全文获取类型
收费全文 | 3918篇 |
免费 | 151篇 |
国内免费 | 577篇 |
专业分类
化学 | 4156篇 |
晶体学 | 31篇 |
力学 | 10篇 |
综合类 | 9篇 |
数学 | 20篇 |
物理学 | 420篇 |
出版年
2024年 | 7篇 |
2023年 | 100篇 |
2022年 | 24篇 |
2021年 | 57篇 |
2020年 | 84篇 |
2019年 | 112篇 |
2018年 | 86篇 |
2017年 | 101篇 |
2016年 | 112篇 |
2015年 | 105篇 |
2014年 | 182篇 |
2013年 | 282篇 |
2012年 | 217篇 |
2011年 | 251篇 |
2010年 | 222篇 |
2009年 | 275篇 |
2008年 | 241篇 |
2007年 | 280篇 |
2006年 | 287篇 |
2005年 | 286篇 |
2004年 | 272篇 |
2003年 | 151篇 |
2002年 | 99篇 |
2001年 | 101篇 |
2000年 | 98篇 |
1999年 | 67篇 |
1998年 | 51篇 |
1997年 | 55篇 |
1996年 | 48篇 |
1995年 | 61篇 |
1994年 | 45篇 |
1993年 | 51篇 |
1992年 | 35篇 |
1991年 | 39篇 |
1990年 | 37篇 |
1989年 | 20篇 |
1988年 | 28篇 |
1987年 | 21篇 |
1986年 | 16篇 |
1985年 | 3篇 |
1984年 | 10篇 |
1982年 | 6篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 2篇 |
排序方式: 共有4646条查询结果,搜索用时 62 毫秒
1.
Simen Gjelseth Antonsen Arne Joakim C. Bunkan Tomas Mikoviny Yngve Stenstrøm Armin Wisthaler 《Molecular physics》2020,118(15)
The kinetics of the O3, OH and NO3 radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k CH2NN+O3?=?(3.2?±?0.4)?×?10?17 and k CH2NN+OH?=?(1.68?±?0.12)?×?10?10 cm3 molecule?1 s?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH2NN?+?NO3 reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed. 相似文献
2.
Liping Zhu Samantha Powell Stephen G. Boyes 《Journal of polymer science. Part A, Polymer chemistry》2015,53(8):1010-1022
Well‐defined tertiary amine‐based pH‐responsive homopolymers and block copolymers were synthesized via reversible addition‐fragmentation chain transfer (RAFT) polymerization using 4‐cyanopentanoic acid dithiobenzoate (CPAD) as the RAFT agent for homopolymers and a poly(ethylene glycol) (PEG) macro‐RAFT agent for the block copolymers. 1H NMR and gel permeation chromatography results confirmed the successful synthesis of these homopolymers and block copolymers. Kinetics studies indicated that the formation of both the homopolymers and the block copolymers were well defined. The pKa titration experiments suggested that the homopolymers and the related block copolymers have a similar pKa. The dynamic light scattering investigation showed that all of the block copolymers underwent a sharp transition from unimers to micelles around their pKa and the hydrodynamic diameter (Dh) was not only dependent on the molecular weight but also on the composition of the block copolymers. The polymer solution of PEG‐b‐PPPDEMA formed the largest micelle compare to the PEG‐b‐PDPAEMA and PEG‐b‐PDBAEMA with a similar molecular weight. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1010–1022 相似文献
3.
4.
《Physics letters. A》2019,383(30):125920
Based on the topological nature of Chern insulator and magnetoelectric coupling of chiral metamaterial, we investigate the electrodynamics for the interface associated with the two media. The Fresnel coefficients of the interface between Chern insulator and chiral metamaterial, as well as the corresponding polarization rotation angles, are derived. The reflection characteristics of the linearly polarized incident wave at the interface, such as complete polarization conversion and change of polarization state, are discussed. Under the combined influence of Chern insulator and chiral metamaterial, the partial polarization conversion may be enhanced to the complete polarization conversion, and the chiral metamaterial may compensate for the suppression effect of longitudinal conductivity of Chern insulator on the polarization conversion. 相似文献
5.
Wenwen Zhang Xinran Wang Shupeng Yang Qingsheng Niu Liming Wu Yi Li Jinhui Zhou 《Biomedical chromatography : BMC》2020,34(2):e4740
The use of honeybee venom in traditional medicine is increasing due to its unexpected beneficial effects in the treatment of diseases. In this study, a simple and environmentally friendly sample preparation procedure was developed to quantify five biogenic amines—histamine, 5-hydroxytryptamine, dopamine, adrenaline, and noradrenaline—in honeybee venom using high-performance liquid chromatography tandem mass spectrometry. The instrument and sample preparation method were optimized to achieve stable, sensitive, and accurate quantification of the five biogenic amines. The peak purities of five biogenic amines in bee venom were examined using a diode array detector to ensure that endogenous impurities will not interfere with biogenic amines during the chromatographic separation procedure. The correlation coefficient of each compound was higher than 0.998 in the range of 0.5–1000 ng/mL. The limits of detection and quantification of the developed method ranged between 0.09 and 0.17, and 0.3 and 0.59 μg/g, respectively. The average recoveries of spiked biogenic amines with different concentrations were higher than 70.95%, and the intra- and intermediate-day precisions were lower than 7.51% and 10.17%, respectively. The carry-over between each injection and the stability of the target analytes were also evaluated to ensure the effectiveness of this method. The data obtained are presented in various formats, including boxplot, heat map, and principal component analysis diagram, to visualize the differences in the biogenic amine contents of the honeybee venoms from different subspecies. This method hopes to provide the opportunity to distinguish the bee venom produced by different subspecies. 相似文献
6.
Hindered amine light stabilizers are used to protect polymers from heat- and light-induced degradation. In this study the oligomeric stabilizer Tinuvin 622 was analysed in-depth employing high performance liquid chromatography/time of flight mass spectrometry (HPLC/TOF-MS) to differentiate products of different manufacturers in respect of their terminating groups and oligomer length. Additionally, the behaviour of the stabilizer in uncured and cured polyester powder coatings was investigated regarding its interaction with the other coating components and chemical changes during the crosslinking process. The extraction efficiency was determined as a function of oligomer length and coating colour. 相似文献
7.
The development of catalysts capable of catalyzing amidation of esters with amines to construct amides under mild conditions is of great importance. Compared to aliphatic amines, the direct catalytic amidation of esters with less nucleophilic aromatic amines is rather difficult. Employing simple lanthanide tris (amide) complexes Ln[N (SiMe3)2]3(μ-Cl)Li (THF)3 as the catalysts, it was found a broad range of aromatic amines and esters were efficiently converted into various amides in good yields under mild conditions. A plausible mechanism for this transformation was experimentally supported as starting from an amide exchange reaction between the lanthanide tris (amide) complex and the substrate amine. 相似文献
8.
Majid Rezaeivala Musa Ahmadi Burjor Captain Serap Şahin-Bölükbaşı Ahmad Ali Dehghani-Firouzabadi Robert William Gable 《应用有机金属化学》2020,34(2):e5325
A new unsymmetrical five-coordinate Schiff base ligand (HL) with an N4O donor set ( 2 ) has been prepared by condensation of N1-(2-morpholinoethyl)-N1-([pyridine-2-yl]methyl)propane-1,3-diamine with 2-hydroxy-benzaldehyde. Metal complexes [ML]n+ (M = Zn2+, Cd2+, Mn2+, Cu2+, Ni2+, Ag+, Fe3+, and Co2+ ( 3–10 ) were synthesized by the reaction of the ligand and metal salts in ethanol. The resulting products were characterized by elemental analyses, infrared, 1H and 13C nuclear magnetic resonance spectra (in the case of Cd and Zn complexes), UV–Vis, electrospray ionization-mass spectrometric, and conductivity measurements. The structure of the complexes [ZnL](ClO4) ( 3 ), [CdL](ClO4) ( 4 ), and [CuL](ClO4) ( 7 ) has been determined by single-crystal X-ray diffraction analysis. The metal complexes were determined to have a distorted trigonal bipyramidal (Zn and Cd) or a distorted square pyramidal (Cu) geometry. The cytotoxic potential of each compound (1–10) against MCF-7 and MDA-MB-231 (breast cancer cells), PC-3 (prostate cancer cells), and WI-38 human normal lung fibroblast cells was evaluated using the MTT (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyl tetrazolium bromide) assay. Compounds 1, 2, and 10 did not display any activity toward any cell line tested. None of the compounds except compound 8 was cytotoxic toward PC-3. Compounds 4 and 8 showed the highest cytotoxic activity against the MCF-7 and MDA-MB-231 cell lines. Because compounds 3, 6, and 9 have similar half-maximal inhibitory concentration values against cancer cells and normal cells, these compounds displayed poor selectivity between cancer and normal cells. More importantly, it was observed that compound 5 acts differently toward different types of cell lines. For example, it displays lower cytotoxicity against the WI-38 normal cell line than it does against the MDA-MB-231 cell line. 相似文献
9.
《Arabian Journal of Chemistry》2020,13(1):883-899
We describe here the synthesis of enantiomerically pure chalcogenoethers obtained through the reaction of nucleophilic species of chalcogen (S, Se and Te), generated in situ from the respective diorganyl dichalcogenides, with (R)- and (S)-tosyl solketal. Furthermore, some of the chalcogenoethers were treated with acidic cation exchange resin Dowex-(H+) leading to the respective deprotected enantiomerically pure 3-phenylchalcogenyl-1,2-diols. In order to explore the biological potential of these molecules, the antioxidant activity of some organochalcogens was evaluated by several in vitro assays. Overall, the chalcogenoethers containing Te were better scavengers of DPPH and ABTS+ radicals, had higher ferric reducing capacity and prevented lipid peroxidation. To analyze the effects of these compounds in vivo, we used the alternative model Caenorhabditis elegans. Chalcogenoethers treatment, especially (S)- and (R)-2,2-dimethyl-4-(phenylselanylmethyl)-1,3-dioxolane, conferred protection against the mortality-induced by hydrogen peroxide. Accordingly, these chalcogenoethers were able to modulate the antioxidant enzyme catalase. Notably, the compounds did not present toxicity in worm’s reproduction. To sum up, our study demonstrated that Te- containing chalcogenoethers were promising in vitro scavengers, while Se molecules were more prone to protect against a stressor in vivo. In this sense, the antioxidant activity of chalcogenoethers, especially with Se and Te, indicates that these molecules may have biological application in an attempt to reduce the oxidative stress. 相似文献
10.
Ning-Fang Li Jiuyang Ji Wei Jiang Jia-Peng Cao Ye-Min Han Peng Yuan Yan Xu 《无机化学与普通化学杂志》2020,646(10):463-468
The usage of the achiral ligand, in lanthanide chemistry, successfully obtained two series of chiral lanthanide complexes, formulated d - and l -{Gd[IN][HIN][CH2OCH2O]}n (abbreviated as Gd ) and d - and l -{Dy[IN][HIN][CH2OCH2O]}n (abbreviated as Dy , HIN = isonicotinic acid). Crystallographic researches determined that four compounds are all one-dimensional (1D) chain structures and crystallized in a chiral space group. In addition, CH2OHCH2OH acts as not only solvent but also the bridge ligand. Besides, single crystal circular dichroism (CD) spectra conformed compounds Gd-L and Gd-D , Dy-L and Dy-D are enantiomers respectively. Magnetically, compound Gd showed predominant magnetocaloric effect (MCE) of 26.20 J · kg–1 · K–1 at 2.5 K for ΔH = 7 T, while there is ferromagnetic interactions in compound Dy . 相似文献