全文获取类型
收费全文 | 11396篇 |
免费 | 195篇 |
国内免费 | 46篇 |
专业分类
化学 | 5754篇 |
晶体学 | 85篇 |
力学 | 352篇 |
数学 | 1630篇 |
物理学 | 2444篇 |
无线电 | 1372篇 |
出版年
2022年 | 97篇 |
2021年 | 120篇 |
2020年 | 133篇 |
2019年 | 140篇 |
2018年 | 144篇 |
2017年 | 113篇 |
2016年 | 221篇 |
2015年 | 175篇 |
2014年 | 190篇 |
2013年 | 583篇 |
2012年 | 387篇 |
2011年 | 473篇 |
2010年 | 354篇 |
2009年 | 317篇 |
2008年 | 457篇 |
2007年 | 447篇 |
2006年 | 402篇 |
2005年 | 370篇 |
2004年 | 386篇 |
2003年 | 320篇 |
2002年 | 318篇 |
2001年 | 238篇 |
2000年 | 234篇 |
1999年 | 186篇 |
1998年 | 149篇 |
1997年 | 167篇 |
1996年 | 209篇 |
1995年 | 161篇 |
1994年 | 153篇 |
1993年 | 177篇 |
1992年 | 174篇 |
1991年 | 187篇 |
1990年 | 143篇 |
1989年 | 139篇 |
1988年 | 158篇 |
1987年 | 190篇 |
1986年 | 161篇 |
1985年 | 208篇 |
1984年 | 195篇 |
1983年 | 162篇 |
1982年 | 171篇 |
1981年 | 184篇 |
1980年 | 178篇 |
1979年 | 179篇 |
1978年 | 167篇 |
1977年 | 168篇 |
1976年 | 145篇 |
1975年 | 164篇 |
1974年 | 128篇 |
1973年 | 130篇 |
排序方式: 共有10000条查询结果,搜索用时 11 毫秒
991.
Nonreactive and reactive computational fluid dynamic simulations were applied to optimize the design of a laboratory scale jet stirred reactor for measuring intrinsic kinetics of gas‐phase and gas‐solid reactions, i.e. kinetics determined by chemical steps only and not by heat or mass transfer. In the past these reactors were designed and tested based on empirical design criteria and residence time distribution experiments. This work shows that these do not always capture important local effects that are vital for kinetic studies. First the degree of macro–mixing was evaluated for three different geometries (down case, 45° case and 90° case) by performing in silico residence time distribution experiments at 900 K, showing that with these type of experiments only minor differences are observed. However, the ethane steam cracking simulations revealed major differences, with the 45° case being the most uniform in terms of temperature and the 90° case being by far the worst. The species nonuniformity in all geometries was acceptable and was in some cases even partly masked by important shortcut streams such as those observed in the 90° case. The existing gradients on the substrate surface are sufficiently small to be neglected in modeling efforts. As temperature is the major parameter determining the rate of the surface reactions, the 45° case is suggested as the best geometry for measuring intrinsic kinetics. 相似文献
992.
Saveyn P Cocquyt J Bomans P Frederik P De Cuyper M Van der Meeren P 《Langmuir : the ACS journal of surfaces and colloids》2007,23(9):4775-4781
Extruded vesicles, which are often used as models for living cells, can change their morphology when they are diluted into a hyperosmotic medium. Different morphological changes were observed with extruded dioctadecyldimethylammonium chloride (DODAC) vesicles after dilution with a nonionic (sucrose) and ionic (CaCl2) osmotic agent above and below the gel-to-liquid crystalline transition temperature. By means of turbidimetry, dynamic light scattering, and cryo-transmission electron microscopy, it was seen that the vesicles only deflated when they were in the gel state, whereas in the liquid crystalline state, an ionic osmotic agent could induce twinning of the vesicles, reminiscent to endocytosis. The latter could occur as a result of the combined effects of reduced repulsion, local dehydration, and reduced bending rigidity induced by the ionic agent. 相似文献
993.
Katleen Boussu Jérémie De Baerdemaeker Charles Dauwe Marc Weber Kelvin G Lynn Diederik Depla Steliana Aldea Ivo F J Vankelecom Carlo Vandecasteele Bart Van der Bruggen 《Chemphyschem》2007,8(3):370-379
This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly. 相似文献
994.
The ionization of 46 anabolic steroids has been studied. The absence of basic or acidic moieties in most of these analytes makes their direct ionization as [M + H]+ by atmospheric pressure interfaces difficult. The formation of adducts with different components of the mobile phase has been found to be an efficient way to ionize anabolic steroids by electrospray. Different mobile phases using methanol (MeOH) or acetonitrile as organic solvent and HCOOH, Na+ or NH4+ as additives have been tested to favor the adduct formation. A direct correlation between the chemical structure of the anabolic steroid and the possibility to ionize it in a particular chromatographic condition has been found. According to their ionization, anabolic steroids can be divided into seven different groups depending on both the nature and the relative position of their functional groups. The formation of different adducts such as [M + Na + MeOH]+ or [M + H + CH3 CN - H2O]+ is required in order to ionize some of these groups and the optimal mobile phase composition for each group of anabolic steroids is proposed. Despite the ionization limitations due to their chemical structure, most of tested anabolic steroids could be ionized using the adduct formation approach. 相似文献
995.
996.
Pozo OJ Van Eenoo P Deventer K Delbeke FT 《Analytical and bioanalytical chemistry》2007,389(4):1209-1224
A screening method for the urinary detection of 34 exogenous anabolic steroids has been developed. The method involves an
enzymatic hydrolysis, liquid-liquid extraction and detection by liquid chromatography-tandem mass spectrometry. The use of
some adducts such as [M+NH4]+, [M+CH3COO]− and [M+H+MeOH]+ was necessary in order to detect some analytes at the required level (lower than 10 ng/ml). Two transitions were selected
for each analyte. Different concentration factors have been studied in order to increase the sensitivity. A concentration
factor of 50 was selected for the screening method although the high ion suppression observed under these conditions can hamper
its application as a quantitative method. The method was validated and limits of detection were obtained by spiking ten different
blank urine samples at five different concentration levels. Up to 29 analytes were detected in all spiked urines at the required
level. Limits of detection between 1 and 10 ng/ml were obtained for most analytes which fulfil current requirements. The applicability
of the method was shown by analysing positive samples. 相似文献
997.
Van Tang Nguyen Hong Ngoc Thuy Pham Michael C. Bowyer Ian A. van Altena Christopher J. Scarlett 《Chemical Papers》2016,70(5):556-566
Phyllanthus amarus (P. amarus) is a herbal plant used in the treatment of various diseases such as hepatitis, diabetes, and cancer. Efficiency of its bioactive compounds extraction and therefore the biological activity of the extracts are significantly influenced by both solvent character and extraction method. This study is aimed at the determination of the influence of six various solvents (water, acetonitrile, ethanol, methanol, ethyl acetate, and dichloromethane) and nine different extraction methods (conventional, ultrasound-assisted, microwave-assisted, and six novel methods) on the extraction efficiency and antioxidant capacity of P. amarus. The results indicated that water extracted the maximal amount of phenolics from P. amarus and had the highest antioxidant capacity, while microwave-assisted extraction provided the highest yields of phenolics and saponins, and the highest antioxidant capacity with the lowest energy consumption when compared to the other extraction methods. These findings implied that water and microwave-assisted extraction are recommended as the most effective solvent and method for the extraction of bioactive compounds from P. amarus for potential application in the pharmaceutical and nutraceutical industries. 相似文献
998.
Dr. Joice Thomas Dr. Liliana Dobrzańska Prof. Luc Van Meervelt Prof. Mario Alfredo Quevedo Prof. Krzysztof Woźniak Marcin Stachowicz Prof. Mario Smet Prof. Wouter Maes Prof. Wim Dehaen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(3):979-987
A synthetic route towards homodiselenacalix[4]arene macrocycles is presented, based on the dynamic covalent chemistry of diselenides. The calixarene inner rim is decorated with either alkoxy or tert‐butyl ester groups. Single‐crystal X‐ray analysis of two THF solvates with methoxy and ethoxy substituents reveals the high similarity of their molecular structures and alterations on the supramolecular level. In both crystal structures, solvent channels are present and differ in both shape and capacity. Furthermore, the methoxy‐substituted macrocycle undergoes a single‐crystal‐to‐single‐crystal transformation during which the molecular structure changes its conformation from 1,3‐alternate (loaded with THF/water) to 1,2‐alternate (apohost form). Molecular modelling techniques were applied to explore the conformational and energetic behaviour of the macrocycles. 相似文献
999.
Saveyn P Van der Meeren P Cocquyt J Drakenberg T Olofsson G Olsson U 《Langmuir : the ACS journal of surfaces and colloids》2007,23(21):10455-10462
Lipid freezing in dilute sonicated vesicular dispersions was studied using differential scanning calorimetry (DSC) and 1H NMR. For charged, anionic, or cationic lipids, approximately half of the lipids remain in a fluid state when cooled 20 degrees C below the main chain melting temperature. With a zwitterionic phospholipid, on the other hand, essentially no supercooling of the liquid state was observed. The observations are analyzed in terms of the nucleation and growth of flat solid domains in originally fluid spherical vesicles. As the solid domains grow, the remaining fluid domain is deformed, resulting in a curvature stress. Depending on the vesicle size and the bilayer bending rigidity, the solid domain growth may terminate as the gain in cohesive free energy is balanced by the curvature stress of the remaining fluid domain. It is argued that high bending rigidities are required for having a significant supercooling, which is why it is only observed for charged lipids. 相似文献
1000.
The catalytic system methylaluminoxane (MAO) and bis(n-butylcyclopentadienyl)zirconium dichloride ((nBuCp)2ZrCl2) was immobilized on commercial silica, silica-alumina and aluminophosphate calcined at different temperatures. The properties of the supports were determined by using N2 adsorption-desorption isotherms at 77 K, FT-IR spectroscopy and SEM. After aluminium and zirconium impregnation, the catalysts were analyzed by ICP-AES, FT-IR and UV-vis spectroscopy. Ethylene polymerizations were carried out in a Schlenk tube at 70 °C and 1.2 bar of ethylene pressure. The polyethylene obtained was characterized by GPC, DSC and SEM.Catalysts supported on silica-alumina exhibited higher polymerization activity than those supported on silica and aluminophosphate. Besides, the activity of MAO/(nBuCp)2ZrCl2 catalytic system supported on silica-alumina and aluminophosphate decreased strongly with support calcination temperature, while remained almost constant when silica was employed as support. All these experimental features suggest a role of the support acid properties and hydroxyl group population in the generation of active polymerization species. 相似文献