全文获取类型
收费全文 | 73390篇 |
免费 | 12850篇 |
国内免费 | 7279篇 |
专业分类
化学 | 50810篇 |
晶体学 | 657篇 |
力学 | 4738篇 |
综合类 | 310篇 |
数学 | 8194篇 |
物理学 | 28810篇 |
出版年
2024年 | 279篇 |
2023年 | 1601篇 |
2022年 | 2717篇 |
2021年 | 2787篇 |
2020年 | 3105篇 |
2019年 | 2906篇 |
2018年 | 2562篇 |
2017年 | 2335篇 |
2016年 | 3569篇 |
2015年 | 3472篇 |
2014年 | 4134篇 |
2013年 | 5304篇 |
2012年 | 6729篇 |
2011年 | 6725篇 |
2010年 | 4467篇 |
2009年 | 4251篇 |
2008年 | 4591篇 |
2007年 | 4107篇 |
2006年 | 3754篇 |
2005年 | 3129篇 |
2004年 | 2425篇 |
2003年 | 1919篇 |
2002年 | 1751篇 |
2001年 | 1470篇 |
2000年 | 1355篇 |
1999年 | 1533篇 |
1998年 | 1304篇 |
1997年 | 1291篇 |
1996年 | 1289篇 |
1995年 | 1050篇 |
1994年 | 921篇 |
1993年 | 763篇 |
1992年 | 674篇 |
1991年 | 580篇 |
1990年 | 501篇 |
1989年 | 384篇 |
1988年 | 335篇 |
1987年 | 274篇 |
1986年 | 249篇 |
1985年 | 204篇 |
1984年 | 143篇 |
1983年 | 102篇 |
1982年 | 80篇 |
1981年 | 67篇 |
1980年 | 65篇 |
1979年 | 33篇 |
1978年 | 30篇 |
1977年 | 40篇 |
1976年 | 30篇 |
1973年 | 28篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The intact fungal spores of several strains of four Aspergillus species, Aspergillus flavus, A. oryzae, A. parasiticus, and A. sojae, were directly analyzed by matrix-assisted laser desorption/ionization (MALDI) time-of-flight mass spectrometry. Very simple MALDI mass spectra are obtained by directly mixing spores with a matrix such as alpha-cyano-4-hydroxycinnamic acid or sinapinic acid. The mass spectra are obtained from the ablation of cell walls of spores owing to the acidity of the matrix solution. The MALDI results show that aflatoxigenic strains and non-aflatoxigenic strains have different mass peak profiles. Furthermore, the MALDI results of non-aflatoxigenic A. flavus and A. parasiticus spores resemble those of the closely related A. oryzae and A. sojae spores, respectively. 相似文献
992.
Zhiming Liu Jiming Hao Lixin Fu Tianle Zhu Junhua Li Xiangyu Cui 《Reaction Kinetics and Catalysis Letters》2003,80(1):45-52
SnO2/Al2O3 catalyst prepared by sol-gel method showed higher activity than those prepared by impregnation method, and their activity
was significantly improved by pre-treatment in the reaction gas. The increased activity is closely related to the agglomeration
of SnO2 species and the re-exposure of Al2O3, which was previously covered by dispersed SnO2 species.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
993.
A new method based on hollow fiber-protected liquid-phase microextraction (LPME) was developed for the simultaneous determination
of atrazine, desethyl atrazine and desisopropyl atrazine in environmental water samples. In LPME, analytes were extracted
into 1-octanol immobilized in the micropores of a poly(vinylidene fluoride) porous hollow fiber membrane, and back extracted
into the acceptor (4 M HCl) filled in the lumen of the hollow fiber. After LPME, the analytes trapped in the acceptor were
analyzed with high-performance liquid chromatography after neutralization. The effect of extraction factors such as sample
pH, acceptor pH, salinity, extraction time, stirring rate, and humic acid were studied. Under the optimized conditions, the
limits of detection and relative standard deviations were respectively in the range of 0.5–1.0 μg L−1 and 3.9–4.7% (n = 5). The proposed method was applied to determine atrazine, desethyl atrazine and desisopropyl atrazine in wastewater and
groundwater samples. The three analytes were below the limits of detection, but good relative spiked recoveries over 90.1
± 5.9% at 5 μg L−1 spiked level were obtained. 相似文献
994.
995.
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
996.
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
997.
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
998.
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
999.
Xu LC Li ZY Tan W He TJ Liu FC Chen DM 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):850-862
The vibrational spectra of meso-tetraphenylporphyrin diacid (H4TPP2+) have been studied with the density functional theory. Raman and IR spectra of H4TPP2+ and its N-deuterated analogue (D4TPP2+) are measured and compared with the computational results. Complete assignments of observed IR and Raman bands were proposed on the bases of calculation results. The DFT calculations reproduce 140 observed fundamentals with the RMS 8.6 cm-1. The computational as well as the experimental results reveal that the saddle-distortion of porphyrin macrocycle for the diacid leads to a significant effect on its vibrational spectra. Especially, several out-of-plane skeletal modes, which were either unobserved or very weak in the Raman spectra of CuTPP and H2TPP, are activated in the Raman spectra of the diacids. In addition, enhancement for the Raman bands of phenyl CC stretching modes were observed and attributed to the conjugation effect of pi-systems of the phenyl and the porphyrinato macrocycles. 相似文献
1000.
Snyder DA Chen Y Denissova NG Acton T Aramini JM Ciano M Karlin R Liu J Manor P Rajan PA Rossi P Swapna GV Xiao R Rost B Hunt J Montelione GT 《Journal of the American Chemical Society》2005,127(47):16505-16511
X-ray crystallography and NMR spectroscopy provide the only sources of experimental data from which protein structures can be analyzed at high or even atomic resolution. The degree to which these methods complement each other as sources of structural knowledge is a matter of debate; it is often proposed that small proteins yielding high quality, readily analyzed NMR spectra are a subset of those that readily yield strongly diffracting crystals. We have examined the correlation between NMR spectral quality and success in structure determination by X-ray crystallography for 159 prokaryotic and eukaryotic proteins, prescreened to avoid proteins providing polydisperse and/or aggregated samples. This study demonstrates that, across this protein sample set, the quality of a protein's [15N-1H]-heteronuclear correlation (HSQC) spectrum recorded under conditions generally suitable for 3D structure determination by NMR, a key predictor of the ability to determine a structure by NMR, is not correlated with successful crystallization and structure determination by X-ray crystallography. These results, together with similar results of an independent study presented in the accompanying paper (Yee, et al., J. Am. Chem. Soc., accompanying paper), demonstrate that X-ray crystallography and NMR often provide complementary sources of structural data and that both methods are required in order to optimize success for as many targets as possible in large-scale structural proteomics efforts. 相似文献