全文获取类型
收费全文 | 15401篇 |
免费 | 745篇 |
国内免费 | 139篇 |
专业分类
化学 | 10375篇 |
晶体学 | 102篇 |
力学 | 431篇 |
数学 | 2725篇 |
物理学 | 2652篇 |
出版年
2023年 | 139篇 |
2022年 | 103篇 |
2021年 | 298篇 |
2020年 | 402篇 |
2019年 | 386篇 |
2018年 | 256篇 |
2017年 | 223篇 |
2016年 | 606篇 |
2015年 | 478篇 |
2014年 | 566篇 |
2013年 | 869篇 |
2012年 | 1123篇 |
2011年 | 1315篇 |
2010年 | 675篇 |
2009年 | 584篇 |
2008年 | 987篇 |
2007年 | 942篇 |
2006年 | 934篇 |
2005年 | 837篇 |
2004年 | 719篇 |
2003年 | 489篇 |
2002年 | 461篇 |
2001年 | 128篇 |
2000年 | 109篇 |
1999年 | 106篇 |
1998年 | 80篇 |
1997年 | 105篇 |
1996年 | 145篇 |
1995年 | 104篇 |
1994年 | 109篇 |
1993年 | 118篇 |
1992年 | 82篇 |
1991年 | 92篇 |
1990年 | 69篇 |
1989年 | 68篇 |
1988年 | 83篇 |
1987年 | 68篇 |
1986年 | 63篇 |
1985年 | 98篇 |
1984年 | 104篇 |
1982年 | 114篇 |
1981年 | 122篇 |
1980年 | 96篇 |
1979年 | 84篇 |
1978年 | 113篇 |
1977年 | 92篇 |
1976年 | 73篇 |
1975年 | 71篇 |
1974年 | 64篇 |
1973年 | 68篇 |
排序方式: 共有10000条查询结果,搜索用时 250 毫秒
31.
Synthesis of polyphosphodiesters by ring‐opening polymerization of cyclic phosphates bearing allyl phosphoester protecting groups 下载免费PDF全文
Benoït Clément Daniel G. Molin Christine Jérôme Philippe Lecomte 《Journal of polymer science. Part A, Polymer chemistry》2015,53(22):2642-2648
The allyl phosphoester group is shown to be a protecting group for the synthesis of anionic polyphosphodiesters. Our strategy relies on the synthesis of a cyclic phosphate monomer bearing a pendant allyl phosphoester group, its easy purification by fractional distillation, its organocatalyzed ring‐opening polymerization by 1,8‐diazobicyclo[5.4.0]undec‐7‐ene (DBU) and 1‐[3,5‐bis(trifluoromethyl)phenyl]‐3‐cyclohexyl‐thiourea (TU). Finally, the deprotection of the allyl phosphoester group is carried out by reaction with sodium benzenethiolate in the absence of any detectable degradation. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2642–2648 相似文献
32.
Pd0‐Catalyzed Intramolecular α‐Arylation of Sulfones: Domino Reactions in the Synthesis of Functionalized Tetrahydroisoquinolines 下载免费PDF全文
Prof.Dr. Daniel Solé Ferran Pérez‐Janer Dr. Raffaella Mancuso 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(12):4580-4584
A new strategy for the synthesis of tetrahydroisoquinolines based on the Pd0‐catalyzed intramolecular α‐arylation of sulfones is reported. The combination of this Pd‐catalyzed reaction with intermolecular Michael and aza‐Michael reactions allows the development of two‐ and three‐step domino processes to synthesize diversely functionalized scaffolds from readily available starting materials. 相似文献
33.
34.
35.
36.
Quantification of myo‐inositol, 1,5‐anhydro‐ D‐sorbitol,and D‐chiro‐inositol using high‐performance liquid chromatography with electrochemical detection in very small volume clinical samples 下载免费PDF全文
Karen J. Schimpf Claudia C. Meek Richard D. Leff Dale L. Phelps Daniel J. Schmitz Christopher T. Cordle 《Biomedical chromatography : BMC》2015,29(11):1629-1636
Inositol is a six‐carbon sugar alcohol and is one of nine biologically significant isomers of hexahydroxycyclohexane. Myo‐inositol is the primary biologically active form and is present in higher concentrations in the fetus and newborn than in adults. It is currently being examined for the prevention of retinopathy of prematurity in newborn preterm infants. A robust method for quantifying myo‐inositol (MI), D ‐chiro‐inositol (DCI) and 1,5‐anhydro‐ D ‐sorbitol (ADS) in very small‐volume (25 μL) urine, blood serum and/or plasma samples was developed. Using a multiple‐column, multiple mobile phase liquid chromatographic system with electrochemical detection, the method was validated with respect to (a) selectivity, (b) accuracy/recovery, (c) precision/reproducibility, (d) sensitivity, (e) stability and (f) ruggedness. The standard curve was linear and ranged from 0.5 to 30 mg/L for each of the three analytes. Above‐mentioned performance measures were within acceptable limits described in the Food and Drug Administration's Guidance for Industry: Bioanalytical Method Validation. The method was validated using blood serum and plasma collected using four common anticoagulants, and also by quantifying the accuracy and sensitivity of MI measured in simulated urine samples recovered from preterm infant diaper systems. The method performs satisfactorily measuring the three most common inositol isomers on 25 μL clinical samples of serum, plasma, milk, and/or urine. Similar performance is seen testing larger volume samples of infant formulas and infant formula ingredients. MI, ADS and DCI may be accurately tested in urine samples collected from five different preterm infant diapers if the urine volume is greater than 2–5 mL. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
37.
Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters 下载免费PDF全文
Maria Camila Blanco Jaimes Alexander Ahrens Daniel Pflästerer Dr. Matthias Rudolph Prof. Dr. A. Stephen K. Hashmi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(1):427-433
Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact. 相似文献
38.
39.
Daniel Loof Oliver Thüringer Dr. Marco Schowalter Dr. Christoph Mahr Anmona Shabnam Pranti Prof. Dr. Walter Lang Prof. Dr. Andreas Rosenauer Dr. Volkmar Zielasek Dr. Sebastian Kunz Prof. Dr. Marcus Bäumer 《ChemistryOpen》2021,10(7):697-712
Porous networks of Pt nanoparticles interlinked by bifunctional organic ligands have shown high potential as catalysts in micro-machined hydrogen gas sensors. By varying the ligand among p-phenylenediamine, benzidine, 4,4‘‘-diamino-p-terphenyl, 1,5-diaminonaphthalene, and trans-1,4-diaminocyclohexane, new variants of such networks were synthesized. Inter-particle distances within the networks, determined via transmission electron microscopy tomography, varied from 0.8 to 1.4 nm in accordance with the nominal length of the respective ligand. While stable structures with intact and coordinatively bonded diamines were formed with all ligands, aromatic diamines showed superior thermal stability. The networks exhibited mesoporous structures depending on ligand and synthesis strategy and performed well as catalysts in hydrogen gas microsensors. They demonstrate the possibility of deliberately tuning micro- and mesoporosity and thereby transport properties and steric demands by choice of the right ligand also for other applications in heterogeneous catalysis. 相似文献
40.