全文获取类型
收费全文 | 6505篇 |
免费 | 208篇 |
国内免费 | 10篇 |
专业分类
化学 | 3865篇 |
晶体学 | 39篇 |
力学 | 162篇 |
数学 | 1362篇 |
物理学 | 1295篇 |
出版年
2023年 | 42篇 |
2022年 | 56篇 |
2021年 | 70篇 |
2020年 | 88篇 |
2019年 | 87篇 |
2018年 | 112篇 |
2017年 | 98篇 |
2016年 | 168篇 |
2015年 | 164篇 |
2014年 | 181篇 |
2013年 | 391篇 |
2012年 | 402篇 |
2011年 | 986篇 |
2010年 | 251篇 |
2009年 | 220篇 |
2008年 | 344篇 |
2007年 | 327篇 |
2006年 | 297篇 |
2005年 | 308篇 |
2004年 | 255篇 |
2003年 | 202篇 |
2002年 | 184篇 |
2001年 | 96篇 |
2000年 | 80篇 |
1999年 | 66篇 |
1998年 | 57篇 |
1997年 | 57篇 |
1996年 | 64篇 |
1995年 | 46篇 |
1994年 | 37篇 |
1993年 | 33篇 |
1992年 | 32篇 |
1991年 | 30篇 |
1990年 | 38篇 |
1988年 | 25篇 |
1987年 | 25篇 |
1986年 | 22篇 |
1985年 | 55篇 |
1984年 | 59篇 |
1983年 | 31篇 |
1982年 | 50篇 |
1981年 | 40篇 |
1980年 | 59篇 |
1979年 | 46篇 |
1978年 | 41篇 |
1977年 | 46篇 |
1976年 | 44篇 |
1975年 | 33篇 |
1974年 | 24篇 |
1973年 | 29篇 |
排序方式: 共有6723条查询结果,搜索用时 15 毫秒
91.
Gioacchini AM Menotta M Bertini L Rossi I Zeppa S Zambonelli A Piccoli G Stocchi V 《Rapid communications in mass spectrometry : RCM》2005,19(17):2365-2370
This study describes a rapid method to identify different truffle species by analysis of their volatile compound fraction using static headspace solid-phase microextraction gas chromatography/mass spectrometry. The volatile organic compounds (VOCs) were extracted using a new 2-cm 50/30 microm DVB/CAR/PDMS fiber placed for 10 min in the headspace of the truffle sample with the vial maintained at 20 degrees C (in a thermostatically controlled analysis room). The mass spectra of the VOC chromatograms were represented as 'fingerprints' of the analysed samples. Next, stepwise factorial discriminant analysis afforded a limited number of characteristic fragment ions that allowed a classification of the truffle species studied. This new method provides an effective approach to rapid quality control and identification of truffle species by analysis of their volatile fraction. Moreover, this method offers the advantage of minimizing thermal, mechanical, and chemical modifications of the truffles, thereby reducing the risk of analytical artifacts. 相似文献
92.
93.
Viviane Cândida da Silva Andréia de Oliveira Faria Vanderlan da Silva Bolzani Márcia Nasser Lopes 《Helvetica chimica acta》2007,90(9):1781-1785
Phytochemical investigations of the stems of a specimen of Alibertia macrophylla led to the isolation and characterization of the new diterpene ent‐kaurane‐2β,3α,16α‐triol ( 1 ), along with triterpenes 2 – 8 , iridoids 9 – 12 , and phenolic acids 13 – 15 . The structure of 1 was established based on spectroscopic studies (1H‐ and 13C‐NMR, IR, and HR‐ESI‐MS). This is the first report of the isolation of a diterpene from the Alibertia genus in Rubiaceae. 相似文献
94.
Rossi LM Shi L Quina FH Rosenzweig Z 《Langmuir : the ACS journal of surfaces and colloids》2005,21(10):4277-4280
We have developed a simple method to prepare bright and photostable luminescent silica nanoparticles of different sizes and narrow size distribution in high yield. The method is based on the use of St?ber synthesis in the presence of a fluorophore to form bright silica nanoparticles. Unlike micro-emulsion-based methods often used to prepare luminescent silica particles, the St?ber method is a one-pot synthesis that is carried out at room temperature under alkaline conditions in ethanol:water mixtures and avoids the use of potentially toxic organic solvents and surfactants. Our luminescent particles contained the transition metal complex tris(1,10-phenanthroline) ruthenium(II) chloride, [Ru(phen)3]Cl2. They showed higher photostability and a longer fluorescence lifetime compared to free Ru(phen)3 solutions. Leakage of dye molecules from the silica particles was negligible, which was attributed to strong electrostatic attractions between the positively charged ruthenium complex and the negatively charged silica. To demonstrate the utility of the highly luminescent silica nanoparticles in bioassays, we further modified their surface with streptavidin and demonstrated their binding to biotinylated glass slides. The study showed that digital counting of the luminescent nanoparticles could be used as an attractive alternative to detection techniques involving analogue luminescence detection in bioanalytical assays. 相似文献
95.
The binding and availability of metals (Al, Ca, Cd, Co, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Zn) in therapeutically applied peat (Grosses Gifhorner Moor, Sassenburg/North Germany) was characterized by means of a versatile extraction approach. Aqueous extracts of peat were obtained by a standardized batch equilibrium procedure using high-purity water (pH 4.5 and 5.0), 0.01 mol l(-1) calcium chloride solution, 0.01 mol l(-1) ethylenediaminetetraacetic acid (EDTA) and 0.01 mol l(-1) diethylenetriamine pentaacetic acid (DTPA) solution as metal extractants. In addition, the availability of peat-bound metal species was kinetically studied by collecting aliquots of extracts after different periods of extraction time (5, 10, 15, 30, 60 and 120 min). Metal determinations were performed by atomic spectrometry methods (AAS, ICP-OES) and dissolved organic matter (DOM) was characterized by UV/Vis measurements at 254 and 436 nm, respectively. Of the extractants studied Ca, Mg and Mn were the most available metals, in contrast to peat-bound Fe and Al. The relative standard deviation s(r) of the developed extraction procedures was mostly in the range of 4 to 20%, depending on the metal and its concentration in peat. A pH increase favored the extraction of metals and DOM from peat revealing complex extraction kinetics. Moreover, a competitive exchange between peat-bound metal species and added Cu(II) ions showed that >100 mg of Cu(II) per 50 g wet peat was necessary to exchange the maximum of bound metals (e.g. 21.8% of Al, 3.9% of Fe, 79.0% of Mn, 81.9% of Sr, related to their total content). 相似文献
96.
Grancher D Jaussaud P Durix A Berthod A Fenet B Moulard Y Bonnaire Y Bony S 《Journal of chromatography. A》2004,1059(1-2):73-81
This paper describes a new method of purification of the Lolitrem B, a tremorgenic mycotoxin produced in planta by the endophytic fungus Neotyphodium lolii. The method is based on the large-scale isolation of the toxin by countercurrent chromatography (CCC). The lolitrem B content in endophyted ryegrass seed, 11 microg/g or 11 ppm, is extracted by stirring finely ground seeds with ethanol for 3 h at room temperature. The concentrated crude extract contains about 0.6 mg/g or 600 ppm of lolitrem B. It is then submitted to CCC purification with a biphasic four-solvent liquid system. A 160-fold enrichment was obtained in one step producing a raffinate containing 10% or 100 mg/g of the toxin. Further purifications were then performed by thin layer and low pressure liquid chromatography. Twenty-eight micrograms of lolitrem B with a 96% purity grade were obtained from 8 kg of seeds (yield 32%). 相似文献
97.
Andrés J Moliner V Safont VS Domingo LR Picher MT 《The Journal of organic chemistry》1996,61(22):7777-7783
As a model of the chemical reactions that take place in the active site of gluthatione reductase, the nature of the molecular mechanism for the hydride transfer step has been characterized by means of accurate quantum chemical characterizations of transition structures. The calculations have been carried out with analytical gradients at AM1 and PM3 semiempirical procedures, ab initio at HF level with 3-21G, 4-31G, 6-31G, and 6-31G basis sets and BP86 and BLYP as density functional methods. The results of this study suggest that the endo relative orientation on the substrate imposed by the active site is optimal in polarizing the C4-Ht bond and situating the system in the neighborhood of the quadratic region of the transition structure associated to the hydride transfer step on potential energy surface. The endo arrangement of the transition structure results in optimal frontier HOMO orbital interaction between NADH and FAD partners. The geometries of the transition structures and the corresponding transition vectors, that contain the fundamental information relating reactive fluctuation patterns, are model independent and weakly dependent on the level of theory used to determine them. A comparison between simple and complex molecular models shows that there is a minimal set of coordinates describing the essentials of hydride transfer step. The analysis of transition vector components suggests that the primary and secondary kinetic isotope effects can be strongly coupled, and this prompted the calculation of deuterium and tritium primary, secondary, and primary and secondary kinetic isotope effects. The results obtained agree well with experimental data and demonstrate this coupling. 相似文献
98.
Néouze MA Le Bideau J Leroux F Vioux A 《Chemical communications (Cambridge, England)》2005,(8):1082-1084
The confinement of ionic liquids within a porous silica matrix was performed by a one-step non-hydrolytic sol-gel route, leading to hybrid materials (called "ionogels") featuring both the mechanical and transparency properties of silica gels and the high ionic conductivity and thermal stability of ionic liquids. 相似文献
99.
G. Wytze Meindersma Lara M. Galán Sánchez Antje R. Hansmeier André B. de Haan 《Monatshefte für Chemie / Chemical Monthly》2007,138(11):1125-1136
Summary. Ionic liquids offer tremendous opportunities to intensify reactions and separations in process technologies by tuning their
physical and chemical properties. Several ionic liquids are suitable for the separation of aromatic and aliphatic hydrocarbons.
CO2 absorption behavior was influenced by the functionalized chains appended to the room temperature ionic liquid (RTIL) cation.
Ionic liquids seem able to combine the chemical features of amine solutions with the characteristic advantages of the physical
solvents used for CO2 absorption. 相似文献
100.
B. Sourd P. André J. Aubreton M.-F. Elchinger 《Plasma Chemistry and Plasma Processing》2007,27(1):35-50
In this paper, calculated values of the viscosity and thermal conductivity of atomic nitrogen, taking into account three species
(the ground and two excited states), are presented. The calculations, which assume that the temperature dependent probability
of occupation of the states is given by the Boltzmann factor, are performed for atmospheric-pressure in the temperature range
from 1,000 to 20,000 K. Six collision integrals are used in calculating the transport coefficients and we have introduced
new averaged collision integrals where the weight associated at each interacting species pair is the probable collision frequency.
The influence of the collision integral values and energy transfer between two different species is studied. These results
are compared which those of published theoretical studies. 相似文献