全文获取类型
收费全文 | 14690篇 |
免费 | 1893篇 |
国内免费 | 3112篇 |
专业分类
化学 | 12543篇 |
晶体学 | 177篇 |
力学 | 921篇 |
综合类 | 211篇 |
数学 | 633篇 |
物理学 | 5210篇 |
出版年
2024年 | 44篇 |
2023年 | 264篇 |
2022年 | 519篇 |
2021年 | 715篇 |
2020年 | 698篇 |
2019年 | 554篇 |
2018年 | 446篇 |
2017年 | 677篇 |
2016年 | 790篇 |
2015年 | 718篇 |
2014年 | 921篇 |
2013年 | 1078篇 |
2012年 | 1010篇 |
2011年 | 939篇 |
2010年 | 831篇 |
2009年 | 992篇 |
2008年 | 949篇 |
2007年 | 924篇 |
2006年 | 832篇 |
2005年 | 826篇 |
2004年 | 765篇 |
2003年 | 545篇 |
2002年 | 437篇 |
2001年 | 347篇 |
2000年 | 375篇 |
1999年 | 289篇 |
1998年 | 310篇 |
1997年 | 266篇 |
1996年 | 226篇 |
1995年 | 237篇 |
1994年 | 189篇 |
1993年 | 174篇 |
1992年 | 161篇 |
1991年 | 85篇 |
1990年 | 97篇 |
1989年 | 79篇 |
1988年 | 89篇 |
1987年 | 62篇 |
1986年 | 37篇 |
1985年 | 42篇 |
1984年 | 32篇 |
1983年 | 30篇 |
1982年 | 41篇 |
1981年 | 18篇 |
1980年 | 5篇 |
1979年 | 14篇 |
1978年 | 3篇 |
1973年 | 2篇 |
1971年 | 3篇 |
1957年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 355 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.
Yanxia Xu Yanbing Lv Ruili Wu Huaibin Shen Huawei Yang Han Zhang Jinjie Li Lin Song Li 《Particle & Particle Systems Characterization》2020,37(3):1900441
Indium phosphide (InP) quantum dots (QDs) are ideal substitutes for widely used cadmium-based QDs and have great application prospects in biological fields due to their environmentally benign properties and human safety. However, the synthesis of InP core/shell QDs with biocompatibility, high quantum yield (QY), uniform particle size, and high stability is still a challenging subject. Herein, high quality (QY up to 72%) thick shell InP/GaP/ZnS core/shell QDs (12.8 ± 1.4 nm) are synthesized using multiple injections of shell precursor and extension of shell growth time, with GaP serving as the intermediate layer and 1-octanethiol acting as the new S source. The thick shell InP/GaP/ZnS core/shell QDs still keep high QY and photostability after transfer into water. InP/GaP/ZnS core/shell QDs as fluorescence labels to establish QD-based fluorescence-linked immunosorbent assay (QD-FLISA) for quantitative detection of C-reactive protein (CRP), and a calibration curve is established between fluorescence intensity and CRP concentrations (range: 1–800 ng mL−1, correlation coefficient: R2 = 0.9992). The limit of detection is 2.9 ng mL−1, which increases twofold compared to previously reported cadmium-free QD-based immunoassays. Thus, InP/GaP/ZnS core/shell QDs as a great promise fluorescence labeling material, provide a new route for cadmium-free sensitive and specific immunoassays in biomedical fields. 相似文献
3.
Yuwei Wang Jia-Jun Yan Shengnan Hu Prof. David James Young Prof. Hong-Xi Li Prof. Zhi-Gang Ren 《化学:亚洲杂志》2021,16(18):2681-2686
A photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water. 相似文献
4.
Thalia Tsiaka Panagiotis Zoumpoulakis Vassilia J. Sinanoglou Constantinos Makris Georgios A. Heropoulos Antony C. Calokerinos 《Analytica chimica acta》2015
High-energy assisted extraction techniques, like ultrasound assisted extraction (UAE) and microwave assisted extraction (MAE), are widely applied over the last years for the recovery of bioactive compounds such as carotenoids, antioxidants and phenols from foods, animals and herbal natural sources. Especially for the case of xanthophylls, the main carotenoid group of crustaceans, they can be extracted in a rapid and quantitative way with the use of UAE and MAE. 相似文献
5.
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
6.
Liming Fan Feng Wang Dongsheng Zhao Yuxin Peng Yuxin Deng Yinwei Luo Xiutang Zhang 《应用有机金属化学》2020,34(12):e5960
Guided by the self-penetrating features can improve the stability of metal organic frameworks (MOFs), an unprecedented 3D self-penetrated framework, {[Zn (tptc)0.5(bimb)]·H2O}n ( NUC-6 , here NUC corresponding to North University of China), with 3D (4,4)-c {86} net, was designed. Benefit from the high chemical stability and excellent luminescent property, NUC-6 can be act as an efficient multi-response chemo-sensor in detecting dichloronitroaniline pesticide and nitrofuran antibiotics in water with the detection limits are 116 ppb for DCN pesticide, 16 ppb for NFT antibiotic, and 12 ppb for NTZ antibiotic. Besides, the mechanisms of luminescence quenching were revealed from the viewpoint of internal filter effect (IFE) and photo-induced electron transfer (PET), implied by the optical spectroscopy and quantum chemical calculation. This work provides a promising strategy to design stable MOFs by improving the self-penetrating features and to expand their practical applications in the detection of organic pollutants in aqueous medium. 相似文献
7.
Wenqing Zhang Dr. Jiuxing Li Prof. Dr. Bruno Salena Prof. Dr. Yingfu Li 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):592-596
DNA detection is usually conducted under nondenaturing conditions to favor the formation of Watson–Crick base-paring interactions. However, although such a setting is excellent for distinguishing a single-nucleotide polymorphism (SNP) within short DNA sequences (15–25 nucleotides), it does not offer a good solution to SNP detection within much longer sequences. Here we report on a new detection method capable of detecting SNP in a DNA sequence containing 35–90 nucleotides. This is achieved through incorporating into the recognition DNA sequence a previously discovered DNA molecule that forms a stable G-quadruplex in the presence of 7 molar urea, a known condition for denaturing DNA structures. The systems are configured to produce both colorimetric and fluorescent signals upon target binding. 相似文献
8.
9.
光寻址电位传感器的幅度检测方法易受噪声干扰,灵敏度差,信噪比和精度低,且受调制光源的影响较大,影响检测结果的准确性.为此提出了一种基于正交相位检波的光寻址电位传感器检测方法.该方法是将光寻址电位传感器的输出光电流信号分别与两路正交信号相乘,通过低通滤波提取直流分量并相除,即可得到光寻址电位传感器的输出信号相位信息.与已有的光寻址电位传感器相位检测方法相比,该方法具有算法复杂度低、实时性高的优点.实验研究了调制光源光强对光寻址电位传感器幅度检测和相位检测的影响,对比分析了光寻址电位传感器的传统幅度检测方法与正交相位检波检测方法对pH检测的灵敏度、线性度及信噪比.结果表明,相比于幅度检测方法,调制光源光强对光寻址电位传感器的相位检测影响更小,在频率为10 kHz,pH的范围为1.68~10.01的情况下,相位检测方法比幅度检测方法测得的灵敏度增加了7 mV/pH,精度提高了14.9 mpH,非线性误差减小了0.003%,均方差减少了0.1051×10^-5,信噪比增加了8.2827 dB.该方法特别适用于弱光下的光寻址电位传感器检测. 相似文献
10.
Benni Du 《Molecular physics》2020,118(2)
Kinetics and mechanism of the gas-phase reaction of CH3C(O)OCH(CH3)CH2OCH3 (MPA) with OH radicals in the presence of O2 and NO have been investigated theoretically by performing a high and reliable level of theory, viz., CCSD(T)/6-311?+?G(d,p)//BH&HLYP/6-311++G(d,p)?+?0.9335×ZPE. The calculations predict that the H-abstraction from the ?CH2?O? position of MPA is the most facile channel, which leads to the formation of the corresponding alkoxy radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 under atmospheric conditions. This activated radicals CH3C(O)OCH(CH3)C(O ?)HOCH3 will undergo further rearrangement, fragmentation and oxidative reactions and predominantly leads to the formation of various products (methyl formate HC(O)OCH3 and acetic anhydride CH3C(O)OC(O)CH3). In the presence of water, acetic anhydride can convert into acetic acid CH3C(O)OH via the hydrolysis reaction. The calculated total rate constants over the temperature range 263–372?K are used to derive a negative activation energy (Ea= ?5.88 kJ/mol) and an pre-exponential factor (A?=?1.78×10?12 cm3 molecule?1 s?1). The obtained Arrhenius parameters presented here are in strong agreement with the experimental values. Moreover, the temperature dependence of the total rate constant over a temperature range of 263?1000?K can be described by k?=?5.60 × 10?14×(T/298?K)3.4×exp(1725.7?K/T) cm3 molecule?1 s?1. 相似文献