全文获取类型
收费全文 | 2129篇 |
免费 | 150篇 |
国内免费 | 6篇 |
专业分类
化学 | 1565篇 |
晶体学 | 16篇 |
力学 | 45篇 |
数学 | 301篇 |
物理学 | 358篇 |
出版年
2024年 | 2篇 |
2023年 | 37篇 |
2022年 | 50篇 |
2021年 | 67篇 |
2020年 | 120篇 |
2019年 | 98篇 |
2018年 | 40篇 |
2017年 | 41篇 |
2016年 | 150篇 |
2015年 | 112篇 |
2014年 | 103篇 |
2013年 | 123篇 |
2012年 | 151篇 |
2011年 | 198篇 |
2010年 | 109篇 |
2009年 | 80篇 |
2008年 | 139篇 |
2007年 | 127篇 |
2006年 | 100篇 |
2005年 | 109篇 |
2004年 | 76篇 |
2003年 | 51篇 |
2002年 | 47篇 |
2001年 | 12篇 |
2000年 | 19篇 |
1999年 | 12篇 |
1998年 | 10篇 |
1997年 | 5篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 9篇 |
1993年 | 6篇 |
1992年 | 5篇 |
1991年 | 7篇 |
1989年 | 2篇 |
1987年 | 4篇 |
1986年 | 7篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1982年 | 3篇 |
1979年 | 2篇 |
1978年 | 8篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 2篇 |
1967年 | 1篇 |
1924年 | 2篇 |
排序方式: 共有2285条查询结果,搜索用时 15 毫秒
131.
Gräwert T Span I Bacher A Groll M 《Angewandte Chemie (International ed. in English)》2010,49(47):8802-8809
The biosynthesis of natural products is a treasure trove of unusual reaction mechanisms. This Minireview summarizes recent work on the structure and mechanism of IspH protein, which catalyzes the reductive dehydroxylation of an allyl alcohol in a biosynthetic pathway leading to isoprenoid precursors. 相似文献
132.
Jan P. Weyrauch Dr. A. Stephen K. Hashmi Prof. Dr. Andreas Schuster Dipl.‐Chem. Tobias Hengst Dipl.‐Chem. Stefanie Schetter Anna Littmann Dipl.‐Chem. Matthias Rudolph Dr. Melissa Hamzic Dr. Jorge Visus Jan W. Bats Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(3):956-963
The substrate scope, the mechanistic aspects of the gold‐catalyzed oxazole synthesis, and substrates with different aliphatic, aromatic, and functional groups in the side chain were investigated. Even molecules with several propargyl amide groups could easily be converted, delivering di‐ and trioxazoles with interesting optical properties. Furthermore, the scope of the gold(I)‐catalyzed alkylidene synthesis was investigated. Further functionalizations of these isolable intermediates of the oxazole synthesis were developed and chelate ligands can be obtained. The use of Barluenga’s reagent offers a new and mild access to the synthetically valuable iodoalkylideneoxazoles from propargylic amides, this reagent being superior to other sources of halogens. 相似文献
133.
134.
Christian Huber Christian Krause Tobias Werner Otto S. Wolfbeis 《Mikrochimica acta》2003,142(4):245-253
This article describes the preparation and performance of an optical sensor for continuous measurement of chloride at extracellular (serum) levels (20–200mM). The sensor is based on dynamic quenching of the fluorescence of lucigenin which was photo-immobilized on a hydrogel. Quenching occurs via a collisional mechanism, and the decrease in fluorescence intensity on exposure to 100mM chloride typically is –60%. It allows the determination of chloride in the 1 to 200mM concentration range, with a precision of ±3mM at 120mM. Bromide, iodide and salicylate act as interferents, while the effect of pH and oxygen is negligibly small. The sensor displays strong fluorescence intensity, excellent reproducibility, long-term stability, response times in the order of 2–5min, and is used in a commercial serum and blood chloride analyzer.Received January 21, 2003; accepted April 6, 2003
Published online July 28, 2003 相似文献
135.
Weidner T Zharnikov M Hoβbach J Castner DG Siemeling U 《The journal of physical chemistry. C, Nanomaterials and interfaces》2010,114(35):14975-14982
Self-assembled monolayers (SAMs) can decorate surfaces with `smart′ functional units possessing reversible stimulus-response behavior for optical, thermal, magnetic or redox-chemical stimuli. An independent performance of individual functional groups in such a film is desirable, which can be, in particular, ensured by fairly large lateral separations between tailgroups in the SAM. Adsorbate molecules with multiple attachment points are very promising in this context owing to their large surface footprint, which covers a surface area exceeding the lateral dimensions of the functional groups. To address these design constraints, novel tridentate long-chain tripodal thioether ligands with central adamantine units and a redox-active ferrocenyl tailgroup, 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-octylsulfanyl)phenyl]adamantine (T8) and 1-[4-(ferrocenylethynyl)phenyl]-3,5,7-tri[(4-n-dodecylsulfanyl)phenyl]adamantine (T12), were synthesized and used as tripodal adsorbate molecules for the fabrication of redox-active ferrocenyl-terminated SAMs on Au(111). These SAMs were characterized by X-ray photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and sum frequency generation spectroscopy. The data suggest that T8 and T12 form almost contamination-free, well-aligned and fairly densely-packed SAMs on Au(111) with laterally separated ferrocenyl units. The SAMs show a homogeneous binding chemistry, an important requirement for high fidelity SAMs. SFG results indicate lateral interactions between neighboring molecules via the long-chain binding units. 相似文献
136.
Rico Packheiser Tobias Rüffer Petra Ecorchard Prof. Dr. Heinrich Lang 《无机化学与普通化学杂志》2010,636(15):2607-2616
The synthesis of a unique series of heteromultinuclear transition metal compounds is reported. Complexes 1‐I‐3‐Br‐5‐(FcC≡C)‐C6H3 ( 4 ), 1‐Br‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C6H3 ( 6 ), 1,3‐(bpy‐C≡C)2‐5‐(FcC≡C)‐C6H3 ( 7 ), 1‐(XC≡C)‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C6H3 ( 8 , X = SiMe3; 9 , X = H), 1‐(HC≡C)‐3‐[(CO)3ClRe(bpy‐C≡C)]‐5‐(FcC≡C)‐C6H3 ( 11 ), 1‐[(Ph3P)AuC≡C]‐3‐[(CO)3ClRe(bpy‐C≡C)]‐5‐(FcC≡C)‐C6H3 ( 13 ), 1‐[(Ph3P)AuC≡C]‐3‐(bpy‐C≡C)‐5‐(FcC≡C)‐C6H3 ( 14 ), [1‐[(Ph3PAuC≡C]‐3‐[{[Ti](C≡CSiMe3)2}Cu(bpy‐C≡C)]‐5‐(FcC≡C)‐C6H3]PF6 ( 16 ), and [1,3‐[(tBu2bpy)2Ru(bpy‐C≡C)]2‐5‐(FcC≡C)‐C6H3](PF6)4 ( 18 ) (Fc = (η5‐C5H4)(η5‐C5H5)Fe, bpy = 2,2′‐bipyridiyl‐5‐yl, [Ti] = (η5‐C5H4SiMe3)2Ti) were prepared by using consecutive synthesis methodologies including metathesis, desilylation, dehydrohalogenation, and carbon–carbon cross‐coupling reactions. In these complexes the corresponding metal atoms are connected by carbon‐rich bridging units comprising 1,3‐diethynyl‐, 1,3,5‐triethynylbenzene and bipyridyl units. They were characterized by elemental analysis, IR and NMR spectroscopy, and partly by ESI‐TOF mass spectrometry., The structures of 4 and 11 in the solid state are reported. Both molecules are characterized by the central benzene core bridging the individual transition metal complex fragments. The corresponding acetylide entities are, as typical, found in a linear arrangement with representative M–C, C–CC≡C and C≡C bond lengths. 相似文献
137.
Moritz Beck‐Broichsitter Marcel Thieme Juliane Nguyen Thomas Schmehl Tobias Gessler Werner Seeger Seema Agarwal Andreas Greiner Thomas Kissel 《Macromolecular bioscience》2010,10(12):1527-1535
Novel ‘nano in nano’ composites consisting of biodegradable polymer nanoparticles incorporated into polymer nanofibers may efficiently modulate drug delivery. This is shown here using a combination of model compound‐loaded biodegradable nanoparticles encapsulated in electrospun fibers. The dye coumarin 6 is used as model compound for a drug in order to simulate drug release from loaded poly(lactide‐co‐glycolide) nanoparticles. Dye release from the nanoparticles occurs immediately in aqueous solution. Dye‐loaded nanoparticles which are encapsulated by electrospun polymer nanofibers display a significantly retarded release.
138.
Salvatore Abate Yun Gyong Ahn Tobias Kind Tommaso R. I. Cataldi Oliver Fiehn 《Rapid communications in mass spectrometry : RCM》2010,24(8):1172-1180
Many metabolomic applications use gas chromatography/mass spectrometry (GC/MS) under standard 70 eV electron ionization (EI) parameters. However, the abundance of molecular ions is often extremely low, impeding the calculation of elemental compositions for the identification of unknown compounds. On changing the beam‐steering voltage of the ion source, the relative abundances of molecular ions at 70 eV EI were increased up to ten‐fold for alkanes, fatty acid methyl esters and trimethylsilylated metabolites, concomitant with 2‐fold absolute increases in ion intensities. We have compared the abundance, mass accuracy and isotope ratio accuracy of molecular species in EI with those in chemical ionization (CI) with methane as reagent gas under high‐mass tuning. Thirty‐three peaks of a diverse set of trimethylsilylated metabolites were analyzed in triplicate, resulting in 342 ion species ([M+H]+, [M–CH3]+ for CI and [M]+ . , [M–CH3]+ . for EI). On average, CI yielded 8‐fold more intense molecular species than EI. Using internal recalibration, average mass errors of 1.8 ± 1.6 mm/z units and isotope ratio errors of 2.3 ± 2.0% (A+1/A ratio) and 1.7 ± 1.8% (A+2/A ratio) were obtained. When constraining lists of calculated elemental compositions by chemical and heuristic rules using the Seven Golden Rules algorithm and PubChem queries, the correct formula was retrieved as top hit in 60% of the cases and within the top‐3 hits in 80% of the cases. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
139.
140.
Katie Pei Dustin Banham Fangxia Feng Tobias Fürstenhaupt Siyu Ye Viola Birss 《Electrochemistry communications》2010,12(11):1666-1669
Two mesoporous carbons (with 15 (CIC-15) and 26 nm (CIC-26) diameter pores) were synthesized using a silica colloid imprinting method, loaded with 10 wt.% Pt, and then evaluated (against Vulcan? carbon (VC)) as oxygen reduction (ORR) catalysts for use in proton exchange membrane fuel cells. Both Pt/CICs reproducibly out-performed Pt/VC, with Pt/CIC-15 demonstrating higher ORR activity than Pt/CIC-26, despite its smaller pore size and lower surface area. Transmission electron tomography showed that the Pt nanoparticles (4–5 nm diameter) are fully deposited throughout the pores of the CICs and that the pore distribution in CIC-26 is partially ordered, while CIC-15 shows no ordering of its pores. Importantly, using the powerful imaging capabilities of transmission electron tomography, a first-time correlation is demonstrated between the ORR activity and the wall thickness of the carbon support materials. Pt/CIC-15 has significantly thicker walls, giving a lower measured electronic resistance, a lower ORR Tafel slope, and thus better performance overall compared to Pt/CIC-26. 相似文献