全文获取类型
收费全文 | 30949篇 |
免费 | 5783篇 |
国内免费 | 3528篇 |
专业分类
化学 | 22374篇 |
晶体学 | 357篇 |
力学 | 1800篇 |
综合类 | 151篇 |
数学 | 3108篇 |
物理学 | 12470篇 |
出版年
2024年 | 51篇 |
2023年 | 682篇 |
2022年 | 777篇 |
2021年 | 1166篇 |
2020年 | 1416篇 |
2019年 | 1378篇 |
2018年 | 1161篇 |
2017年 | 1039篇 |
2016年 | 1603篇 |
2015年 | 1496篇 |
2014年 | 1920篇 |
2013年 | 2385篇 |
2012年 | 2894篇 |
2011年 | 2969篇 |
2010年 | 1946篇 |
2009年 | 1897篇 |
2008年 | 2100篇 |
2007年 | 1834篇 |
2006年 | 1725篇 |
2005年 | 1364篇 |
2004年 | 1045篇 |
2003年 | 830篇 |
2002年 | 821篇 |
2001年 | 639篇 |
2000年 | 514篇 |
1999年 | 626篇 |
1998年 | 531篇 |
1997年 | 502篇 |
1996年 | 496篇 |
1995年 | 429篇 |
1994年 | 352篇 |
1993年 | 284篇 |
1992年 | 285篇 |
1991年 | 234篇 |
1990年 | 205篇 |
1989年 | 153篇 |
1988年 | 96篇 |
1987年 | 82篇 |
1986年 | 107篇 |
1985年 | 78篇 |
1984年 | 38篇 |
1983年 | 44篇 |
1982年 | 27篇 |
1981年 | 22篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1976年 | 1篇 |
1975年 | 1篇 |
1957年 | 4篇 |
1923年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 529 毫秒
991.
Shuhui Yu Kui Yao Francis Eng Hock Tay 《Journal of Sol-Gel Science and Technology》2007,42(3):357-364
The preferential formation of a pyrochlore structure is a knotty problem in the preparation of Pb(Zn1/3Nb2/3)O3 (PZN)-based thin film materials and its presence is significantly detrimental to the dielectric and piezoelectric properties.
In this study, 40 mol% of PZN was replaced with Pb(Mg1/3Nb2/3)O3 (PMN) for obtaining a perovskite composition around a morphotropic phase boundary (MPB), (1−x)(0.6PZN-0.4PMN)-xPT ((1−x)PZMN-xPT, PT: PbTiO3) where x = 0.23. The thin films with this composition were prepared with a polyethylene glycol (PEG) modi-fied sol-gel method on LaAlO3 substrates. The microstructural evolution of the films on heat treatment was examined with X-ray diffraction. With the aid
of PEG, the formation of the pyrochlore phase was suppressed and the perovskite phase formed directly from the amorphous gel
film. The multilayer films with a thickness around 0.25 μm showed a single perovskite phase without any detectable pyrochlore
structure. Microscopic images showed uniform grain size of a few tens of nanometers. The role of the polymer dramatically
promoting the perovskite phase was investigated with the aid of X-ray photoelectron spectroscopy and thermal analysis. The
dielectric constant of the obtained film was 4160 at 1 kHz. The film demonstrated typical ferroelectric hysteresis loops and
exhibited excellent piezoelectric performance. 相似文献
992.
The voltammetric behavior of the LMF-Mg(II) complex with DNA at a mercury electrode is reported for the first time. In NH3–NH4Cl buffer (pH=9.10), the adsorption phenomena of the LMF–Mg(II) complex were observed by linear sweep voltammetry. The mechanism of the electrode reaction was found to be a reduction of LMF in the complex, and the composition of the LMF–Mg(II) complex is 2:1. In the presence of calf thymus DNA (ctDNA), the peak current of LMF–Mg(II) complex decreased considerably, and a new well-defined adsorptive reduction peak appeared at −1.63 V (vs. SCE). The electrochemical kinetic parameters and the binding number of LMF–Mg(II) with ctDNA were also obtained. Moreover, the new peak currents of LMF–Mg(II)–DNA system increased linearly correlated to the concentration of DNA in the 4.00×10−7–2.60×10−6 g ml−1 range when the concentrations of LMF–Mg(II) complex was fixed at 5.00×10−6 mol l−1, with the detection limits of 2.33×10−7 g ml−1. An electrostatic interaction was suggested by electrochemical method. 相似文献
993.
Hanhua Zhao Curtis P. Berlinguette John Bacsa Shane E. Tichy Kim R. Dunbar 《Journal of Cluster Science》2003,14(3):235-252
The preparation and characterization of two new mixed-valence, trinuclear species, [Mn3O(O2CCF3)6(H2O)3]CF3COOH4/3H2O (1) and [Mn3O(O2CCF3)6(CH3COOH)3] (2), is reported. Compound 1 crystallizes in the triclinic space group, P¯1 (No. 2), with the parameters, a=12.3131(9) Å, b=12.4427(9) Å, c=12.965(1) Å, =72.593(4)°, =73.453(5)°, =68.345(4)°, V=1727.2(2) Å3, and Z=2. A total of 14060 reflections were collected in the range 1.6827.52°. The final weighted and non-weighted agreement indices, R1=0.0589 and wR2=0.1445 were based on a total of 6953 unique reflections with an R
int value of 0.0542. Compound 2 crystallizes in the monoclinic space group, P21/n (No. 14), with the parameters, a=12.876(3) Å, b=12.212(4) Å, c=17.732(4) Å, =100.40(3)°, V=3640.4(1) Å3, and Z=4. A total of 32197 reflections were collected in the range 1.7227.13°. The final weighted and non-weighted agreement factors, R1=0.0647 and wR2=0.1609 were based on a total of 8018 unique reflections with an R
int
value of 0.0462. An investigation of the physical properties revealed that both compounds display an intermediate ground state of S=3/2 as a consequence of intramolecular antiferromagnetic coupling. The magnetic data for compound 1 was best fit to the parameters g=2.09, J=–5.5 cm–1, J=–3.4 cm–1, and D
Mn(III)=–4.5 cm–1; the data for compound 2 was best fit to the parameters g=2.10, J=–2.9 cm–1, J=–5.5 cm–1, and D
Mn(III)=–4.5 cm–1. 相似文献
994.
The photocatalytic degradation for some kinds of dye-constituent aromatics with TiO2 in the presence of phosphate anions in aqueous dispersion was investigated under both visible light (λ>480 nm) and UV irradiation. The influences of phosphate anion upon the degradation of organics under these different conditions was revealed by the measurement of point of zero ξ-potential (P ZC) of TiO2, UV-VIS spectra, HPLC and LC-MS. The adsorption and photodegradation of some organics, which adsorb on the surface of TiO2 by a dominating group bearing a positive charge, was enhanced, while that of others, which adsorb on the surface of TiO2 by a dominating group bearing negative charge, was depressed by the presence of phosphate anions under UV irradiation at the experimental conditions (pH 4.3). It was confirmed that better adsorption of organics on the surface of TiO2 had an advantage in their photocatalytic degradation under UV irradiation. On the other hand, although the adsorption of rhodamine B (RhB) and methylene Blue (MB) markedly increased, their degradation under visible light irradiation was depressed in the presence of phosphate anions. It is suggested that phosphate anion greatly blocked the electron transfer from excited RhB and MB molecules as RhB and MB molecules predominantly adsorbed on the surface of TiO2 through the electrostatic interaction with surface adsorbed phosphate anions. 相似文献
995.
Junbiao Chang Rongfeng Chen Ruiyun Guo Chunhong Dong Kang Zhao 《Helvetica chimica acta》2003,86(6):2239-2246
Two biphenyl lignans, α‐ and β‐DDB ( 1 and 2 , respectively) were efficiently synthesized without contamination by other regio‐isomers. The different yields of the Ullmann coupling reactions for the synthesis of 1 and 2 were rationalized by calculating steric hindrance, stability, entropy change, and heat‐of‐formation values. The enantiomers of 1 and 2 were readily separated by HPLC on a chiral stationary phase. Their configurations were assigned based on the Cotton effect of the authentic natural products. 相似文献
996.
Rong-Qiao He Chuan-You Li Jung Xu Xiu-An Zhao 《Applied biochemistry and biotechnology》1996,60(3):229-244
Estimation of the optimal concentrations of residual sugar in medium for a fed-batch culture of Baker’s yeast has been studied and practiced. The concentrations, however, depended on different species and targets of the biomass, which was expected to be made. Kinetic changes of the residual phosphate salt in the medium conformed to a logarithmic process until the fourth hour during an 11-h culture. The parabolic method (see ref. 9 later in article) might be qualified to maintain the concentrations of residual sugar around 0.15 g/L. It was demonstrated that cell growth followed a sigmoid process during a fed-batch culture, because the cells consumed the nutrient with two metabolic pathways, one was for cell conversion and another was for non-cell conversion. With the parabolic method, we can estimate kinetics of cell growth and cell growth rate during the culture. 相似文献
997.
998.
The coordination compound [Co(C10H7COO)2(H2O)3]2n
· 4nH2O was prepared by the reaction of 1-naphthoic acid and cobalt(II) acetate tetrahydrate in basic solution, and was fully characterized
by X-ray diffraction, element analysis, FTIR, TG-DTA and luminescent spectra. In the crystal the six-coordinated Co(II) centers
are linked into one-dimensional zigzag chains by water molecules, which are further assembled into a two-dimensional network through weak inter-chain C–H···π interactions.
The solid complex exhibits favorable fluorescent properties similar to those of free ligand at room temperature, which can
be assigned to the intraligand electronic transfer. 相似文献
999.
LiLi Liu WanHong Ma WenJing Song ChunCheng Chen Jun Lin JinCai Zhao XinHua Qian ShiBo Zhang 《中国科学:化学(英文版)》2007,50(6):770-775
This study investigated the visible-light catalysis mediated by zeolite NaY on the oxidation of dyes with H2O2. The results demonstrated that zeolite NaY acts as a sink for the electron from the photo-excited dye in the heterogeneous catalysis. Furthermore, the electron can effectively activate H2O2 to produce ·OH radical that is a powerful oxidant for the oxidation of dye at room temperature. The effects of the framework topology, Si/Al ratio, and exchangeable cation of the zeolite on the oxidation of various dyes were also shown. 相似文献
1000.
Zhao Z Xiong S Liu X Xin B Wang G 《European journal of mass spectrometry (Chichester, England)》2003,9(3):203-211
We report the application of matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry, with delayed extraction in the reflectron mode, for the characterization of low molecular weight dendrimers. 20 dendrimer samples were measured and 4 typical dendrimers, as examples, are discussed in detail. Several factors that affect the analysis including the matrices used, the concentrations of sample, the solvents and cationization reagent used, were investigated in detail. Experimental results indicate that the type of solvent can greatly influence exact mass measurement. However, sample preparation is generally not very critical for dendrimer analysis using MALDI-ToF since many kinds of matrices and a wide range of sample concentrations can be used efficiently. In addition, the Cs(+) ion can be used to enhance the efficiency of cationization. Some reasons for this behavior are discussed on the basis of results of calculations using Gaussian94 software (a connected system of programs for performing a variety of semi-empirical and ab initio molecular orbital (MO) calculations). 相似文献