全文获取类型
收费全文 | 1077篇 |
免费 | 51篇 |
国内免费 | 1篇 |
专业分类
化学 | 776篇 |
晶体学 | 3篇 |
力学 | 24篇 |
数学 | 142篇 |
物理学 | 184篇 |
出版年
2023年 | 10篇 |
2022年 | 7篇 |
2021年 | 18篇 |
2020年 | 38篇 |
2019年 | 28篇 |
2018年 | 13篇 |
2017年 | 7篇 |
2016年 | 37篇 |
2015年 | 27篇 |
2014年 | 33篇 |
2013年 | 34篇 |
2012年 | 59篇 |
2011年 | 73篇 |
2010年 | 38篇 |
2009年 | 37篇 |
2008年 | 61篇 |
2007年 | 53篇 |
2006年 | 49篇 |
2005年 | 53篇 |
2004年 | 44篇 |
2003年 | 24篇 |
2002年 | 28篇 |
2001年 | 8篇 |
2000年 | 13篇 |
1999年 | 15篇 |
1998年 | 12篇 |
1997年 | 16篇 |
1996年 | 11篇 |
1995年 | 14篇 |
1994年 | 17篇 |
1993年 | 11篇 |
1992年 | 9篇 |
1991年 | 7篇 |
1990年 | 5篇 |
1988年 | 5篇 |
1987年 | 9篇 |
1986年 | 7篇 |
1985年 | 11篇 |
1983年 | 8篇 |
1980年 | 8篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 5篇 |
1974年 | 7篇 |
1923年 | 6篇 |
1892年 | 4篇 |
1888年 | 5篇 |
1887年 | 4篇 |
1882年 | 5篇 |
1881年 | 6篇 |
排序方式: 共有1129条查询结果,搜索用时 140 毫秒
41.
Stefan?DiethelmEmail author Joseph?Sfeir Frank?Clemens Jan?Van herle Daniel?Favrat 《Journal of Solid State Electrochemistry》2004,8(9):611-617
Dense planar and tubular oxygen separation membranes of La0.6Ca0.4Fe0.75Co0.25O3– were investigated as reactors for the partial oxidation (POX) of methane to syngas. Their permeation properties were measured in an air/argon
pO2 gradient as a function of temperature. At 900 °C, the oxygen flux through a 1.26-mm-thick membrane was 0.075 mol/cm2·s and through a 0.25-mm-thick tube, 0.24 mol/cm2·s.For the POX measurements, a catalyst was added to the membrane and methane was introduced on the argon side. This resulted in a gradual increase of the oxygen flux with increasing concentration of methane, reaching 2 mol/cm2·s at 900 °C with pure methane. For the planar reactor, the CO selectivity reached 99% and the CH4 conversion 75% at 918 °C with pure methane. For the tubular reactor, the CO selectivity and CH4 conversion were 83 and 99%, respectively, under the same conditions. After 1,400 h of operation in a tubular POX reactor, the membrane was examined revealing phase demixing and local decomposition.Presented at the OSSEP Workshop Ionic and Mixed Conductors: Methods and Processes, Aveiro, Portugal, 10–12 April 2003 相似文献
42.
The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the [110] facets only in the NR, which have higher surface energy. 相似文献
43.
Siemeling U Bausch K Fink H Bruhn C Baldus M Angerstein B Plessow R Brockhinke A 《Dalton transactions (Cambridge, England : 2003)》2005,(14):2365-2374
The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed that the di(acetylide)pi-tweezer of the latter binds a molecule of chloroform through C-H...pi hydrogen bonds. The redox and optical properties of 1 and its complexes were investigated by (spectro-)electrochemistry, UV-Vis and luminescence spectroscopy, and an energy level diagram was derived for [Pt(1)(C triple bond C-Fc)2] and related compounds on the basis of the data collected. The ferrocenyl-substituted Pt(II) complexes are donor-sensitiser assemblies. Intramolecular quenching of the photoexcited Pt(II) diimine unit leads to very short luminescence lifetimes for [Pt(1)(C triple bond C-p-C(6)H(4)-C triple bond C-Fc)2](2 ns) and [Pt(1)(C triple bond C-Fc)2](0.3 ns), as opposed to [Pt(1)(C triple bond C-Ph)2](0.7 micros). Excimer formation has been observed for [Pt(1)(C triple bond C-Ph)(2)] at room temperature in dichloromethane and at low temperatures in frozen glassy dichloromethane and 2-methyltetrahydrofuran solution, but not in the solid state. 相似文献
44.
45.
Yin M Wu CK Lou Y Burda C Koberstein JT Zhu Y O'Brien S 《Journal of the American Chemical Society》2005,127(26):9506-9511
It is well-known that inorganic nanocrystals are a benchmark model for nanotechnology, given that the tunability of optical properties and the stabilization of specific phases are uniquely possible at the nanoscale. Copper (I) oxide (Cu(2)O) is a metal oxide semiconductor with promising applications in solar energy conversion and catalysis. To understand the Cu/Cu(2)O/CuO system at the nanoscale, we have developed a method for preparing highly uniform monodisperse nanocrystals of Cu(2)O. The procedure also serves to demonstrate our development of a generalized method for the synthesis of transition metal oxide nanocrystals. Cu nanocrystals are initially formed and subsequently oxidized to form highly crystalline Cu(2)O. The volume change during phase transformation can induce crystal twinning. Absorption in the visible region of the spectrum gave evidence for the presence of a thin, epitaxial layer of CuO, which is blue-shifted, and appears to increase in energy as a function of decreasing particle size. XPS confirmed the thin layer of CuO, calculated to have a thickness of approximately 5 A. We note that the copper (I) oxide phase is surprisingly well-stabilized at this length scale. 相似文献
46.
Zinc(II) and mercury(II) complexes were prepared by reacting isatin-3-thiosemicarbazone (ISTSCH) with zinc(II) acetate or mercury(II) bromide. The complexes were characterized by IR, Raman, diffuse reflectance, 1H and 13C NMR spectra and elemental analysis. Tetrahedral structures for Zn(ISTSC)2 and Hg(ISTSCH)Br2 are suggested. 相似文献
47.
P. J. Martin E. Clemens L. Zehnle V. Kempter 《Zeitschrift für Physik A Hadrons and Nuclei》1979,289(4):373-381
The differential cross section for the processK(42 S)+N2, CO→K(42 P)+ N2, CO is presented for reduced scattering angles τ<2·104 eV deg. The inelastic process is identified by determining the time-correlation between the inelastically scattered potassium atom and the emittedK(42 P→42 S)photon. The performance of different coincidence techniques is compared. From the differential cross sections values for the position of the curve crossing responsible for the excitation process are derived (R c=2.77, 2.48 Å andV(R c )=0.55, 1.00 eV for K-N2, CO respectively). The values indicate that the lowest ionic intermediate state of the form K+-N 2 ? , CO? is responsible for the excitation process. 相似文献
48.
49.
Dr. Christiane Stoll Prof. Dr. Mihail Atanasov Jascha Bandemehr Prof. Dr. Frank Neese Clemens Pietzonka Prof. Dr. Florian Kraus Prof. Dr. Antti J. Karttunen Dr. Markus Seibald Assoc. Prof. Dr. Gunter Heymann Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(38):9801-9813
As a consequence of the static Jahn-Teller effect of the 5E ground state of MnIII in cubic structures with octahedral parent geometries, their octahedral coordination spheres become distorted. In the case of six fluorido ligands, [MnF6]3− anions with two longer and four shorter Mn−F bonds making elongated octahedra are usually observed. Herein, we report the synthesis of the compound K3[MnF6] through a high-temperature approach and its crystallization by a high-pressure/high-temperature route. The main structural motifs are two quasi-isolated, octahedron-like [MnF6]3− anions of quite different nature compared to that met in ideal octahedral MnIII Jahn-Teller systems. Owing to the internal electric field of Ci symmetry dominated by the next-neighbour K+ ions acting on the MnIII sites, both sites, the pseudo-rhombic (site 1) and the pseudo-tetragonally elongated (site 2) [MnF6]3− anions are present in K3[MnF6]. The compound was characterized by single-crystal and powder X-ray diffraction, and magnetometry as well as by FTIR, Raman, and ligand field spectroscopy. A theoretical interpretation of the electronic structure and molecular geometry of the two Mn sites in the lattice is given by using a vibronic coupling model with parameters adjusted from multireference ab-initio cluster calculations. 相似文献
50.
Structures of Highly Twisted Amides Relevant to Amide N−C Cross‐Coupling: Evidence for Ground‐State Amide Destabilization
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Vittorio Pace Prof. Dr. Wolfgang Holzer Guangrong Meng Shicheng Shi Prof. Dr. Roger Lalancette D.Sc. Roman Szostak Prof. Dr. Michal Szostak 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(41):14494-14498
Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N?C activation/cross‐coupling reactions are highly twisted around the N?C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The 15N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N?C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds. 相似文献