全文获取类型
收费全文 | 5198篇 |
免费 | 407篇 |
国内免费 | 545篇 |
专业分类
化学 | 2532篇 |
晶体学 | 20篇 |
力学 | 316篇 |
综合类 | 55篇 |
数学 | 545篇 |
物理学 | 680篇 |
综合类 | 2002篇 |
出版年
2024年 | 15篇 |
2023年 | 57篇 |
2022年 | 107篇 |
2021年 | 83篇 |
2020年 | 122篇 |
2019年 | 133篇 |
2018年 | 110篇 |
2017年 | 152篇 |
2016年 | 175篇 |
2015年 | 167篇 |
2014年 | 220篇 |
2013年 | 296篇 |
2012年 | 359篇 |
2011年 | 315篇 |
2010年 | 220篇 |
2009年 | 289篇 |
2008年 | 344篇 |
2007年 | 335篇 |
2006年 | 335篇 |
2005年 | 315篇 |
2004年 | 271篇 |
2003年 | 238篇 |
2002年 | 177篇 |
2001年 | 167篇 |
2000年 | 152篇 |
1999年 | 146篇 |
1998年 | 112篇 |
1997年 | 104篇 |
1996年 | 88篇 |
1995年 | 100篇 |
1994年 | 85篇 |
1993年 | 64篇 |
1992年 | 66篇 |
1991年 | 60篇 |
1990年 | 44篇 |
1989年 | 40篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 8篇 |
1985年 | 6篇 |
1984年 | 6篇 |
1983年 | 7篇 |
1982年 | 9篇 |
1981年 | 8篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1976年 | 1篇 |
1974年 | 3篇 |
1973年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有6150条查询结果,搜索用时 10 毫秒
71.
The interaction of fluorocarbon containing hydrophobically modified polyelectrolyte(FMPAANa) with two kinds of nonionic surfactants(hydrogenated and fluorinated)in a semidilute (0.5wt%) aqueous solution had been studied by rheological measurements,Association behavior was found in both systems.The hydrophobic interaction of FMPAANa with fluorinated surfactant(FC171) is much stronger than that with hydrogenated surfactant(NP7.5) at low surfactoant concentrations.The interaction is strengthened by surfactants being added for the density of active junctions increased.Whereas distinct phenomena for FC171 and NP7.5 start to be found as the surfactants added over their respective certain concentration.The interaction of polyelectrolyte with fluorinated surfactant increases dramatical ly while that with hydrogenated surfactant decreases. 相似文献
72.
A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb2+ and Cd2+ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd2+) and −0.91 V (Pb2+) demonstrates the possibility of simultaneous determination of Pb2+ and Cd2+. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10−7-1.5×10−5 mol l−1 (Pb2+) and 2.5×10−7-2.5×10−5 mol l−1 (Cd2+), respectively. For 5 min preconcentration, detection limits of 1×10−8 mol l−1 (Pb2+) and 4×10−8 mol l−1 (Cd2+) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10−7 mol l−1 Pb2+ and Cd2+ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb2+) and 3.2% (Cd2+), respectively. Interferences by some metals were investigated. Only Ni2+ and Hg2+ apparently affected the peak currents of Pb2+ and Cd2+. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb2+ and Cd2+ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb2+ and Cd2+. 相似文献
73.
《Electroanalysis》2006,18(12):1202-1207
A new type of current sensor, Langmuir–Blodgett (LB) film of calixarene on the surface of glassy carbon electrode (GCE) was prepared for determination of mercury by anodic stripping voltammetry (ASV). An anodic stripping peak was obtained at 0.15 V (vs. SCE) by scanning the potential from ?0.6 to +0.6 V. Compared with a bare GCE, the LB film coated electrode greatly improves the sensitivity of measuring mercury ion. The fabricated electrode in a 0.1 M H2SO4+0.01 M HCl solution shows a linear voltammetric response in the range of 0.07–40 μg L?1 and detection limit of 0.04 μg L?1 (ca. 2×10?10 M). The high sensitivity, selectivity, and stability of this LB film modified electrode demonstrates its practical application for a simple, rapid and economical determination of Hg2+ in a water sample. 相似文献
74.
Karen Wright Marco CrismaClaudio Toniolo Roland TörökAntal Péter Michel WakselmanJean-Paul Mazaleyrat 《Tetrahedron letters》2003,44(16):3381-3384
Amination of 3-carboxymethyl-1-oxyl-2,2,6,6-tetramethyl-4-piperidone with (R)-α-methylbenzylamine, NaBH3CN reduction of the resulting enamine and removal of the chiral auxiliary from the separated diastereoisomers, led to enantiomerically pure (3S,4S) and (3R,4R) methyl 4-amino-1-oxyl-2,2,6,6-tetramethylpiperidine-3-carboxylates. 相似文献
75.
《Electroanalysis》2006,18(12):1173-1178
Nano‐scale zeolite Y crystals were synthesized, and palladium nanoparticles were prepared in the supercage of the zeolite by “ship‐in‐a‐bottle” approach. A novel method to fabricate zeolite‐modified electrode (ZME) loading Pd nanoparticles was developed, in which the zeolite Y loading Pd2+ ions was self‐assembled on (3‐mercaptopropyl) trimethoxysilane‐attached Au surface to form the stable and density packed multilayers (SAM‐ZME). The structures of zeolite Y and the SAM‐ZME were investigated by using TEM, XRD and SEM techniques. Pd2+ ions in the SAM‐ZME were converted into Pd nanoparticles (Pdn0) by two steps consisting of the electrochemical reduction as well as the succeeding admission and release of CO. The redox couple [Fe(CN)6]3?/4? was used to probe the electron‐transfer barrier properties during self‐assembling process. Moreover, the special properties of the SAM‐ZME loading Pdn0 were studied by using cyclic voltammetry and CO‐probe in situ FTIR spectroscopy. The results illustrated that Pdn0 in the SAM‐ZME exhibits higher electrocatalytic activity for oxidation of adsorbed CO than that of ZME prepared in our previous study by zeolite coating method. The present study is of importance in design and preparation of SAM‐ZME, which poccesseses excellent properties for the immobilization of electrocatalysts or biomolecules. 相似文献
76.
基于SnO2为修饰层的Au-Pt / SnO2 / Au复合电极研究 总被引:1,自引:0,他引:1
用真空镀膜法在Au电极上沉积SnO2薄膜,在HAuCl4和H2PtCl4的混合溶液中利用直接还原法,将Au-Pt双金属纳米颗粒组装在SnO2 / Au电极上,得到Au-Pt / SnO2 / Au复合电极。采用SEM、TEM、XPS及CV曲线测定对Au-Pt / SnO2 / Au复合电极进行了表征。结果表明:复合电极上双金属纳米颗粒分布均匀,粒子粒径约为25 nm左右。SnO2作为修饰层以配位键与双金属纳米粒子结合。Au-Pt / SnO2 / Au复合电极具有良好对甲醇氧化的电化学性能。 相似文献
77.
Determination of Dopamine in the Presence of Ascorbic Acid Using a Poly(Amidosulfonic Acid) Modified Glassy Carbon Electrode 总被引:3,自引:0,他引:3
Yuzhong?ZhangEmail author Guiying?Jin Zhousheng?Yang Hong?Zhao 《Mikrochimica acta》2004,147(4):225-230
A glassy carbon electrode (GCE) was modified with electropolymerized films of amidosulfonic acid in pH 7.0 phosphate buffer solution (PBS) by cyclic voltammetry (CV). The modified electrode showed an excellent electrocatalytical effect on the oxidation of dopamine (DA). In pH 7.0 PBS, the anodic peak current increased linearly with the concentration of DA in the range of 5.0×10–7 1.0×10–4moldm–3, with a correlation coefficient of 0.9932, and a detection limit (S/N=3) of 1.0× 10–7moldm–3. The relative standard deviation of 10 successive scans was 2.5% for 1.0×10–6moldm–3 DA. The interference of ascorbic acid (AA) with the determination of DA could be eliminated because of the very distinct attracting interaction between DA cations and the negatively poly(amidosulfonic acid) film in pH 7.0 PBS. The proposed method exhibited good recovery and reproducibility. 相似文献
78.
Miyuki Narita Fumio Hamada Mayumi Sato Iwao Suzuki Tetsuo Osa 《Journal of inclusion phenomena and macrocyclic chemistry》1999,34(4):421-430
Flexible hosts, 6A,6B-; 6A,6C-; 6A,6D-; and 6A,6E-bis dansylglycine-modified -cyclodextrins (-1, -2, -3, and -4, respectively) have been synthesized as a sensing molecule for organic guests including terpenoids and bile acids. These host compounds show a pure monomer fluorescence whose intensity is decreased or enhanced upon addition of guest species. The value I/I0, where I and I0 are fluorescence intensities in the presence and absence of a guest and I is I0- I, was used as a parameter of sensitivity. These hosts exhibit highly sensitive and selective molecular recognition ability, particularly, for lithochoic acid, chenodeoxycholic acid, and ursodeoxycholic acid. The behaviors of the appended moieties of these hosts when host–guest complexation occurs are studied by induced circular dichroism (ICD) spectra and fluorescence spectral change on accommodation of a guest. The ICD pattern of these hosts alone or on accommodation of a guest is very similar, indicating that the behavior of the appended moieties are very similar. The guest-induced variations in the fluorescence or ICD intensity suggest that the appended moieties act as a hydrophobic cap that enables the cyclodextrin to form 1 : 1 host–guest complexes. 相似文献
79.
This work describes the preparation of a new modified electrode containing a ruthenium complex (cis-aquadimethylbipyridyltriphenylphosphineruthenium II), bonded to a stable polyphenol film. This modified electrode promotes the fast electrocatalytic oxidation of safrol (5-allyl-benzo[1,3]dioxole) and isosafrol (5-propenyl-benzo[1,3]dioxole), giving two interesting products benzo[1,3]dioxole-5-carbaldehyde (piperonal) and 3-benzo[1,3]dioxol-5-yl-propenal respectively, with good yields. The electrode preparation can be carried out at a potential range which does not interfere on the anchored electroactive ruthenium complex, but it allows for the phenol oxidation to occur and therefore polymerize forming the polyphenol film. The catalytic character of this modified electrode is showed by its high turnover numbers. The procedure to isolate the products is very simple. 相似文献
80.
Adsorption stripping voltammetry, a very sensitive electroanalytical method, was employed to determine reserpine, a kind of anti-hypertensive drug. In 0.1M phosphate buffer with a pH of 6.0, reserpine was accumulated at a multi-wall carbon nanotubes (MWNT)-modified glassy carbon electrode (GCE) surface under the condition of open-circuit. In the following anodic sweep from 0.20 to 1.00V, reserpine, adsorbed at the MWNT-modified GCE surface, was oxidized and yielded a sensitive oxidation peak at 0.64V. Due to its unique structure and extraordinary properties, MWNT shows a ten times higher accumulation efficiency toward reserpine, compared with a bare GCE. Hence, the amount of reserpine at the MWNT-modified GCE surface increases significantly, and finally the oxidation peak current improves greatly. The experimental conditions, such as supporting electrolyte, pH value, the amount of MWNT-DHP suspension, accumulation time and scan rate, were optimized for the measurement of reserpine, and a sensitive electroanalytical method was proposed for reserpine determination. The oxidation peak current varies linearly with the concentration of reserpine over the range of 2×10–8 to 1×10–5M, and the detection limit is 7.5×10–9M after 4min open-circuit accumulation. The relative standard deviation at 1×10–6M reserpine was about 4.7% (n=7), indicating excellent reproducibility. This new method was successfully demonstrated with reserpine injections and tablets. 相似文献