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Adam W Alsters PL Neumann R Saha-Möller CR Seebach D Beck AK Zhang R 《The Journal of organic chemistry》2003,68(21):8222-8231
The epoxidation of allylic alcohols is shown to be efficiently and selectively catalyzed by the oxidatively resistant sandwich-type polyoxometalates, POMs, namely [WZnM(2)(ZnW(9)O(34))(2)](q)(-) [M = OV(IV), Mn(II), Ru(III), Fe(III), Pd(II), Pt(II), Zn(II); q = 10-12], with organic hydroperoxides as oxygen source. Conspicuous is the fact that the nature of the transition metal M in the central ring of polyoxometalate affects significantly the reactivity, chemoselectivity, regioselectivity, and stereoselectivity of the allylic alcohol epoxidation. For the first time, it is demonstrated that the oxovanadium(IV)-substituted POM, namely [ZnW(VO)(2)(ZnW(9)O(34))(2)](12-), is a highly chemoselective, regioselective, and also stereoselective catalyst for the clean epoxidation of allylic alcohols. A high enantioselectivity (er values up to 95:5) has been achieved with [ZnW(VO)(2)(ZnW(9)O(34))(2)](12)(-) and the sterically demanding TADOOL-derived hydroperoxide TADOOH as regenerative chiral oxygen source. Thus, a POM-catalyzed asymmetric epoxidation of excellent catalytic efficiency (up to 42 000 TON) has been made available for the development of sustainable oxidation processes. The high reactivity and selectivity of this unprecedented oxygen-transfer process are mechanistically rationalized in terms of a peroxy-type vanadium(V) template. 相似文献
75.
O.V. Kallistov Ju.E. Svetlov I.G. Silinskaya V.P. Sklizkova V.V. Kudriavtsev M.M. Koton 《European Polymer Journal》1982,18(12):1103-1107
The hydrodynamic characteristics and weight-average molecular weights of some samples of poly-(4,4′-oxydiphenylene) pyromellitamic acid (I) and poly (4,4′-phenylene) pyromellitamic acid (II) in DMF have been obtained by sedimentation, viscometry and light scattering. For (I) the dependence of S0 on M was obtained and it was found that the hydrodynamic parameters depend on M up to M = 105. The experimental results were treated by using two models, viz. a Yamakawa-Fujii persistent chain and a rotational isomeric chain with free rotation about valence bonds. It was shown that the hydrodynamic behaviour of macromolecules of (I) with a pin-joint oxygen atom in the main chain is satisfactorily described by the rotational isomeric chain model with free rotation about valence bonds. The dependence of [η] on M was obtained and the constants K and a in an equation of the Mark-Kuhn-Houwink type were determined for (II). The flexibility of the chain was estimated and the Kuhn segment was found to be 200 Å using the Yamakawa-Fujii theory. The flexibilities of the chains of (I) and (II) are compared; it is shown that the rigidity of the chain of (II) without a pin-joint oxygen atom in the monomer unit is much higher than that of the chain of (I). The dependence of S0 on M obtained for (II) suggests that its macromolecules show a more pronounced tendency for formation of aggregates than those of (I). 相似文献
76.
激光光散射研究丙烯酰胺-二甲基二烯丙基氯化铵共聚物的溶液行为 总被引:6,自引:0,他引:6
用激光光散射技术表征了阳离子含量受控的丙烯酰胺 二甲基二烯丙基氯化铵共聚物 (简称P(AM DMDAAC) )在 0 1mol LNaCl溶液中的基本参数和溶液行为 .表观基本参数 : Mw ,app =5 0 4× 10 5g·mol- 1 、app =39 9nm和A2 ,APP =1 5× 10 - 4cm3·mol·g- 2 .动态光散射研究结果表明 ,扩散系数Dt 与角度、浓度皆呈非线性依赖关系 ,当C >C 或在较大的散射角域 ,Dt 偏离线性关系所预示的理论值而向减小的方向发展 ,表明存在缔合物 ;流体力学半径Rh 分布有大、小两个范围 ,并随温度升高向小尺寸方向发展 ,证明了体系中存在缔合行为以及升温的解缔合作用 .在一定条件下 ,“亚稳定性”的存在有力地旁证了体系的缔合行为 相似文献
77.
This paper compares the kinetics of exchanges of phenylethanethiolate ligands (PhC2S-) of the monolayer-protected clusters (MPCs) Au(38)(SC2Ph)(24) and Au(140)(SC2Ph)(53) with p-substituted arylthiols (p-X-PhSH), where X = NO(2), Br, CH(3), OCH(3), and OH. First-order rate constants at 293 K for exchange of the first ca. 25% of the ligands on the molecule-like Au(38)(SC2Ph)(24) MPC, measured using (1)H NMR, vary linearly with the in-coming arythiol concentration; ligand exchange is an overall second-order reaction. Remarkably, the second-order rate constants for ligand exchange on Au(38)(SC2Ph)(24) are very close to those of corresponding exchange reactions on the larger nanoparticle Au(140)(SC2Ph)(53) MPCs. These are the first results that quantitatively show that the chemical reactivity of different sized nanocrystals is almost independent of size; presumably, this is because the locus of the initial ligand exchanges is a common kind of site, thought to be the nanocrystal vertexes. The rates of later stages of exchange (beyond ca. 25%) differ for Au(38) and Au(140) cores, the latter being much slower presumably due to its larger terrace-like surface atom content. The reverse exchange reaction was studied for Au(38)(p-X-arylthiolate)(24) MPCs (X = NO(2), Br, and CH(3)), where the in-coming ligand is now phenylethanethiol. Remarkably, the rate constants of both forward and reverse exchanges display identical substituent effects, which implies a concurrent bonding of both in-coming and leaving ligands to the Au core in the rate-determining step, as in an associative mechanism. X = NO(2) gives the fastest rates, and the ratio of forward and reverse rate constants gives an equilibrium constant of K(EQ,PE) = 4.0 that is independent of X. 相似文献
78.
Rui Qi SONG * Jian Qing ZENG Bing ZHONG Guangzhou Institute of Chemistry Chinese Academy of Sciences Guangzhou State Key Laboratory of Coal Chemistry Institute of Coal Chemistry Chinese Academy of Sciences Taiyuan School of 《中国化学快报》2002,13(10)
We have studied the palladium-catalyzed alkoxycarbonylation of allyl bromide in supercritical (sc) CO2 and found the reaction rate in sc CO2 was lower than those in some organic solvents1. The possible reason was the lower solubility of sc CO2 for the palladium catalyst. As an effective approach to improve the solubility of varieties of solutes, cosolvent such as ethanol has been widely used in the sc CO2 extraction2,3. Based on the above consideration, we chose several organic reagents… 相似文献
79.
The glassy transition of the polyethylene terephthalate (PET) sampleswhich have been subjected to solvent induced crystallization (SINC) was investigated bymodulated differential scanning calorimetry (MDSC) and density measurement. The dif-ferential of heat capacity signal, d C_p/dT from MDSC, was used to monitor the SINCprocess. It reveals that the T_g temperature shifts to higher value with the advancement ofSINC. When the toluene-immersing time was longer (168h), the detection of T_g becomemore difficult, because some smaller peaks emerged at the lower temperatures and theseare explained as the movement of small segments in the amorphous region. These observedresults are due to the morphology and structure introduced by the SINC process. 相似文献
80.
A new calix[4]crown chemosensor based on dual sensing probes reveals Pb2+ ion selectivity over other metal ions, which arises from a hypsochromic shift of azo units in UV spectrum as well as a fluorescence enhancement of pyrenyl parts in fluorescence spectrum via a suppressed FRET. 相似文献