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991.
A side‐chain polysiloxane cholesteric liquid crystalline elastomer (ChLCE) with binaphthalene derivate as crosslinkings and cholesterol derivate as liquid crystalline monomers was designed and synthesized. A binaphthyl chiral dopant (CD) was synthesized as well. The chemical structures and liquid crystalline properties of the ChLCE and the CD were characterized by Fourier transform infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, element analyses, differential scanning calorimetry and polarizing optical microscopy measurements. The helical twisting power of the ChLCE exhibited a turning point with changing temperature and was smaller than that of the CD. In addition, the effect of the ChLCE on phase transition temperatures and thermal‐optical properties of a liquid crystal that show smectic A (SmA)‐cholesteric (Ch) phase transition was studied. Worthily, the testing of the reflection wavelength with changing temperature suggested that the adding of the ChLCE in liquid crystals that show SmA‐Ch phase transition can expedite their SmA‐Ch transition. In addition, the network structure of the ChLCE may play a significant role in the accelerating of the transition. These properties provided theoretical and experimental foundations for applying ChLCE in thermally sensitive liquid crystal devices requiring fast response, such as thermally controllable windows, materials and displays. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
992.
993.
Latifa Latrous Jeanine Tortajada Violette Haldys Emmanuelle Léon Catarina Correia Jean‐Yves Salpin 《Journal of mass spectrometry : JMS》2013,48(7):795-806
Gas‐phase interactions of organotins with glycine have been studied by combining mass spectrometry experiments and quantum calculations. Positive‐ion electrospray spectra show that the interaction of di‐ and tri‐organotins with glycine results in the formation of [(R)2Sn(Gly)‐H]+and [(R)3Sn(Gly)]+ ions, respectively. Di‐organotin complexes appear much more reactive than those involving tri‐organotins. (MS/MS) spectra of the [(R)3Sn(Gly)]+ ions are indeed simple and only show elimination of intact glycine, generating the [(R)3Sn]+ carbocation. On the other hand, MS/MS spectra of [(R)2Sn(Gly)‐H]+complexes are characterized by numerous fragmentation processes. Six of them, associated with elimination of H2O, CO, H2O + CO and formation of [(R)2SnOH]+ (?57 u),[(R)2SnNH2]+( ?58 u) and [(R)2SnH]+ (?73 u), are systematically observed. Use of labeled glycines notably concludes that the hydrogen atoms eliminated in water and H2O + CO are labile hydrogens. A similar conclusion can be made for hydrogens of [(R2)SnOH]+and [(R2)SnNH2]+ions. Interestingly, formation [(R)2SnH]+ ions is characterized by a migration of one the α hydrogen of glycine onto the metallic center. Finally, several dissociation routes are observed and are characteristic of a given organic substituent. Calculations indicated that the interaction between organotins and glycine is mostly electrostatic. For [(R)2Sn(Gly)‐H]+complexes, a preferable bidentate interaction of the type η2‐O,NH2 is observed, similar to that encountered for other metal ions. [(R)3Sn]+ ions strongly stabilize the zwitterionic form of glycine, which is practically degenerate with respect to neutral glycine. In addition, the interconversion between both forms is almost barrierless. Suitable mechanisms are proposed in order to account for the most relevant fragmentation processes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
994.
995.
Dr. Seiji Shirakawa Prof. Dr. Keiji Maruoka 《Angewandte Chemie (International ed. in English)》2013,52(16):4312-4348
Phase‐transfer catalysis has been recognized as a powerful method for establishing practical protocols for organic synthesis, because it offers several advantages, such as operational simplicity, mild reaction conditions, suitability for large‐scale synthesis, and the environmentally benign nature of the reaction system. Since the pioneering studies on highly enantioselective alkylations promoted by chiral phase‐transfer catalysts, this research field has served as an attractive area for the pursuit of “green” sustainable chemistry. A wide variety of asymmetric transformations catalyzed by chiral onium salts and crown ethers have been developed for the synthesis of valuable organic compounds in the past several decades, especially in recent years. 相似文献
996.
Sandeep Ippalapalli A. Dileep Ranaprathapan Dr. Sachchida N. Singh Dr. G. Harikrishnan 《Chemphyschem》2013,14(6):1190-1196
Two‐way multicomponent diffusion processes in polymeric nanocomposite foams, where the condensed phase is nanoscopically reinforced with impermeable fillers, are investigated. The diffusion process involves simultaneous outward permeation of the components of the dispersed gas phase and inward diffusion of atmospheric air. The transient variation in thermal conductivity of foam is used as the macroscopic property to track the compositional variations of the dispersed gases due to the diffusion process. In the continuum approach adopted, the unsteady‐state diffusion process is combined with tortuosity theory. The simulations conducted at ambient temperature reveal distinct regimes of diffusion processes in the nanocomposite foams owing to the reduction in the gas‐transport rate induced by nanofillers. Simulations at a higher temperature are also conducted and the predictions are compared with experimentally determined thermal conductivities under accelerated diffusion conditions for polyurethane foams reinforced with clay nanoplatelets of varying individual lamellar dimensions. Intermittent measurements of foam thermal conductivity are performed while the accelerated diffusion proceeded. The predictions under accelerated diffusion conditions show good agreement with experimentally measured thermal conductivities for nanocomposite foams reinforced with low and medium aspect‐ratios fillers. The model shows higher deviations for foams with fillers that have a high aspect ratio. 相似文献
997.
998.
以二丙胺异构体(二正丙胺DPA和二异丙胺D-iPA)为结构导向剂,在200℃加热2组反应原料物质的量之比不同的初始凝胶,合成出了高结晶度的磷酸铝分子筛AlPO4-11。利用X射线粉末衍射分析、元素分析等表征手段,研究了凝胶的晶化过程和液相的pH值以及Al和P的浓度演化。初始凝胶各组分物质的量之比为nAl2O3:nP2O5:nDPA/D-iPA:nH2O2=1.0:1.0:1.2:75时,以DPA为结构导向剂,晶化过程中无中间相生成,而以D-iPA为结构导向剂时,晶化过程中生成了具有12元环孔道结构的磷酸铝分子筛AlPO4-5中间相;初始凝胶各组分物质的量之比为nAl2O3:nP2O5:nDPA/D-iPA:nH2O2=1.0:1.0:1.0:75时,以DPA为结构导向剂,晶化过程中生成了具有18元环孔道结构的磷酸铝分子筛VPI-5中间相,而以D-iPA为结构导向剂时,晶化过程中同时出现了VPI-5及AlPO4-5两种中间相。表明对于同一种有机胺,凝胶物质的量之比的改变影响了其结构导向效应。理论计算结果显示质子化的DPA及D-iPA中N原子上的电荷有差异,表明有机胺的结构微调影响其结构导向效应,但该影响依赖于凝胶组成。 相似文献
999.
Min Huang Wen-Jing Chen Ying Zhou Ru Feng Jie Fu Jing-Yi Ma Xiang-Shan Tan Chi-Yu He Qi-Ming Zhang Wen-Yi He Yu-Lin Deng Yu-Kui Zhang Xian-Feng Zhang Yan Wang 《中国化学快报》2013,24(9):840-844
The chiral separations of four pharmaceutical racemates which contain N-alkyl groups were satisfactorily resolved using SBE-β-CD as a chiral mobile phase additive(CMPA)in a RP-HPLC system(the resolution is 2.701 for ondansetron hydrochloride,1.996 for sulpiride,1.293 for clenbuterol hydrochloride and 0.816 for omeprazole).In addition,the effects of different parameters such as CD type and CD concentration were investigated.The separation mechanism arises through the combination of several potential interactions,including electrostatic interactions as well as hydrogen bonding interactions and hydrophobic inclusion interactions,which allow for the SBE-β-CD–drug complexation with strong stereoselectivity and stability.The resolution also relates to the number and location of N atoms in the enantiomers.This method will be applicable to the isolation of various types of biologically important enantiomers containing N-alkyl groups. 相似文献
1000.
采用溶胶-浸渍法,以CuSO4为烧结助剂在碳纤维表面制得TiO2涂层。利用XRD、SEM和TEM分析了涂层相组成及形貌,通过静态等温氧化实验考察了涂层碳纤维抗氧化性能。结果表明:掺杂CuSO4制备TiO2涂层均匀完整致密,涂层相组成均为锐钛矿型TiO2,且涂层厚度从45 nm提高至185 nm;与普通TiO2涂层碳纤维相比,完全氧化温度从667 ℃上升到800 ℃,氧化活化能从118.390 kJ·mol-1提高到152.562 kJ·mol-1,CuSO4的掺杂大大提高了TiO2涂层碳纤维的抗氧化性能。 相似文献