全文获取类型
收费全文 | 4501篇 |
免费 | 719篇 |
国内免费 | 416篇 |
专业分类
化学 | 3163篇 |
晶体学 | 42篇 |
力学 | 271篇 |
综合类 | 46篇 |
数学 | 425篇 |
物理学 | 1689篇 |
出版年
2024年 | 14篇 |
2023年 | 125篇 |
2022年 | 171篇 |
2021年 | 184篇 |
2020年 | 211篇 |
2019年 | 163篇 |
2018年 | 145篇 |
2017年 | 126篇 |
2016年 | 207篇 |
2015年 | 181篇 |
2014年 | 252篇 |
2013年 | 279篇 |
2012年 | 394篇 |
2011年 | 360篇 |
2010年 | 267篇 |
2009年 | 265篇 |
2008年 | 282篇 |
2007年 | 273篇 |
2006年 | 271篇 |
2005年 | 182篇 |
2004年 | 126篇 |
2003年 | 110篇 |
2002年 | 99篇 |
2001年 | 86篇 |
2000年 | 86篇 |
1999年 | 99篇 |
1998年 | 90篇 |
1997年 | 90篇 |
1996年 | 66篇 |
1995年 | 90篇 |
1994年 | 74篇 |
1993年 | 44篇 |
1992年 | 58篇 |
1991年 | 45篇 |
1990年 | 40篇 |
1989年 | 26篇 |
1988年 | 16篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 1篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1980年 | 1篇 |
排序方式: 共有5636条查询结果,搜索用时 15 毫秒
141.
建立了基于微波辅助-顶空液相微萃取在线联用、高效液相色谱法测定水样中邻硝基苯酚的分析方法。采用L16(45)正交实验设计对影响萃取的各种因素,如萃取有机溶剂、微波辐射功率、萃取时间、离子强度、样品液体积,进行了优化。优化后萃取条件为,以乙酸丁酯作为萃取溶剂,功率和时间分别为100W和12min条件下,离子强度为0的样品溶液体积为20mL。在优化萃取条件下,邻硝基苯酚的检出限LOD(S/N=3)为0.94μg/L,萃取富集倍数为30,实际水样的加标回收率为85.2%。理论分析和实验结果表明,微波辅助-顶空液相微萃取在线联用方法具有简便、快速、高效、节省溶剂、选择性好、应用范围广的特点。 相似文献
142.
In the present study the capacity of Radix Paeoniae Rubra aqueous extract (RPRAE) as an antioxidant to protect against carbon tetrachloride (CCl(4))-induced oxidative stress and hepatotoxicity in Wistar rats was investigated. Six groups of rats were used. Radix Paeoniae Rubra aqueous extract (100 or 200 or 300 mg/kg of bw) or bifendate (100 mg/kg of bw) were given daily by gavage to the animals on 28 consecutive days to elucidate the protective effects against CCl(4)-induced hepatotoxicity. The 20% CCl(4)/olive oil was gavage of gastric tube twice a week (on the third and seventh days of each week). The animals of normal control group were given only vehicle. The animals of CCl(4)-treated group were administered with CCl(4) twice a week (on the third and seventh days of each week) and with vehicle on rest of the days. The test materials were found effective as hepatoprotective agents, as evidenced by plasma and liver biochemical parameters. Therefore, the results of this study show that Radix Paeoniae Rubra aqueous extract can protect the liver against CCl(4)-induced oxidative damage in rats, and the hepatoprotective effects might be correlated with its antioxidant and free radical scavenger effects. 相似文献
143.
Effects of preparation conditions of Au/FeO_x /Al_2O_3 catalysts prepared by a modified two-step method on the stability for CO oxidation 下载免费PDF全文
Composite oxide FeO x /Al 2 O 3 -supported gold catalysts were prepared by a modified two-step method. The effects of preparation conditions on the initial catalytic activity and long-time stability were studied for CO oxidation. XRD, XPS and in situ FTIR were employed to investigate the state of FeO x and the species on the catalyst surface. The results showed that Au/FeO x /Al 2 O 3 catalysts prepared by this method exhibited high activity and high stability in a wide pH value range. Calcination pretreatm... 相似文献
144.
Three novel conjugated polymers bearing 3,4-bis(4-hexylthiophen-2-yl)-3-cyclobutene-1,2-dione unit in their main chain have been synthesized successfully in good yields through Suzuki or Stille coupling reaction.Their molecular structures have been confirmed by FT-IR,1H NMR and 13C NMR.All these copolymers exhibit broad and strong absorption bands in UV-vis region,and their optical band gaps are calculated to be 1.6-2.0 eV.suggesting that they have good coverage with the solar spectrum.These polymers have good thermostability and solubility in common organic solvents.Moreover,all these objective macromolecules possess high electron affinity of~3.8 eV determined from cyclic voltammetry measurement,implying that they are potential n-type polymeric photovoltaic materials. 相似文献
145.
Mingming Zou Ying Li Jun Wang Qi Wang Yumei Kong Jingqun Gao Ping Fan 《Journal of solution chemistry》2013,42(4):849-865
The interaction between bovine serum albumin (BSA) and FeIII complexes with three binary organic acid (biorga) ligands, [FeIII(oxa)(H2O)4]+ (oxa = oxalic acid), [FeIII(pra)(H2O)4]+ (pra = propanedioic acid) and [FeIII(sua)(H2O)4]+ (sua = succinic acid), as well as the sonocatalytic damage of BSA in the presence of these three FeIII–biorga complexes under ultrasonic irradiation, were studied by UV–vis and fluorescence spectra. The experimental results show that the fluorescence quenching process of BSA caused by three FeIII–biorga complexes are all static quenching and the corresponding quenching rate constants (K q), equilibrium constants (K A) and the binding site numbers (n) were calculated. The results reveal that, under ultrasonic irradiation, the BSA molecules were obviously damaged by these FeIII–biorga complexes. In addition, the effects of several factors on the damage of BSA molecules were examined. The experimental results demonstrate that the damage degree of BSA increased with an increase of ultrasonic irradiation time, FeIII–biorga complex concentration, and ionic strength. In comparison, [FeIII(pra)(H2O)4]+ exhibited higher sonocatalytic activity than [FeIII(oxa)(H2O)4]+ and [FeIII(sua)(H2O)4]+. Finally, the extent of generation of $ \cdot {\text{O}}_{2}^{ - } $ · O 2 ? and ·OH during sonocatalytic processes was estimated. Perhaps, the results will be significant for promoting sonodynamic treatment (SDT) of tumors at the molecular level. 相似文献
146.
The mixed adsorption of a cationic gemini surfactant, ethanediyl-1,2-bis(dodecyldimethylammonium bromide) (abbreviated as 12-2-12), and an anionic conventional surfactant, sodium dodecyl sulfate (SDS), was examined using surface tension measurements. The viscoelastic properties of the mixed films were investigated by dilational interfacial rheology technique. The results showed that the addition of SDS promoted the close packing of adsorbed molecules at the interface, which increased the dilational elasticity of the mixed films. The stability of the foams was determined by the half-life of foam height collapse. The foams generated by 12-2-12/SDS mixtures were more stable than that formed by pure 12-2-12. In the presence of sodium bromide, the foam stability was further enhanced and the surfactant concentration required to attain the maximum effect in stabilizing foams was greatly reduced. The high foam stability could well relate to the high elasticity of the film. 相似文献
147.
Yuan-Kai Wang Ya-Xian Yan Zi-Wei Mao Heng-an Wang Qi Zou Qian-Wen Hao Wen-Hui Ji Jian-He Sun 《Mikrochimica acta》2013,180(3-4):187-193
We have developed a highly sensitive electrochemical immunoassay for the quantitation of zearalenone (ZEN), a mycotoxin produced by Fusarium species. In this enzyme linked immunosorbent assay, the enzymatic conversion of the substrate p-nitrophenylphosphate is detected by a microplate reader and the signal subsequently converted into an electrical signal. The concentrations of coating antigen (ZEN-ovalbumin), of monoclonal antibody, and of goat anti-mouse antibody labeled with alkaline phosphatase were optimized. In terms of electrochemical detection, the types and pH values of the buffers, the conditions for agitating, and scanning frequency were optimized. The effective detection range of this immunoassay is quite wide (0.004 to 9.5 ng?mL?1), and the limit of detection is 2 pg?mL?1. ZEN-free corn, wheat, and grain-based food samples were spiked with ZEN and analyzed by this method, and recoveries were found to range from 91.6 % to 113.0 %. Unlike previously described electrochemical methods, this method is both highly sensitive and has a wide working range. The method is fast and thus provides a platform for high-throughput analysis that meets the current need to monitor trace levels of analytes in grain and grain-based food. Figure
Scheme of test procedure of electrochemical immunosensor (procedure of immune-reaction: from a to f) 相似文献
148.
Zhenbin Zhang Fangjun Wang Junjie Ou Hui Lin Jing Dong Hanfa Zou 《Analytical and bioanalytical chemistry》2013,405(7):2265-2271
A butyl–silica hybrid monolithic column for bioseparation by capillary liquid chromatography (cLC) was prepared with butyl methacrylate and alkoxysilanes through a “one-pot” process. The effects of polycondensation temperature, volume percentage of N,N′-dimethylformamide, and content of cetyltrimethylammonium bromide and butyl methacrylate on the morphologies of the hybrid monolithic columns prepared were investigated in detail. Baseline separations of proteins and small peptides on the hybrid monolithic column were achieved by cLC with gradient elution. In addition, the resulting hybrid column was also applied for analysis of tryptic digests of bovine serum albumin by cLC coupled with tandem mass spectrometry. The results demonstrate its potential application in separation of complex biological samples. 相似文献
149.
Weigang Zhang Zhenlei Zou Yuanheng Wang Yi Wang Yong Liang Zhengguang Wu Youxuan Zheng Yi Pan 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(2):634-637
Redox‐active esters (RAEs) as alkyl radical precursors have been extensively developed for C?C bond formations. However, the analogous transformations of fluoroalkyl radicals from the corresponding acid or ester precursors remain challenging because of the high oxidation potential of the fluoroalkyl carboxylate anions. The newly developed N‐hydroxybenzimidoylchloride (NHBC) ester provides a general leaving group assisted strategy to generate a portfolio of fluoroalkyl radicals, and can be successfully applied in photoinduced decarboxylative hydrofluoroalkylation and heteroarylation of unactivated olefins. In addition, DFT calculations revealed that the NHBC ester proceeds by the fluorocarbon radical pathway, whereas other well‐known RAEs proceed by the nitrogen radical pathway. 相似文献
150.
Meng Zheng Tong Jiang Wen Yang Yan Zou Haigang Wu Xiuhua Liu Fengping Zhu Rongjun Qian Daishun Ling Kerrie McDonald Jinjun Shi Bingyang Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(15):4992-4996
Nanoparticles show great potential for drug delivery. However, suitable nanostructures capable of loading a range of drugs together with the co‐delivery of siRNAs, which avoid the problem of cation‐associated cytotoxicity, are lacking. Herein, we report an small interfering RNA (siRNA)‐based vesicle (siRNAsome), which consists of a hydrophilic siRNA shell, a thermal‐ and intracellular‐reduction‐sensitive hydrophobic median layer, and an empty aqueous interior that meets this need. The siRNAsome can serve as a versatile nanostructure to load drug agents with divergent chemical properties, therapeutic proteins as well as co‐delivering immobilized siRNAs without transfection agents. Importantly, the inherent thermal/reduction‐responsiveness enables controlled drug loading and release. When siRNAsomes are loaded with the hydrophilic drug doxorubicin hydrochloride and anti‐P‐glycoprotein siRNA, synergistic therapeutic activity is achieved in multidrug resistant cancer cells and a tumor model. 相似文献