全文获取类型
收费全文 | 5313篇 |
免费 | 645篇 |
国内免费 | 589篇 |
专业分类
化学 | 3054篇 |
晶体学 | 33篇 |
力学 | 201篇 |
综合类 | 72篇 |
数学 | 2146篇 |
物理学 | 1041篇 |
出版年
2024年 | 2篇 |
2023年 | 42篇 |
2022年 | 55篇 |
2021年 | 88篇 |
2020年 | 155篇 |
2019年 | 158篇 |
2018年 | 158篇 |
2017年 | 213篇 |
2016年 | 175篇 |
2015年 | 197篇 |
2014年 | 276篇 |
2013年 | 947篇 |
2012年 | 260篇 |
2011年 | 294篇 |
2010年 | 253篇 |
2009年 | 310篇 |
2008年 | 331篇 |
2007年 | 350篇 |
2006年 | 339篇 |
2005年 | 284篇 |
2004年 | 269篇 |
2003年 | 241篇 |
2002年 | 187篇 |
2001年 | 123篇 |
2000年 | 149篇 |
1999年 | 99篇 |
1998年 | 123篇 |
1997年 | 69篇 |
1996年 | 83篇 |
1995年 | 74篇 |
1994年 | 58篇 |
1993年 | 36篇 |
1992年 | 28篇 |
1991年 | 16篇 |
1990年 | 17篇 |
1989年 | 15篇 |
1988年 | 16篇 |
1987年 | 12篇 |
1986年 | 7篇 |
1985年 | 4篇 |
1984年 | 9篇 |
1982年 | 3篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 5篇 |
1978年 | 3篇 |
1974年 | 1篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1936年 | 1篇 |
排序方式: 共有6547条查询结果,搜索用时 18 毫秒
41.
42.
Dr. Bozheng Sun Dr. Meagan S. Oakley Dr. Kota Yoshida Yanwen Yang Prof. Matteo Tommasini Dr. Chiara Zanchi Dr. Andrea Lucotti Dr. Michael J. Ferguson Dr. Frank Hampel Prof. Mariusz Klobukowski Prof. Rik R. Tykwinski 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(38):e202200616
Cyclic tetraaryl[5]cumulenes ( 1 a–f ) have been synthesized and studied as a function of increasing ring strain. The magnitude of ring strain is approximated by the extent of bending of the cumulenic core as assessed by a combination of X-ray crystallographic analysis and DFT calculations. Trends are observed in 13C NMR, UV-vis, and Raman spectra associated with ring strain, but the effects are small. In particular, the experimental HOMO-LUMO gap is not appreciably affected by bending of the [5]cumulene framework from ca. 174° (λmax=504 nm) in 1 a to ca. 178° (λmax=494 nm) in 1 f . 相似文献
43.
Facile synthesis of dopa‐functional polycarbonates via thiol‐Ene‐coupling chemistry towards self‐healing gels 下载免费PDF全文
Kristina Olofsson Michael Malkoch Anders Hult 《Journal of polymer science. Part A, Polymer chemistry》2016,54(15):2370-2378
Since extraction of the naturally occurring mussel‐foot proteins is expensive and time‐consuming, routes towards synthetic analogues are continuously being explored. Often, these methods involve several protection and deprotection steps, making the synthesis of synthetic analogues time‐consuming and expensive as well. Herein, we show that UV‐initiated thiol‐ene coupling between a thiol‐functional dopamine derivative and an allyl‐functional aliphatic polycarbonate can be used as a fast and facile route to dopa‐functional materials. Different thiol‐to‐allyl ratios and irradiation protocols were used and it was found that nearly 50% of the allyl groups could be functionalized with dopa within short reaction times, without the need of protecting the catechol. It is also demonstrated herein that the dopa‐functional polymers can be used to form self‐healing gels through complexation with Fe3+ ions at increased pH. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2370–2378 相似文献
44.
Synthesis and UCST‐type phase behavior of polypeptide with alkyl side‐chains in alcohol or ethanol/water solvent mixtures 下载免费PDF全文
Wenjun Liu Mengxiang Zhu Jiang Xiao Ying Ling Haoyu Tang 《Journal of polymer science. Part A, Polymer chemistry》2016,54(21):3425-3435
A series of thermoresponsive polypeptides bearing 1‐butyl, 1‐hexyl, or 1‐dodecyl side‐chains (i.e., 6a ‐ 6c ) were synthesized by copper‐mediated 1,3‐dipolar cycloaddition with high grafting efficiency (>95%) between side‐chain “clickable” polypeptide, namely poly(γ‐4‐(propargoxycarbonyl)benzyl‐L‐glutamate) ( 5 ) and 1‐azidoalkanes. 5 with different degree of polymerization (DP = 48–86) were prepared from triethylamine initiated ring‐opening polymerization of γ‐4‐(propargoxycarbonyl)benzyl‐L‐glutamic acid based N‐carboxyanhydride ( 4 ). 1H NMR, FTIR, and GPC results revealed the successful preparation of the resulting polypeptides. 6a ‐ 6c showed reversible UCST‐type phase behaviors in methanol, ethanol, and ethanol/water solvent mixtures depending on the polymer main‐chain length, alkyl side‐chain length, weight percentage of ethanol (fw) in the binary solvent, and so forth. FTIR analysis revealed the presence of the van der Waals interaction between the alkyl pendants of polypeptides and alkyl groups of alcoholic solvents. Variable‐temperature UV‐vis spectroscopy revealed that the UCST‐type phase transition temperature (Tpt) increased as polymer main‐chain length or concentration increased. In ethanol/water solvent mixtures, polypeptide with short alkyl pendant (i.e., 1‐butyl group) and short main‐chain length (DP = 41) showed the widest fw range and Tpts in the range of 61.0–71.1 °C. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3425–3435 相似文献
45.
46.
Back Cover: Constrained Peptides with Target‐Adapted Cross‐Links as Inhibitors of a Pathogenic Protein–Protein Interaction (Angew. Chem. Int. Ed. 9/2014) 下载免费PDF全文
47.
48.
Size controlled synthesis of ornithine‐based polypeptides by ring‐opening polymerization of α‐(amino acid)‐N‐carboxyanhydrides 下载免费PDF全文
49.
Rhodium(II)‐Catalyzed Annulation of Azavinyl Carbenes Through Ring‐Expansion of 1,3,5‐Trioxane: Rapid Access to Nine‐Membered 1,3,5,7‐Trioxazonines 下载免费PDF全文
Dr. Jola Pospech Dr. Raffaella Ferraccioli Dr. Helfried Neumann Prof. Dr. Matthias Beller 《化学:亚洲杂志》2015,10(12):2624-2630
The rhodium(II)‐catalyzed denitrogenative coupling of N‐alkylsulfonyl 1,2,3‐triazoles with 1,3,5‐trioxane led to nine‐membered‐ringed trioxazonines in moderate‐to‐good yields. 1,3,5‐Trioxane, acting as an oxygen nucleophile, reacted with the α‐aza‐vinylcarbene intermediate, giving rise to ylide formation, which was probably the key step in the reaction. Triazoles that contained aryl substituents with various electronic and steric features on the C4 carbon atom were well‐tolerated. The synthesis of trioxazonine derivatives was achieved through a one‐pot, two‐step procedure from 1‐mesylazide and a terminal alkyne by combining CuI‐catalyzed 1,3‐dipolar cycloaddition and rhodium‐catalyzed transformations. 相似文献
50.
Christina Schjoeth-Eskesen Paul Robert Hansen Andreas Kjaer Nic Gillings 《ChemistryOpen》2015,4(1):65-71
Aziridines can undergo a range of ring-opening reactions with nucleophiles. The regio- and stereochemistry of the products depend on the substituents on the aziridine. Aziridine ring-opening reactions have rarely been used in radiosynthesis. Herein we report the ring opening of activated aziridine-2-carboxylates with [18F]fluoride. The aziridine was activated for nucleophilic attack by substitution of various groups on the aziridine nitrogen atom. Fluorine-18 radiolabelling was followed by ester hydrolysis and removal of the activation group. Totally regioselective ring opening and subsequent deprotection was achieved with tert-butyloxycarbonyl- and carboxybenzyl-activated aziridines to give α-[18F]fluoro-β-alanine in good radiochemical yield. 相似文献