全文获取类型
收费全文 | 1849篇 |
免费 | 168篇 |
国内免费 | 272篇 |
专业分类
化学 | 1937篇 |
晶体学 | 23篇 |
力学 | 9篇 |
综合类 | 18篇 |
数学 | 40篇 |
物理学 | 262篇 |
出版年
2024年 | 2篇 |
2023年 | 23篇 |
2022年 | 52篇 |
2021年 | 76篇 |
2020年 | 70篇 |
2019年 | 72篇 |
2018年 | 59篇 |
2017年 | 79篇 |
2016年 | 99篇 |
2015年 | 91篇 |
2014年 | 108篇 |
2013年 | 171篇 |
2012年 | 100篇 |
2011年 | 122篇 |
2010年 | 86篇 |
2009年 | 131篇 |
2008年 | 111篇 |
2007年 | 106篇 |
2006年 | 104篇 |
2005年 | 102篇 |
2004年 | 91篇 |
2003年 | 63篇 |
2002年 | 64篇 |
2001年 | 29篇 |
2000年 | 29篇 |
1999年 | 30篇 |
1998年 | 24篇 |
1997年 | 30篇 |
1996年 | 19篇 |
1995年 | 26篇 |
1994年 | 15篇 |
1993年 | 22篇 |
1992年 | 19篇 |
1991年 | 13篇 |
1990年 | 13篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1987年 | 2篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 2篇 |
1983年 | 4篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有2289条查询结果,搜索用时 46 毫秒
41.
Electrochemical Oxidation of Quercetin 总被引:1,自引:0,他引:1
《Electroanalysis》2003,15(22):1745-1750
The mechanism of electrochemical oxidation of quercetin on a glassy carbon electrode has been studied using cyclic, differential pulse and square‐wave voltammetry at different pH. It proceeds in a cascade mechanism, related with the two catechol hydroxyl groups and the other three hydroxyl groups which all present electroactivity, and the oxidation is pH dependent. Quercetin also adsorbs strongly on the electrode surface; and the final oxidation product is not electroactive and blocks the electrode surface. The oxidation of the catechol 3′,4′‐dihydroxyl electron‐donating groups, occurs first, at very low positive potentials, and is a two electron two proton reversible reaction. The hydroxyl group oxidized next was shown to undergo an irreversible oxidation reaction, and this hydroxyl group can form a intermolecular hydrogen bond with the neighboring oxygen. The other two hydroxyl groups also have an electron donating effect and their oxidation is reversible. 相似文献
42.
A procedure for estimation of measurement uncertainty of routine pH measurement (pH meter with two-point calibration, with
or without automatic temperature compensation, combination glass electrode) based on the ISO method is presented. It is based
on a mathematical model of pH measurement that involves nine input parameters. Altogether 14 components of uncertainty are
identified and quantified. No single uncertainty estimate can be ascribed to a pH measurement procedure: the uncertainty of
pH strongly depends on changes in experimental details and on the pH value itself. The uncertainty is the lowest near the
isopotential point and in the center of the calibration line and can increase by a factor of 2 (depending on the details of
the measurement procedure) when moving from around pH 7 to around pH 2 or 11. Therefore it is necessary to estimate the uncertainty
separately for each measurement. For routine pH measurement the uncertainty cannot be significantly reduced by using more
accurate standard solutions than ±0.02 pH units – the uncertainty improvement is small. A major problem in estimating the
uncertainty of pH is the residual junction potential, which is almost impossible to take rigorously into account in the framework
of a routine pH measurement.1
Received: 11 August 2001 Accepted: 22 February 2002 相似文献
43.
Jean-Louis Brisset 《Journal of solution chemistry》1976,5(8):587-604
Various water-pyridine mixtures have been selected in order to compare several of the most popular extrathermodynamic assumptions involved in the determination of the transfer activity coefficient of the proton, t(H+). Two techniques have been utilized for this purpose: voltammetry [study of the ferrocene, ferricyanide, or thallium(1) systems] and potentiometry at equilibrium (emf measurements of various galvanic cells, including liquid junctions and hydrogen electrode or silver electrode as a test electrode). The assumptions have been classified into various groups [e.g., t(Zp+)=t(Zq+) or t(X–)=t(Y+)], and the values of t(H+) have been experimentally determined in each case. The results vary depending upon the basic assumption (several pH units); less important differences (e.g., 0.5 pH unit) occur within a given group, and this may be assigned to the nature of the reference species chosen. A simple model of solvation has been also examined; the application of the law of mass action to the corresponding equilibrium provides results close to the t(X–) =t(Y+)type of assumptions which ultimately leads to most self-consistent results. 相似文献
44.
农业供应链金融为涉农企业融资难问题提供了新思路。本文以上市涉农上市企业2016~2018年的财务数据为样本,探讨了农业供应链金融对缓解企业融资约束的影响,以及涉农企业参与精准扶贫对缓解融资约束的调节作用。研究发现:涉农企业普遍面临融资约束问题,而农业供应链金融显著缓解了涉农企业的融资约束,且对参与精准扶贫企业的融资约束缓解更为显著。本文揭示了:农业供应链金融能有效缓解涉农企业的融资约束问题,再次证明了农业供应链金融缓解涉农企业融资约束的重要性和必要性,拓展了供应链金融研究的领域,同时对企业参与精准扶贫,响应新时期涉农企业社会责任的具体要求,形成政府、企业等共同承担社会责任的多元化减贫治理机制,助力乡村振兴提供相应借鉴。 相似文献
45.
Y. -K. Leong 《Colloid and polymer science》1997,275(9):869-875
The effect of pH on the flow behavior of ZrO2 suspensions containing polyacrylic and octanoic acids was evaluated. In the flocculated pH regime, the flow behavior is highly
shearthinning and can be described by a power-law model. The shear-thinning behavior increases with increasing degree of flocculation.
Maximum shearthinning was observed at the zero zeta potential condition. Hydrophobic interaction arising from adsorbed octanoic
acid was found to enhance the shear-thinning behavior. No such enhancement was observed for adsorbed polyacrylic acid. It
was also illustrated that the viscosity–pH behavior is a mirror image of the yield stress–pH behavior. A quantitative particle-pair
interactions model incorporating steric and hydrophobic interactions was proposed to explain the effects of polyacrylic and
octanoic acids on the maximum yield stress.
Received: 23 May 1997 Accepted: 4 June 1997 相似文献
46.
Zhaofeng Mao 《Journal of solid state chemistry》2007,180(2):453-460
The ability of malic acid to control calcium carbonate morphology has been investigated by aging calcium chloride solution in the presence of urea in a 90 °C bath. Malic acid favors the formation of calcite. A transition from single block to aggregate with special morphology occurs upon increasing malic acid concentration. The morphological development of CaCO3 crystal obviously depends on the starting pH. CaCO3 crystal grows from spindle seed to dumbbell in the pH regime from 7 to 11; while it evolves from spindle seed, through peanut, to sphere at pH=11.5. Both dumbbell and sphere consist of rods that are elongated along c-axis and capped with three smooth, well-defined rhombic {1 0 4} faces. A tentative growth mechanism is proposed based on the fractal model suggested by R. Kniep and S. Busch [Angew. Chem. Int. Ed. Engl. 35 (1996) 2624]. 相似文献
47.
48.
49.
固定pH滴定法测定弱酸弱碱性药物 总被引:8,自引:0,他引:8
报道一种水溶液吕测定弱酸弱碱性药物的新型滴定分析方法-固定pH滴定法,其理论基础是弱酸弱碱在水溶液中各种存在形式的分布系数在pH值固定时为常数,对甲硝唑,盐酸美西律等离散常数在10^-8至10^-11范围内的7种弱酸弱碱性药物进行测定。结果与药典法吻合,回收率在99.4%~100.6%,方法简便,快速,准确,制剂中的赋形剂及色物不影响测定。 相似文献
50.
《Electroanalysis》2006,18(15):1493-1498
Titanium nitride was used as pH‐sensitive material to fabricate all solid‐state pH electrode. The fabrication and the response performance of the pH electrode were described in the paper. The TiN film electrode showed a linear response in the pH range of 2–12 with a near‐Nenstian response (?55 mV/pH). The response time was within 1 min, and the electrode had good reproducibility, stability and low sensitivities for different species. Compared with the glass pH electrode, the electrode exhibited some advantages, for example, without activation, rapid response and high mechanical strength. In addition, the electrode performed excellently in a corrosion medium containing F?(1 M). Electrochemical behaviors of TiN electrode in Britton‐Robinson buffers were studied with Electrochemical Impedance Spectroscopy (EIS). 相似文献