全文获取类型
收费全文 | 6936篇 |
免费 | 974篇 |
国内免费 | 2559篇 |
专业分类
化学 | 7143篇 |
晶体学 | 150篇 |
力学 | 704篇 |
综合类 | 109篇 |
数学 | 330篇 |
物理学 | 2033篇 |
出版年
2024年 | 26篇 |
2023年 | 194篇 |
2022年 | 425篇 |
2021年 | 381篇 |
2020年 | 441篇 |
2019年 | 305篇 |
2018年 | 247篇 |
2017年 | 324篇 |
2016年 | 413篇 |
2015年 | 317篇 |
2014年 | 372篇 |
2013年 | 555篇 |
2012年 | 461篇 |
2011年 | 474篇 |
2010年 | 400篇 |
2009年 | 499篇 |
2008年 | 480篇 |
2007年 | 459篇 |
2006年 | 421篇 |
2005年 | 403篇 |
2004年 | 394篇 |
2003年 | 312篇 |
2002年 | 262篇 |
2001年 | 223篇 |
2000年 | 253篇 |
1999年 | 162篇 |
1998年 | 207篇 |
1997年 | 165篇 |
1996年 | 137篇 |
1995年 | 140篇 |
1994年 | 133篇 |
1993年 | 112篇 |
1992年 | 104篇 |
1991年 | 51篇 |
1990年 | 45篇 |
1989年 | 34篇 |
1988年 | 38篇 |
1987年 | 23篇 |
1986年 | 9篇 |
1985年 | 14篇 |
1984年 | 14篇 |
1983年 | 14篇 |
1982年 | 11篇 |
1981年 | 4篇 |
1979年 | 4篇 |
1977年 | 1篇 |
1973年 | 1篇 |
1971年 | 1篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 312 毫秒
1.
Weiyi Li Geng Leng Caiqin Li Yajing Lyu 《International journal of quantum chemistry》2020,120(8):e26150
The mechanisms of CO2 coupling with the propargylic alcohol using alkali carbonates M2CO3 (M = Li, Na, K, Cs) have been investigated by means of density functional theory calculations. The calculations reveal that the target product tetronic acid (TA) is yielded through two stages: (a) the formation of the α-alkylidene cyclic carbonate (αACC) intermediate via Cs2CO3-mediated carboxylative cyclization of the propargylic alcohol with CO2, and (b) the conversion of the αACC intermediate with Cs2CO3 to produce the cesium salt of the TA. Since the overall kinetic barriers for the two stages are comparable and affordable, the excellent chemoselectivity to the TA should be primarily originated from the high thermodynamic stability of the cesium salt of the TA. Moreover, relative to the TA, the possibility to yield the by-product acyclic carbonate can be excluded due to the both kinetics and thermodynamic inferiority. This result is different from the organic base-mediated reaction. Alternatively, our calculations predict that CsHCO3 together generated with the cesium salt of the TA might also be an available mediating reagent for the incorporation of CO2 with the propargylic alcohol. Compared to other alkali carbonates M2CO3 (M = Li, Na, K), the stronger basicity of Cs2CO3 and the lower ionic potential of cesium ion can raise the effective concentration of the αACC intermediate, and thus the conversion of the αACC intermediate into the cesium salt of the TA can be achieved with high yield. 相似文献
2.
《Arabian Journal of Chemistry》2021,14(11):103421
Processing of Carapa guianensis seeds to obtain oil on an industrial scale generates a significant amount of by-product, approximately 66% w/w, which is called cake and is a potential source of biomolecules, including simple phenolic structures. For this reason, studies were carried out on the chemical profiles of hydrolyzed extract from this agro-industrial by-product through High Performance Thin-Layer Chromatography (HPTLC) and Gas Chromatography coupled to Mass Spectrometry (GC–MS). These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product. The sample antioxidant capacity was determined by methods of 2,2-diphenyl-1-picrylhydrazyl (DPPH)and 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS+) radicals direct sequestration. The hydrolyzed fraction showed a total of 63.47% in the relative abundance of the total of compounds, standing out: p-hydroxybenzoic acid (39.19%) and protocatechuic acid (3,4-dihydroxybenzoic acid) (5.62%), both from hydroxybenzoic acids and 3-(3,4-dihydroxyphenyl)lactic acid, (7.76%) hydroxycinnamic acids derivatives. In these results, the fraction rich in simple phenolic acids was obtained, attributing the prominent behavior of this matrix antioxidant activity, expressed by (IC50: of 16.42 µg/mL and 6.52 µg/mL for DPPH and ABTS+ radicals, respectively). The research demonstrated an alternative to applicability that involves sustainability from agro-industrial. These techniques were used to detect metabolic classes and/or groups, and to identify, for the first time, thirteen simple phenolic acids in this by-product, generating a process capable of converting biomass into a bioproduct, consisting of bioactive compounds, in addition to adding value to the industrial chain. 相似文献
3.
《Journal of Saudi Chemical Society》2022,26(6):101573
In this study, vanadium nanoparticles (VNPs) were green synthesized using Foeniculum vulgare extract. VNPs were characterized using chemical analysis techniques including FT-IR, XRD, FE-SEM, TEM and EDS. The microscopy techniques revealed a spherical morphology for the particles with size less than 50 nm. According to XRD data V2O5 was confirmed for VNPs. Maybe significant anti-human acute leukemia potentials of the synthesized nanoparticles against common human acute leukemia cell lines are linked to their antioxidant activities. MTT assay was used on common acute leukemia cell lines i.e., 32D-FLT3-ITD, MOLT-3 and Jurkat, Clone E6-1 to survey the cytotoxicity and anti-acute leukemia effects of the synthesized nanoparticles. The synthesized nanoparticles had very low cell viability and high anti-acute leukemia activities dose-dependently against 32D-FLT3-ITD, MOLT-3 and Jurkat, Clone E6-1 cell lines without cytotoxicity on the normal cell line (HUVEC). To determine the antioxidant properties of the synthesized nanoparticles, the DPPH test was used in the presence of butylated hydroxytoluene as the positive control. The IC50 of VNPs were 25, 33 and 26 µg/mL against 32D-FLT3-ITD, MOLT-3 and Jurkat, Clone E6-1 cell lines, respectively. The synthesized nanoparticles inhibited half of the DPPH molecules in the concentration of 28 µg/mL. 相似文献
4.
当前锂离子动力电池电化学模型存在模型复杂、建模难度大、计算效率低、老化评估效果差的问题,本文提出一种考虑电池衰退老化的机理模型(ADME).本文首先通过有限差分法对伪二维(P2D)电化学模型进行离散降阶处理,得到简化伪二维(SP2D)模型.在SP2D模型的基础上,基于阴阳两极发生的副反应导致的衰退老化现象,提出一种考虑电池衰退老化的机理模型.其次,使用多变量偏差补偿最小二乘法实现模型参数辨识.最后通过动力电池衰退老化性能循环实验,对比分析了恒流、脉冲工况下SP2D模型和ADME模型的终端电压输出.结果表明:ADME模型较为简单、计算效率和估算精度高,可以有效评估电池容量老化衰退,得到理想的锂离子动力电池外特性曲线. 相似文献
5.
6.
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
7.
DFT mechanistic study of the H2‐assisted chain transfer copolymerization of propylene and p‐methylstyrene catalyzed by zirconocene complex 下载免费PDF全文
Cheng‐Gen Zhang Shu‐Yuan Yu Liaoyun Zhang Huayi Li Zhi‐Xiang Wang 《Journal of polymer science. Part A, Polymer chemistry》2015,53(4):576-585
DFT computations have been performed to investigate the mechanism of H2‐assisted chain transfer strategy to functionalize polypropylene via Zr‐catalyzed copolymerization of propylene and p‐methylstyrene (pMS). The study unveils the following: (i) propylene prefers 1,2‐insertion over 2,1‐insertion both kinetically and thermodynamically, explaining the observed 1,2‐insertion regioselectivity for propylene insertion. (ii) The 2,1‐inserion of pMS is kinetically less favorable but thermodynamically more favorable than 1,2‐insertion. The observation of 2,1‐insertion pMS at the end of polymer chain is due to thermodynamic control and that the barrier difference between the two insertion modes become smaller as the chain length becomes longer. (iii) The pMS insertion results in much higher barriers for subsequent either propylene or pMS insertion, which causes deactivation of the catalytic system. (iv) Small H2 can react with the deactivated [Zr]?pMS?PPn facilely, which displace functionalized pMS?PPn chain and regenerate [Zr]? H active catalyst to continue copolymerization. The effects of counterions are also discussed. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 576–585 相似文献
8.
《Comptes Rendus Chimie》2015,18(9):993-1000
The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism. 相似文献
9.
The present study was designed to evaluate the contents of different antioxidants compounds and their antioxidant activities in Jalopeno peppers (Capsicum annuum) cultivars (El Dorido, Grande, Tula, Sayula and El Rey) extracts. Free radical scavenging activity of Grande was recorded as high as 87% followed by El Dorido (83%). Results of reducing power (Fe3+ to Fe2+) showed that Grande (0.85%) and El Dorido (0.81%) fruit extract absorbance value were close to synthetic antioxidant BHT (0. 97%) obtained at100 μg/mL. The results showed that total phenolic content of El Dorido and Grande were significantly higher compared to other Jalapeno pepper. Results indicated strong and positive correlation between antioxidant activity and carotenoids content (r = 0.75), vitamin C (r = 0.78) and total capsaicinoids (r = 0.84), respectively. The results of the antioxidant activity assays showed that the El Dorido and Grande had strongest antioxidant activity compared to other peppers cultivars in this study. 相似文献
10.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献