全文获取类型
收费全文 | 49012篇 |
免费 | 3209篇 |
国内免费 | 2755篇 |
专业分类
化学 | 30122篇 |
晶体学 | 276篇 |
力学 | 4814篇 |
综合类 | 673篇 |
数学 | 8526篇 |
物理学 | 10565篇 |
出版年
2024年 | 97篇 |
2023年 | 499篇 |
2022年 | 1400篇 |
2021年 | 1380篇 |
2020年 | 1447篇 |
2019年 | 1327篇 |
2018年 | 1211篇 |
2017年 | 1443篇 |
2016年 | 1970篇 |
2015年 | 1544篇 |
2014年 | 2050篇 |
2013年 | 3740篇 |
2012年 | 2812篇 |
2011年 | 2559篇 |
2010年 | 2137篇 |
2009年 | 2680篇 |
2008年 | 2619篇 |
2007年 | 3021篇 |
2006年 | 2509篇 |
2005年 | 2294篇 |
2004年 | 2178篇 |
2003年 | 1825篇 |
2002年 | 1456篇 |
2001年 | 1163篇 |
2000年 | 1140篇 |
1999年 | 1024篇 |
1998年 | 957篇 |
1997年 | 857篇 |
1996年 | 768篇 |
1995年 | 740篇 |
1994年 | 617篇 |
1993年 | 550篇 |
1992年 | 506篇 |
1991年 | 418篇 |
1990年 | 376篇 |
1989年 | 247篇 |
1988年 | 252篇 |
1987年 | 167篇 |
1986年 | 143篇 |
1985年 | 166篇 |
1984年 | 135篇 |
1983年 | 66篇 |
1982年 | 106篇 |
1981年 | 66篇 |
1980年 | 59篇 |
1979年 | 88篇 |
1978年 | 42篇 |
1977年 | 20篇 |
1976年 | 31篇 |
1973年 | 17篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
61.
A new, highly sensitive, fast responding and stable potentiometric biosensor for creatinine determination is developed. The biosensor is based on an ammonium ion-selective electrode. Creatinine deiminase (EC 3.5.4.21) is chemically immobilized on the surface of the polymeric ion-sensitive membrane in the form of monomolecular layer using a simple, one-step carbodiimide covalent attachment method. The resulting enzyme electrodes are useful for measurement under flow injection analysis (FIA) conditions. The biosensors exhibit excellent operational and storage stability. The enzyme electrodes retain over 70% of initial sensitivity after ten weeks of work under FIA conditions. The storage stability at 4 °C is longer than half a year without loss of sensitivity. Under optimized conditions near 30 samples per hour can be analyzed and the determination range (0.02-20.0 mmol l−1) fully covers creatinine concentrations important from clinical and biomedical point of view. The simple biosensor/FIA system has been successfully used for determination of creatinine in urine, serum and posthemodialysate samples. 相似文献
62.
Philip J. Cox Olga A. Melvin Simon J. Garden James L. Wardell 《Journal of chemical crystallography》1995,25(8):469-475
The title organotin carbohydrate, C31H36O6Sn, has been synthesized and its molecular structure has been determined in solution and in the solid state. NMR, infrared, mass and X-ray crystallographic techniques were used. The chiral molecules crystallize in the monoclinic space group P21 withZ=2. The triphenyltin and carbohydrate moieties are linked by a trans methylene-oxygen-methylene arrangement. The pyranosyl ring adopts a twist-boat conformation and the isopropylidene rings adopt different (half-chair and envelope) forms. Solution and solid-state conformations are similar as only three 13C shift values are greater than 2ppm; the 119Sn value is 12 ppm. 相似文献
63.
Prasain JK Moore R Hurst JS Barnes S van Kuijk FJ 《Journal of mass spectrometry : JMS》2005,40(7):916-923
Carotenoids have been implicated in protection of the eye from light-mediated photo-toxicity caused by free radicals. Under conditions of normal oxidative stress the carotenoids serve as protective antioxidants; however, when the oxidative stress exceeds the antioxidant capacity, carotenoids can be oxidized into numerous cleavage products. The determination and identification of oxidized carotenoids in biological samples remains a major challenge due to the small sample size and low stability of these compounds. We investigated the reaction of various zeaxanthin cleavage products with O-ethyl hydroxylamine to evaluate their levels in a biological sample. For this, a sensitive and specific electrospray tandem mass spectrometry (ESI-MS/MS) was developed, avoiding the classical lower sensitive and specific HPLC-UV and fluorescence absorption methods. Protonated molecules [M + H](+) of carotenoids upon collision-induced dissociation produced a number of structurally characteristic product ions. A series of complicated clusters of product ions differing in 14 (CH(2))and 26 (C(2)H(2))Da was characteristic of the polyene chain of intact carotenoids. All carotenoid ethyl oximes of zeaxanthin cleavage products were characterized by the losses of 60 and 61 Da in their MS/MS spectra. Through the application of the LC/MS/MS method, we identified two oxime derivatives of 3-hydroxy-beta-ionone and 3-hydroxy-14'-apocarotenal with protonated molecules at m/z 252 and m/z 370 respectively, in a human eye sample. 相似文献
64.
H. Kienitz 《Angewandte Chemie (International ed. in English)》1969,8(10):733-750
The important advances being made in modern analytical methods are indicative of the fundamental changes that are occuring in the theory and practice of “analytical chemistry”. “Information optimization” demands a new approach in teaching and research, and calls for the intergration of chemistry with other scientific and technical disciplines. 相似文献
65.
Thyme (Thymus vulgaris) has been known, long time ago, for its aromatic properties. It contains essential oils and polymers such as cellulose (mixture of hemicellulose and cellulose) and lignin. The thyme, studied in this work, was gathered from the same place, in the period from November 1999 to October 2000. The chemical analysis (water, total ash, essential oils, extractive substances, cellulose, holocellulose and lignin) can be used roughly in the characterisation of the four periods that correspond to the four seasons of the year. The cellulose level was found to be more than lignin level in the wet periods (growth of the plant). The opposite was found in the dry periods. The total ash and essential oil levels were found to be high during the period of high pluviometry. The thermal decomposition of cellulose and holocellulose was found to fit well with the first-order kinetics. The activation energy, under air flow, was 185 and 196 kJ mol−1 for cellulose and holocellulose, respectively. The maximum decomposition rate and thermal analysis heating rate of lignin were found to have a direct linear relationship. 相似文献
66.
银微电极微分电位溶出分析法研究 总被引:3,自引:1,他引:3
本文首次报道了银微电极微分电位溶出分析法。用化学刻蚀法方便地制作了银微电极,用于DPSA具有背景值低,分辨率好、精密度及灵敏度高,在不搅拌,仅需一定酸度而酸度而无其它介质的条件下就能测试等优点,对人工试样及自来水样分析,结果令人满意。 相似文献
67.
Upon the electrochemical oxidation of tris(2,2′-bipyridyl) ruthenium(II) [Ru(bpy)2+3] and hydroxyl carboxylic acids, for instance, citric acid, tartaric acid, malic acid, and
-gluconic acid, bright electrochemiluminescences (ECLs) were observed. Different luminescent reactions were presented depending on the applied potential. The light emission was mainly caused by the reaction between alkoxide radical ion and Ru(bpy)3+3below the potential +1.80 V (vs Ag/AgCl). The luminescence intensity obviously increased because of the more complex reaction process. The luminescence wavelength of 608 nm, which could be found either at higher potential than +1.80 V or in the potential range from +1.30 to +1.80 V, confirmed that ECL was caused by Ru(bpy)2+3*. The factors which affect the determination and HPLC separation of the four acids were also investigated. 相似文献
68.
Biosensors for environmental pollutants and food contaminants 总被引:4,自引:0,他引:4
Baeumner AJ 《Analytical and bioanalytical chemistry》2003,377(3):434-445
This review article provides an overview of the most recent literature on biosensors for environmental pollutants and food contaminants. Due to the large number of publications, only papers published between 2000 and January 2003 were considered. Also, while not all of the published literature could be reviewed here, over 200 references are cited to provide a good overview of research undertaken in the last two years. Older publications are covered by a number of earlier review articles. This article provides an introduction into the field including specific consideration of the application areas, describes the typical biosensor assay format used, and is subsequently structured according to the biorecognition elements used (i.e., nucleic acids, enzymes, whole cells, tissue and whole organisms, antibodies and receptors, and biomimetic materials). In addition, a section on microbiosensing systems is provided. Since only very few microbiosensors with applications in environmental and food systems have been published, enabling technology is also covered in this article.Abbreviations BOD biological oxygen demand - cfu colony forming units - DNP dinitrophenol - GFP green fluorescent protein - NASBA nucleic acid sequence-based amplification - PCR polymerase chain reaction - ppt parts per trillion - QCM quartz crystal microbalance - SPR surface plasmon resonance 相似文献
69.
R.?Mitchell C.?M.?CarrEmail author M.?Parfitt J.?C.?Vickerman C.?Jones 《Cellulose (London, England)》2005,12(6):629-639
The surface chemical composition of raw unscoured cotton was successfully investigated by the surface analytical techniques
X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The presence of non-cellulosic
material at the fibre surface was established and determined to be a complex mixture of fatty acids, alcohols, alkanes, esters
and glycerides. The effect of scouring and bleaching was to reduce the surface concentration of these materials but even after
aqueous processing some non-cellulosic material residue was still detected at the fibre surface. 相似文献
70.
Christoph Kratky Heinz Falk Ulrich Zrunek 《Monatshefte für Chemie / Chemical Monthly》1985,116(5):607-623
The molecular and crystal structures of the two racemic diastereomeric 3,4-dihydropyrromethenone derivatives1 and2 of configurations (Z) and (E) were determined at 93 K (1, 2) and at room temperature (1). From an analysis of the crystallographically observed temperature coefficients a pseudorotation flexibility of the pyrrolidinone ring in the crystal is deduced. In both compounds a nearly orthogonal arrangement between the two heterocyclic ring systems is observed, which is ascribed to the steric bulk of the substituents in positions 1 and 3 of the pyrrolidinone ring.Herrn Prof.Josef Schurz zum 60. Geburtstag gewidmet. 相似文献