全文获取类型
收费全文 | 4297篇 |
免费 | 131篇 |
国内免费 | 37篇 |
专业分类
化学 | 2741篇 |
晶体学 | 9篇 |
力学 | 170篇 |
数学 | 928篇 |
物理学 | 617篇 |
出版年
2023年 | 25篇 |
2022年 | 95篇 |
2021年 | 95篇 |
2020年 | 102篇 |
2019年 | 90篇 |
2018年 | 89篇 |
2017年 | 66篇 |
2016年 | 179篇 |
2015年 | 148篇 |
2014年 | 180篇 |
2013年 | 275篇 |
2012年 | 314篇 |
2011年 | 323篇 |
2010年 | 157篇 |
2009年 | 197篇 |
2008年 | 270篇 |
2007年 | 259篇 |
2006年 | 217篇 |
2005年 | 201篇 |
2004年 | 205篇 |
2003年 | 144篇 |
2002年 | 102篇 |
2001年 | 47篇 |
2000年 | 38篇 |
1999年 | 35篇 |
1998年 | 39篇 |
1997年 | 37篇 |
1996年 | 49篇 |
1995年 | 22篇 |
1994年 | 28篇 |
1993年 | 16篇 |
1992年 | 31篇 |
1991年 | 21篇 |
1990年 | 23篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 18篇 |
1986年 | 15篇 |
1985年 | 34篇 |
1984年 | 28篇 |
1983年 | 27篇 |
1982年 | 30篇 |
1981年 | 15篇 |
1980年 | 20篇 |
1979年 | 11篇 |
1978年 | 19篇 |
1977年 | 13篇 |
1976年 | 14篇 |
1974年 | 11篇 |
1967年 | 4篇 |
排序方式: 共有4465条查询结果,搜索用时 0 毫秒
71.
Irene Dini Vittoria Alborino Stefania Lanzuise Nadia Lombardi Roberta Marra Anna Balestrieri Alberto Ritieni Sheridan L. Woo Francesco Vinale 《Molecules (Basel, Switzerland)》2022,27(12)
The contamination of agricultural products with mycotoxins causes risks to animal and human health and severe economic losses. Mycotoxicoses can be reduced by preventing fungal infection using chemical and biological approaches. The chemical strategies can release toxic molecules; therefore, strategies for biological control are being evaluated, such as using nontoxic fungi and their metabolites. This work evaluated the effect of exoenzymes produced by the beneficial fungus Trichoderma afroharzianum strain T22 in degrading Aflatoxin B1 (AFB1) and Ochratoxin A (OTA). The ability of Trichoderma to produce hydrolases was stimulated by using different inducing substrates. The highest AFB1 and OTA degradation activity was obtained using a medium containing lyophilized mushrooms and crude fiber. The T. afroharzianum T22’s ability to reduce mycotoxins may be attributed to peroxidase enzymes. This study showed that T. afroharzianum strain T22 or its peroxidase supplementation could represent a sustainable strategy for the degradation of AFB1 and OTA in feed and food products. 相似文献
72.
Roberto del Río-Rodríguez Lorena Fragoso-Jarillo Alberto F. Garrido-Castro M. Carmen Maestro Jose A. Fernndez-Salas Jos Alemn 《Chemical science》2022,13(22):6512
Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. Primary, secondary and tertiary alkyl radicals have been shown to be efficiently generated and coupled with a large variety of N-heteroarenes. The method presents a very high functional group tolerance, including various heterocyclic-based natural products, which highlights the robustness of the methodology. This applicability has been further proved in the synthesis of various interesting biologically valuable building blocks. In addition, we have proposed a mechanism based on different proofs and pieces of electrochemical evidence.Herein, we report, a general, facile and environmentally friendly Minisci-type alkylation of N-heteroarenes under simple and straightforward electrochemical conditions using widely available alkyl halides as radical precursors. 相似文献
73.
The capability of certain heavy metal ions to induce fluorescence decrease by a quenching mechanism suggested us to design
and build a sensor potentially tunable for different ions at different concentrations. We propose a quenching-based sensor
exploiting a nanostructured architecture in which fluorescent molecules (the sensing probe) are entrapped to recognize a specific
analyte (heavy metal ions) through an optical transduction. The polyelectrolyte nanostructured system, named nanocapsule,
improves the fluorophore-ion quenching sensitivity allowing a micromolar detection. Furthermore we couple our sensor with
an electrical device in order to refine the sensing procedure: the electric field created allows a metal ions spatial gradient,
necessary to detect a specific element on a single sample solution, avoiding a comparative analysis with an intensity reference
value. Results obtained will show the advantages and the potentialities of our system as a smart toolbox for metal ions detection. 相似文献
74.
Dario Romano Efren Alberto Andablo‐Reyes Sara Ronca Sanjay Rastogi 《Journal of polymer science. Part A, Polymer chemistry》2013,51(7):1630-1635
The use of a hindered phenol to trap free trimethylaluminum (TMA) in methylaluminoxane (MAO) solutions has been reported to improve the performance of single‐site, homogeneous catalysts for olefin polymerization. In the present study, with the help of rheological analyses, we have investigated and compared the molecular weight, molecular weight distribution and entanglement density of ultrahigh molecular weight polyethylene synthesized with a single‐site catalyst activated by MAO and phenol‐modified MAO. While the number average molecular weight (Mn) of the obtained polymers remains the same for both activations, a higher yield and a higher entanglement density are found in the initial stages of polymerization on using phenol‐modified MAO as the cocatalyst. These results suggest that on using the phenol‐modified MAO as activator, a higher number of active sites are obtained. Surprisingly in the presence of untreated MAO, a tail in the higher molecular mass region is produced. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 相似文献
75.
Alberto García‐Peñas José M. Gómez‐Elvira Ernesto Pérez María L. Cerrada 《Journal of polymer science. Part A, Polymer chemistry》2013,51(15):3251-3259
Terpolymers based on propylene with 1‐pentene and 1‐hexene as comonomeric units are satisfactorily synthesized using a metallocene catalyst. Thus, several terpolymers are prepared with distinct overall compositions in comonomers as well as three different 1‐pentene/1‐hexene ratios at a given composition to evaluate the influence on polymerization activity, intrinsic viscosity, and microstructural details. The new trigonal δ polymorph is observed in those quenched terpolymers with a global content in comonomers of about 14 mol %, independently of the ratio between both comonomers. However, preliminary results indicate a profound influence of that ratio on the crystallization rate. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3251–3259 相似文献
76.
Abstract The conformational maps of eight derivatives of the disaccharide α-D-Galp-(1→3)-β-D-Galp sulfated in different positions were obtained using the MM3 force-field specially parameterized for sulfate ester groups. As occurred with MM2, the conformational flexibility of the glycosidic linkage is only slightly hindered by sulfation. A substantial effect of sulfation of the β-D-galactose unit on position 4 shifts the global minimum to positive ΨH (C1′-O3-C3-H3) angles, while sulfation at position 2 of the same unit deepens the well at negative ΨH angles. On the other hand, sulfation on the α-D-galactose unit has a lesser effect, which in any case tends to stabilize the minimum at negative ΨH angles. 相似文献
77.
Prof. Dr. José Luis García Ruano Dr. José Alemán Leyre Marzo Dr. Cuauhtémoc Alvarado Dr. Mariola Tortosa Dr. Sergio Díaz‐Tendero Dr. Alberto Fraile 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8414-8422
We describe the unexpected behavior of the arylsulfonylacetylenes, which suffer an “anti‐Michael” addition of organolithiums producing their alkynylation under very mild conditions. The broad scope, excellent yields, and simplicity of the experimental procedure are the main features of this methodology. A rational explanation of all these results can be achieved by theoretical calculations, which suggest that the association of the organolithiums to the electrophile is a previous step of their intramolecular attack and is responsible for the unexpected “anti‐Michael” reactions observed for substituted sulfonylacetylenes. 相似文献
78.
Arnald Grabulosa Alberto Mannu Antonio Mezzetti Guillermo Muller 《Journal of organometallic chemistry》2012,696(26):4221-4228
A family of eight neutral, pseudotetrahedral piano-stool ruthenium complexes C, of the type [RuCl2(p-cymene)(PArPhR)] (Ar = 1-naphthyl, 9-phenanthryl and 2-biphenylyl; R = Me, i-Pr, OMe, –CH2SiMe3 and –CH2SiPh3) have been prepared and characterised, including the X-ray crystal structure for C6 (Ar = 2-biphenylyl; R = i-Pr). These complexes catalyse the asymmetric hydrogen transfer reaction of acetophenone in refluxing 2-propanol in the presence of potassium tert-butoxyde, reaching full conversions and up to 45% ee after 24 h towards the S enantiomer of 1-phenylethanol. Cationic complexes formed upon treatment of C with one equivalent of AgSbF6 or (Et3O)PF6 are active in the cyclopropanation reaction of styrene and α-methylstyrene by ethyl diazoacetate. Low to moderate conversions (up to 58%), diastereoselectivities (up to 40% de), and moderate enantioselectivities (up to 69% ee) have been found. For both reactions, bulky complexes and C6 in particular lead to the best results. 相似文献
79.
Roberta Sanna Davide Sanna Valeria Alzari Daniele Nuvoli Sergio Scognamillo Massimo Piccinini Massimo Lazzari Emilia Gioffredi Giulio Malucelli Alberto Mariani 《Journal of polymer science. Part A, Polymer chemistry》2012,50(19):4110-4118
Thermoresponsive poly(N‐vinylcaprolactam) nanocomposite hydrogels containing graphene were successfully prepared by frontal polymerization. High concentration of graphene (5.0 mg/mL) was obtained by direct graphite sonication in the self‐same liquid monomer, thus avoiding any chemical manipulation and obtaining “real” graphene as nanofiller instead of one of its more or less oxidized derivative, which is what generally reported in published reports. Furthermore, the corresponding nanocomposites were obtained without using any solvent to be eventually removed. The materials were fully characterized by RAMAN, SEM, and TEM, and their swelling behavior and rheological properties were investigated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012 相似文献
80.