全文获取类型
收费全文 | 2044篇 |
免费 | 77篇 |
国内免费 | 110篇 |
专业分类
化学 | 1355篇 |
晶体学 | 14篇 |
力学 | 183篇 |
综合类 | 7篇 |
数学 | 12篇 |
物理学 | 660篇 |
出版年
2024年 | 7篇 |
2023年 | 16篇 |
2022年 | 44篇 |
2021年 | 41篇 |
2020年 | 94篇 |
2019年 | 152篇 |
2018年 | 78篇 |
2017年 | 93篇 |
2016年 | 76篇 |
2015年 | 61篇 |
2014年 | 55篇 |
2013年 | 256篇 |
2012年 | 100篇 |
2011年 | 127篇 |
2010年 | 81篇 |
2009年 | 110篇 |
2008年 | 81篇 |
2007年 | 128篇 |
2006年 | 100篇 |
2005年 | 127篇 |
2004年 | 72篇 |
2003年 | 52篇 |
2002年 | 44篇 |
2001年 | 28篇 |
2000年 | 29篇 |
1999年 | 37篇 |
1998年 | 18篇 |
1997年 | 25篇 |
1996年 | 18篇 |
1995年 | 20篇 |
1994年 | 15篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 6篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 1篇 |
1984年 | 1篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有2231条查询结果,搜索用时 15 毫秒
31.
2,3-Dihydroxypyridine loaded (via –N=N–linker) Amberlite XAD-2 (AXAD-2-DHP) was prepared and characterized by elemental analyses, TGA and FT-IR spectra. It (1g packed in a column of 1cm diameter; surface area 135.5m2g–1) was found to be an effective solid phase sorbent for enriching Zn2+, Mn2+, Ni2+, Pb2+, Cd2+, Cu2+, Fe3+ and Co2+ at pH 3.5 to 7.0 using flow rates between 1.0–5.0mLmin–1. For desorption (recovery 97.0–99.8%) of the metal ions, 8 to 10mL of 2.0molL–1 HCl or 1.5molL–1 HNO3 at a flow rate of between 2.0 and 4.0mLmin–1 were found most suitable. The t1/2 (time for 50% sorption) is between 2 and 10min when a 50mL solution (containing a total amount of metal of 2mg) was equilibrated with 0.5g of resin. Sorption of all metal ions except Pb2+ follows the Langmuir model, whereas for Pb the data fits with the Freundlich model. The sorption capacity is between 60.7 (for Cd) and 406.7 (for Cu) µmolg–1. The resin can withstand an acid concentration of 6molL–1 and can be reused for thirty cycles of sorption–desorption. The preconcentration factor varies between 100 and 300. For Cd, Ni and Cu the sorption capacity of 2,3-dihydroxypyridine loaded cellulose is lower than that of the present resin. The tolerance limits of electrolytes, humic acid, complexing agents, Ca2+ and Mg2+ in the enrichment of all metal ions are reported. The limits of detection are 3.88, 5.37, 8.72, 13.88, 4.71, 1.24, 0.59 and 0.30µgL–1 for Zn2+, Mn2+, Ni2+, Pb2+, Cd2+, Cu2+, Fe3+ and Co2+, respectively. The calibration curves for flame AAS determination were linear in the ranges 0.018–1.0, 0.067–5.0, 0.2–5.0, 0.9–20, 0.028–2.0, 0.077–5.0, 0.19–10 and 0.1–3.5µgmL–1, respectively. All the eight metal ions in river and synthetic water samples, Co in vitamin tablets and Zn in milk samples have been quantitatively enriched with Amberlite XAD-2-DHP and determined by flame atomic absorption spectrometry. 相似文献
32.
Beyond traditional polymer stabilization, sterically hindered piperidine derivatives move into new application areas where radical functions are key elements. Recent achievements in using nitroxyl derivatives in degradation, polymerization and grafting processes are discussed together with the involved chemical reactions and the resulting material properties. The examples shown cover selected nitroxylethers (NORs) performing as flame retardants and flame retardant synergists or replacing peroxides in manufacturing controlled rheology polypropylene (PP). Furthermore, NORs and nitroxyl radicals mediate radical polymerization processes resulting in tailor-made intermediates for polymer modification via radical and condensation steps and offer access to complex polymer architecture. To cite this article: R. Pfaendner, C.R. Chimie 9 (2006). 相似文献
33.
Ali MOGHIMI Mohammad SABER‐TEHRANI Syed WAQIF‐HUSAIN Majid MOHAMMADHOSSEINI 《中国化学》2007,25(12):1859-1865
A novel and selective method for the fast determination of trace amounts of chromium species in water samples has been developed. The procedure is based on the selective formation of chromium diethyldithiocarbamate complexes at different pH in the presence of Mn(II) as an enhancement agent of chromium signals followed by elution with organic eluents and determination by atomic flame absorption spectrometry. The maximum capacity of the employed disks was found to be (396±3) µg and (376±2) µg for Cr(III) and Cr(VI), respectively. The detection limit of the proposed method is 49 and 43 ng·L?1 for Cr(III) and Cr(VI), respectively. The proposed method was successfully applied for determination of chromium species Cr(III) and Cr(VI) in different water samples. 相似文献
34.
Kanchi Suvardhan Kailasa Suresh Kumar Dasari Rekha Pantrangam Subrahmanyam Kapuvedi Kiran Bellum Jayaraj Surasura Ramanaiah Kandhukuri Janardhanam Pattium Chiranjeevi 《Mikrochimica acta》2007,157(3-4):237-244
Cloud point extraction was applied as a method for preconcentration of rhodium after formation of a complex with 2-propylpiperidine-1-carbodithioate
(2-PPC), and later determined by flame atomic absorption spectrometry using TritonX-114 as surfactant. Rhodium was complexed
with 2-PPC in an aqueous phase and kept for 15 min in a thermostatted bath at 40 °C. Separation of the two phases was accomplished
by centrifugation for 15 min at 4000 rpm. The chemical variables affecting the cloud point extraction were optimized and successfully
applied to rhodium determination in various water samples. Under optimized conditions, the preconcentration system (100 mL
sample) permitted an enhancement factor of 50. The detection limits obtained under optimal conditions was 0.052 ng mL−1. The extraction efficiency was investigated at different rhodium concentrations (7.0–42.0 μg mL−1), and good recoveries (96.42–99.14%) were obtained using this method. It has been applied to the determination of rhodium
in water and was compared with reported methods in terms of Student’s ‘t’-test and variance ratio ‘f’-test. 相似文献
35.
Peter L. Simon Serafim Kalliadasis John H. Merkin Stephen K. Scott 《Journal of mathematical chemistry》2002,31(3):313-332
The steady propagation of a planar laminar premixed flame, with a one-step exothermic reaction and linear heat loss, is studied. The corresponding travelling wave equations are solved numerically. The dependence of the flame velocity on the heat loss parameter is determined and compared with known results obtained by asymptotic expansion and other approximations. Due to the introduction of an ignition temperature the problem can be reduced to a bounded interval (of length L) and the graph of flame speed versus heat loss parameter can be parametrised by L. The numerical method is tested in the case of a step function nonlinearity when the exact solution of the differential equations can also be calculated. 相似文献
36.
在常重力下模拟微重力燃烧对载人航天器的火灾安全具有重要意义.窄通道就是这样一种可以有效限制自然对流的模拟设施.但是,不同重力下火焰传播的相似性仍然是有待研究的问题.本文用实验和数值模拟的方法,比较了不同重力下有限空间内热薄材料表面的逆风传播火焰.不同重力下火焰形状和火焰传播速度的比较表明,1cm高的水平窄通道可以有效地限制自然对流,在常重力下用这种通道能够模拟微重力下相同几何尺寸的通道中的火焰传播.因此,在地面上首先利用水平窄通道,模拟相同环境中的微重力火焰传播,然后考虑通道尺寸变化对火焰传播的影响,有可能成为地面模拟其他尺寸的空间中的微重力燃烧的方法. 相似文献
37.
卓琳 《广东微量元素科学》2008,15(3):51-54
采用火焰原子吸收光谱法和表面增敏的方法测定了红花中Cu、Fe、Zn的含量。实验表明,使用表面活性剂十二烷基硫酸钠(SDS),可使Zn的吸光度增感34.91%,使Cu增感37.39%,Fe增感232.10%。该法的检测限分别为Zn1.85×10-3μg/mL;Fe1.50×10-2μg/mL;Cu3.50×10-2μg/mL,加标回收率在99.37%~104.23%之间。该法灵敏度高,结果准确,可用于红花等中草药中Cu、Fe、Zn的同时测定。 相似文献
38.
Yue Jia Tingji Yao Guangcai Ma Qi Xu Xianglong Zhao Hui Ding Xiaoxuan Wei Haiying Yu Zhiguo Wang 《Molecules (Basel, Switzerland)》2022,27(9)
Biotransformation of organophosphorus flame retardants (OPFRs) mediated by cytochrome P450 enzymes (CYPs) has a potential correlation with their toxicological effects on humans. In this work, we employed five typical OPFRs including tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(1-chloro-2-propyl) phosphate (TCIPP), tri(2-chloroethyl) phosphate (TCEP), triethyl phosphate (TEP), and 2-ethylhexyl diphenyl phosphate (EHDPHP), and performed density functional theory (DFT) calculations to clarify the CYP-catalyzed biotransformation of five OPFRs to their diester metabolites. The DFT results show that the reaction mechanism consists of Cα-hydroxylation and O-dealkylation steps, and the biotransformation activities of five OPFRs may follow the order of TCEP ≈ TEP ≈ EHDPHP > TCIPP > TDCIPP. We further performed molecular dynamics (MD) simulations to unravel the binding interactions of five OPFRs in the CYP3A4 isoform. Binding mode analyses demonstrate that CYP3A4-mediated metabolism of TDCIPP, TCIPP, TCEP, and TEP can produce the diester metabolites, while EHDPHP metabolism may generate para-hydroxyEHDPHP as the primary metabolite. Moreover, the EHDPHP and TDCIPP have higher binding potential to CYP3A4 than TCIPP, TCEP, and TEP. This work reports the biotransformation profiles and binding features of five OPFRs in CYP, which can provide meaningful clues for the further studies of the metabolic fates of OPFRs and toxicological effects associated with the relevant metabolites. 相似文献
39.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(11):1128-1132
The sustainable resveratrol‐based phthalonitrile was used in the preparation of E‐glass fiber‐reinforced phthalonitrile composite panels fabricated by hot pressed prepreg consolidation with bis[4‐(3‐aminophenoxy)phenyl]sulfone (m‐BAPS) as the curing additive. This amorphous monomer exhibited excellent viscosities at temperatures below 200 °C, which is applicable to standard processing conditions. Rheometric measurements were used to evaluate the cure of the composite as a function of the postcure conditions. The composite retains >95% of its room temperature storage modulus up to 450 °C based on these postcuring parameters. More importantly, flammability performance of the composite—which was determined in terms of ignitability, heat release, and mass loss rate—excels over other state‐of‐the‐art polymer/glass composites. Even under the most extreme heat fluxes (e.g., 100 kW⋅m−2), the composite performs exceptionally well suggesting that resveratrol‐based phthalonitrile composites can be used in fire‐resistant applications. Published 2018.† J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1128–1132 相似文献
40.
Michael F. Rectenwald Joshua R. Gaffen Prof. Arnold L. Rheingold Dr. Alexander B. Morgan Prof. John D. Protasiewicz 《Angewandte Chemie (International ed. in English)》2014,53(16):4173-4176
The functionalized catecholate, tetraethyl (2,3‐dihydroxy‐1,4‐phenylene)bis(phosphonate) (H2‐DPC), has been used to prepare a series of lithium salts Li[B(DPC)(oxalato)], Li[B(DPC)2], Li[B(DPC)F2], and Li[P(DPC)3]. The phosphoryl‐rich character of these anions was designed to impart flame‐retardant properties for their use as potential flame‐retardant ions (FRIONs), additives, or replacements for other lithium salts for safer lithium‐ion batteries. The new materials were fully characterized, and the single‐crystal structures of Li[B(DPC)(oxalato)] and Li[P(DPC)3] have been determined. Thermogravimetric analysis of the four lithium salts show that they are thermally stable up to around 200 °C. Pyrolysis combustion flow calorimetry reveals that these salts produce high char yields upon combustion. 相似文献