt3 in catalyst system resulted in low conversion for polymerization of NBE. For copolymerization of NBE and NBE‐OCOMe, involvement of AlEt3 in catalyst is necessary. Slight addition of NBE‐OCOMe in copolymerization of NBE and NBE‐OCOMe gives rise to significant increase of catalyst activity for catalytic system bis(β‐ketonaphthylamino)Ni(II)/B(C6F5)3/AlEt3. Nevertheless, excess increase of the NBE‐OCOMe content in the comonomer feed ratios results in decrease of conversion as well as activity of catalyst. The achieved copolymers were confirmed to be vinyl‐addition copolymers through the analysis of FTIR, 1H NMR, and 13C NMR spectra. 13C NMR studies further revealed the composition of the copolymer and the incorporation rate was 7.6–54.1 mol % ester units at a content of 30–90 mol % of the NBE‐OCOMe in the monomer feeds ratios. TGA analysis results showed that the copolymer exhibited good thermal stability (Td > 410 °C) and failed to observe the glass transitions temperature over 300 °C. The copolymers are confirmed to be noncrystalline by WAXD analysis results and show good solubility in common organic solvents. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3990–4000, 2009 相似文献
967.
通过利用地理信息系统(GIS)的空间分析功能,对杭州市地面水中的有机污染现状(用高锰酸盐指数CODMn表示)进行区域分析,使环境信息数据定性、定位、可视,并能便捷地找出环境信息在时间上和空间上所呈现的规律性,为GIS深入应用于环境科学领域作了有益的尝试。 相似文献
968.
969.
Hans R. Kricheldorf Heiko Hachmann‐Thiessen 《Journal of polymer science. Part A, Polymer chemistry》2005,43(15):3268-3277
ε‐Caprolactone and glycolide were copolymerized in bulk either with tin(II) 2‐ethylhexanoate (SnOct2) or with bismuth(III) n‐hexanoate (BiHex3) as initiators and with tetra(ethylene glycol) as a coinitiator. The temperature was varied from 100 to 160 °C. The sequences were characterized with 1H and 13C NMR spectroscopy. Surprisingly, it was found that higher temperatures favored the formation of alternating sequences. Furthermore, the content of alternating dyads was significantly higher when BiHex3 was used instead of SnOct2. An increase in reaction time caused partial randomization of the sequences regardless of the initiator. Size exclusion chromatography measurements in chloroform yielded number‐average molecular weights in agreement with the feed ratios. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3268–3277, 2005 相似文献
970.
The oxidation of 34 organic sulphides hy 2,2′-hipyridinium chlorochromate (BPCC) resulted in the formation of the corresponding
sulphoxides. The reaction is first order with respect to both BPCC and the sulphide, and is catalysed by hydrogen ions. The
hydrogen-ion dependence has the form:k
obs = a+b[H+]. The oxidation was studied in 19 different organic solvents. An analysis of the solvent effect by Swain’s equation showed
that the both cation-and anion-solvating powers of the solvents play important roles. The rates of oxidation meta- andp-substituted phenyl methyl sulphides were correlated with Charton’s LDR equation. The rates of theo-compounds showed excellent correlation with the LDRS equation. Oxidation of thep-compounds is more susceptible to the delocalizationeffect. Oxidation of themcompounds exhibited a greater dependence on the field effect. In the oxidation of theo-compounds, the contribution of delocalized effect is slightly more than that of the field effect. The oxidation of alkyl
phenyl sulphides is subject to both polar and steric effects of the alkyl groups. Polar reaction constants are negative, indicating
an electron-deficient sulphur centre in the rate-determining step. A mechanism involving formation of a sulphurane intermediate
in the slow step has been proposed. 相似文献