全文获取类型
收费全文 | 9894篇 |
免费 | 2348篇 |
国内免费 | 595篇 |
专业分类
化学 | 1353篇 |
晶体学 | 48篇 |
力学 | 2539篇 |
综合类 | 125篇 |
数学 | 2355篇 |
物理学 | 6417篇 |
出版年
2024年 | 25篇 |
2023年 | 97篇 |
2022年 | 169篇 |
2021年 | 198篇 |
2020年 | 295篇 |
2019年 | 242篇 |
2018年 | 257篇 |
2017年 | 311篇 |
2016年 | 326篇 |
2015年 | 267篇 |
2014年 | 543篇 |
2013年 | 622篇 |
2012年 | 603篇 |
2011年 | 727篇 |
2010年 | 598篇 |
2009年 | 602篇 |
2008年 | 677篇 |
2007年 | 685篇 |
2006年 | 642篇 |
2005年 | 619篇 |
2004年 | 589篇 |
2003年 | 542篇 |
2002年 | 418篇 |
2001年 | 404篇 |
2000年 | 335篇 |
1999年 | 273篇 |
1998年 | 267篇 |
1997年 | 216篇 |
1996年 | 175篇 |
1995年 | 170篇 |
1994年 | 128篇 |
1993年 | 139篇 |
1992年 | 116篇 |
1991年 | 114篇 |
1990年 | 76篇 |
1989年 | 75篇 |
1988年 | 63篇 |
1987年 | 50篇 |
1986年 | 26篇 |
1985年 | 27篇 |
1984年 | 26篇 |
1983年 | 14篇 |
1982年 | 25篇 |
1981年 | 17篇 |
1980年 | 10篇 |
1979年 | 11篇 |
1978年 | 3篇 |
1977年 | 4篇 |
1973年 | 6篇 |
1971年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 656 毫秒
221.
铜(Ⅱ)和锌(Ⅱ)分别在0.1mol/LKH_2PO_4-Na_2HPO_4缓冲溶液(pH6.5)和0.25mol/LNH_4Cl溶液中,与氟哌酸形成良好的络合吸附波,峰电位分别为-0.26V和-1.28V(vs;SCE);络合比分别为1:3和1:2;峰电流与铜(Ⅱ)和锌(Ⅱ)的浓度均在4.0×10 ̄(-7)~5.0×10 ̄(-6)mol/L范围内呈线性关系,检测限分别为7.0×10 ̄(-8)和5.0×10 ̄(-8)mol/L。用线性扫描和循环伏安法等手段研究体系的行为,表明均具吸附性,而铜(Ⅱ)-氟哌酸体系属络合物中铜(Ⅱ)的两电子还原的可逆过程。 相似文献
222.
一种新型的表面声波阻抗传感器及其在液相体系中的应用姚守拙,陈康,刘德忠,聂利华(湖南大学化学化工系,长沙,410082)关键词表面声波,阻抗传感器,液相应用表面声波传感器(SAWS)具有较高的灵敏度和检测精度,已广泛应用于气体微量组分分析、色谱检测和... 相似文献
223.
钴(Ⅱ)与5-(5-硝基-2-吡啶偶氮)-2,4-二氨基甲苯络合物吸附波及其应用 总被引:4,自引:1,他引:4
钴 (Ⅱ )在NH3·H2O -NH2OH·HCl-5_(5_硝基_2_吡啶偶氮)_2,4_二氨基甲苯体系中有一灵敏的极谱波 ,其峰电位Vp 为 -1.20V(vsSCE) ,钴质量浓度在0.25~25μg/L范围内与峰电流Ip′有良好的线性关系 ,检出限为0.12μg/L;经多种电化学方法证明该波为络合物吸附波 ,其电极过程为不可逆过程 ,电子转移数为2 ,此外还试验了多种离子对峰电流Ip′的影响;所拟方法已用于维生素B12 和模拟样中痕量钴的测定 相似文献
224.
铟(Ⅲ)-芦丁极谱络合吸附波的研究 总被引:3,自引:0,他引:3
在pH6.0的乙酸盐缓冲底液中,用单扫极谱法可获得高灵敏度的铟(Ⅲ)-芦丁的络合吸附波,其检测下限达3.0×10~(-10)mol/L。成功地用于纯金属锌中10~(-5)%铟的测定。测得吸附电活性络合物的组成为:In(Ⅲ):芦丁=1∶2,条件稳定常数为1.8×10~(10)。电极反应是吸附络合物中的In(Ⅲ)还原为In(Hg)。测得电极反应的转移系数α=0.51,表面电化学反应的标准速率常数k_s=0.43/s 相似文献
225.
在极谱催化波和吸附波方面,国内进行了大量的研究,但汞的络合物吸附波至今未见报道。钯试剂已用于光度法测定钯等。我们在研究该试剂与金属离子络合的极谱行为时发现,在硼砂介质中,试剂与Hg~(2+)可形成电活性络合物并可用于汞的测定。 相似文献
226.
Joseph P. Sattler George J. Simonis 《International Journal of Infrared and Millimeter Waves》1984,5(4):465-473
We report the refractive indices and absorption coefficients for four beryllia (BeO) ceramic samples. These dielectric properties have been measured over the range from 4 to 18 cm–1 by use of a Michelson interferometer. The index n, follows the linear relationship n=0.6517 cm3/g×+0.7130 with density, , over the range 2.8<<3.0 g/cm3. 相似文献
227.
Jingjing Xu Yidong Lu Baohong Liu Chunhe Xu Jilie Kong 《Journal of Solid State Electrochemistry》2007,11(12):1689-1695
An ultrathin, ordered, and packed protein film, consisting of the 2-mercaptoacetic acid (MAA), polydimethyldiallylammonium
chloride (PDDA), and wild-type (WT) photosynthetic reaction center (RC; termed as WT-RC) or its pheophytin (Phe)-replaced
counterpart (termed as Phe-RC), was fabricated by self-assembling technique onto gold electrode for facilitating the electron
transfer (ET) between RC and the electrode surface. Near-infrared (NIR)-visible (Vis) absorption and fluorescence (FL) emission
spectra revealed the influence of pigment substitution on the cofactors arrangement and excitation relaxation of the proteins,
respectively. Square wave voltammetry (SWV) and photoelectric tests were employed to systematically address the differences
between the WT-RC films and mutant ones on the direct and photo-induced ET. The electrochemical results demonstrated that
ET initiated by the oxidation of the primary donor (P) was obviously slowed down, and the formed P+ had more population as well as more positive redox potential in the Phe-RC films compared with those in the WT ones. The
photoelectrochemical results displayed the dramatically enhanced photoelectric performances of the mutant ones, further suggesting
the slow-down formation of final charge-separated state in Phe-RC. The functionalized protein films introduced in this paper
provided an efficient approach to sensitively probe the redox cofactors and ET differences resulting from only minor changes
in pigment arrangement in the pigment–protein complex. The favored ET process observed for the membrane proteins RC was potentially
valuable for a deep understanding of the multi-step biological ET process and development of versatile bioelectronic devices. 相似文献
228.
This work reports the simultaneous determination of Cd(II), Pb(II) and Zn(II) at the low μg l−1 concentration levels by square wave anodic stripping voltammetry (SWASV) on a bismuth-film electrode (BFE) plated in situ. The metal ions and bismuth were simultaneously deposited by reduction at −1.4 V on a rotating glassy carbon disk electrode. Then, the preconcentrated metals were oxidised by scanning the potential of the electrode from −1.4 to 0 V using a square-wave waveform. The stripping current arising from the oxidation of each metal was related to the concentration of each metal in the sample. The parameters for the simultaneous determination of the three metals were investigated with the view to apply this type of voltammetric sensor to real samples containing low concentrations of metals. Using the selected conditions, the limits of detection were 0.2 μg l−1 for Cd and for Pb and 0.7 μg l−1 for Zn at a preconcentration time of 10 min. Finally, BFE's were successfully applied to the determination of Pb and Zn in tapwater and human hair and the results were in satisfactory statistical agreement with atomic absorption spectroscopy (AAS). 相似文献
229.
Laura Gagliardi Giorgio Orlandi Fernando Bernardi Alessandro Cembran Marco Garavelli 《Theoretical chemistry accounts》2004,111(2-6):363-372
In the present paper we report the results of a multiconfigurational computational study on potential-energy curves of azobenzene along the NN twisting to clarify the role of this coordinate in the decay of the S2(*) and S1(n*) states. We have found that there is a singlet state, S3 at the trans geometry, on the basis of the doubly excited configuration n2*2, that has a deep minimum at about 90° of twisting, where it is the lowest excited singlet state. The existence of this state provides an explanation for the short lifetime of S2(*) and for the wavelength-dependence of azobenzene photochemistry. We have characterized the S1(n*) state by calculating its vibrational frequencies, which are found to correspond to the recently observed transient Raman spectrum. We have also computed the potential-energy curve for the triplet T1(n*) at the density functional theory B3LYP level, which indicates that in this state the isomerization occurs along the twisting coordinate.Acknowledgement The financial support from MIUR (project Modellistica delle proprietà spettroscopiche di sistemi molecolari complessi funds ex 60% and project Dinamiche molecolari in sistemi di interesse chimico funds ex 40%), from the University of Bologna (Funds for Selected Research Topics) is gratefully acknowledged.Contribution to the Jacopo Tomasi Honorary Issue 相似文献
230.
Toshikatsu Koga 《Theoretical chemistry accounts》1989,75(6):417-424
Based on momentum- and position-space analyses of the moment operators for two-electron atoms, it is shown that there exists a family of two-electron wave functions which satisfy a proportionality relation, r/
1
v
/r
12
v
=p/
1
v
/p
12
v
=2–v/2, between the one and two-electron moments in position and momentum spaces, where v is an arbitrary number for which the moments are well-defined. 相似文献