全文获取类型
收费全文 | 2948篇 |
免费 | 108篇 |
国内免费 | 429篇 |
专业分类
化学 | 2720篇 |
晶体学 | 8篇 |
力学 | 80篇 |
综合类 | 10篇 |
数学 | 331篇 |
物理学 | 336篇 |
出版年
2024年 | 2篇 |
2023年 | 9篇 |
2022年 | 27篇 |
2021年 | 32篇 |
2020年 | 57篇 |
2019年 | 54篇 |
2018年 | 44篇 |
2017年 | 79篇 |
2016年 | 82篇 |
2015年 | 84篇 |
2014年 | 128篇 |
2013年 | 219篇 |
2012年 | 166篇 |
2011年 | 180篇 |
2010年 | 169篇 |
2009年 | 181篇 |
2008年 | 194篇 |
2007年 | 208篇 |
2006年 | 160篇 |
2005年 | 178篇 |
2004年 | 171篇 |
2003年 | 141篇 |
2002年 | 100篇 |
2001年 | 91篇 |
2000年 | 91篇 |
1999年 | 71篇 |
1998年 | 75篇 |
1997年 | 75篇 |
1996年 | 59篇 |
1995年 | 70篇 |
1994年 | 66篇 |
1993年 | 59篇 |
1992年 | 45篇 |
1991年 | 22篇 |
1990年 | 20篇 |
1989年 | 24篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有3485条查询结果,搜索用时 609 毫秒
121.
José Roberto Caetano da RochaLúcio Angnes Mauro Bertotti Koiti ArakiHenrique Eisi Toma 《Analytica chimica acta》2002,452(1):23-28
The modification of a glassy carbon surface by coating with an electrostatically assembled film of tetraruthenated cobalt porphyrin/(meso-tetra(4-sulphonatephenyl)porphyrinate zinc(II) yields an indicator electrode that allows the determination of nitrite to be performed with a limit of detection of 0.1 μM in a flow injection configuration. The dynamic range extends up to 1000 μM and the repeatability of the measurements was evaluated to be 1.5% with a throughput of 50 samples per hour. The efficiency of the bilayered film to mediate the electron transfer allows the determinations to be performed at a less positive potential (+0.75 V) with enhanced sensitivity. The coating also prevents the surface poisoning and its stability is maintained over several weeks. The same detector was used for determination of nitrate after reduction to nitrite in a reductor column containing copperised cadmium. This method was used for the determination of nitrate and nitrite in mineral water, saliva and cured meats, the results being in agreement with certified values and those obtained by using recommended procedures. 相似文献
122.
双波长分光光度法同时测定浆料中的聚乙烯醇和淀粉 总被引:1,自引:0,他引:1
本文报道了用双波长分光光度法同时测定变性聚乙烯醇和淀粉醋酸酯的一种新方法。分别选择670.0~540.0nm以及590.0~730.0nm波长对测定变性聚乙烯醇和淀粉醋酸酯。变性聚乙烯醇)~32μg/ml,淀粉醋酸酯0~130μg/ml浓度范围内,吸光度差值△A遵循比耳定律。当淀粉醋酸酯与变性聚乙烯醇的浓度比在1.3~16范围内,变性聚乙烯醇和淀粉醋酸酯的样品回收率分别为99.5~105%和97~108%。所拟定的方法可测定浆料中变性聚乙烯醇和淀粉醋酸酯。本法与盐酸水解淀粉法测定的聚乙烯醇含量相吻合。本法简便快速。 相似文献
123.
辅酶I(NAD+)在0.005moL/LTris 0.01moL/LNaCl溶液(pH7.0)中,于钴离子注入修饰碳纤维电极上出现一个S形的还原波,半波电位为-1.45V(vs.SCE)。峰电流与NAD+的浓度在2.38×10-5~4.76×10-4mol/L(r=0 9992)和4.76×10-4~1.78×10-3mol/L(r=0.9982)之间成线性关系,检出限为1.19×10-5mol/L,回收率在96.7%~103.4%之间。用线性扫描、循环伏安法研究了钴离子注入修饰碳纤维电极上NAD+的电化学行为。电极反应机理为:NAD++e NAD·;NAD·+e+H+ NADH;2NAD·→NAD2。另外,钴离子注入修饰碳纤维电极对NAD+具有电催化作用。 相似文献
124.
《Electroanalysis》2003,15(13):1109-1114
The electrochemical characterization of a hydrogen peroxide sensor based on a ferrocene‐containing polymer electrochemically deposited onto a platinum electrode is described. The redox polymer consists of a siloxane‐based homopolymer, with pendant electronically communicated ferrocenyl moieties. The electrodes were used as the transducer for glucose and lactate‐sensing enzyme sensors. Amperometric biosensors were prepared by immobilization of glucose oxidase (Gox) or lactate oxidase (Lox) onto these modified electrodes. The steady‐state amperometric response of the sensors is investigated as a function of the applied potential and substrate concentration. Interferences, sensitivity and stability of the sensors were also studied. 相似文献
125.
离子注入修饰电极检测硝基苯 总被引:9,自引:0,他引:9
离子注入是一种新技术,可按人们的意愿和需要,将不同的离子注入不同的基本电极表面,制成具有催化活性强,稳定性高,重现性好等特点的修饰电极。作者研究了离子注入钴和注入镍的玻碳电极在0.1mol/LHAc-NaAc缓冲溶液中硝基苯的行为及测定。 相似文献
126.
溶胶-凝胶-钴-邻菲啰啉修饰电极对一氧化氮的电催化氧化及其测定 总被引:3,自引:0,他引:3
报道了溶胶 凝胶 钴 邻菲口罗啉膜修饰电极的制备方法及其在一氧化氮(NO)检测中的应用,采用循环伏安法(CV)研究修饰电极的电化学特性,差示脉冲伏安法(DPV)对NO进行检测。该修饰电极对NO的电化学氧化具有很好的催化作用,使其氧化电位负移了210mV,氧化峰电流与NO浓度在5.6×10-8~2.8×10-5mol/L范围内呈良好的线性关系,相关系数r=0.999,检测限为1.4×10-8mol/L,且生物体内常见的干扰物质如抗坏血酸、NO2-和儿茶酚胺类神经递质的代谢物等不干扰测定。 相似文献
127.
The microstructure of a series of high conversion copolymers of methyl acrylate (MA) and N-vinylcarbazole (NVC) was characterized by NMR. 1H- and 13C-NMR spectra were assigned by comparison to the homopolymers and by using heteronuclear shift correlation spectroscopy. MA-centered triad distributions were obtained from the carbonyl carbon. Distributions of NVC sequences were determined from aromatic carbons 1 and 8a, and aromatic proton 1 These experimentally determined sequence distributions were compared to those calculated from reactivity ratios approximated from the copolymer compositions. Agreement was very good for low NVC content copolymers. Three signals were particularly useful in providing rapid assessment of the distribution of NVC units within low NVC content copolymers: proton 1 and carbon 1 of NVC and the carbonyl carbon of MA. © 1992 John Wiley & Sons, Inc. 相似文献
128.
129.
C. Bibaut‐Renauld D. Burget J. P. Fouassier C. G. Varelas J. Thomatos G. Tsagaropoulos L. O. Ryrfors O. J. Karlsson 《Journal of polymer science. Part A, Polymer chemistry》2002,40(18):3171-3181
The efficiency of several α‐diketones as visible light photoinitiators for the crosslinking of waterborne latex dispersions in the presence of acrylic monomers was evaluated. Among the eight α‐diketones studied, camphorquinone allows the fastest curing speed, and the curing of the acrylic waterborne coating is not affected by the presence of oxygen. The properties of the sunlight‐cured volatile organic compound (VOC)‐free pigmented paints prepared from the waterborne latex are as good or better than the equivalent conventional paint containing VOCs. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3171–3181, 2002 相似文献
130.
The retention behavior of uranium, thorium and lanthanides has been investigated with amide modified reversed phase C18 supports using α-hydroxy isobutyric acid (α-HIBA) as the mobile phase. Four structurally different amide moieties namely, 4-hydroxy-N,N-dihexyl butyramide (4HHBA), 4-hydroxy-N,N-di-2-ethylhexylhexanamide (4HEHHA), bis(N,N,N′,N′-2-ethylhexyl)malonamide (B2EHM) and N-methyl-tris(dihexylcarbamoyl-3-methoxy)pivolamide (MTDCMPA) have been synthesized and studied. Among the various amide coated columns, the supports modified with 4HHBA, B2EHM and MTDCMPA exhibit an interesting retention for uranium and thorium, which is different from 4HEHHA modified support. The retention time for uranium and thorium increases with increasing amide concentration for 4HHBA, B2EHM and MTDCMPA supports, while the same decreases with increasing 4HEHHA content. However, the separation factor for uranium and thorium is greater on a 4HEHHA support, compared to an unmodified C18 column, reflecting the amide's preferential complexation of uranium over thorium.Columns modified with 4HHBA, B2EHM and MTDCMPA exhibit relatively higher retentions for lanthanides. However, MTDCMPA modified support shows a different elution profile for lanthanides compared to 4HHBA, and B2EHM modified columns. Individual separations of heavier lanthanides, i.e., from gadolinium to lutetium also have been achieved using 4HHBA and B2EHM modified supports.The influence of modifier content, mobile phase concentration and its pH on the retention of metal ions has also been studied. Based on these investigations, an efficient high performance liquid chromatographic method (HPLC) has been developed for the rapid separation of uranium from thorium as well as for the individual separation of heavier lanthanides. 相似文献