全文获取类型
收费全文 | 2242篇 |
免费 | 94篇 |
国内免费 | 19篇 |
专业分类
化学 | 1494篇 |
晶体学 | 14篇 |
力学 | 50篇 |
数学 | 425篇 |
物理学 | 372篇 |
出版年
2023年 | 12篇 |
2022年 | 16篇 |
2021年 | 25篇 |
2020年 | 41篇 |
2019年 | 41篇 |
2018年 | 30篇 |
2017年 | 31篇 |
2016年 | 75篇 |
2015年 | 64篇 |
2014年 | 85篇 |
2013年 | 96篇 |
2012年 | 121篇 |
2011年 | 157篇 |
2010年 | 97篇 |
2009年 | 90篇 |
2008年 | 138篇 |
2007年 | 149篇 |
2006年 | 131篇 |
2005年 | 112篇 |
2004年 | 125篇 |
2003年 | 55篇 |
2002年 | 62篇 |
2001年 | 30篇 |
2000年 | 31篇 |
1999年 | 26篇 |
1998年 | 23篇 |
1997年 | 27篇 |
1996年 | 30篇 |
1995年 | 23篇 |
1994年 | 27篇 |
1993年 | 18篇 |
1992年 | 15篇 |
1991年 | 14篇 |
1990年 | 11篇 |
1989年 | 17篇 |
1988年 | 17篇 |
1986年 | 13篇 |
1985年 | 18篇 |
1984年 | 20篇 |
1983年 | 21篇 |
1982年 | 18篇 |
1981年 | 20篇 |
1980年 | 18篇 |
1979年 | 13篇 |
1978年 | 19篇 |
1977年 | 22篇 |
1976年 | 12篇 |
1975年 | 12篇 |
1974年 | 17篇 |
1973年 | 17篇 |
排序方式: 共有2355条查询结果,搜索用时 62 毫秒
121.
Matthias Ermer Julian Mehler Björn Rosenberger Dr. Marcus Fischer Dr. Peter S. Schulz Prof. Martin Hartmann 《ChemistryOpen》2021,10(2):233-242
Using ionic liquids (ILs) as linker precursors, the well-known metal-organic framework (MOF) UiO-66 (Universitetet i Oslo) and the recently reported MOF hcp UiO-66 (hexagonal closed packed) have been successfully synthesized and characterized. The advantage of the applied novel synthesis approach is an economically and environmentally benign work-up procedure, due to the better solubility of the IL. Additionally, the reactivity of the terephthalate anions is increased compared to terephthalic acid, resulting in faster MOF formation with an increased amount of defects in the MOF structure. In order to explore to the influence of defects on the catalytic performance, the cyclisation of citronellal to isopulegol was employed as test reaction. The activity of hcp UiO-66 and fcc UiO-66 (face centered cubic) is improved compared to other MOF or zeolite based catalysts, while the selectivity is similar. 相似文献
122.
Dr. Goutam Kumar Kole Dr. Julia Merz Dr. Anissa Amar Dr. Bruno Fontaine Dr. Abdou Boucekkine Dr. Jörn Nitsch Sabine Lorenzen Dr. Alexandra Friedrich Dr. Ivo Krummenacher Marta Košćak Prof. Dr. Holger Braunschweig Prof. Dr. Ivo Piantanida Prof. Dr. Jean-François Halet Prof. Dr. Klaus Müller-Buschbaum Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(8):2837-2853
Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm−1. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc+ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents. 相似文献
123.
124.
Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion
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)
Jörn Bruns Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7222-7227
For the first time, direct oxidation of elemental platinum by a mineral acid to its tetravalent state was observed in course of the reaction of platinum with oleum (65 % SO3) in the presence of barium carbonate. The reaction has been carried out in torch‐sealed glass ampoules at 160 °C and gave yellow single crystals of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 (triclinic, P$\bar 1$ , Z=2, a=992.05(2), b=1069.07(3), c=1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°, V=1033.95(5) Å3). The structure of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 exhibits the unique tris‐(disulfato)‐platinate anion [Pt(S2O7)3]2? with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba2+ ions, which are coordinated by (S2O7)2? groups from the platinate complex and by disordered sulfuric acids and disulfuric acid molecules. Thermal decomposition of the bulk material revealed elemental platinum and barium sulfate as decomposition residual. 相似文献
125.
HP‐CsB5O8: Synthesis and Characterization of an Outstanding Borate Exhibiting the Simultaneous Linkage of All Structural Units of Borates
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)
Gerhard Sohr Daniel M. Többens Prof. Dr. Jörn Schmedt auf der Günne Prof. Dr. Hubert Huppertz 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(51):17059-17067
The new cesium pentaborate HP‐CsB5O8 is synthesized under high‐pressure/high‐temperature conditions of 6 GPa and 900 °C in a Walker‐type multianvil apparatus. The compound crystallizes in the orthorhombic space group Pnma (Z=4) with the parameters a=789.7(1), b=961.2(1), c=836.3(1) pm, V=0.6348(1) nm3, R1=0.0359 and wR2=0.0440 (all data). The new structure type of HP‐CsB5O8 exhibits the simultaneous linkage of trigonal BO3 groups, corner‐sharing BO4 tetrahedra, and edge‐sharing BO4 tetrahedra including the presence of threefold‐coordinated oxygen atoms. With respect to the rich structural chemistry of borates, HP‐CsB5O8 is the second structure type possessing this outstanding combination of the main structural units of borates in one compound. The structure consists of corrugated chains of corner‐ and edge‐sharing BO4 tetrahedra interconnected through BO3 groups forming octagonal channels. Inside these channels, cesium is 13+3‐fold coordinated by oxygen atoms. 11B MQMAS NMR spectra are analyzed to estimate the isotropic chemical shift values and quadrupolar parameters. IR and Raman spectra are obtained and compared to the calculated vibrational frequencies at the Γ‐point. The high‐temperature behavior is examined by means of temperature‐programmed powder diffraction. 相似文献
126.
Casper Jon Steenbjerg Ibsen Bjørn Fridur Mikladal Uffe Bjørnholt Jensen Assoc. Prof. Henrik Birkedal 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(49):16112-16120
Three dimensional hierarchical materials are widespread in nature but are difficult to synthesize by using self‐assembly/organization. Here, we employ a gel–liquid interface to obtain centimeter‐long ~100 μm diameter tubes with complex mineral wall structures that grow from the interface into solution. The gel, made from gelatin, is loaded with metal chloride salt, whereas the solution is a high pH anion source. Tubes were obtained with a range of cations (Ca2+, Sr2+, Ba2+, Cu2+, and Zn2+) and anions (CO32? and PO43?). The crystalline phases found in the tube walls corresponded to expectations from solution chemistries and phase solubilities. The growth mechanism is found to be akin to that of chemical gardens. The divalent cations modify the strength of the gelatin gel in a manner that involves not only simple electrostatic screening, but also ion‐specific effects. Thus, tubes were not obtained for those ions and/or concentrations that significantly changed the gel’s mechanical structure. At high Cu2+ loading, for example, vertical convection bands, not Liesegang bands, were observed in the gels. 相似文献
127.
Total Synthesis of the Anti‐inflammatory and Pro‐resolving Lipid Mediator MaR1n−3 DPA Utilizing an sp3–sp3 Negishi Cross‐Coupling Reaction
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)
Jørn Eivind Tungen Dr. Marius Aursnes Dr. Jesmond Dalli Dr. Hildur Arnardottir Prof. Dr. Charles Nicholas Serhan Prof. Dr. Trond Vidar Hansen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(45):14575-14578
The first total synthesis of the lipid mediator MaR1n?3 DPA ( 5 ) has been achieved in 12 % overall yield over 11 steps. The stereoselective preparation of 5 was based on a Pd‐catalyzed sp3–sp3 Negishi cross‐coupling reaction and a stereocontrolled Evans–Nagao acetate aldol reaction. LC‐MS/MS results with synthetic material matched the biologically produced 5 . This novel lipid mediator displayed potent pro‐resolving properties stimulating macrophage efferocytosis of apoptotic neutrophils. 相似文献
128.
Radical S‐Adenosyl Methionine Epimerases: Regioselective Introduction of Diverse D‐Amino Acid Patterns into Peptide Natural Products
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Brandon I. Morinaka Dr. Anna L. Vagstad Maximilian J. Helf Dr. Muriel Gugger Dr. Carsten Kegler Dr. Michael F. Freeman Prof. Dr. Helge B. Bode Prof. Dr. Jörn Piel 《Angewandte Chemie (International ed. in English)》2014,53(32):8503-8507
PoyD is a radical S‐adenosyl methionine epimerase that introduces multiple D ‐configured amino acids at alternating positions into the highly complex marine peptides polytheonamide A and B. This novel post‐translational modification contributes to the ability of the polytheonamides to form unimolecular minimalistic ion channels and its cytotoxic activity at picomolar levels. Using a genome mining approach we have identified additional PoyD homologues in various bacteria. Three enzymes were expressed in E. coli with their cognate as well as engineered peptide precursors and shown to introduce diverse D ‐amino acid patterns into all‐L peptides. The data reveal a family of architecturally and functionally distinct enzymes that exhibit high regioselectivity, substrate promiscuity, and irreversible action and thus provide attractive opportunities for peptide engineering. 相似文献
129.
Gerardo Algara‐Siller Dr. Nikolai Severin Samantha Y. Chong Dr. Torbjörn Björkman Dr. Robert G. Palgrave Andrea Laybourn Prof. Dr. Markus Antonietti Prof. Yaroslav Z. Khimyak Dr. Arkady V. Krasheninnikov Prof. Dr. Jürgen P. Rabe Prof. Dr. Ute Kaiser Prof. Andrew I. Cooper Prof. Dr. Arne Thomas Dr. Michael J. Bojdys 《Angewandte Chemie (International ed. in English)》2014,53(29)
130.
Björn Johansson Prof. Fredrik Höök Prof. David Klenerman Dr. Peter Jönsson 《Chemphyschem》2014,15(3):486-491
An important and characteristic property of a cell membrane is the lateral mobility of protein molecules in the lipid bilayer. This has conventionally been measured by labeling the molecules with fluorescent markers and monitoring their mobility by different fluorescence‐based techniques. However, adding the label to the studied molecule may affect the system, so it is an assumption in almost all experiments that the measured mobility of the biomolecule with its label is the same as that of the unlabeled molecule. However, this assumption is rarely tested due to a lack of suitable methods. In this work, a new technique to perform label‐free diffusivity measurements is developed and used to measure the effect of the label for two common protein–lipid systems: 1) streptavidin (SA) coupled to a supported lipid bilayer (SLB) through biotinylated lipids and 2) the extracellular part of the T‐cell adhesion protein CD2, coupled to an SLB through histidine tags to nickel‐chelating lipids. A measurable (≈12 %) decrease in diffusivity is found for both labeled proteins, even though the molecular mass of the label is almost 100 times smaller than those of the proteins (≈50 kDa). The results illustrate the importance of being able to study different biophysical properties of cell membranes and their mimics without relying on fluorescent labels, especially if fluorescent labeling is difficult or is expected to affect the nature of the intermolecular interactions being studied. 相似文献