全文获取类型
收费全文 | 1270篇 |
免费 | 97篇 |
国内免费 | 23篇 |
专业分类
化学 | 940篇 |
晶体学 | 2篇 |
力学 | 85篇 |
数学 | 131篇 |
物理学 | 232篇 |
出版年
2024年 | 2篇 |
2023年 | 11篇 |
2022年 | 42篇 |
2021年 | 47篇 |
2020年 | 69篇 |
2019年 | 80篇 |
2018年 | 113篇 |
2017年 | 73篇 |
2016年 | 113篇 |
2015年 | 73篇 |
2014年 | 99篇 |
2013年 | 165篇 |
2012年 | 109篇 |
2011年 | 88篇 |
2010年 | 57篇 |
2009年 | 42篇 |
2008年 | 48篇 |
2007年 | 43篇 |
2006年 | 36篇 |
2005年 | 28篇 |
2004年 | 20篇 |
2003年 | 8篇 |
2002年 | 7篇 |
2001年 | 4篇 |
2000年 | 2篇 |
1999年 | 1篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1989年 | 1篇 |
1985年 | 1篇 |
1981年 | 1篇 |
1980年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有1390条查询结果,搜索用时 15 毫秒
11.
The influence of group 15 various substituents and effect of metal centers on metal-borane interactions and structural isomers of transition metal-borane complexes W(CO)5(BH3 · AH3) and M(CO)5(BH3 · PH3) (A = N, P, As, and Sb; M = Cr, Mo, and W), were investigated by pure density functional theory at BP86 level. The following results were observed: (a) the ground state is monodentate, η1, with C1 point group; (b) in all complexes, the η1 isomer with CS symmetry on potential energy surface is the transition state for oscillating borane; (c) the η2 isomer is the transition state for the hydrogens interchange mechanism; (d) in W(CO)5(BH3 · AH3), the degree of pyramidalization at boron, interaction energy as well as charge transfer between metal and boron moieties, energy barrier for interchanging hydrogens, and diffuseness of A increase along the series A = Sb < As < P < N; (e) in M(CO)5(BH3 · PH3), interaction energy is ordered as M = W > Cr > Mo, while energy barrier for interchanging hydrogens decreases in the order of M = Cr > W > Mo. 相似文献
12.
Afshin Zarghi Sayed M. Foroutan Alireza Shafaati Arash Khoddam 《Chromatographia》2007,66(9-10):747-750
A simple, rapid and sensitive HPLC method has been developed and validated for the analysis of letrozole in human plasma. The separation was achieved on a monolithic silica column using acetonitrile–phosphate buffer. A fluorescence detector was used for the quantitation with excitation and emission wavelengths at 230 and 295 nm. The assay enables the measurement of letrozole for therapeutic drug monitoring with a minimum quantification limit (LOQ) of 0.5 ng mL?1. The method involves a simple, one-step extraction procedure with complete recovery. Calibration was linear over the concentration range 0.5–80 ng mL?1. The coefficients of variation for inter-day and intra-day assay were found to be less than 8%. 相似文献
13.
Talebi M Ghassempour A Talebpour Z Rassouli A Dolatyari L 《Journal of separation science》2004,27(13):1130-1136
A simple and rapid microwave-assisted extraction (MAE) procedure was developed and optimized for the extraction of paclitaxel (Taxol) from the needles of yew trees Taxus baccata L. grown in Iranian habitats. The samples, immersed in a methanol-water mixture, were irradiated with microwaves in a closed-vessel system. The method was evaluated using a factorial design approach based on parameters such as extraction time, temperature, methanol concentration in water (v/v), and the ratio of grams of sample to 10 mL of solvent. Statistical treatment of the results revealed that the selected parameters were all significant except the extraction time. Optimum conditions would be 1.5 g samples in 10 mL solvent (90% methanol), an extraction temperature of 95 degrees C, and an extraction time of 7 min. The extracts has been analyzed by reverse-phase high-performance liquid chromatography with UV detection (LC/UV) at 227 nm for quantification. Liquid chromatography-tandem mass spectrometry (LC-MS/MS) was used for confirmation. The main advantage of the proposed MAE method versus conventional solvent extraction (CSE) are the considerable reductions in time (7 min versus 16 h) and in solvent consumption (20 mL versus 150 mL). The MAE procedure yielded extracts that could be analyzed directly without any preliminary clean-up or solvent exchange steps. Both extraction methods show RSDs lower than 10% and lead to comparable recoveries of paclitaxel (87-92%). 相似文献
14.
Raissi H Nowroozi A Farzad F Bojd MS 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(1-3):343-352
Fourier transform infrared and Fourier transform Raman spectra of Cu(II) bis-acetylacetone have been obtained. The geometry, frequency and intensity of the vibrational bands of this compound and its 1,5-(13)C(2), 3-(13)C, 1,3,5-(13)C(3), 2,4-(13)C(2), (18)O(2) and 2,4-(13)C(2)-(18)O(2) derivatives were obtained by the density functional theory (DFT) with the B3LYP functional and using the 6-31G(*) and 3-21G(*) basis sets. The calculated frequencies are compared with the solid infrared and Raman spectra. All the measured infrared and Raman bands were interpreted in terms of the calculated vibrational modes. The percentage of deviation of the bond lengths and bond angles gives a good picture of the normal modes, and serves as a basis for the assignment of the wavenumbers. Most computed bands are predicted to be at higher wavenumbers than the experimental bands. The calculated geometrical parameters show slight differences compared with the experimental results. These differences can be explained by the different physical state of Cu(II) bis-acetylacetone. The DFT-B3LYP calculations assumed a free molecule in the gas phase. Analysis of the vibrational spectra indicates a strong coupling between the chelated ring modes. 相似文献
15.
In this study, we present a longitudinal analysis of the evolution of interorganizational disaster coordination networks (IoDCNs) in response to natural disasters. There are very few systematic empirical studies which try to quantify the optimal functioning of emerging networks dealing with natural disasters. We suggest that social network analysis is a useful method for exploring this complex phenomenon from both theoretical and methodological perspective aiming to develop a quantitative assessment framework which could aid in developing a better understanding of the optimal functioning of these emerging IoDCN during natural disasters. This analysis highlights the importance of utilizing network metrics to investigate disaster response coordination networks. Results of our investigation suggest that in disasters the rate of communication increases and creates the conditions where organizational structures need to move at that same pace to exchange new information. Our analysis also shows that inter-organizational coordination network structures are not fixed and vary in each period during a disaster depending on the needs. This may serve the basis for developing preparedness among agencies with an improved perspective for gaining effectiveness and efficiency in responding to natural disasters. 相似文献
16.
17.
Host–Guest Assembly of a Molecular Reporter with Chiral Cyanohydrins for Assignment of Absolute Stereochemistry 下载免费PDF全文
Hadi Gholami Dr. Mercy Anyika Jun Zhang Dr. Chrysoula Vasileiou Prof. Dr. Babak Borhan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(27):9235-9239
The absolute stereochemistry of cyanohydrins, derived from ketones and aldehydes, is obtained routinely, in a microscale and derivatization‐free manner, upon their complexation with Zn‐MAPOL, a zincated porphyrin host with a binding pocket comprised of a biphenol core. The host–guest complex leads to observable exciton‐coupled circular dichroism (ECCD), the sign of which is easily correlated to the absolute stereochemistry of the bound cyanohydrin. A working model, based on the ECCD signal of cyanohydrins with known configuration, is proposed. 相似文献
18.
An efficient and eco-friendly method is reported for the synthesis of 2-substituted-2,3-dihydroquinazolin -4(1 H)-ones from direct cyclocondensation of anthranilamide with aldehydes and ketones using N-propylsulfamic acid supported onto magnetic Fe3O4 nanoparticles(MNPs-PSA) as a recoverable and recyclable nanocatalyst in good to excellent yields in water at 70℃.The catalyst was readily separated using an external magnet and reusable without significant loss of their catalytic efficiency. 相似文献
19.
Marzieh Yadavi Alireza Badiei Ghodsi Mohammadi Ziarani Alireza Abbasi 《Chemical Papers》2013,67(7):751-758
Fluorene-functionalised nanoporous silica (FL-NH2-SBA-15) was prepared using the post-synthesis grafting method of SBA-15. The material thus obtained was characterised by means of small- and wide-angle X-ray diffraction, nitrogen adsorption-desorption, Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, and elemental analysis. The results showed that the organised structure is preserved after the post-grafting procedure. Surface area and pore-size decreased by attaching functional groups to the pore surface. In addition, the pore volume was reduced with functionalisation. The amount of fluorene grafted onto the surface of SBA-15 was 0.55 mmol with a yield of approximately 46 %. The emission spectra of FL-NH2-SBA-15 in acidic media were studied and are discussed in detail. The structural change between FL-NH2-SBA-15 and the protonated form might be an effective candidate for acid-dependent molecular-sensor models for advanced application in molecular sensors in the future. 相似文献
20.
B. Movassagh M. M. Lakouraj A. Gholami 《Phosphorus, sulfur, and silicon and the related elements》2013,188(7):1507-1511
Silver carbonate supported on celite (Ag 2 CO 3 /Celite) is used as a mild heterogeneous reagent for conversion of a variety of thioamides into their corresponding amides in acetonitrile at room temperature. 相似文献