全文获取类型
收费全文 | 3972篇 |
免费 | 98篇 |
国内免费 | 16篇 |
专业分类
化学 | 2466篇 |
晶体学 | 16篇 |
力学 | 274篇 |
数学 | 833篇 |
物理学 | 497篇 |
出版年
2023年 | 19篇 |
2022年 | 78篇 |
2021年 | 101篇 |
2020年 | 83篇 |
2019年 | 72篇 |
2018年 | 56篇 |
2017年 | 46篇 |
2016年 | 122篇 |
2015年 | 112篇 |
2014年 | 109篇 |
2013年 | 201篇 |
2012年 | 220篇 |
2011年 | 237篇 |
2010年 | 168篇 |
2009年 | 147篇 |
2008年 | 203篇 |
2007年 | 208篇 |
2006年 | 200篇 |
2005年 | 179篇 |
2004年 | 160篇 |
2003年 | 111篇 |
2002年 | 141篇 |
2001年 | 39篇 |
2000年 | 44篇 |
1999年 | 40篇 |
1998年 | 32篇 |
1997年 | 41篇 |
1996年 | 47篇 |
1995年 | 35篇 |
1994年 | 32篇 |
1993年 | 42篇 |
1992年 | 47篇 |
1991年 | 31篇 |
1990年 | 14篇 |
1989年 | 21篇 |
1988年 | 21篇 |
1987年 | 33篇 |
1986年 | 15篇 |
1985年 | 33篇 |
1984年 | 36篇 |
1983年 | 39篇 |
1982年 | 34篇 |
1981年 | 48篇 |
1980年 | 47篇 |
1979年 | 41篇 |
1978年 | 26篇 |
1977年 | 29篇 |
1976年 | 23篇 |
1975年 | 19篇 |
1967年 | 13篇 |
排序方式: 共有4086条查询结果,搜索用时 15 毫秒
121.
[reaction: see text] 2,3-Disubstituted furo[3,2-b]pyridines, 2,3-disubstituted furo[2,3-b]pyridines, and 2,3-disubstituted furo[2,3-c]pyridines are readily prepared under mild conditions via the palladium-catalyzed cross-coupling of 1-alkynes with o-iodoacetoxy- or o-iodobenzyloxypyridines, followed by electrophilic cyclization by I(2) or by PdCl(2) under a balloon of carbon monoxide. 相似文献
122.
Isotope dilution determination of polycyclic aromatic hydrocarbons in olive pomace oil by gas chromatography-mass spectrometry 总被引:2,自引:0,他引:2
Diletti G Scortichini G Scarpone R Gatti G Torreti L Migliorati G 《Journal of chromatography. A》2005,1062(2):247-254
A gas chromatographic (GC) method with mass spectrometry detection (MS) for the determination of eight polycyclic aromatic hydrocarbons (PAHs) in olive pomace oil has been developed. The oil was diluted with n-pentane and extracted by liquid-liquid partition with dimethyl sulphoxide (DMSO). After water addition and back-extraction with cyclohexane, a thin-layer chromatography on silica gel was performed as a further purification step. The PAHs spot was scraped off from the plate and the final extract was concentrated and analysed by GC-MS in full scan mode. The eight PAHs under investigation were determined in the presence of the corresponding labelled compounds added as internal standards to the sample at the beginning of the analytical process. The identified PAHs were then quantified by the isotope dilution methodology assuring the compensation of the concentration of each analyte for any variation in the sample preparation. The method precision was satisfactory with relative standard deviation (R.S.D.) values in the range 3.6-12.7% for all PAHs. The average recovery rates ranged from 69.0 to 97.5%. Accuracy was also calculated for benzo[k]fluoranthene, benzo[a]pyrene, indeno[1,2,3-cd]pyrene and benzo[ghi]perylene by analysing a certified reference material (CRM 458, coconut oil) with adequate results. All response curves exhibited a linear fit from 0.1 to 10 microg ml(-1) and the determination coefficients R2 were better than 0.9942. The limits of detection (0.1-0.4 microg kg(-1)) were acceptable when compared with the maximum permitted limit of 2 microg kg(-1) for each of the eight considered PAHs and 5 microg kg(-1) for the sum of the eight PAHs established by the Italian legislation. Measurement uncertainty was finally calculated identifying and quantifying the uncertainty components of the analytical process. The relative expanded uncertainties (Uc), expressed as percent values were in the range 8.5-11.4% thus appropriate for residues quantification in the range of concentrations considered in the present study. 相似文献
123.
Dalpozzo R De Nino A Maiuolo L Procopio A Tagarelli A Sindona G Bartoli G 《The Journal of organic chemistry》2002,67(25):9093-9095
A new and chemoselective method for the cleavage of alkyl and cyclic acetals and ketals at room temperature in wet nitromethane by using catalytic cerium(III) trifluoromethane sulfonate is presented. The high yields, the observed selectivity, the very gentle reaction conditions, and the almost neutral pH make this procedure particularly attractive for multistep synthesis. 相似文献
124.
Both cis- and trans-N-benzyl-azetidine-2,4-dimethanols5 and 6 were prepared and submitted to acetylation in organic solvents catalyzed by lipases. Asymmetrization of diol 5 gave ohe corresponding monoacetate 7, while double sequential kinetic resolution of reacemic 6 gave optically enriched diol 6b and its enantiomer as the corresponding diacetate 10a. Optimized reaction conditions furnished 7, 6b and 10a with e.e. > 99%. 相似文献
125.
Alberto Plaza Ciro Balestrieri Giuseppe Bifulco Arafa Hamed Sonia Piacente 《Tetrahedron》2005,61(31):7470-7480
Eight new 14,15-secopregnane glycosides, namely argelosides C-J, possessing two ketal functions involved in three five-membered rings, have been isolated from the hairy seeds of Solenostemma argel. Their structures have been established by MS and NMR experiments, combined with quantum mechanical calculations of the 13C chemical shifts for the interpretation of the experimental data. On the basis of the obtained results, the structures of argelosides A and B have been revised. Additionally, the effect of these compounds on the VEGF-induced in Kaposi's sarcoma cell proliferation was evaluated. Results indicated that all the compounds reduced the cell proliferation in a dose-dependent manner. 相似文献
126.
Gianni Zotti Sandro Zecchin Giuseppe Pilloni 《Journal of organometallic chemistry》1979,181(2):375-386
The new iron compound, trans-[Fe(DPE)2(MeCN)2] (ClO4)2 (DPE=PPh2CH2CH2PPh2), has been prepared and investigated electrochemically. In acetonitrile the complex shows two reduction steps, consistent with the formation of the stable iron(I) species, [Fe(DPE)2(MeCN)]+ and the rather labile π-bonded acetonitrile adduct, Fe(DPE)2(π-MeCN), respectively. Acetonitrile substitution by carbon monoxide leads to formation of the carbonylated species, which have been characterized, and examined by electrochemical techniques. A significant feature is that trans-[Fe(CO)2(DPE)2]2+, unlike trans-[Fe(DPE)2(MeCN)2]2+, takes up two electrons in a single process, the unstable d7 intermediate undergoing a fast disproportionation. A tentative interpretation of this behaviour is suggested. 相似文献
127.
Giuseppe Werber Francesco Buccheri Manlio Gentile 《Journal of heterocyclic chemistry》1977,14(7):1263-1265
The ambident nucleophilic behaviour of some 2-amino-5-H-1,3,4-thiadiazoles in alkylation, acylation and nitrosation reaction has been verified. The structures assigned to the 2-amino-1,3,4-thiadiazoles ( 1a-i ) and to the Δ2-1,3,4-thiadiazolines ( 2a-e ) agree with the spectral data. 相似文献
128.
Cristina Rota Lino Liverani Franco Spelta Giuseppe Mascellani Aldo Tomasi Anna Iannone 《Research on Chemical Intermediates》2006,32(1):73-81
The use of low-molecular-weight heparins (LMWHs) has become common, since compared to unfractionated heparin (UFH), they have
a much longer plasma half-life and lower incidence of side effects. LMWHs are derived from the depolymerization of UFH, obtained
either chemically, physically or enzymatically. We employed electron spin resonance (ESR) spectroscopy to study the depolymerization
of UFH by copper in the presence of hydrogen peroxide. A stable nitroxide radical was detected. This could be generated by
the hydroxyl radical attack either to the N-SO−3 group or to free amino groups present in the UFH preparation. 相似文献
129.
Fungaloi P Waterman P Nigri G Statius-van Eps R Sluiter W van Urk H LaMuraglia G 《Photochemistry and photobiology》2003,78(5):475-480
Photodynamic therapy (PDT) is based on a photochemical reaction using a photosensitizer and light to produce reactive oxygen species that have biological effects. Although its application in some fields is largely based on thrombosis, in the vascular setting thrombosis must be prevented. In this study we examined the effects of PDT on the changes in activity of thrombomodulin (TM) and tissue factor (TF) as important regulators of the coagulation process of endothelial cells. Human umbilical vein endothelial cells were treated with PDT (chloro-aluminum-sulfonated phthalocyanine, lambda = 630 nm) at different light-energy doses, and TM and TF levels were measured using fluorescence spectroscopy. Microparticles (MP) were analyzed using flow cytometry analysis. PDT alters the thrombogenic state of endothelial cells by causing decreased expression of TM and increased expression of functional TF in a light-energy dose-dependent way. PDT-treated endothelial cells shed large numbers of MP containing high levels of TF. TF functionality of PDT-treated cells, measured by a Factor Xa-generating assay, was high. TF was located mostly intracellularly and in MP. The disturbed anticoagulant balance described in this study may explain the occurrence of thrombosis induced by PDT and, if not contained, dispute the suitability of PDT as an adjuvant modality to treat vascular restenosis. 相似文献
130.
Grasso D Grasso G Guantieri V Impellizzeri G La Rosa C Milardi D Micera G Osz K Pappalardo G Rizzarelli E Sanna D Sóvágó I 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,12(2):537-547
An abnormal interaction between copper and the prion protein is believed to play a pivotal role in the pathogenesis of prion diseases. Copper binding has been mainly attributed to the N-terminal domain of the prion protein, but this hypothesis has recently been challenged in some papers which suggest that the C-terminal domain might also compete for metal anchoring. In particular, the segment corresponding to the helix II region of the prion protein, namely PrP180-193, has been shown both to bind copper and to exhibit a copper-enhanced cytotoxicity, as well as to interact with artificial membranes. The present work is aimed at extending these results by choosing the most representative model of this domain and by determining its copper affinity. With this aim, the different role played by the electrostatic properties of the C- and N-termini of PrP180-193 (VNITIKQHTVTTTT) in determining its conformational behaviour, copper coordination and ability to perturb model membranes was investigated. Owing to the low solubility of PrP180-193, its copper affinity was evaluated by using the shorter PrPAc184-188NH2 (IKQHT) analogue as a model. ESI-MS, ESR, UV/Vis, and CD measurements were carried out on the copper(II)/PrPAc184-188NH2 and copper(II)/PrP180-193NH2 systems, and showed that PrPAc184-188NH2 is a reliable model for the metal interaction with the helix II domain. The affinity of copper(II) for the helix II fragment is higher than that for the octarepeat and PrP106-126 peptides. Finally, the different ability of PrP180-193 analogues to perturb the DPPC model membrane was assessed by DSC measurements. The possible biological consequences of these findings are also discussed briefly. 相似文献