全文获取类型
收费全文 | 736篇 |
免费 | 43篇 |
国内免费 | 1篇 |
专业分类
化学 | 560篇 |
晶体学 | 2篇 |
力学 | 7篇 |
数学 | 89篇 |
物理学 | 122篇 |
出版年
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 13篇 |
2020年 | 15篇 |
2019年 | 26篇 |
2018年 | 15篇 |
2017年 | 7篇 |
2016年 | 28篇 |
2015年 | 39篇 |
2014年 | 28篇 |
2013年 | 49篇 |
2012年 | 48篇 |
2011年 | 35篇 |
2010年 | 29篇 |
2009年 | 25篇 |
2008年 | 31篇 |
2007年 | 33篇 |
2006年 | 48篇 |
2005年 | 45篇 |
2004年 | 46篇 |
2003年 | 30篇 |
2002年 | 24篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 9篇 |
1998年 | 9篇 |
1997年 | 11篇 |
1996年 | 10篇 |
1995年 | 4篇 |
1994年 | 5篇 |
1993年 | 3篇 |
1992年 | 4篇 |
1990年 | 2篇 |
1989年 | 4篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 4篇 |
1985年 | 5篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 2篇 |
1976年 | 4篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1973年 | 3篇 |
1972年 | 2篇 |
1962年 | 2篇 |
1936年 | 1篇 |
排序方式: 共有780条查询结果,搜索用时 329 毫秒
41.
42.
Dr. Sonja Pullen Dr. Alexander Hegmans Prof. Wolf G. Hiller André Platzek Prof. Eva Freisinger Prof. Bernhard Lippert 《ChemistryOpen》2021,10(1):28-45
The conversion of the 1 : 1-complex of Cisplatin with 1-methyluracil (1MeUH), cis-[Pt(NH3)2(1MeU-N3)Cl] ( 1 a ) to the aqua species cis-[Pt(NH3)2(1MeU-N3)(OH2)]+ ( 1 b ), achieved by reaction of 1 a with AgNO3 in water, affords a mixture of compounds, the composition of which strongly depends on sample history. The complexity stems from variations in condensation patterns and partial loss of NH3 ligands. In dilute aqueous solution, 1 a , and dinuclear compounds cis-[(NH3)2(1MeU-N3)Pt(μ-OH)Pt(1MeU-N3)(NH3)2]+( 3 ) as well as head-tail cis-[Pt2(NH3)4(μ-1MeU-N3,O4)2]2+ ( 4 ) represent the major components. In addition, there are numerous other species present in minor quantities, which differ in metal nuclearity, stoichiometry, stereoisomerism, and Pt oxidation state, as revealed by a combination of 1H NMR and ESI-MS spectroscopy. Their composition appears not to be the consequence of a unique and repeating coordination pattern of the 1MeU ligand in oligomers but rather the coexistence of distinctly different condensation patterns, which include μ-OH, μ-1MeU, and μ-NH2 bridging and combinations thereof. Consequently, the products obtained should, in total, be defined as a heterogeneous mixture rather than a mixture of oligomers of different sizes. In addition, a N2 complex, [Pt(NH3)(1MeU)(N2)]+ appears to be formed in gas phase during the ESI-MS experiment. In the presence of Na+ ions, multimers n of 1 a with n=2, 3, 4 are formed that represent analogues of non-metalated uracil quartets found in tetrastranded RNA. 相似文献
43.
The vibrational spectroscopy of lithium dichloride anions microhydrated with one to three water molecules, [LiCl2(H2O)1–3]−, is studied in the OH stretching region (3800–2800 cm−1) using isomer-specific IR/IR double-resonance population labelling experiments. The spectroscopic fingerprints of individual isomers can only be unambiguously assigned after anharmonic effects are considered, but then yield molecular level insight into the onset of salt dissolution in these gas phase model systems. Based on the extent of the observed frequency shifts ΔνOH of the hydrogen-bonded OH stretching oscillators solvent-shared ion pair motifs (<3200 cm−1) can be distinguished from intact-core structures (>3200 cm−1). The characteristic fingerprint of a water molecule trapped directly in-between two ions of opposite charge provides an alternative route to evaluate the extent of ion pairing in aqueous electrolyte solutions. 相似文献
44.
Kim C Liu Y Kühnle A Hess S Viereck S Danner T Mahadevan L Weitz DA 《Physical review letters》2007,99(2):028303
Colloidal suspensions are susceptible to gravitationally induced phase separation. This can be mitigated by the formation of a particle network caused by depletion attraction. The effectiveness of this network in supporting the buoyant weight of the suspension can be characterized by its compressional modulus. We measure the compressional modulus for emulsion networks induced by depletion attraction and present a model that quantitatively predicts their gravitational stability. We also determine the relationship between the strength of the depletion attraction and the magnitude of the compressional modulus. 相似文献
45.
Abe K Adachi I Aihara H Arinstein K Asano Y Aulchenko V Aushev T Aziz T Bakich AM Balagura V Barbero M Bedny I Bitenc U Bizjak I Bondar A Bracko M Brodzicka J Browder TE Chao Y Chen A Cheon BG Chistov R Choi SK Choi Y Choi YK Chuvikov A Cole S Dalseno J Danilov M Dash M Drutskoy A Eidelman S Epifanov D Fratina S Gabyshev N Gershon T Gokhroo G Golob B Ha HC Haba J Hasegawa Y Hayasaka K Hayashii H Hazumi M Hinz L Hoshi Y Hou S Hou WS Hsiung YB Iijima T Ishikawa A Iwasaki M Iwasaki Y Kapusta P 《Physical review letters》2007,98(8):082001
We report the first observation of a charmoniumlike state recoiling from the J/psi in the inclusive process e+e- -->J/psi+anything at a mass of (3.943+/-0.006+/-0.006) GeV/c{2}. We also observe the decay of this state into D*D[over ] and determine its intrinsic width to be less than 52 MeV/c{2} at the 90% C.L. These results are obtained from a 357 fb{-1} data sample collected with the Belle detector near the Upsilon(4S) resonance, at the KEKB asymmetric-energy e+e- collider. 相似文献
46.
Queiroz Ana Luiza P. Kerins Brian M. Yadav Jayprakash Farag Fatma Faisal Waleed Crowley Mary Ellen Lawrence Simon E. Moynihan Humphrey A. Healy Anne-Marie Vucen Sonja Crean Abina M. 《Cellulose (London, England)》2021,28(14):8971-8985
Cellulose - Microcrystalline cellulose (MCC) is a semi-crystalline material with inherent variable crystallinity due to raw material source and variable manufacturing conditions. MCC crystallinity... 相似文献
47.
Valerie Derpmann David Mueller Iustinian Bejan Hannah Sonderfeld Sonja Wilberscheid Ralf Koppmann Klaus J. Brockmann Thorsten Benter 《Journal of the American Society for Mass Spectrometry》2014,25(3):329-342
We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2 – or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2 – leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry. Figure
? 相似文献
48.
Solid-phase micro extraction (SPME) and headspace derivatization of clenbuterol followed by GC–FID and GC–SIMMS quantification 总被引:1,自引:0,他引:1
Solid-phase micro extraction (SPME) and on-fiber derivatization followed by Gas Chromatography coupled with Flame Ionization Detection (GC-FID) or Selected Ion Monitoring Mass Spectrometry (GC-SIMMS) allows for simple yet sensitive quantification for the hexamethyldisilazane derivative of the beta-agonist clenbuterol. Using an 85- micro m polyacrylate fiber, the analysis method is optimized with respect to extraction time, derivatization time and temperature, and solution pH. In addition, the use of a rapid temperature ramping injection port allows for optimization of fiber desorption conditions. Under optimal conditions, the limits of detection for the hexamethyldisilazane derivative of clenbuterol are 1.1 ppb by FID and 0.20 ppb by SIMMS. 相似文献
49.
Sonja Eichholz Martin Lerch Michael Heck Dirk Walter 《Journal of Thermal Analysis and Calorimetry》2012,110(1):437-441
Nano-sized carbon dusts are suspected of having negative effects on human health. An exact characterization of such particles is necessary to understand possible toxic effects, i.e. in the lung. Observed by transmission electron microscopy (TEM), the carbon dusts are a composite of very small primary particles and larger agglomerates of these. A differentiation of the primary particles and agglomerates according to source is not possible by TEM, however, thermogravimetry investigations in synthetic air atmosphere are helpful. Standardized carbon black and graphite show a single-step oxidation behaviour, whereas ethene soot and diesel soot, for example, show more complex-reaction mechanisms. The results of ethene soot exemplarily demonstrate the oxidation mechanism. In addition to the oxidation reaction to carbon dioxide, a sintering process takes place. To confirm the oxidation mechanism, thermal behaviour of ethene soot has been simulated by kinetic modulation using a three-step reaction mechanism of n-th order. The reaction order indicates a complex mechanism for the first-reaction step. For the second and third-reaction step, a phase boundary mechanism could be suggested. 相似文献
50.
Minimalistic Ditopic Ligands: An α‐S,N‐Donor‐Substituted Alkyne as Effective Intermetallic Conjugation Linker
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)
Julia Rüger Christopher Timmermann Dr. Alexander Villinger Alexander Hinz Dr. Dirk Hollmann Prof. Dr. Wolfram W. Seidel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(32):11191-11195
The capability of donor‐substituted alkynes to link different metal ions in a side‐on carbon donor‐chelate coordination mode is extended from the donor centers S and P to the second period element N. The complex [Tp′W(CO)2{η2‐C2(S)(NHBn)}] (Tp′=hydrido‐tris(3,5‐dimethylpyrazolyl)borate, Bn=benzyl) bearing a terminal sulfur atom and a secondary amine substituent is accessible by a metal‐template synthesis. Subsequent deprotonation allowed the formation of remarkably stable heterobimetallic complexes with the [(η5‐C5H5)Ru(PPh3)] and the [Ir(ppy)2] moiety. Electrochemical and spectroscopic investigations (cyclic voltammetry, IR, UV/Vis, luminescence, EPR), as well as DFT calculations, and X‐ray structure determinations of the W–Ru complex in two oxidation states reveal a strong metal–metal coupling but also a limited delocalization of excited states. 相似文献