全文获取类型
收费全文 | 1786篇 |
免费 | 60篇 |
国内免费 | 7篇 |
专业分类
化学 | 1371篇 |
晶体学 | 4篇 |
力学 | 50篇 |
数学 | 229篇 |
物理学 | 199篇 |
出版年
2023年 | 15篇 |
2022年 | 66篇 |
2021年 | 87篇 |
2020年 | 43篇 |
2019年 | 41篇 |
2018年 | 13篇 |
2017年 | 31篇 |
2016年 | 63篇 |
2015年 | 56篇 |
2014年 | 73篇 |
2013年 | 95篇 |
2012年 | 112篇 |
2011年 | 139篇 |
2010年 | 75篇 |
2009年 | 87篇 |
2008年 | 118篇 |
2007年 | 114篇 |
2006年 | 107篇 |
2005年 | 100篇 |
2004年 | 80篇 |
2003年 | 72篇 |
2002年 | 68篇 |
2001年 | 21篇 |
2000年 | 13篇 |
1999年 | 15篇 |
1998年 | 16篇 |
1997年 | 13篇 |
1996年 | 17篇 |
1995年 | 8篇 |
1994年 | 11篇 |
1993年 | 13篇 |
1992年 | 7篇 |
1991年 | 6篇 |
1990年 | 5篇 |
1989年 | 12篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1979年 | 4篇 |
1978年 | 2篇 |
1977年 | 1篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1964年 | 1篇 |
1963年 | 1篇 |
1911年 | 1篇 |
1909年 | 2篇 |
排序方式: 共有1853条查询结果,搜索用时 0 毫秒
91.
Eduardo Sommella Giacomo Pepe Francesco Pagano Gian Carlo Tenore Paola Dugo Michele Manfra Pietro Campiglia 《Journal of separation science》2013,36(20):3351-3355
We have developed a fast ultra HPLC with ion‐trap TOF‐MS method for the analysis of flavonoids in Citrus bergamia juice. With respect to the typical methods for the analysis of these matrices based on conventional HPLC techniques, a tenfold faster separation was attained. The use of a core–shell particle column ensured high resolution within the fast analysis time of only 5 min. Unambiguous determination of flavonoid identity was obtained by the employment of a hybrid ion‐trap TOF mass spectrometer with high mass accuracy (average error 1.69 ppm). The system showed good retention time and peak area repeatability, with maximum RSD% values of 0.36 and 3.86, respectively, as well as good linearity (R2 ≥ 0.99). Our results show that ultra HPLC can be a useful tool for ultra fast qualitative/quantitative analysis of flavonoid compounds in citrus fruit juices. 相似文献
92.
Augusto Rivera Jaime Ríos-Motta Ginna Paola Trujillo Derly Marcela González Daniel Alcázar 《合成通讯》2013,43(6):791-799
A series of 2,2′-(dihydropyrimidine-1,3(2H,4H)-diyldimethanediyl)bis(substituted-phenols) was synthesized using a Mannich-type reaction between the macrocyclic aminal 1,3,7,9,13,15,19,21-octaazapentacyclo[19.3.1.13,7.19,13.115,19]octacosane (OAPO) (1) and substituted phenols in basic media. These previously unreported compounds were separated from the reaction mixture by column chromatography in highly pure form with 25–75% yields. The most stable conformer was predicted using AM1-type semiempirical quantum chemical calculations. 相似文献
93.
Cesare Accinelli Anna Barra Caracciolo Paola Grenni 《International journal of environmental analytical chemistry》2013,93(8):579-587
Numerous studies have documented that a wide number of pharmaceuticals used in human and veterinary medicine have the potential to enter the aquatic ecosystem. The antiviral prodrug oseltamivir phosphate has received recent attention with regard to its possible use against the highly pathogenic H5N1 virus. This preliminary laboratory study investigated the persistence of the active antiviral drug, oseltamivir carboxylate (OSC), in water samples taken from an irrigation canal. After an initial rapid decrease, OSC concentrations slowly decreased during the remaining incubation period. Approximately 65% of the initial OSC amount remained in water at the end of the 36-day incubation period. A small amount of OSC was lost both from sterilized water and from sterilized water/sediment samples, suggesting a significant role for microbial degradation. Stimulating microbial processes by the addition of sediments resulted in reduced OSC persistence. Presence of OSC (1.5?µg?mL?1) did not significantly affect the metabolic potential of the water microbial population, estimated by glyphosate and metolachlor mineralization. In contrast, OSC caused an initial transient decrease in the size of the indigenous microbial population of water samples. 相似文献
94.
95.
Paola Rizzo Vincenzo Venditto Gaetano Guerra Antonio Vecchione 《Macromolecular Symposia》2002,185(1):53-63
The different kinds of crystalline orientations which can occur in industrially relevant isotactic polypropylene (i-PP) films are compared with those generally observed for other semicrystalline polymers. The peculiar bimodality typical of the uniplanar-axial orientation which is present in two-step biaxially stretched i-PP films is rationalized in terms of the two alternative stackings on the (0k0) face of bilayers of macromolecules of the monoclinic unit cell. 相似文献
96.
Aimed to obtain new materials for the conservation of stone substrates, we report here on the synthesis of a polymer which has been obtained by inducing polymerization on a methacrylate monomer functionalized by alchoxysilane groups. Two lithotypes, the Comiso calcarenite and Mistretta quartzite, stones largely used in artworks of north-eastern Sicily, were treated with the above polymer and its conserving efficacy evaluated in terms of porosimetric features, hydric properties and appearance. The collected data were compared to those provided, under the same experimental conditions, by an ethylmethacrylate/methylmethacrylate copolymer and an alkylalchoxysilane, products widely employed in the protection of stones. Experiments aimed to test the durability of the above polymer against UV artificial ageing are also reported. 相似文献
97.
A Dual Photoredox- and Cp2TiCl2-Catalyzed Approach for the Direct Access to α-Vinyl-β-hydroxy Esters
Emanuele Pinosa Prof. Andrea Gualandi Dr. Andrea Fermi Prof. Paola Ceroni Prof. Pier Giorgio Cozzi Dr. Francesco Calogero 《European journal of organic chemistry》2023,26(38):e202300421
For the first time, a dual photoredox- and titanocene-catalyzed methodology for the regioselective access to α-vinyl-β-hydroxy esters towards aldehyde allylation with 4-bromobut-2-enoate is reported. The protocol is based on the Barbier-type properties of the inexpensive and available Cp2TiCl2 in catalytic amount (5 mol%). The developed mild reaction conditions gave access to a library of differently functionalized α-vinyl-β-hydroxy esters in moderate diastereoselectivity, employing the commercially available ethyl 4-bromobut-2-enoate and both aromatic and aliphatic aldehydes. The reaction was realized under visible light irradiation, in the presence of an organophotocatalyst (3DPAFIPN, 2 mol%) combined with Hantzsch's ester as the sacrificial reductant. In contrast to other Barbier-type reactions employing ethyl 4-bromobut-2-enoate, the photoredox system ensures a better regioselectivity. Moreover, the use of preformed organometallic nucleophilic species (e. g., dienolborinates), and the need of metal reductants or stoichiometric amount of transition metals in low oxidation state for Barbier-type reactions, is avoided. To support the experimental evidence, a detailed photophysical study shed light on the mechanism of the reaction. 相似文献
98.
In the last decade, planar chiral ferrocenes have attracted a growing interest in several fields, particularly in asymmetric catalysis, medicinal chemistry, chiroptical spectroscopy and electrochemistry. In this frame, the access to pure or enriched enantiomers of planar chiral ferrocenes has become essential, relying on the availability of efficient asymmetric synthesis procedures and enantioseparation methods. Despite this, in enantioseparation science, these metallocenes were not comprehensively explored, and very few systematic analytical studies were reported in this field so far. On the other hand, enantioselective high-performance liquid chromatography has been frequently used by organic and organometallic chemists in order to measure the enantiomeric purity of planar chiral ferrocenes prepared by asymmetric synthesis. On these bases, this review aims to provide the reader with a comprehensive overview on the enantioseparation of planar chiral ferrocenes by discussing liquid-phase enantioseparation methods developed over time, integrating this main topic with the most relevant aspects of ferrocene chemistry. Thus, the main structural features of ferrocenes and the methods to model this class of metallocenes will be briefly summarized. In addition, planar chiral ferrocenes of applicative interest as well as the limits of asymmetric synthesis for the preparation of some classes of planar chiral ferrocenes will also be discussed with the aim to orient analytical scientists towards ‘hot topics’ and issues which are still open for accessing enantiomers of ferrocenes featured by planar chirality. 相似文献
99.
Raffaele Lamanna Giovanna Imparato Paola Tano Angela Braca Mario D'Ercole Giovanni Ghianni 《Magnetic resonance in chemistry : MRC》2017,55(7):639-647
ABSTRACT Proton NMR profiling is nowadays a consolidated technique for the identification of geographical origin of food samples. The common approach consists in correlating NMR spectra of food samples to their territorial origin by multivariate classification statistical algorithms. In the present work, we illustrate an alternative perspective to exploit territorial information, contained in the NMR spectra, which is based on the implementation of a geographic information system (GIS). Nuclear magnetic resonance spectra are used to build a GIS map permitting the identification of territorial regions having strong similarities in the chemical content of the produced food (terroir units). These terroir units can, in turn, be used as input for labeling samples to be analyzed by traditional classification methods. In this work, we describe the methods and the algorithms that permit to produce GIS maps from NMR profiles and apply the described method to the analysis of the geographical distribution of olive oils in an Italian region. In particular, we analyzed by 1H NMR up to 98 georeferenced olive oil samples produced in the Abruzzo Italian region. By using the first principal component of the NMR variables selected according to the Moran test, we produced a GIS map, in which we identified two regions incidentally corresponding to the provinces of Teramo and Pescara. We then labeled the samples according to the province of provenience and built an LDA model that provides a classification ability up to 99% . A comparison between the variables selected in the geostatistics and classification steps is finally performed. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
100.
Francesca Porta Concetta Bifulco Paola Fermo Claudia L. Bianchi Michaela Fadoni Laura Prati 《Colloids and surfaces. A, Physicochemical and engineering aspects》1999,160(3):1380-290
Nanoparticles of Cu2L2O5 (L=Ho, Er) (15–25 nm in size) were synthesised by the intermediate use of W/O microemulsions. In this process the aqueous cores of water/cetyltrimethylammonium bromide/n-octane/1-butanol microemulsions were used as microreactors for the precipitation of Cu2Ho2(CO3)4(OH)2 (25–30 nm) and Cu2Er2(CO3)4(OH)2 (10–40 nm) as precursors. These mixed salts were separated and further decomposed to the corresponding mixed oxides at 900°C for 16 h. All solids were characterised by scanning and transmission electron microscopy, IR, XRPD, ICP-OES, TGA, XPS measurements and elemental analyses. 相似文献