全文获取类型
收费全文 | 110880篇 |
免费 | 17172篇 |
国内免费 | 12622篇 |
专业分类
化学 | 59868篇 |
晶体学 | 948篇 |
力学 | 5292篇 |
综合类 | 539篇 |
数学 | 9502篇 |
物理学 | 32801篇 |
无线电 | 31724篇 |
出版年
2024年 | 481篇 |
2023年 | 2675篇 |
2022年 | 3533篇 |
2021年 | 4350篇 |
2020年 | 4348篇 |
2019年 | 4051篇 |
2018年 | 3537篇 |
2017年 | 3480篇 |
2016年 | 4787篇 |
2015年 | 5189篇 |
2014年 | 6172篇 |
2013年 | 7782篇 |
2012年 | 9569篇 |
2011年 | 9509篇 |
2010年 | 7039篇 |
2009年 | 6912篇 |
2008年 | 7315篇 |
2007年 | 6591篇 |
2006年 | 6075篇 |
2005年 | 5126篇 |
2004年 | 3866篇 |
2003年 | 3261篇 |
2002年 | 3004篇 |
2001年 | 2536篇 |
2000年 | 2362篇 |
1999年 | 2416篇 |
1998年 | 2045篇 |
1997年 | 1829篇 |
1996年 | 1839篇 |
1995年 | 1534篇 |
1994年 | 1330篇 |
1993年 | 1065篇 |
1992年 | 950篇 |
1991年 | 818篇 |
1990年 | 650篇 |
1989年 | 470篇 |
1988年 | 400篇 |
1987年 | 325篇 |
1986年 | 286篇 |
1985年 | 251篇 |
1984年 | 181篇 |
1983年 | 133篇 |
1982年 | 102篇 |
1981年 | 78篇 |
1980年 | 80篇 |
1979年 | 46篇 |
1978年 | 40篇 |
1977年 | 48篇 |
1976年 | 44篇 |
1973年 | 31篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
961.
Maximum spectrum of continuous wavelet transform and its application in resolving an overlapped signal 总被引:2,自引:0,他引:2
Xiaoquan L Hongde L Zhonghua X Qiang Z 《Journal of chemical information and computer sciences》2004,44(4):1228-1237
To estimate the number of peaks and to find the individual peak positions in an overlapped signal, a new method called maximum spectrum of continuous wavelet transform (MSCWT) was developed by extracting the maximum coefficients of continuous wavelet transform (CWT). The peak position in MSCWT was the same as that in its original signal. In this process, CWT was performed not on a single dilation but on an appreciation dilation range. To obtain such a range, a new criterion was introduced to choose a center dilation, which was used to form the dilation range. If Cdilation denoted the center dilation, the proper dilation range was [Cdilation -6 +/- 2, Cdilation +1 +/- 1]. The Mexican Hat function was an analytical wavelet. Utilizing the information of the peak number and the position detected by MSCWT, a fitting route was performed to recover the original signal. One simulated and four true overlapped signals, including high performance liquid chromatography (HPLC), ultraviolet-visible (UV) spectrum, and differential pulse voltammetric (DPV), were processed, and the results indicated that MSCWT could detect an overlapped peak number and position, and the curve fitting based on information of MSCWT had a higher accuracy. The proposed method was an efficient one in resolving different types of overlapped signals. 相似文献
962.
The growth of cobalt hexacyanoferrate (CoHCF) films on bare and Au-colloid-modified electrodes in nitrate or sulfate solutions was monitored by electrochemical quartz crystal microbalance. The average efficiency of CoHCF film growth for Au colloid modified electrodes is 23 and 12 ng cm(-2) s(-1) in KNO3 and K2SO4 solutions, respectively, while those values for the bare gold electrode are 15 and 9 ng cm(-2) s(-1), respectively. In K2SO4 solution, the apparent molar masses for the Au-colloid-modified electrode at lower and higher potential is 58.4 and 37.3 g mol(-1), respectively, which is larger than those for the bare gold electrode (51.7 and 26.3 g mol(-1), respectively). The respective results were also obtained in KNO3 solution. Furthermore, the difference of the apparent molar masses at lower and higher potential for Au-colloid-modified electrodes is smaller than that for bare gold electrodes in the same electrolyte. Additionally, the mechanism of charge propagation is dependent on different anions in electrolyte solutions at higher potentials where the second redox reaction of CoHCF occurs. Therefore, the existence of Au colloids can accelerate CoHCF film growth and weaken the effect of anions on mass transport. 相似文献
963.
Harpeness R Peng Z Liu X Pol VG Koltypin Y Gedanken A 《Journal of colloid and interface science》2005,287(2):678-684
A rapid polyol process for the synthesis of ruthenium nanoparticles was developed using microwave irradiation. A colloidal solution of monodispersed anisotropic Ru metal nanoparticles (mean particle size 2-6 nm) with different aspect ratios was obtained first. Particles with different degrees of agglomeration have also been synthesized using monodisperse particles as seeds and PVP (poly-N-vinyl-2-pyrrolidone) as the stabilization reagent. The stabilization mechanisms of different protective reagents were studied by UV-vis spectra. The HRTEM images indicated that dendritic particles formed by controlling agglomeration consisted of single-crystal domains with a random crystalline orientation. 相似文献
964.
Liu H Hu Y Yang S Guo W Lu X Zhao L 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(21):6392-6406
We report herein a comprehensive study of photoinduced reactions in complexes of Mg+ with primary (n-propyl- and isopropylamine) and secondary amines (dipropyl- and diisopropylamine) in the spectral range of 230-440 nm. Similar to the methyl- and ethylamine complexes studied previously, N-H bond activation of these complexes is very unfavorable. Instead, the C(alpha)-C, C-N, and C(alpha)-H bond-cleavage photoproducts are observed after photoexcitation of the Mg+ complexes (3(2)P<--3(2)S). For Mg+(primary amine) complexes, for example, Mg+-NH2CH2CH2CH3, and Mg+-NH2CH(CH3)2, the photoproducts resulting from C(alpha)--C rupture prevail after P(z) and charge-transfer excitations, whereas the Mg+ photofragment is predominant upon P(x,y) excitation. However, with further N-alkyl substitution, as in Mg+(secondary amine) complexes, for example, Mg+-NH(CH2CH2CH3)2 and Mg+-NH[CH(CH3)2]2, a novel intracomplex C-C coupling photoreaction dominates on P(x,y) excitation of Mg+, which is believed to arise from Mg+* insertion into the C-N bond. With P(z) and charge-transfer excitation, the Mg-R elimination photoproducts, arising from C(alpha)-C bond cleavage, predominate. The energetics and possible mechanisms of the intracomplex photoreactions are analyzed in detail with the help of extensive quantum mechanics calculations. 相似文献
965.
The bifunctional chiral thiourea-tertiary amine organocatalysts have been applied to a direct asymmetric vinylogous Michael addition of α,α-dicyanoolefins to nitroolefins with 2-10 mol % catalyst loadings. The electronic properties of the thiourea-based catalysts have significant influences on this reaction. Moderate to excellent enantioselectivities (57-95% ee) have been achieved with low to good isolated yields through fine tuning the structures of the bifunctional organocatalysts. Much better ees were obtained for some α,α-dicyanoolefinic substrates compared with that catalyzed by modified cinchona alkaloids. 相似文献
966.
为增强有机锗化合物的生物活性,合成了一系列有机锗氨基酸酯类倍半氧化物,并重点研究了它们的快原子轰击质谱(FABMS)。研究结果表明:该系列化合物的各碎片离子峰与其组成及结构均有很好的对应关系及很强的规律性 相似文献
967.
Chen H Aleksandrov A Chen Y Zha S Liu M Orlando TM 《The journal of physical chemistry. B》2005,109(22):11257-11262
Polycrystalline gadolinia-doped ceria (GDC) surfaces were studied using low-energy (5-400 eV) electron stimulated desorption (ESD). H(+), O(+), and H(3)O(+) were the primary cationic desorption products with H(+) as the dominant channel. H(+), H(3)O(+), and O(+) have a 22 eV threshold followed by a yield change around 40 eV. H(+) also has an additional yield change approximately 75 eV and O(+) has an additional change approximately 150 eV. The O(+) ESD yield change approximately 150 eV may indicate bond breaking of Gd-O and the involvement of oxygen vacancies. The H(+) and H(3)O(+) threshold data collectively indicate the presence of hydroxyl groups and chemisorbed water molecules on the GDC surfaces. ESD temperature dependence measurements show that the interaction of water with GDC surface defect sites, mainly oxygen vacancies, influences the desorption of H(+), O(+), and H(3)O(+). The temperature dependence of the O(+) ESD at 400 eV incident electron energy yields a 0.21 eV activation energy. This is close to the energy needed for oxygen vacancy production next to a pair of Ce(3+) on a CeO(2) surface. These results may indicate a correlation between the O(+) ESD yield and oxygen vacancy density on GDC surfaces and a potential correlation of O(+) ESD and GDC ionic conductivity. 相似文献
968.
Surface plasmon resonance (SPR) has been successfully applied for the simple, rapid, and label-free assay of various biomolecules. This assay evaluates a novel wavelength modulation SPR biosensor for the detection of tetanus toxin. The wavelength modulation SPR biosensor is designed based on fixing the incident angle of light and measuring the reflected intensities in the resonance wavelength range spanning 400-800 nm simultaneously. Tetanus toxin (TeNT), one of the most potent toxins known, is synthesized as a 150 kDa single polypeptide chain. The SPR biosensor has been shown to be capable of directly detecting concentration of tetanus toxin as low as 0.028 Lf ml−1. Under selected experimental conditions, the SPR biosensor has a good reproducibility, sensitivity and reversibility. The results illustrate how wavelength modulation SPR biosensor can be used to detect biomolecular interactions. 相似文献
969.
Petra A. M. van Koppen Andreas J. Illies Shuying Liu Michael T. Bowers 《Journal of mass spectrometry : JMS》1982,17(9):399-402
The effect of the precursor ion internal energy on the branching ratios obtained from collision induced dissociation fragmentation patterns was examined for [NH3]+ and [C2H4N]+. The ion internal energy was changed by varying both the chemical ionization reagent gas and the ion source pressure. Effects observed in the collision induced dissociation fragmentation patterns as a function of the ion source pressure are explained by the reaction exothermicities and by collisional deactivation of internally excited ions (at high pressure). 相似文献
970.
Haifang Liu Yuanqiang Sun Zhaohui Li Ran Yang Jie Yang Aaron Albert Aryee Xiaoge Zhang Jia Ge Lingbo Qu Yuehe Lin 《中国化学快报》2019,30(9):1647-1651
Intracellular pH plays a significant role in various biological processes, including cell proliferation, apoptosis, metabolism, enzyme activity and homeostasis. In this work, a novel design strategy for the preparation of pH responsive carbon dots (CDs-pH) for ratiometric intracellular imaging was reported. By using SciFinder database, fluorescent CDs-pH with the required pKa value of 6.84 were rationally designed, which is vital important for precise sensing of intracellular pH. As a result, the synthesized CDs-pH demonstrated robust ability to test pH fluctuations within the physiological range of 5.4-7.4. The CDs-pH was further utilized for fluorescent ratiometric imaging of pH in living HeLa cells, effectively avoided the influence of autofluorescence from native cellular species. Moreover, real-time monitoring of intracellular pH fluctuation under heat shock was successfully realized. This SciFinder-guided design strategy is simple and flexible, which has a great potential to be used for the development of other types of CDs for various applications. 相似文献