首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   144262篇
  免费   10555篇
  国内免费   6960篇
化学   69364篇
晶体学   1408篇
力学   10994篇
综合类   515篇
数学   39616篇
物理学   39880篇
  2024年   228篇
  2023年   1399篇
  2022年   2281篇
  2021年   2353篇
  2020年   2521篇
  2019年   2423篇
  2018年   12056篇
  2017年   11671篇
  2016年   8701篇
  2015年   3868篇
  2014年   3922篇
  2013年   5132篇
  2012年   9486篇
  2011年   16058篇
  2010年   9439篇
  2009年   9753篇
  2008年   10502篇
  2007年   12239篇
  2006年   3757篇
  2005年   4337篇
  2004年   3942篇
  2003年   3791篇
  2002年   2657篇
  2001年   1752篇
  2000年   1699篇
  1999年   1709篇
  1998年   1518篇
  1997年   1309篇
  1996年   1417篇
  1995年   1183篇
  1994年   1081篇
  1993年   957篇
  1992年   820篇
  1991年   726篇
  1990年   603篇
  1989年   538篇
  1988年   424篇
  1987年   406篇
  1986年   354篇
  1985年   346篇
  1984年   244篇
  1983年   212篇
  1982年   186篇
  1981年   150篇
  1980年   128篇
  1979年   93篇
  1978年   90篇
  1977年   70篇
  1975年   73篇
  1973年   82篇
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
981.
The micellization behavior of an anionic gemini surfactant, GA with nonionic surfactants C12E8 and C12E5 in presence of 0.1 M NaCl at 298 K temperature, has been studied tensiometrically in pure and mixed states, and the related physicochemical parameters (cmc, γ cmc, pC 20, Γ max, and A min) have been evaluated. Tensiometric profile (γ vs log [surfactant]), for conventional surfactants, generally consists of a single point of intersection; a gradually decreasing line (normally linear, or with slight curvature) ultimately saturates in γ at a particular [surfactant], corresponding to complete monolayer saturation. The gemini, in this report, led to two unequivocal breaks in the tensiometric isotherm. An attempt to the interpretation of the two breaks from molecular point of view is provided, depending solely on the chemical structure of the surfactant. The gemini, even in mixed state with the conventional nonionic surfactants C12E5 and C12E8, manifested the dual breaks; of course, the dominance of the feature decreases with increasing mole fraction of the nonionics in the mixture. Theories of Clint, Rosen, Rubingh, Motomura, Georgiev, Maeda, and Nagarajan have been used to determine the interaction between surfactants at the interface and micellar state of aggregation, the composition of the aggregates, the theoretical cmc in pure and mixed states, and the structural parameters according to Tanford and Israelachvili. Several thermodynamic parameters have also been predicted from those theories.  相似文献   
982.
By using hologram quantitative structure-activity relationship (HQSAR) and comparative molecular field analysis (CoMFA) methods, the relationships between the structures of 49 gallic acid derivatives and their analgesic activity have been investigated to yield statistically reliable models with considerable predictive power. The best HQSAR model was generated using atoms, bond and connectivity as fragment distinction parameters and fragment size 5-7 from a hologram length of 307 with 3 components. High conventional r2 (r2 = 0.825) and cross-validation r2 (r2(cv) = 0.726) values were obtained. CoMFA analyses varying lattice size and location, grid spacing, probe charges and using, Tripos standard and Indicator force field were performed. The best model was developed with 4 components using sp3-hybridized carbon atom with +1.0 charge as probe, grid spacing (2 A), lattice offset (1.0, 3.0, -2.5). The CoMFA model showed a conventional correlation coefficient r2 of 0.889 and across-validation r2(cv) equals to 0.633. The robustness and predictive ability of the HQSAR and CoMFA models have been validated by means of an external test set. The results indicate that both models possess high statistical quality in the prediction of analgesic potency of novel gallic acid analogs.  相似文献   
983.
Kinetics as well as the evolution of the agarose gel topology is discussed, and the agarose gelation mechanism is identified. Aqueous high melting (HM) agarose solution (0.5% w/v) is used as the model system. It is found that the gelation process can be clearly divided into three stages: induction stage, gelation stage, and pseudoequilibrium stage. The induction stage of the gelation mechanism is identified using an advanced rheological expansion system (ARES, Rheometric Scientific). When a quench rate as large as 30 deg C/min is applied, gelation seems to occur through a nucleation and growth mechanism with a well-defined induction time (time required for the formation of the critical nuclei which enable further growth). The relationship between the induction time and the driving force which is determined by the final setting temperature follows the 3D nucleation model. A schematic representation of the three stages of the gelation mechanism is given based on turbidity and rheological measurements. Aggregation of agarose chains is promoted in the polymer-rich phase and this effect is evident from the increasing mass/length ratio of the fiber bundles upon gelation. Continuously increasing pore size during gelation may be attributed to the coagulation of the local polymer-rich phase in order to achieve the global minimum of the free energy of the gelling system. The gel pore size determined using turbidity measurements has been verified by electrophoretic mobility measurements.  相似文献   
984.
A series of bridged bis(pyridinylimino) ligands were efficiently synthesized through the condensation reaction of 4,4′-methylene-bis(2,6-disubstituted aniline) with 2-pyridinecarboxaldehyde or 2-benzoylpyridine. They reacted with (DME)NiBr2 to form dinuclear Ni(II) complexes. All resultant compounds were characterized by elemental analysis, IR spectra as well as the single-crystal X-ray diffraction to confirm the structures of ligands and complexes. Activated with methylaluminoxane (MAO), these nickel complexes showed considerably good activities for ethylene oligomerization and polymerization. Their catalytic activities and the properties of PEs obtained were depended on the arched environment of ligand and reaction conditions.  相似文献   
985.
INTRODUCTIONAdsorption has been considered to be the best available technology for removing organics from water in the USSafe Drinking Water Act[1]. Due to many drawbacks of activated carbon[2-7], the most widely used adsorbent,hypercrosslinked polymeric adsorbents developed by Tsyurupa and Davankov[8] have been increasingly viewedas an alternative to activated carbon for selective removal of specific organic substances from contaminatedwater[9-12], and series of researches have been do…  相似文献   
986.
用等离子体增强化学气相沉积(PECVD)的方法,以固定的氢气(H2)流量和不同的硅烷(SiH4)和甲烷(CH4)流量比沉积了一系列的氢化非晶SiC(a-Si,C1-x-H)膜。用这种宽带隙的a-SixC1-x-H材料作为掺铒的基体材料,通过离子注入的方法得到掺铒的a-SixC1-x-H(a-SixC1-x-H:Er)膜。注入以后的样品经过不同温度的退火。用X射线光电子能谱(XPS)、红外吸收光谱(IR)、拉曼散射谱(Raman)等技术研究不同的SiH4/CH4流量比和退火温度对a-SixC1-x-H:Er发光强度的影响。结果表明,高温退火引起了膜中C的分凝,对饵的发光是不利的。通过低温和室温下铒发光强度的比较,表明这种材料具有较弱的温度猝灭效应。  相似文献   
987.
A series of well-defined two-armed polymers containing a crown ether core, poly(stearyl methacrylate)-crown ether-poly(stearyl methacrylate) (PSMA-crown-PSMA), with different molecular weight were synthesized via atom transfer radical polymerization (ATRP). The resultant polymers were characterized by 1H NMR and GPC. The self-assembly behaviors of this kind of polymer in selective solvents were studied by TEM, and it was found that polymers with different molecular weight can directly self-assemble into hollow spheres, solid spheres and a monolayer film with regular pores by varying molecular weight and water content. The possible molecular packing motels for their self-assembly behaviors were proposed.  相似文献   
988.
Fine particles were modified with a thin film of SnO2 by using a barrel sputtering system that is a dry process. The conditions for the preparation of SnO2 were studied by reactive sputtering onto a glass plate substrate. The optimal conditions for the preparation of tetragonal SnO2 were identified as 60% partial oxygen pressure and 1.0 Pa total gas pressure with the substrate at room temperature. Under the optimized conditions, the surfaces of Al flake particles were modified with a thin film of SnO2. XRD and SEM/EDS analysis of the prepared samples showed that the Al particle surfaces were uniformly modified by a thin film of SnO2 in all cases. The film thicknesses were 80, 130, and 180 nm at RF outputs of 195, 350, and 490 W. These measured thicknesses coincided with the values estimated from the interference colors of the samples.  相似文献   
989.
High density (98% of theoretical) was achieved at 900°C for an all-alkoxide derived bulk celsian gel prior to crystallisation. TEM indicated that crystallisation was dominated by volume nucleation and growth of hexagonal disc shaped hexacelsian. Kinetic studies using SEM indicate a maximum nucleation rate at 980°C and an activation energy for crystal growth of 566 KJ/mol. The high rates of densification and of nucleation are attributed to the high OH content in the gel-derived glass.  相似文献   
990.
Chu TY  Chang CH  Liao YC  Chen YC 《Talanta》2001,54(6):1010-1171
A rapid method for the derivatization of phenolic antioxidants using microwave irradiation has been developed. Six antioxidatively active phenolic components of wines and fruits, namely gallic acid, gentisic acid, vanillic acid, caffeic acid, ferulic acid and p-coumaric acid were used in the model study. The solution of phenolic acids was evaporated to dryness on a rotary evaporator followed by further drying under microwave irradiation (600 W, 30 s). The resultant residue was dissolved in pyridene and treated with bis(trimethylsilyl)acetamide while irradiated by microwave using high power for 30 s. Controlled reaction was carried out employing bis(trimethylsilyl)trifluoroacetamide under conventional heating for 30 min. The trimethylsilyl derivatives were identified and quantified on a gas chromatography/mass selective detector. The mass spectral fragmentation patterns of the derivatives obtained by microwave irradiation were identical to those prepared by heating. The yields of microwave-assisted silylation were comparable to those from conventional heating. The rsd were less than 8% for six replicates. The linearity in wine matrix was nearly perfect. This method is a useful protocol to examine the phenolic constituents in wines and agricultural products.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号