全文获取类型
收费全文 | 4856篇 |
免费 | 250篇 |
国内免费 | 593篇 |
专业分类
化学 | 5450篇 |
晶体学 | 16篇 |
力学 | 6篇 |
综合类 | 33篇 |
数学 | 4篇 |
物理学 | 190篇 |
出版年
2024年 | 1篇 |
2023年 | 79篇 |
2022年 | 98篇 |
2021年 | 124篇 |
2020年 | 102篇 |
2019年 | 116篇 |
2018年 | 70篇 |
2017年 | 113篇 |
2016年 | 134篇 |
2015年 | 131篇 |
2014年 | 149篇 |
2013年 | 234篇 |
2012年 | 461篇 |
2011年 | 259篇 |
2010年 | 242篇 |
2009年 | 283篇 |
2008年 | 324篇 |
2007年 | 383篇 |
2006年 | 323篇 |
2005年 | 312篇 |
2004年 | 294篇 |
2003年 | 225篇 |
2002年 | 165篇 |
2001年 | 116篇 |
2000年 | 98篇 |
1999年 | 100篇 |
1998年 | 100篇 |
1997年 | 108篇 |
1996年 | 80篇 |
1995年 | 97篇 |
1994年 | 57篇 |
1993年 | 60篇 |
1992年 | 62篇 |
1991年 | 70篇 |
1990年 | 42篇 |
1989年 | 34篇 |
1988年 | 21篇 |
1987年 | 6篇 |
1986年 | 6篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1975年 | 1篇 |
排序方式: 共有5699条查询结果,搜索用时 31 毫秒
101.
《Electroanalysis》2004,16(10):811-820
A new minicell coupling the liquid‐liquid extraction technique called permeation liquid membrane (PLM) with an integrated Ir‐based Hg‐plated microelectrode array for voltammetric detection has been developed for the speciation of heavy metals in natural waters. Lead and cadmium have been used as model compounds. The PLM consists of a carrier (0.1 M 22DD+0.1 M lauric acid) dissolved in 1 : 1 mixture of toluene/phenylhexane held in the small pores (30 nm) of a hydrophobic polypropylene membrane (Celgard 2500). One side of this membrane is in contact with a flowing source solution, containing the metal ions of interest. An acceptor or strip solution (pyrophosphate) is placed on the other side of the PLM with the microelectrode array placed at 480 μm of the PLM. The analyte is transported by the carrier from the source solution to the strip solution. The originality of the new minicell is that accumulation in the strip solution is voltammetrically followed by the integrated microelectrode array in real time, and at low concentration level, using square‐wave anodic stripping voltammetry (SWASV). In order to protect the Hg microelectrodes from the adsorption of the hydrophobic carrier, the microelectrodes are embedded in a thin gel layer (280 μm) of 1.5% LGL agarose gel containing 10% of hydrophobic silica particles C18. The choice of optimum conditions is discussed in details in this article. Due to the very small effective strip volume of the new cell (less than 1 μL), high enrichment factor can be obtained (e.g., 330 for Pb) after 2 hours of accumulation. No deaeration of the solutions is required for SWASV measurements. Detection limits under these conditions are 2 pM and 75 pM for Pb and Cd, respectively, using a voltammetric deposition time of 5 min. In addition, no fouling effects were observed with natural water samples. 相似文献
102.
I. V. Shchirina-Eingorn L. N. Novikova N. A. Ustynyuk L. I. Denisovich M. G. Peterleitner 《Russian Chemical Bulletin》1996,45(7):1608-1610
The roe of oxidatively induced homolyhc scission a the C(sp3)-H bonds in the iron phenykychhexadienyl complexes Fe(5-6-PhC6H6)(5-C5H5) (1) depends on the spatial orientation of the Ph substitutent. In the case of the (1
endo
+) radical cation this process, resulting in the cationic biphenyl complex (Fe(6 -C6H5C6H5)(5-C5H5)]+ (2
+), is fast and proceeds for several minutes. In the case of the more stable radical cation (1
exo
+) the formation of 2+ is slow and takes tens minutes to complete.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1698–1700, July, 1996. 相似文献
103.
The anodic reaction of Ni in an alkaline solution was studied by the tip–substrate voltammetry mode of scanning electrochemical microscopy (SECM) and cyclic voltammetry (CV). A platinum microdisc electrode was selected as the tip electrode, which functioned as a pH sensor with transient response capability. The pH value of the solution near the Ni electrode surface varied while the Ni substrate oxidation reaction occurred, and the pH variation could be detected by the tip faradic current. The cyclic voltammogram results showed that two types of hydroxides: i.e. α‐Ni(OH)2 and β‐Ni(OH)2 were formed during Ni oxidation in the lower potential region. In the proceedings of α‐Ni(OH)2 → γ‐NiOOH and β‐Ni(OH)2 → β‐NiOOH, the process of OH? concentration decrease in the solution was ahead and behind of electron transfer in the solid phase, respectively. These results indicate that the OH? adsorption process occurs as an elementary step in the former reaction and the H+ diffusion process from the inner to the outer layer of the solid phase occurs as a subsequent step in the latter reaction. The results also revealed that the oxide film on the Ni surface has a two‐layer structure. The real potential of the oxygen evolution reaction (OER) on the Ni surface with different cycles is also analyzed in the paper. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
104.
Discharge performance of K2FeO4 electrode under different conditions was studied by the constant electric current discharge method. The electrochemical characteristics of K2FeO4 electrode were investigated for the first time by means of cyclic voltammetry. The results show that the K2FeO4 electrode made at moderate pressure (20MPa) and discharged at lower current has better discharge performance. It is also found that K2FeO4 electrode is significantly rechargeable. 相似文献
105.
Subash C. Raghu Sheela Berchmans Dr. Kanala L. Phani Dr. Venkatraman Yegnaraman Dr. 《化学:亚洲杂志》2007,2(6):775-781
This paper describes the formation of catalytically active thin films of Pt, Pt/Au, and Pt/Ru on gold substrates stabilized by amine‐terminated polyamidoamine (PAMAM) dendrimers. A monolayer of dendrimer is initially self‐assembled on the gold substrate, which serves as a template for the growth of catalytically active thin films. As dendrimers contain tens to hundreds of functional groups at the periphery, the aggregate strength of the multidentate interactions with the gold substrate leads to the formation of robust films. The films were found to exhibit high catalytic activity for the oxidation of small hydrocarbons such as methanol. Such films offer versatility and scope for the design of effective electrocatalysts, especially in the context of microfuel cells and “dendrichips”; hence, they could find applications in the fields of sensors, fuel cells, and waste‐water treatment. 相似文献
106.
《Electroanalysis》2006,18(1):35-43
A new method is presented for the determination of electrochemically labile iron in estuarine and coastal seawater. The method is based on differential pulse anodic stripping voltammetry (DPASV) at a rotating silver‐alloy disk electrode. The voltammetric parameters include a plating potential of ?1.5 V and an activation potential of ?5 V for 10s; the seawater is at the original sample pH. The main finding is the presence of a peak for low nmol L?1 levels of iron at ?0.55 V ascribed to elemental iron deposited on the bare silver alloy electrode. The peak increased linearly with the iron concentration between <1 and 14 nmol L?1 using a 900 s plating time. At higher concentrations an additional iron peak appeared at ?0.7 V which was also found to increase linearly with the iron concentration but at a higher concentration range from ca. 15 to 90 nmol L?1 using a 300 s plating time. The second peak was ascribed to iron deposited on iron. Additions of chelating agents (EDTA and a siderophore) to seawater caused the iron peak to be masked indicating that this method is suitable for iron speciation as only the electrochemically labile fraction is determined. The detection limit was 0.3 nmol L?1 using a 900 s plating time. The method was used to determine iron in the range of 5 to 50 nmol L?1 in samples from the Mersey estuary near Liverpool and its potential use for in situ monitoring was demonstrated by using it to monitor labile iron (at 2–3 nmol L?1) over a period of 4 days at 1 h intervals in coastal waters in the Trondheim fjord, Norway. 相似文献
107.
研究了酚酞在0.5 mol/L氨水-氯化铵缓冲溶液(pH 10)介质中汞膜电极上的电化学行为,并依此建立了酚酞含量的方波伏安法测定.酚酞于-0.98 V(VS.Ag/AgCl)处出现一灵敏的阴极还原峰,峰高与酚酞的浓度在3.0×10-7-5.0×10-5mol/L范围内有良好的线性关系.方法的最低检出限为1.0×10-7mol/L,方法用于酚酞片中酚酞含量的测定,结果满意. 相似文献
108.
An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10?5 M. 相似文献
109.
M. E. Ahmed M. S. Ibrahim Y. M. Temerk A. M. Kawde 《Monatshefte für Chemie / Chemical Monthly》1996,127(6-7):609-619
Summary A systematic comparative study of the adsorption and association of 3-methylxanthine (3MXan) and 7-methylxanthine (7MXan) at mercury-solution interfaces in acidic, neutral, and alkaline buffer solutions was undertaken by ac voltammetry. At bulk concentrations of3MXan above a threshold value, the stacking interactions between vertically oriented molecules lead to a slow reorientation aroundE
ecm, and the molecules adopt a perpendicular orientation. The association of the adsorbed molecules of7MXan is hindered and is not effective in promoting base-base stacking interactions. The enhanced surface activity of3MXan compared to7MXan results from the different position of the methyl group in the purine moiety. The effect of some divalent metal ions on adsorption stages and association of the investigated compounds has been studied. The results indicate that the complexation of methylated xanthine enhances the stacking interactions and hence would be expected to facilitate the formation of perpendicularly stacked layers ofM(II)-MXan complexes on the electrode surface. The adsorption parameters of the investigated compounds have been computed in absence and presence of Cu(II) at differentpH values. The results are compared with the behaviour of xanthine.
Vergleichende Untersuchungen zur Adsorption und Assoziation von 3-Methylxanthin und 7-Methylxanthin an einer geladenen Grenzfläche
Zusammenfassung Eine systematische vergleichende Untersuchung zur Adsorption und Assoziation von 3-Methylxanthin (3MXan) und 7-Methylxanthin (7MXan) an Quecksilber-Lösungs-Grenzflächen wurde mittels AC-Voltammetrie in sauren, neutralen und basischen Pufferlösungen durchgeführt. Oberhalb einer bestimmten Grenzkonzentration kommt es durch Wechselwirkungen zwischen vertikal angeordneten3MXan-Molekülen zu einer langsamen Reorientierung umE ecm, was zu einer senkrechten Anordnung führt. Die Assoziation von7MXan ist gehindert und erlaubt daher keine ausgeprägten Basen-Basen-Wechselwirkungen. Die erhöhte Oberflächenaktivität von3MXan gegenüber7MXan resultiert aus der unterschiedlichen Stellung der Methylgruppe am Purinrest. Der Effekt einiger zweiwertiger Metallionen auf die Adsorption und Assoziation von3MXan und7MXan wurde untersucht. Die Ergebnisse weisen auf eine Begünstigung der Wechselwirkungen hin; die Bildung von vertikal angeordneten Grenzschichten an der Elektrodenoberfläche sollte daher im Fall vonM(II)-Mxan-Komplexen erleichtert sein. Die Adsorptionsparameter der untersuchten Verbindungen wurden in Abwesenheit und in Gegenwart von Cu(II) bei verschiedenenpH-Werten berechnet. Die Ergebnisse werden mit dem Verhalten von Xanthin verglichen.相似文献
110.
Electrochemical behavior of poly-o-phenylenediamine (PoPhD) films in lithium perchlorate and perchloric acid solutions of different pH and constant ionic strength is studied using cyclic voltammetry, low-amplitude chronoamperometry, chronopotentiometry, and faradaic-impedance spectroscopy. The experimental results point to the diffusion–migration kinetics of charge transfer processes in redox-active PoPhD films and show that two such processes occur during oxidation–reduction of PoPhD. The processes are separated most fully at low concentrations of hydronium ions. Effect of the electrode potential and electrolyte composition on these processes is examined. Different methods yield similar results and permit their more reliable interpretation. 相似文献