全文获取类型
收费全文 | 1761篇 |
免费 | 63篇 |
国内免费 | 6篇 |
专业分类
化学 | 1293篇 |
晶体学 | 14篇 |
力学 | 11篇 |
数学 | 247篇 |
物理学 | 265篇 |
出版年
2024年 | 3篇 |
2023年 | 11篇 |
2022年 | 29篇 |
2021年 | 39篇 |
2020年 | 36篇 |
2019年 | 45篇 |
2018年 | 36篇 |
2017年 | 25篇 |
2016年 | 64篇 |
2015年 | 59篇 |
2014年 | 61篇 |
2013年 | 127篇 |
2012年 | 127篇 |
2011年 | 149篇 |
2010年 | 98篇 |
2009年 | 102篇 |
2008年 | 136篇 |
2007年 | 108篇 |
2006年 | 107篇 |
2005年 | 90篇 |
2004年 | 78篇 |
2003年 | 50篇 |
2002年 | 56篇 |
2001年 | 21篇 |
2000年 | 16篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 15篇 |
1995年 | 13篇 |
1994年 | 2篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 4篇 |
1989年 | 5篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 4篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 8篇 |
1981年 | 2篇 |
1980年 | 8篇 |
1978年 | 5篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1970年 | 3篇 |
排序方式: 共有1830条查询结果,搜索用时 10 毫秒
841.
A simple one-pot and efficient method is described for the synthesis of pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidinone derivatives 6 via a tandem aza-Wittig/heterocumulene-mediated annulation process. The iminophosphorane 3 reacted with aryl isocyanates, followed by heterocyclization on addition of secondary amines to give the corresponding guanidine intermediates 5, which were cyclized in the presence of a catalytic amount of potassium carbonate to tricyclic compounds 6. Similarly, iminophosphorane 3 reacts with phenols, thiophenol, or ROH to give 2-aryl(alkyl)oxy(thio)pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidinone derivatives 7 in good yields. The corresponding carbodiimide 4c and guanidine-type intermediate compounds 5 could be isolated and characterized, thus confirming the suggested reaction pathway. However, two isomeric pyrazinothienopyrimidinones 8 and 9 may be produced in the reaction of iminophosphorane 3 with aromatic isocyanates and subsequent reaction with primary amines in the presence of a catalytic amount of potassium carbonate. The effects of the nucleophiles and isocyanates on the regioselectivity of the cyclization have been investigated. 相似文献
842.
Juan M. Martínezmendoza Eduardo A. Vzquez Lpez Rafael Moreno Esparza Marcos Flores Alamo Elena I. Klimova 《Journal of heterocyclic chemistry》2006,43(4):1115-1121
Cross‐conjugated monoferrocenyltrienes react with 4‐phenyl‐1,2,4‐triazoline‐3,5‐dione to give mono‐ and bis‐[4+2]‐cycloaddition products. Nonsubstituted and 2,4‐disubstituted 3‐ferrocenylmethylidenepenta‐1,4‐dienes afford respective pyridazine and pyridazino[4,5‐c]pyridazine derivatives. Their structures were established based on 1H and 13C NMR data and X‐ray diffraction analysis. 相似文献
843.
A procedure has been developed for the simultaneous determination of traces amounts of Cd, Cr, Cu, Mn, Ni and Pb from saline oil-refinery effluents and digested vegetable samples using inductively coupled plasma optical emission spectrometry (ICP OES). The procedure is based on cloud point extraction (CPE) of these metals as 2-(bromo-2-pyridylazo)-5-diethyl-amino-phenol (Br-PADAP) complexes into a micellar phase of octylphenoxypolyethoxyethanol (Triton X-114). Optimization of the procedure was performed by response surface methodology (RSM) using a Doehlert design. Principal components (PC) were used to simplify the multiple response analysis. A response surface for the first PC score is useful in determining the optimum conditions for the Cd, Cr, Cu, Mn and Pb determinations whereas the second PC is highly correlated with the Ni response. Improvement factors of 22, 36, 46, 25, 65 and 39, along with limits of detection (3σB) of 0.081, 0.79, 0.38, 0.83, 0.28 and 0.69 μg L−1, and precision expressed as relative standard deviation (%R.S.D., n = 8, 20.0 μg L−1) of 1.5, 2.2, 3.5, 2.6, 2.5 and 2.5 were achieved for Cd, Cr, Cu, Mn, Ni and Pb, respectively. The accuracy was evaluated by spike tests in oil-refinery effluent samples and analysis of a vegetable certified reference material (NIST 1571, orchard leaves). Results found were in agreement with certified values. 相似文献
844.
Solvent accessibility prediction from amino acid sequences has been pursued by several researchers. Such a prediction typically starts by transforming the amino acid category (or type) information into numerical representations. All twenty amino acids can be completely and uniquely represented by 20-dimensional vectors. Here, we investigate if the amino acid space defined in this way really requires twenty dimensions. We tried to develop corresponding representations in fewer dimensions. A method for searching optimal codification schema in an arbitrary space using neural networks was developed. The method is used to obtain optimal encoding of amino acids at various levels of dimensionality, and applied to optimize the amino acid codifications for the prediction of the solvent accessibility values of the proteins using feed-forward neural networks. The traditional 20-dimensional codification seems to be redundant in solving the solvent accessibility prediction problem, since a 1-dimensional codification is able to achieve almost the same degree of accuracy as the 20-dimensional codification. Optimal coding in much fewer dimensions could be used to make the predictions of accessible surface area with almost the same degree of accuracy as that obtained by a fully unique 20-dimensional coding. The 1-dimensional amino acid codification for solvent accessibility prediction obtained by a purely mathematical way based on neural networks is highly correlated with a physical property of the amino acids, namely their average solvent accessibility. The method developed to find the optimal codification is general, although the codification thus produced is dependent on the type of estimated property. 相似文献
845.
846.
Hortal AR Martínez-Haya B Lobato MD Pedrosa JM Lago S 《Journal of mass spectrometry : JMS》2006,41(7):960-968
Molecular weight distributions (MWD) of asphaltenes and their aggregates have been investigated in laser desorption ionization (LDI) mass spectrometric experiments. A systematic investigation of the dependence of the measured MWD on the asphaltene sample density and on the laser pulse energy allows the assignment of most probable molecular weights within 300-500 amu and average molecular weights of 800-1000 amu for the monomeric asphaltenes, as well as for the estimation of the contribution from asphaltene clusters in typical LDI measurements. The results serve to reconcile the existing controversy between earlier mass spectrometric characterizations of asphaltenes based on laser desorption techniques by different groups. Furthermore, the MWD measurements performed on particularly dense samples yield an additional differentiated broad band peaking around 9000-10,000 amu and extending over 20,000 amu, not observed previously in LDI experiments, thereby revealing a strong propensity of the asphaltenes to form clusters with specific aggregation numbers, which is in qualitative agreement with previous theoretical predictions and with the interpretation of measurements performed with other techniques. 相似文献
847.
Eberlin MN 《Journal of mass spectrometry : JMS》2006,41(2):141-156
This article discusses the application of gas-phase ion/molecule reactions for fine structural elucidation in mass spectrometry. This approach is illustrated via a representative collection of class- and functional group-selective reactions, a few of historical relevance as well as by more recent and instructive examples, and their applications. The focus is on reactions performed under well-controlled conditions of sequential mass spectrometry, discussing key mechanistic details and potential applications. Recent and innovative strategies that allow these reactions to be performed under ambient conditions, making this fast, selective and sensitive approach for structural investigation much more generally applicable, are also discussed. 相似文献
848.
Computational singular perturbation (CSP) analysis has been used to gain understanding of the complex kinetic behavior associated with two-stage ignition of large hydrocarbon molecules. To this end, available detailed and reduced chemical kinetics models commonly used in numerical simulations of n-heptane oxidation phenomena are directly analyzed to interpret the underlying fundamental steps leading to two-stage ignition. Unlike previous implementations of the CSP methodology, temperature is included as one of the state variables so that factors controlling ignition can be unambiguously determined. The analyzed models show differences in the factors contributing to the initial development and shutdown of the first ignition stage. However, during the second stage, both models show the importance of the degenerate branching decomposition of hydrogen peroxide, which contradicts some previous interpretations of this phenomenon. 相似文献
849.
Verónica R. Elías Marcos I. Oliva Eliana G. Vaschetto Griselda A. Eimer Silvia P. Silvetti 《Journal of magnetism and magnetic materials》2010,322(21):3438-3442
Mesoporous molecular sieves of MCM-48 type were loaded with iron by the wet impregnation method, using Fe(III) nitrate or Fe(II) sulfate aqueous solutions as Fe sources, to obtain a magnetic porous composite. The iron loaded materials were characterized by XRD, N2 adsorption and DRUV-vis and compared with the Si-MCM-48 host. Their magnetic properties were studied by measuring the hysteresis loops up to 1.5 T at different temperatures (5-300 K) and by magnetization vs. temperature curves following the conventional zero field cooling (ZFC) and field cooling (FC) protocols. Materials with high structure regularity and surface area are obtained, which exhibit a mixed paramagnetic and superparamagnetic behavior, arising in isolated iron ions inserted in the host framework, and in small iron oxide clusters or nanoparticles forming inside the pores, respectively. Larger hematite particles (8-13 nm) grown on the external surface provide a quite small ferromagnetic contribution to the hysteresis loop. 相似文献
850.
BV Soares SM Morais RO dos Santos Fontenelle VA Queiroz NS Vila-Nova CM Pereira ES Brito MA Neto EH Brito CS Cavalcante DS Castelo-Branco MF Rocha 《Molecules (Basel, Switzerland)》2012,17(7):8439-8448
The aims of this study were to test the antifungal activity, toxicity and chemical composition of essential oil from C. sativum L. fruits. The essential oil, obtained by hydro-distillation, was analyzed by gas chromatography/mass spectroscopy. Linalool was the main constituent (58.22%). The oil was considered bioactive, showing an LC?? value of 23 μg/mL in the Artemia salina lethality test. The antifungal activity was evaluated against Microsporum canis and Candida spp. by the agar-well diffusion method and the minimum inhibitory concentration (MIC) and the minimum fungicidal concentration (MFC) were established by the broth microdilution method. The essential oil induced growth inhibition zones of 28 ± 5.42 and 9.25 ± 0.5 for M. canis and Candida spp. respectively. The MICs and MFCs for M. canis strains ranged from 78 to 620 and 150 to 1,250 μg/mL, and the MICs and MFCs for Candida spp strains ranged from 310 to 620 and 620 to 1,250 μg/mL, respectively. C. sativum essential oil is active in vitro against M. canis and Candida spp. demonstrating good antifungal activity. 相似文献