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41.
Ethan Zars Lisa Pick Dr. Abinash Swain Dr. Mrinal Bhunia Dr. Patrick J. Carroll Prof. Dr. Dominik Munz Prof. Dr. Karsten Meyer Prof. Dr. Daniel J. Mindiola 《Angewandte Chemie (International ed. in English)》2023,62(51):e202311749
Here we report the use of a base metal complex [(tBupyrpyrr2)Fe(OEt2)] ( 1 -OEt2) (tBupyrpyrr22−=3,5-tBu2-bis(pyrrolyl)pyridine) as a catalyst for intermolecular amination of Csp3−H bonds of 9,10-dihydroanthracene ( 2 a ) using 2,4,6-trimethyl phenyl azide ( 3 a ) as the nitrene source. The reaction is complete within one hour at 80 °C using as low as 2 mol % 1 -OEt2 with control in selectivity for single C−H amination versus double C−H amination. Catalytic C−H amination reactions can be extended to other substrates such as cyclohexadiene and xanthene derivatives and can tolerate a variety of aryl azides having methyl groups in both ortho positions. Under stoichiometric conditions the imido radical species [(tBupyrpyrr2)Fe{=N(2,6-Me2-4-tBu-C6H2)] ( 1 -imido) can be isolated in 56 % yield, and spectroscopic, magnetometric, and computational studies confirmed it to be an S = 1 FeIV complex. Complex 1 -imido reacts with 2 a to produce the ferrous aniline adduct [(tBupyrpyrr2)Fe{NH(2,6-Me2-4-tBu-C6H2)(C14H11)}] ( 1 -aniline) in 45 % yield. Lastly, it was found that complexes 1 -imido and 1 -aniline are both competent intermediates in catalytic intermolecular C−H amination. 相似文献
42.
Woderer S Henninger N Garthe CD Kloetzer HM Hajnsek M Kamecke U Gretz N Kraenzlin B Pill J 《Analytica chimica acta》2007,581(1):7-12
Glucose monitoring is of importance for success of complex therapeutic interventions in diabetic patients. Its impact on treatment and glycemic control is demonstrated in large clinical trials. Up to eight blood glucose measurements per day are recommended. Notwithstanding, a substantial number of diabetic patients cannot or will not monitor their blood glucose appropriately. Considerable progress in control of disturbed metabolism in diabetic patients can be expected by continuous glucose monitoring. The aim of the study was to evaluate the performance of a new amperometric glucose oxidase-based glucose sensor in vitro and in vivo after subcutaneous implantation into rats.For in vitro testing current output of sensors was measured by exposure to increasing and decreasing glucose concentrations up to 472 mg dL−1 over a time period of 7 days. After subcutaneous implantation of sensors into interscapular region of male rats glucose in interstitial fluid was evaluated and compared to glucose in arterial blood up to 7 days. Hyper- and hypoglycaemia were induced by intravenous application of glucose and insulin, respectively. Current of each implanted sensor was converted into glucose concentration using the first blood glucose measurement only.A change of current with glucose of 0.35 nA mg−1 dL−1 indicates high sensitivity of the sensor in vitro. The response time (90% of steady state) was calculated by approximately 60 s. Test strips for blood glucose measurement as reference for sensor readings was found as an appropriate and rapidly available method in rats by comparison with established hexokinase method in an automated lab analyzer with limits of agreement of +32.8 and −25.7 mg dL−1 in Bland-Altman analysis. In normo- and hypoglycaemic range sensor readings in interstitial fluid correlated well with blood glucose measurements whereas hyperglycaemia was not reflected by the sensor completely when blood glucose was changing rapidly.The data given characterize a sensor with high sensitivity, long term stability and short response time. A single calibration of the sensor is required only in measurement periods up to 7 days. The findings demonstrate that the sensor is a highly promising candidate for assessment in humans. 相似文献
43.
Gizem Dübek Franziska Hanusch Dr. Dominik Munz Prof. Shigeyoshi Inoue 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(14):5872-5878
Air- and moisture-stable heterobimetallic tetrahedral clusters [Cp(CO)2MSiR]2 (M=Mo or W; R=SitBu3) were isolated from the reaction of N-heterocyclic carbene (NHC) stabilized silyl(silylidene) metal complexes Cp(CO)2M=Si(SitBu3)NHC with a mild Lewis acid (BPh3). Alternatively, treatment of the NHC-stabilized silylidene complex Cp(CO)2W=Si(SitBu3)NHC with stronger Lewis acids such as AlCl3 or B(C6F5)3 resulted in the reversible coordination of the Lewis acid to one of the carbonyl ligands. Computational investigations revealed that the dimerization of the intermediate metal silylidyne (M≡Si) complex to a tetrahedral cluster instead of a planar four-membered ring is due to steric bulk. 相似文献
44.
Annette Grünwald Dr. Frank W. Heinemann Prof. Dominik Munz 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(47):21274-21281
The homolytic cleavage of O−H and N−H or weak C−H bonds is a key elementary step in redox catalysis, but is thought to be unfeasible for palladium. In stark contrast, reported here is the room temperature and reversible oxidative addition of water, isopropanol, hexafluoroisopropanol, phenol, and aniline to a palladium(0) complex with a cyclic (alkyl)(amino)carbene (CAAC) and a labile pyridino ligand, as is also the case in popular N-heterocyclic carbene (NHC) palladium(II) precatalysts. The oxidative addition of protic solvents or adventitious water switches the chemoselectivity in catalysis with alkynes through activation of the terminal C−H bond. Most salient, the homolytic activation of alcohols and amines allows atom-efficient, additive-free cross-coupling and transfer hydrogenation under mild reaction conditions with usually unreactive, yet desirable reagents, including esters and bis(pinacolato)diboron. 相似文献
45.
Andrii Tarasov Federico Garzelli Christoph Schuessler Stefanie Fritsch Christophe Loisel Alexandre Pons Claus-Dieter Patz Doris Rauhut Rainer Jung 《Molecules (Basel, Switzerland)》2021,26(20)
Storage temperature is one of the most important factors affecting wine aging. Along with bottling parameters (type of stopper, SO2 level and dissolved O2 in wine), they determine how fast wine will evolve, reach its optimum and decline in sensory quality. At the same time, lowering of the SO2 level in wine has been a hot topic in recent years. In the current work, we investigated how Riesling wine evolved on the molecular level in warm (~25 °C) and cool (~15 °C) conditions depending on the SO2 level in the wine (low, medium and high), flushing of the bottle’s headspace with CO2 and three types of stoppers (Diam 30, Diam 30 origin and Diam 5) with different OIR levels (0.8–1.3 mg) and OTR levels (0.3–0.4 mg/year). It was demonstrated that the evolution of primary and secondary aromas, wine color and low molecular weight sulfur compounds (LMWSCs) during the two years of aging mainly depended on the storage temperature. Variation in the SO2 level and CO2 in the headspace affected mostly certain LMWSCs (H2S, MeSH) and β-damascenone. New aspects of C13-norisprenoids and monoterpenoids behavior in Riesling wine with different levels of SO2 and O2 were discussed. All three types of stoppers showed very close wine preservation properties during the two years of storage. The sensory analysis revealed that, after only six months, the warm stored wines with a low SO2 level were more oxidized and different from the samples with medium and high SO2 levels. A similar tendency was also observed for the cool stored samples. 相似文献
46.
47.
E. Bucher S. Schulz M. Ch. Lux-Steiner P. Munz U. Gubler F. Greuter 《Applied Physics A: Materials Science & Processing》1986,40(2):71-77
The work function of 13 polycrystalline transition metal suicides was measured by photoemission in uhv. Their values are discussed in relationship to their Schottky barrier heights on n-Si. While there appears to be a weak correlation for a certain group of transition metal suicides, the values of the 5d-noble metal suicides including some of the lattice matched Ni suicides appear to be completely uncorrelated. Experimental values of work functions are compared to the values proposed previously by Freeouf. 相似文献
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Non-Planar Double Bond in a Crystalline Derivative of anti-Sesquinorbornene (anti-Tetracyclo[6.2.1.13,6.02,7]dodec-2(7)-ene) The olefinic double bond of the title compound 2 has been observed by X-ray techniques to deviate from planarity by 13.2 (0.3)° (symmetric out-of-plane bending). Empirical force field calculations for the parent hydrocarbon 1 (anti-sesquinorbornene) give a much larger corresponding deviation of 35.6°. The calculated nonplanar double bond deformations in anti-sesquinorbornene 1 as well as in the syn-isomer 4 and other related olefins are a consequence of substantial widenings of the exocyclic C(sp3)–C(sp2–Csp3) angles when keeping the double bond planar. The considerable computational exaggeration of this novel out-of-plane bending mechanism is attributed to various possible force field deficiencies. 相似文献