全文获取类型
收费全文 | 1695篇 |
免费 | 65篇 |
国内免费 | 16篇 |
专业分类
化学 | 1060篇 |
晶体学 | 5篇 |
力学 | 67篇 |
数学 | 339篇 |
物理学 | 305篇 |
出版年
2024年 | 3篇 |
2023年 | 19篇 |
2022年 | 44篇 |
2021年 | 55篇 |
2020年 | 36篇 |
2019年 | 43篇 |
2018年 | 34篇 |
2017年 | 30篇 |
2016年 | 47篇 |
2015年 | 47篇 |
2014年 | 73篇 |
2013年 | 89篇 |
2012年 | 140篇 |
2011年 | 156篇 |
2010年 | 97篇 |
2009年 | 82篇 |
2008年 | 100篇 |
2007年 | 105篇 |
2006年 | 85篇 |
2005年 | 66篇 |
2004年 | 75篇 |
2003年 | 81篇 |
2002年 | 67篇 |
2001年 | 34篇 |
2000年 | 11篇 |
1999年 | 13篇 |
1998年 | 17篇 |
1997年 | 16篇 |
1996年 | 7篇 |
1995年 | 11篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 8篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1983年 | 6篇 |
1982年 | 4篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 7篇 |
1978年 | 3篇 |
1975年 | 3篇 |
1972年 | 2篇 |
1902年 | 1篇 |
排序方式: 共有1776条查询结果,搜索用时 0 毫秒
31.
Osei-Twum EY Litorja LA Darkwa J Maisela LL Lesimple A Mamer O 《Journal of the American Society for Mass Spectrometry》2005,16(1):94-99
The mass spectral behavior of a number of organometallic complexes containing the Group 10 metals Ni, Pd, and Pt, together with various thiolate ligands were studied. For Pd, two main types of complexes, differing by the substituents on the phosphorus atom were studied. Types I and II were substituted with bis(diphenylphosphino)ferrocene and bis(diisopropylphosphino)ferrocene ligands, respectively. The Ni complexes, except for one, and the Pd Type I complexes had no molecular radical cations (M(+.)) in their EI spectra. On the other hand, all the Pt complexes showed intense M(+.) ions in their EI spectra indicating that these complexes were more stable as radical cations than those of Ni and Pd. The FAB and MALDI spectra of all the complexes displayed intense quasi-molecular ions (MH(+)) and the fragmentations in both modes were similar. The MALDI spectra of several complexes displayed only M(+.) ions while one gave evidence of both MH(+) and M(+.) ions. Several Pd Type II complexes yielded intense M(+.) in their EI spectra. 相似文献
32.
Jaqueline Cornejo-Campos Yenny Adriana Gmez-Aguirre Jos Rodolfo Velzquez-Martínez Oscar Javier Ramos-Herrera Carolina Estefanía Chvez-Murillo Francisco Cruz-Sosa Carlos Areche Emmanuel Cabaas-García 《Molecules (Basel, Switzerland)》2022,27(12)
Acanthocereus tetragonus (L.) Hummelinck is used as an alternative food source in some Mexican communities. It has been shown that the young stems of A. tetragonus provide crude protein, fiber, and essential minerals for humans. In this work, we analyzed the phytochemical profile, the total phenolic content (TPC), and the antioxidant activity of cooked and crude samples of A. tetragonus to assess its functional metabolite contribution to humans. The phytochemical profile was analyzed using Ultra-High-Performance Liquid Chromatography coupled to High-Resolution Mass Spectrometry (UHPLC-PDA-HESI-Orbitrap-MS/MS). Under the proposed conditions, 35 metabolites were separated and tentatively identified. Of the separated metabolites, 16 occurred exclusively in cooked samples, 6 in crude samples, and 9 in both crude and cooked samples. Among the detected compounds, carboxylic acids, such as threonic, citric, and malic acids, phenolic acids, and glycosylated flavonoids (luteolin-O-rutinoside) were detected. The TPC and antioxidant activity were analyzed using the Folin–Ciocalteu method and the 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical inhibition method, respectively. The TPC and antioxidant activity were significantly reduced in the cooked samples. We found that some metabolites remained intact after the cooking process, suggesting that A. tetragonus represents a source of functional metabolites for people who consume this plant species. 相似文献
33.
Dionysios Raptis Charalampos Livas George Stavroglou Rafaela Maria Giappa Emmanuel Tylianakis Taxiarchis Stergiannakos George E. Froudakis 《Molecules (Basel, Switzerland)》2022,27(11)
The interaction strength of nitrogen dioxide (NO2) with a set of 43 functionalized benzene molecules was investigated by performing density functional theory (DFT) calculations. The functional groups under study were strategically selected as potential modifications of the organic linker of existing metal–organic frameworks (MOFs) in order to enhance their uptake of NO2 molecules. Among the functional groups considered, the highest interaction energy with NO2 (5.4 kcal/mol) was found for phenyl hydrogen sulfate (-OSO3H) at the RI-DSD-BLYP/def2-TZVPP level of theory—an interaction almost three times larger than the corresponding binding energy for non-functionalized benzene (2.0 kcal/mol). The groups with the strongest NO2 interactions (-OSO3H, -PO3H2, -OPO3H2) were selected for functionalizing the linker of IRMOF-8 and investigating the trend in their NO2 uptake capacities with grand canonical Monte Carlo (GCMC) simulations at ambient temperature for a wide pressure range. The predicted isotherms show a profound enhancement of the NO2 uptake with the introduction of the strongly-binding functional groups in the framework, rendering them promising modification candidates for improving the NO2 uptake performance not only in MOFs but also in various other porous materials. 相似文献
34.
Mohamed Abboud Victor Mamane Emmanuel Aubert 《Acta Crystallographica. Section C, Structural Chemistry》2013,69(1):56-60
The crystal packing of the title compound, C24H18Br2N2S2, is rationalized using the PIXEL method, which allows a separation of the intermolecular interaction energy into Coulombic, polarization, dispersion and repulsion contributions. Infinite (01) molecular planes are formed through π–π stacking and other minor interactions, including a Br...S contact, with the σ hole of the Br atom pointing towards the S‐atom lone pair. The title compound has crystallographically imposed twofold symmetry, with the twofold axis at the mid‐point of the central C—C bond. 相似文献
35.
Toshiyuki Fujii Frédéric Moynier Arnaud Agranier Emmanuel Ponzevera Minori Abe Akihiro Uehara Hajimu Yamana 《Journal of Radioanalytical and Nuclear Chemistry》2013,296(1):261-265
Environmental transport of Tl is affected by redox reaction between Tl(I) and Tl(III) and ligand exchange reactions of them. In order to deepen the knowledge of Tl chemistry, we investigated fractionation of Tl stable isotopes (203Tl and 205Tl) in a chemical exchange system. Tl isotopes were fractionated in a liquid–liquid extraction system, in which aqueous and organic phases are hydrochloric acid solution and dichloroethane including a crown ether, respectively. After purification by ion-exchange chemistry, the isotope ratio of 205Tl/203Tl in equilibrated aqueous phase was measured precisely by multiple-collector–inductively-coupled-plasma–mass-spectrometry. A large isotope fractionation >1 ‰ was found. Electronic structures of possible Tl species (hydrated Tl+, Tl3+, and Tl chlorides) were calculated by ab initio methods, and the isotope fractionation factor was theoretically obtained. The isotope fractionation via intramolecular vibrations was calculated to be much smaller than the experimental result. The isotope fractionation via isotopic change in nuclear volume, named the nuclear field shift effect, was calculated to be >1 ‰ in Tl(I)–Tl(III) redox systems and/or ligand exchange systems of Tl(III). The nuclear field shift effect was found to be the major origin of Tl isotope fractionation. 相似文献
36.
Thiago Henrique Napoleão Teodomiro Gomes dos Santos-Filho Emmanuel Viana Pontual Rodrigo da Silva Ferreira Luana Cassandra Breitenbach Barroso Coelho Patrícia Maria Guedes Paiva 《Applied biochemistry and biotechnology》2013,171(3):744-755
This work reports the use of matrices containing Cratylia mollis lectins (Cramoll 1,2,3-Sepharose and Cramoll 3-Sepharose) for isolation of glycoproteins from fetal bovine serum, human colostrum, hen egg white, and human blood plasma. Cramoll 1,2,3-Sepharose was able to bind a glycoprotein from fetal bovine serum which showed the same fetuin electrophoretic profile. The data indicate that this protein adsorbed to the matrix by interaction with Cramoll 3. Cramoll 1,2,3-Sepharose was not efficient to retain glycoproteins from human colostrum or commercial ovalbumin. Cramoll 3-Sepharose bound ovalbumin, and the support retained protein from hen egg white. Protein peaks eluted from the column with 1.0 M NaCl or 0.3 M galactose showed apparent molecular mass of ovalbumin. Two main proteins from blood plasma with apparent molecular mass 67 (similar to albumin) and 50 kDa (similar to fetuin) adsorbed on Cramoll 3-Sepharose and were eluted with 1.0 M NaCl as a single peak. Elution of adsorbed plasma proteins with 0.3 M galactose was less selective than with 1.0 M NaCl as revealed by SDS-PAGE. In conclusion, the Cramoll 1,2,3-Sepharose and Cramoll 3-Sepharose matrices were useful to separate glycoproteins from complex protein mixtures, and the adsorption phenomena was a carbohydrate-dependent event. 相似文献
37.
Emmanuel Mikros George Labrinidis Serge Pérez 《Journal of carbohydrate chemistry》2013,32(9):1319-1349
ABSTRACT Relaxed-residue energy maps based on the MM3 force field were computed for the methyl glycosides of eight C-linked D-glucosyl disaccharides: the two-bond axial-equatorial linked disaccharides β-kojibioside [(1→2)α–], β-nigeroside [(1→3)α–] and β-maltose [(1→4)α–], the two-bond equatorial-equatorial linked disaccharides β-sophoroside [(1→2)β–], β–laminarabioside [(1→3)β-], β–cellobioside [(1→4)β–] and the three-bond-linked (1→6) disacharides C-isomaltoside and C-gentiobioside. Optimized structures were calculated on a 20° grid spacing of the torsional angles about the C-glycosidic bonds and the final isoenergy surfaces were based on 11664 conformations, for the two-bond-linked disaccharides and 69984 conformations for the three-bond-linked disaccharides. Boltzmann-weighted 3J coupling constants were calculated and compared to the experimental values. They are satisfactory except for maltose where hydrogen bonds cause an over-estimation of the energy differences between the conformers. The energy maps are similar to maps of the corresponding O-disaccharides, but there are differences in the locations and the relative energies of the minima. The preferred conformations of the C-glycosidic bonds are as if they were conforming to the exo-anomeric effect but are closer to staggered conformations than shown by the MM3 results for the O-linkages. 相似文献
38.
Dr. Lynnie Trzoss Dr. Jing Xu Michelle H. Lacoske Prof. Dr. William C. Mobley Prof. Dr. Emmanuel A. Theodorakis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(20):6398-6408
Majucin‐type sesquiterpenes from Illicium sp., such as jiadifenolide ( 2 ), jiadifenin ( 3 ), and (1R,10S)‐2‐oxo‐3,4‐dehydroxyneomajucin ( 4 , ODNM), possess a complex caged chemical architecture and remarkable neurotrophic activities. As such, they represent attractive small‐molecule leads against various neurodegenerative diseases. We present an efficient, enantioselective, and unified synthesis of 2 , 3 , and 4 and designed analogues that diverge from tetracyclic key intermediate 7 . The synthesis of 7 is highlighted by the use of an enantioselective Robinson annulation reaction (construction of the AB rings), a Pd‐mediated carbomethoxylation reaction (construction of the C ring), and a one‐pot oxidative reaction cascade (construction of the D ring). Evaluation of the neurotrophic activity of these compounds led to the identification of several highly potent small molecules that significantly enhanced the activity of nerve growth factor (NGF) in PC‐12 cells. Moreover, efforts to define the common pharmacophoric motif suggest that substitution at the C‐10 center significantly affects bioactivity, while the hemiketal moiety of 2 and 3 and the C‐1 substitution might not be critical to the neurotrophic activity. 相似文献
39.
40.
Emmanuel Urandu Mapesa Ludwig Popp Wycliffe Kiprop Kipnusu Martin Tress Friedrich Kremer 《Soft Materials》2014,12(4):S22-S30
Broadband Dielectric Spectroscopy (BDS) is used to probe the molecular dynamics of Type A polymer, poly(cis-1,4-isoprene), when confined in the 1-dimensional (1D) exploring space of thin layers and the 2-dimensional (2D) constraining geometry of unidirectional anodic aluminum oxide (AAO) nanopores. For both cases, it was observed that the structural relaxation remains bulk-like in its mean relaxation rate, although the distribution of its relaxation times is broadened in 2D confinement. Furthermore, the fluctuation of the end-to-end vector is interrupted, with the 1D case being relatively less pronounced. By this clear-cut comparison, it is demonstrated that the effects of confinement on molecular dynamics depend, inter alia, on the dimensionality of the restricting space. 相似文献