全文获取类型
收费全文 | 5077篇 |
免费 | 595篇 |
国内免费 | 884篇 |
专业分类
化学 | 5561篇 |
晶体学 | 55篇 |
力学 | 70篇 |
综合类 | 34篇 |
数学 | 14篇 |
物理学 | 822篇 |
出版年
2024年 | 18篇 |
2023年 | 129篇 |
2022年 | 231篇 |
2021年 | 264篇 |
2020年 | 268篇 |
2019年 | 243篇 |
2018年 | 176篇 |
2017年 | 227篇 |
2016年 | 310篇 |
2015年 | 288篇 |
2014年 | 311篇 |
2013年 | 462篇 |
2012年 | 426篇 |
2011年 | 320篇 |
2010年 | 293篇 |
2009年 | 319篇 |
2008年 | 300篇 |
2007年 | 325篇 |
2006年 | 305篇 |
2005年 | 253篇 |
2004年 | 213篇 |
2003年 | 172篇 |
2002年 | 134篇 |
2001年 | 73篇 |
2000年 | 64篇 |
1999年 | 83篇 |
1998年 | 69篇 |
1997年 | 55篇 |
1996年 | 30篇 |
1995年 | 49篇 |
1994年 | 37篇 |
1993年 | 28篇 |
1992年 | 28篇 |
1991年 | 8篇 |
1990年 | 12篇 |
1989年 | 7篇 |
1988年 | 7篇 |
1987年 | 7篇 |
1986年 | 7篇 |
1985年 | 1篇 |
1982年 | 2篇 |
1979年 | 1篇 |
1970年 | 1篇 |
排序方式: 共有6556条查询结果,搜索用时 0 毫秒
61.
Direct reaction of iron pentacarbonyl with 1-N,N-disubstituted-cyclohexa-2,5-dicnecarboxamide and 1-N,N-disubstituted-cyclohexa-1,3-dienecarboxamide mixture (in which the disubstkuted group is diethyl or diphenyl) gave the isomeric tricarbonyl iron complexes of 2-N,N-disubstituted-1,4-η-cyclohexa-1,3-dienccarboxamide (1), 1-N,N-disubslituted-1,4-η-cyclohexa-1,3-dienecarboxamide (2), and 5-N,N-disubstituted-1,4-η-cyclohexa-1,3-dienecarboxamide (3) and tricarbonyliron complexes of l-N,N-disubstituted-cyclohexenecarboxamide (4). These complexes were separated and characterized by IR, UV-VIS, 1H NMR, elemental analysis, and mass spectra. Only 1 isomerized to give 2 under acidic conditions; both 1 and 2 undergo hydride abstraction with triphenylmethyl hexafluorophosphatc. Complexes 3, undergo neither isomcrization nor hydride abstraction. According to the spectral data, the possible interaction between carboxamide and iron carbonyl moiety was investigated. The irreversible electrochemical behavior of these complexes were studied. 相似文献
62.
Smaragda Grammenudi Marlene Franke Fritz Vögtle Eberhard Steckhan 《Journal of inclusion phenomena and macrocyclic chemistry》1987,5(6):695-707
The tris-bipyridine ligand3a and its stoichiometric Rh3+ complex have been prepared. Cyclovoltammograms of the complex at pH 7.4 using a glassy carbon disk electrode reveal a strong reduction peak at –620 mV and two weak reduction peaks at more negative voltage. The reduction potential of the new complex is shifted by 300 mV to more positive values as compared to [Rh(bipy)3]3+. There is no reversible reoxidation peak of the Rh(I) complex formed due to the decomplexation of one of the three bipyridine units in the course of the transition Rh(III)Rh(I). The Rh(III) complex of3a was also studied with respect to its function as a possible redox mediator for the electrochemical regeneration of NADH from NAD+. The preparative electrolysis of the Rh3+ complex of3a in the presence of NAD+ yields a selective formation of NADH, whereas NAD dimers were not detected. On the other hand, a significant acceleration of this reaction compared to [Rh(bipy)3]3+ was not observed. 相似文献
63.
Mg-based hydrogen storage alloys Mg0.9Ti0.1-xZrxNi (x=0.02, 0.04, 0.06) were successfully prepared by means of mechanical alloying (MA). The effects of Zr addition on the discharge capacity and the cycle performance of the Mg-based electrodes were also studied. It was found that the discharge capacities were improved with addition of a small amount of Zr and the cycle performances of the alloy were stabilized with the addition of Ti. The effects of surface modification or coating on the properties of Mg0.9Ti0.06Zr0.04Ni were also studied. The results indicated that coating with graphite improved both the discharge capacity and cycle life of the amorphous Mg0.9Ti0.06Zr0.04Ni electrode. 相似文献
64.
The characteristics,performance and application of membrane electrode based on ion associate of diclofenac with base dye Safranine T are described.The electrode response to diclofenac has the sensitivity of 47±1.0 mV decade~(-1)over the range of 5×10~(-5)to 5×10~(-2)mol/L at pH 6-12,and the detection limit of 3.2×10~(-5)mol/L.The electrode is easy assembled at a relatively low cost has fast response time(2-4 s)and can be used for a period up to 3.5 months without any considerable divergence in potential.The proposed sensor displayed good selectivity for diclofenac in the presence of different substances.It was used to determine diclofenac in pharmaceuticals by means of the standard addition method. 相似文献
65.
Drechsler U Erdogan B Rotello VM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(22):5570-5579
Monolayer and mixed-monolayer protected clusters (MPCs and MMPCs) have great potential to combine molecular functionality with the intrinsic properties of nanometer-sized scaffolds. This synergy can be used to create complex functional devices, including redox-active, electronic, or magnetic storage devices, solution-based sensors, and highly efficient catalysts. This review outlines some of the recent developments in nanoscale receptors based on synthetic and nonbiological recognition elements. In these nanoparticle systems, molecular recognition is achieved by covalent attachment of receptors on the nanoparticles coupled with noncovalent interactions to target substrates. Synthetic host-guest systems, hydrogen bonding, change in redox states, pi-pi stacking, rotaxane formation, and ion recognition are the main topics covered in this review. 相似文献
66.
A sequential injection analysis (SIA) system was developed with the aim of obtaining an automatic and versatile way to prepare standards needed in the study of systems with higher dimensional sensor signals. To illustrate this, different analytical techniques were used in determinations of several analytes. Automated potentiometric calibrations of different potentiometric sensors, with and without interference, were carried out. Useful determinations of selectivity coefficients with two degrees of freedom were obtained. Simultaneous voltammetric determinations have also been done. Firstly, simultaneous determinations of lead and cadmium, using epoxy-graphite composite as the working electrode, have enabled a separate calibration for each metal to be obtained. Next, a voltammetric electronic tongue was designed and applied to the determination of oxidizable species. The use of artificial neural networks has solved the overlapped signal of ascorbic acid, 4-aminophenol and 4-acetamidophenol (paracetamol). A set of 63 data points was prepared automatically and has facilitated the training of an electronic tongue for these three analytes. Accurate predictions of test solutions, in the range of 12–410 μM for ascorbic acid, 17–530 μM for 4-aminophenol and 10–420 μM for paracetamol, have been achieved with RMSEs lower than 0.10 μM. 相似文献
67.
《Electroanalysis》2005,17(3):223-230
There is a need to develop analytical methods that are capable of rapidly measuring small biological markers in the field of metabolomics. Among others, carbohydrates play an important role biologically yet are traditionally hard to detect since they have no chromophore or fluorophore. In the present report, the first application of integrated pulsed amperometric detection (iPAD) coupled with microchip electrophoresis to the analysis of glucose, mannose, sucrose, maltose, glucosamine, lactose, maltotriose and galactose is demonstrated. iPAD is an electrochemical detection mode that can be used for direct detection of carbohydrates, amines and sulfur containing compounds. The effect of different solution parameters, including the buffer concentration, pH and the concentration of SDS on both separation and detection response was analyzed. In addition, a comparison study between PAD and iPAD was performed using glucose, glucosamine, sucrose and maltose as model carbohydrates. 相似文献
68.
V. V. Ozeryanskaya V. E. Guterman I. L. Shukaev V. P. Grigor'ev 《Russian Chemical Bulletin》1998,47(8):1481-1486
Comparative study of the regularities of the reaction and specific features of phase formation during electrochemical incorporation
of lithium from propylene carbonate solutions in intermetallic aluminum-based compounds (CuAl2, Mg2Al3, and NiAl) and pure metals (Al, Cu, Mg, and Ni) was performed. The initial stage of the process was shown to be dissolution
of lithium in the solid phase limited by diffusion for all studied substrates. Trace amounts of lithium-containing by-products,
were detected in NiAl, Ni, and Cu samples. The subsequent change in the limiting stage is related to the beginning of formation
of a new phase: metallic lithium (on Mg2Al3, NiAl, Mg, Ni, and Cu) or LiAl (on Al and CuAl2 cathodes). In the latter case, the solid-phase substitution occurs, which is formally described by the equation: CuAl2+2Li++2e→2LiAl+Cu. Thus, the specific features of phase formation on the CuAl2 electrode correspond to the highest (among three intermetallides studied) concentration of Al atoms in the crystal lattice
of the compound.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8. pp. 1525–1530, August, 1998. 相似文献
69.
Vinod Kumar Gupta Ashok Kumar Singh Sameena Mehtab Barkha Gupta 《Analytica chimica acta》2006,566(1):5-10
A new PVC membrane electrode for Co2+ based on N,N′-bis(salicylidene)-3,4-diaminotoluene, an excellent neutral carrier, has been fabricated using sodium tetraphenylborate (NaTPB) as an anionic excluder and dioctylphthalte (DOP) as a solvent mediator. The electrode exhibits a linear potential response in the concentration range of 7.9 × 10−8 to 1.0 × 10−1 M with a slope of 30 ± 0.2 mV per decade. The detection limit of the proposed sensor is 5.0 × 10−8 M and it can be used over a period of 5 months. The proposed sensor revealed good selectivity over a wide variety of other cations including alkali, alkaline earth, heavy and transition metals and could be used in the pH range of 2.0-9.0. This electrode was successfully applied for the determination of Co2+in real samples and as an indicator electrode in potentiometric titration of cobalt ions. 相似文献
70.
Electrochemical impedance spectroscopy is used to characterize thin p-doped polypyrrole (PPy) films in propylene carbonate (PC) solutions and poly(trifluorophenyl)thiophene (PTFPT), in solutions based on sulfolane (SF). It appears that the latter film is much less swelled compared to the former one. One consequence of this difference is that the PTFPT film shows a much higher bulk resistance compared to that for the PPy film. Another important consequence is that the swelling of the PTFPT film is essentially physically non-homogeneous. Two parallel, uncoupled paths, with different chemical diffusion coefficients, model the experimental results adequately. In order to quantify the impedance spectra for both polymer films, we use a model proposed by Rubinstein et al. explaining the difference in the diffusion coefficients of Ru(bpy)3+/2+
3 within a thin Nafion film. The model can also predict the impedance spectra for composite powdery electrodes containing different particle sizes, such as composite cathodes and graphite anodes used in lithium batteries. 相似文献