全文获取类型
收费全文 | 1860篇 |
免费 | 55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 |
无线电 | 91篇 |
出版年
2024年 | 4篇 |
2023年 | 11篇 |
2022年 | 29篇 |
2021年 | 41篇 |
2020年 | 38篇 |
2019年 | 45篇 |
2018年 | 42篇 |
2017年 | 28篇 |
2016年 | 70篇 |
2015年 | 61篇 |
2014年 | 65篇 |
2013年 | 136篇 |
2012年 | 136篇 |
2011年 | 155篇 |
2010年 | 102篇 |
2009年 | 107篇 |
2008年 | 138篇 |
2007年 | 112篇 |
2006年 | 109篇 |
2005年 | 95篇 |
2004年 | 80篇 |
2003年 | 51篇 |
2002年 | 61篇 |
2001年 | 22篇 |
2000年 | 19篇 |
1999年 | 18篇 |
1998年 | 12篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 13篇 |
1994年 | 2篇 |
1993年 | 10篇 |
1992年 | 11篇 |
1991年 | 4篇 |
1990年 | 5篇 |
1989年 | 6篇 |
1987年 | 5篇 |
1986年 | 4篇 |
1985年 | 5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 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 3篇 |
1971年 | 1篇 |
1970年 | 3篇 |
排序方式: 共有1921条查询结果,搜索用时 15 毫秒
51.
52.
Mozaniel Santana de Oliveira Jorddy Neves Cruz Oberdan Oliveira Ferreira Daniel Santiago Pereira Natanael Santiago Pereira Marcos Enê Chaves Oliveira Giorgio Cristino Venturieri Giselle Maria Skelding Pinheiro Guilhon Antnio Pedro da Silva Souza Filho Eloisa Helena de Aguiar Andrade 《Molecules (Basel, Switzerland)》2021,26(11)
Propolis is a balsamic product obtained from vegetable resins by exotic Africanized bees Apis mellifera L., transported and processed by them, originating from the activity that explores and maintains these individuals. Because of its vegetable and natural origins, propolis is a complex mixture of different compound classes; among them are the volatile compounds present in the aroma. In this sense, in the present study we evaluated the volatile fraction of propolis present in the aroma obtained by distillation and simultaneous extraction, and its chemical composition was determined using coupled gas chromatography, mass spectrometry, and flame ionization detection. The majority of compounds were sesquiterpene and hydrocarbons, comprising 8.2–22.19% α-copaene and 6.2–21.7% β-caryophyllene, with additional compounds identified in greater concentrations. Multivariate analysis showed that samples collected from one region may have different chemical compositions, which may be related to the location of the resin’s production. This may be related to other bee products. 相似文献
53.
Karla-Alejandra Lpez-Gastlum Enrique F. Velzquez-Contreras Juventino J. García Marcos Flores-Alamo Gerardo Aguirre Daniel Chvez-Velasco Jayanthi Narayanan Fernando Rocha-Alonzo 《Molecules (Basel, Switzerland)》2021,26(23)
Two new glycine-Schiff base copper(II) complexes were synthesized. Single crystal X-ray diffraction (SCXRD) allowed us to establish the structure of both complexes in the solid state. The glycine-Schiff base copper(II) complex derived from 2′-hydroxy-5′-nitroacetophenone showed a mononuclear hydrated structure, in which the Schiff base acted as a tridentate ligand, and the glycine-Schiff base copper(II) complex derived from 2′-hydroxy-5′-methylacetophenone showed a less common tetranuclear anhydrous metallocyclic structure, in which the Schiff base acted as a tetradentate ligand. In both compounds, copper(II) had a tetracoordinated square planar geometry. The results of vibrational, electronic, and paramagnetic spectroscopies, as well as thermal analysis, were consistent with the crystal structures. Both complexes were evaluated as catalysts in the olefin cyclopropanation by carbene transference, and both led to very high diastereoselectivity (greater than 98%). 相似文献
54.
Marcos J Pascual JA de la Torre X Segura J 《Journal of mass spectrometry : JMS》2002,37(10):1059-1073
A fast and sensitive method for the comprehensive screening of anabolic agents and other banned doping substances using gas chromatography/tandem mass spectrometry (GC/MS/MS) with an external ionization ion trap mass spectrometer is presented. The method takes advantage of the resolving power of MS/MS to eliminate background interferences, thus speeding up the chromatographic analysis. For each compound, different fragmentation reactions were studied and their collision energies optimized to obtain the best sensitivity in terms of their signal-to-noise ratio (S/N). A dramatic reduction in overall analysis time was achieved compared with other common approaches. More than 50 substances could finally be monitored in less than 7.4 min with detection limits (S/N >3) lower than 0.5 ng ml(-1) for most of the compounds with special sensitivity requirements according to the International Olympic Committee (IOC). A validation procedure for qualitative analysis was performed. The selectivity of the method showed that no interfering peaks were observed at the retention time of the analytes. Good intermediate precision, below 25% for most of the compounds, and robustness were observed. The optimized method was successfully applied to analyse more than 100 real human urine samples with optimum sensitivity and specificity rates. 相似文献
55.
Marcos Vilario Josune García-Sanmartín Laura Ochoa-Callejero Alberto Lpez-Rodríguez Jaime Blanco-Urgoiti Alfredo Martínez 《Molecules (Basel, Switzerland)》2020,25(24)
Mushrooms have been used for millennia as cancer remedies. Our goal was to screen several mushroom species from the rainforests of Costa Rica, looking for new antitumor molecules. Mushroom extracts were screened using two human cell lines: A549 (lung adenocarcinoma) and NL20 (immortalized normal lung epithelium). Extracts able to kill tumor cells while preserving non-tumor cells were considered “anticancer”. The mushroom with better properties was Macrocybe titans. Positive extracts were fractionated further and tested for biological activity on the cell lines. The chemical structure of the active compound was partially elucidated through nuclear magnetic resonance, mass spectrometry, and other ancillary techniques. Chemical analysis showed that the active molecule was a triglyceride containing oleic acid, palmitic acid, and a more complex fatty acid with two double bonds. The synthesis of all possible triglycerides and biological testing identified the natural compound, which was named Macrocybin. A xenograft study showed that Macrocybin significantly reduces A549 tumor growth. In addition, Macrocybin treatment resulted in the upregulation of Caveolin-1 expression and the disassembly of the actin cytoskeleton in tumor cells (but not in normal cells). In conclusion, we have shown that Macrocybin constitutes a new biologically active compound that may be taken into consideration for cancer treatment. 相似文献
56.
Bikiel DE González Solveyra E Di Salvo F Milagre HM Eberlin MN Corrêa RS Ellena J Estrin DA Doctorovich F 《Inorganic chemistry》2011,50(6):2334-2345
A new family of compounds is presented as potential carbon monoxide releasing molecules (CORMs). These compounds, based on tetrachlorocarbonyliridate(III) derivatives, were synthesized and fully characterized by X-ray diffraction, electrospray mass spectrometry, IR, NMR, and density functional theory calculations. The rate of CO release was studied via the myoglobin assay. The results showed that the rate depends on the nature of the sixth ligand, trans to CO, and that a significant modulation on the release rate can be produced by changing the ligand. The reported compounds are soluble in aqueous media, and the rates of CO release are comparable with those for known CORMs, releasing CO at a rate of 0.03-0.58 μM min(-1) in a 10 μM solution of myoglobin and 10 μM of the complexes. 相似文献
57.
In this work a laboratory polymerization scale process was studied for the production of polybutadiene with high content of cis-1,4 repeating units. A Ziegler-Natta catalytic system based on neodymium versatate (catalyst), diisobutylaluminium hydride (cocatalyst) and tert-butyl chloride (chlorinating agent) was used. The influence of solvent nature (pure grade) and possible contaminants (electron donors) in a recovered solvent from a butadiene-styrene anionic polymerization industrial plant on the stereoselectivity and catalytic activity, molecular weight and molecular weight distribution of the resultant polybutadienes was studied. The polymers were characterized by infrared spectroscopy and size exclusion chromatography. Polybutadienes with cis-1,4 units content in the range of 99-98% were produced. The polymers weight-average molecular weight, , varied from 2.23 × 105 to 4.47 × 105 and the molecular weight distribution, MWD, from 3.1 to 5.1. 相似文献
58.
Pastor E Matveeva E Valle-Gallego A Goycoolea FM Garcia-Fuentes M 《Colloids and surfaces. B, Biointerfaces》2011,88(2):601-609
Mesoporous silicon is a biocompatible, biodegradable material that is receiving increased attention for pharmaceutical applications due to its extensive specific surface. This feature enables to load a variety of drugs in mesoporous silicon devices by simple adsorption-based procedures. In this work, we have addressed the fabrication and characterization of two new mesoporous silicon devices prepared by electrochemistry and intended for protein delivery, namely: (i) mesoporous silicon microparticles and (ii) chitosan-coated mesoporous silicon microparticles. Both carriers were investigated for their capacity to load a therapeutic protein (insulin) and a model antigen (bovine serum albumin) by adsorption. Our results show that mesoporous silicon microparticles prepared by electrochemical methods present moderate affinity for insulin and high affinity for albumin. However, mesoporous silicon presents an extensive capacity to load both proteins, leading to systems were protein could represent the major mass fraction of the formulation. The possibility to form a chitosan coating on the microparticles surface was confirmed both qualitatively by atomic force microscopy and quantitatively by a colorimetric method. Mesoporous silicon microparticles with mean pore size of 35 nm released the loaded insulin quickly, but not instantaneously. This profile could be slowed to a certain extent by the chitosan coating modification. With their high protein loading, their capacity to provide a controlled release of insulin over a period of 60-90 min, and the potential mucoadhesive effect of the chitosan coating, these composite devices comprise several features that render them interesting candidates as transmucosal protein delivery systems. 相似文献
59.
Rivera-Tirado E López-Casillas M Wesdemiotis C 《Rapid communications in mass spectrometry : RCM》2011,25(23):3581-3586
Diazeniumdiolates (also called NONOates) have been analyzed by electrospray ionization mass spectrometry (ESI-MS). The samples used are commercially available and included Diethylamine NONOate, DETA NONOate, Spermine NONOate, MAHMA NONOate, PROLI NONOate, Dipropylenetriamine NONOate, PAPA NONOate, and Sulpho NONOate. These compounds have been found to ionize upon ESI by protonation, deprotonation and sodiation. The MS(n) experiments provided strong evidence that such ions release NO, HNO, N(2)O, NO(2), N(2)O(2), N(3)O(3), N(4)O(3) and N(4)O(4) when collisionally activated. Thus, the facile donation of NO units is a property of such compounds. Negative-mode mass spectrometry has been particularly useful for the analysis of most of the NONOates studied here. The experiments have demonstrated the capabilities of mass spectrometry, along with CAD (MS/MS), to detect and characterize such compounds. 相似文献
60.
Silvania Lanfredi Iara A.O. Brito Marcos A.L. Nobre 《Journal of solid state chemistry》2011,184(5):990-89
The Curie temperature and its correlation with the magnitude of the displacement of the niobium atom from the center of [NbO6] octahedra in NaSr2Nb5O15 nanostructured powder were investigated. A single powder was prepared by high-energy ball milling. A powder with an average crystallite size of 37 nm was prepared by calcining the precursor at 1423 K. The refinement of the structural parameters was carried out by the Rietveld method. NaSr2Nb5O15 exhibits tetragonal symmetry with the tungsten bronze structure (a=b=12.3495 (6) Å, c=3.8911 (2) Å, V=593.432 (5) Å3, and Z=2). The site occupancy of the Na+ and Sr2+ cations and the interatomic distances between the niobium and oxygen atoms were derived. The [NbO6] octahedron undergoes both rotation and tilting depending on the crystallographic site. The Curie temperature of the powder was derived using both the impedance and infrared spectroscopy methods. 相似文献