全文获取类型
收费全文 | 12881篇 |
免费 | 2004篇 |
国内免费 | 2201篇 |
专业分类
化学 | 10491篇 |
晶体学 | 183篇 |
力学 | 692篇 |
综合类 | 155篇 |
数学 | 1496篇 |
物理学 | 4069篇 |
出版年
2024年 | 21篇 |
2023年 | 141篇 |
2022年 | 370篇 |
2021年 | 347篇 |
2020年 | 394篇 |
2019年 | 479篇 |
2018年 | 398篇 |
2017年 | 432篇 |
2016年 | 565篇 |
2015年 | 651篇 |
2014年 | 783篇 |
2013年 | 979篇 |
2012年 | 1129篇 |
2011年 | 1186篇 |
2010年 | 874篇 |
2009年 | 890篇 |
2008年 | 995篇 |
2007年 | 868篇 |
2006年 | 759篇 |
2005年 | 712篇 |
2004年 | 617篇 |
2003年 | 458篇 |
2002年 | 513篇 |
2001年 | 430篇 |
2000年 | 331篇 |
1999年 | 252篇 |
1998年 | 218篇 |
1997年 | 176篇 |
1996年 | 147篇 |
1995年 | 125篇 |
1994年 | 133篇 |
1993年 | 103篇 |
1992年 | 98篇 |
1991年 | 84篇 |
1990年 | 90篇 |
1989年 | 60篇 |
1988年 | 59篇 |
1987年 | 47篇 |
1986年 | 41篇 |
1985年 | 27篇 |
1984年 | 14篇 |
1983年 | 18篇 |
1982年 | 16篇 |
1981年 | 8篇 |
1980年 | 9篇 |
1979年 | 6篇 |
1977年 | 6篇 |
1975年 | 3篇 |
1957年 | 4篇 |
1936年 | 8篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
961.
A novel graft copolymer consisting of polyisoprene backbone and hydrophilic side chain with carbamic acid ester functional group was prepared via thiol-ene"click"reaction and alcohol-isocyanate reactions.Polyisoprene was synthesized by anionic polymerization using n-butyl lithium as initiator,and the pendant hydroxyl groups were introduced by the thiol-ene reaction of mercaptoethanol with the double bond of 1,2-addition units of PI backbone in the presence of radical initiator azobisisobutyronitrile. Isocyanate end group capped poly(ethylene glycol)(mPEG-NCO) was grafted onto the PI backbone through alcoholisocyanate reaction between the pendant hydroxyl groups and isocyanate group of mPEG-NCO.The structure of the graft copolymer were characterized and confirmed by means of size-exclusion chromatography,~1H NMR and FTIR spectroscopy. 相似文献
962.
Guangwu Liu Bin Zhou Xingyuan Ni Jun Shen Guangming Wu Ai Du Guoqing Zu 《Journal of Sol-Gel Science and Technology》2012,62(2):126-133
The experimental results of thermal process on the microstructural and physical properties of ambient pressure dried hydrophobic
silica aerogel monoliths are reported and discussed. With sodium silicate as precursor, ethanol/hexamethyldisiloxane/hydrochloric
acid as surface modification agent, the crack-free and high hydrophobic silica aerogel monoliths was obtained possessing the
properties as low density (0.096 g/cm3), high surface area (651 m2/g), high hydrophobicity (~147°) and low thermal conductivity (0.0217 Wm/K). Silica aerogels maintained hydrophobic behavior
up to 430 °C. After a thermal process changing from room temperature to 300 °C, the hydrophobicity remained unchanged (~128°),
of which the porosity was 95.69% and specific density about 0.094 g/cm3. After high temperature treatment (300–500 °C), the density of final product decreased from 0.094 to 0.089 g/cm3 and porosity increased to 96.33%. With surface area of 466 m2/g, porosity of 91.21% and density about 0.113 g/cm3, silica aerogels were at a good state at 800 °C. Thermal conductivities at desired temperatures were analyzed by the transient
plane heat source method. Thermal conductivity coefficients of silica aerogel monoliths changed from 0.0217 to 0.0981 Wm/K
as temperature increased to 800 °C, revealed an excellent heat insulation effect during thermal process. 相似文献
963.
Dou Junqing Kang Xueya Wumaier Tuerdi Hua Ning Han Ying Xu Guoqing 《Journal of Solid State Electrochemistry》2012,16(5):1925-1931
LiFePO4/C composite is synthesized by oxalic acid-assisted rheological phase method. Fe2O3 and LiH2PO4 are chosen as the starting materials, sucrose as carbon sources, and oxalic acid as the additive. The crystalline structure
and morphology of the products are characterized by X-ray diffraction and field emission scanning electron microscopy. The
charge–discharge kinetics of LiFePO4 electrode is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. It is found that the introduction
of appropriate amount of oxalic acid leads to smaller particle sizes, more homogeneous size distribution, and some Fe2P produced in the final products, resulting in reduced polarization, impedance, and improved Li+ ion diffusion coefficient. The best cell performance is delivered by the sample with R = 1.5 (R of the molar ratio of oxalic acid to LiH2PO4). Its discharge capacity is 154 mAh g−1 at 0.2 C rate and 120 mAh g−1 at 5.0 C rate. At the same time, it exhibits an excellent cycling stability; no obvious decrease even after 1,000 cycles
at 1.0 C rate. 相似文献
964.
基于适配体的高特异识别能力和可扩增性,构建了经磁分离后实时定量PCR检测重组人促红细胞生成素-α(rHuEPO -α)的新方法;针对实际血清样品中高丰度蛋白质等的干扰,利用碱基互补配对原理设计合成了分别与适配体两端引物区结合的互补链,通过凝胶迁移阻滞分析(EMSA)筛选出最佳的互补链,并将生物素化的互补链连接到链霉亲和素磁珠上,以此为探针捕获复杂基质中形成的待测复合物.研究结果表明,结合该样品前处理策略,该方法可成功地应用于正常人血清中的rHuEPO -α定量检测,检出限为25pmol/L,线性范围为50 pmol/L~ 50 nmol/L. 相似文献
965.
Hua ZhangZeinab Khalil Melissa M. ConteFabien Plisson Robert J. Capon 《Tetrahedron letters》2012,53(29):3784-3787
Biological screening of a deep-water Great Australian Bight marine sponge, Axinella sp., detected inhibition against the neurodegenerative disease kinase targets CDK5/p25, CK1δ, and GSK3β, as well as significant levels of antibacterial activity. Chemical fractionation returned 18 secondary metabolites identified by detailed spectroscopic analysis as three new bromopyrrolo-2-aminoimidazoles, 14-O-sulfate massadine (1), 14-O-methyl massadine (2), and 3-O-methyl massadine chloride (3), together with the known metabolites massadine chloride (4), massadine (5), stylissadine B (6), axinellamines A-C (7-9), hymenin (10), stevensine (also known as odiline) (11), tauroacidin A (12), hymenidin (13), taurodispacamide A (14), oroidin (15), debromohymenialdisine (16), hymenialdisine (17), and aldisin (18). Armed with this focused natural product chemical diversity library, we re-established that 16 and 17 were nM kinase inhibitors, and determined that 3, 6, and 12-15 were sub μM antibacterials. 相似文献
966.
通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加. 相似文献
967.
Zeng Y Zhang W Xu C Xiao N Huang Y Yu DY Hng HH Yan Q 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(13):4026-4030
Single-crystalline TiOF(2) nanotubes were prepared by a one-step solvothermal method. The nanotubes are rectangular in shape with a length of 2-3?μm, width of 200-300?nm, and wall thickness of 40-60?nm. The formation of TiOF(2) nanotubes is directly driven by the interaction between TiF(4) and oleic acid in octadecane to form the 1D nanorods, and this is followed by a mass diffusion process to form the hollow structures. The synthesis approach can be extended to grow TiOF(2) nanoparticles and nanorods. Compared with TiO(2), which is the more commonly considered anode material in lithium-ion batteries, TiOF(2) has the advantages of a lower Li-intercalation voltage (e.g., to help increase the total voltage of the battery cell) and higher specific capacities. The TiOF(2) nanotubes showed good Li-storage properties with high specific capacities, stable cyclabilities, and good rate capabilities. 相似文献
968.
Wang H Lang X Gao J Liu W Wu D Wu Y Guo L Li J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(15):4620-4626
Synthesis of inorganic single crystals with exposed high-reactivity facets is a desirable target in the catalytic chemistry field. Polyhedral AgBr microcrystals with an increased percentage of exposed high-reactivity {111} facets have been successfully prepared for the first time, and the photocatalytic performance of these microcrystals when used as an AgBr/Ag plasmonic photocatalyst was investigated. The results indicate that the as-prepared sample has high photocatalytic activity and, under the same measurement conditions, the photodegradation rate of methyl orange dye over these microcrystals is at least four times faster than with other shapes of AgBr/Ag microstructure, as well as 20?times faster than with the highly efficient Ag(3)PO(4) photocatalyst. DFT calculations suggest that the AgBr (111) surface is mainly composed of unsaturated Ag atoms and has a relatively high surface energy, both of which are favorable for enhancing the photocatalytic activity of the AgBr/Ag polyhedron photocatalyst. This work not only provides a highly efficient plasmonic photocatalyst of polyhedral AgBr/Ag microcrystals with an increased percentage of exposed high-reactivity AgBr {111} facets, but also demonstrates that the shape and crystalline quality of the exposed facets have an important influence on the photocatalytic activities. 相似文献
969.
For the first time the computed mechanisms for the novel reaction of 2-naphthol with N-methyl-N-phenylhydrazine, leading to 1-amino-2-naphthol (Tang et al., J Am Chem Soc 2008, 130, 5840), have been investigated using the density functional theory. Four distinct possible pathways were evaluated: two amination mechanisms with the attack of NH(2) group respectively at the α-position C1 and β-position C3 atoms of 2-naphthol (pathways 1 and 2) as well as two rearrangement processes with displacement of the phenolic hydroxyl group followed by the benzidine-like rearrangement at the α-position C1 and β-position C3 atoms of 2-naphthol, respectively (pathways 3 and 4). Solvent effect has been tested based on the optimized geometries of the stationary points in solution at the B3LYP/PCM/6-31+G(d,p) level of theory with an averaged dielectric constant of binary solvent. Single-point energies of the optimized structures have been calculated using three hybrid density functionals, B3LYP, MPW3LYP, and B3PW91 with the 6-311++G(3df,2p) basis set. Our computed results clearly manifest that pathway 1 (α-amination) has the highest possibility to occur, with the Gibbs free energies being lower by 6 to 20 kcal/mol compared with the other three pathways, which leads to 1-amino-2-naphthol and N-methylaniline as products. It is in excellent agreement with the experimental observation. 相似文献
970.
Xu L Kuang H Xu C Ma W Wang L Kotov NA 《Journal of the American Chemical Society》2012,134(3):1699-1709
Multiple properties of plasmonic assemblies are determined by their geometrical organization. While high degree of complexity was achieved for plasmonic superstructures based on nanoparticles (NPs), little is known about the stable and structurally reproducible plasmonic assemblies made up from geometrically diverse plasmonic building blocks. Among other possibilities, they open the door for the preparation of regiospecific isomers of nanoscale assemblies significant both from a fundamental point of view and optical applications. Here, we present a synthetic method for complex assemblies from NPs and nanorods (NRs) based on selective modification of NRs with DNA oligomers. Three types of assemblies denoted as End, Side, and Satellite isomers that display distinct elements of regiospecificity were prepared with the yield exceeding 85%. Multiple experimental methods independently verify various structural features, uniformity, and stability of the prepared assemblies. The presence of interparticle gaps with finely controlled geometrical parameters and inherently small size comparable with those of cellular organelles fomented their study as intracellular probes. Against initial expectations, SERS intensity for End, Side, and Satellite isomers was found to be dependent primarily on the number of the NPs in the superstructures rationalized with the help of electrical field simulations. Incubation of the label-free NP-NR assemblies with HeLa cells indicated sufficient field enhancement to detect structural lipids of mitochondria and potentially small metabolites. This provided the first proof-of-concept data for the possibility of real-time probing of the local organelle environment in live cells. Further studies should include structural optimization of the assemblies for multitarget monitoring of metabolic activity and further increase in complexity for applications in transformative optics. 相似文献