全文获取类型
收费全文 | 52736篇 |
免费 | 20556篇 |
国内免费 | 2756篇 |
专业分类
化学 | 63408篇 |
晶体学 | 211篇 |
力学 | 2092篇 |
综合类 | 190篇 |
数学 | 3047篇 |
物理学 | 7100篇 |
出版年
2024年 | 194篇 |
2023年 | 4432篇 |
2022年 | 1895篇 |
2021年 | 2942篇 |
2020年 | 5253篇 |
2019年 | 2860篇 |
2018年 | 2840篇 |
2017年 | 1160篇 |
2016年 | 6255篇 |
2015年 | 6220篇 |
2014年 | 5755篇 |
2013年 | 6248篇 |
2012年 | 4247篇 |
2011年 | 2364篇 |
2010年 | 4290篇 |
2009年 | 4205篇 |
2008年 | 2067篇 |
2007年 | 1584篇 |
2006年 | 974篇 |
2005年 | 872篇 |
2004年 | 721篇 |
2003年 | 585篇 |
2002年 | 632篇 |
2001年 | 516篇 |
2000年 | 457篇 |
1999年 | 420篇 |
1998年 | 319篇 |
1997年 | 301篇 |
1996年 | 346篇 |
1995年 | 325篇 |
1994年 | 310篇 |
1993年 | 392篇 |
1992年 | 236篇 |
1991年 | 230篇 |
1990年 | 187篇 |
1989年 | 160篇 |
1988年 | 167篇 |
1987年 | 135篇 |
1986年 | 114篇 |
1985年 | 117篇 |
1980年 | 115篇 |
1977年 | 162篇 |
1976年 | 185篇 |
1975年 | 186篇 |
1974年 | 197篇 |
1972年 | 154篇 |
1971年 | 124篇 |
1970年 | 210篇 |
1969年 | 125篇 |
1968年 | 133篇 |
排序方式: 共有10000条查询结果,搜索用时 187 毫秒
51.
Richiro Ushimaru Zhang Chen Houyuan Zhao Po-hsun Fan Prof. Dr. Hung-wen Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(9):3586-3590
Albomycin δ2 is a sulfur-containing sideromycin natural product that shows potent antibacterial activity against clinically important pathogens. The l -serine-thioheptose dipeptide partial structure, known as SB-217452, has been found to be the active seryl-tRNA synthetase inhibitor component of albomycin δ2. Herein, it is demonstrated that AbmF catalyzes condensation between the 6′-amino-4′-thionucleoside with the d -ribo configuration and seryl-adenylate supplied by the serine adenylation activity of AbmK. Formation of the dipeptide is followed by C3′-epimerization to produce SB-217452 with the d -xylo configuration, which is catalyzed by the radical S-adenosyl-l -methionine enzyme AbmJ. Gene deletion suggests that AbmC is involved in peptide assembly linking SB-217452 with the siderophore moiety. This study establishes how the albomycin biosynthetic machinery generates its antimicrobial component SB-217452. 相似文献
52.
53.
Yi Han Zibo Xue Dr. Guangwu Li Dr. Yanwei Gu Dr. Yong Ni Dr. Shaoqiang Dong Prof. Chunyan Chi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(23):9111-9116
Incorporation of a non-hexagonal ring into a nanographene framework can lead to new electronic properties. During the attempted synthesis of naphthalene-bridged double [6]helicene and heptagon-containing nanographene by the Scholl reaction, an unexpected azulene-embedded nanographene and its triflyloxylated product were obtained, as confirmed by X-ray crystallographic analysis and 2D NMR spectroscopy. A 5/7/7/5 ring-fused substructure containing two formal azulene units is formed, but only one of them shows an azulene-like electronic structure. The formation of this unique structure is explained by arenium ion mediated 1,2-phenyl migration and a naphthalene to azulene rearrangement reaction according to an in-silico study. This report represents the first experimental example of the thermodynamically unfavorable naphthalene to azulene rearrangement and may lead to new azulene-based molecular materials. 相似文献
54.
Jie Lu Ju-Kang Wu Yao Jiang Dr. Peng Tan Lin Zhang Yu Lei Prof. Xiao-Qin Liu Prof. Lin-Bing Sun 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(16):6490-6496
Hierarchically porous metal–organic frameworks (HP-MOFs) are promising in various applications. Most reported HP-MOFs are prepared based on the generation of mesopores in microporous frameworks, and the formed mesopores are connected by microporous channels, limiting the accessibility of mesopores for bulky molecules. A hierarchical structure is formed by constructing microporous MOFs in uninterrupted mesoporous tunnels. Using the confined space in as-prepared mesoporous silica, highly dispersed metal precursors for MOFs are coated on the internal surface of mesoporous tunnels. Ligand vapor-induced crystallization is employed to enable quantitative formation of MOFs in situ, in which sublimated ligands diffuse into mesoporous tunnels and react with metal precursors. The obtained hierarchically porous composites exhibit record-high adsorption capacity for the bulky molecule trypsin. The thermal and storage stability of trypsin is improved upon immobilization on the composites. 相似文献
55.
56.
Synthesis of Small‐Sized,Porous, and Low‐Toxic Magnetite Nanoparticles by Thin POSS Silica Coating 下载免费PDF全文
Dr. Swee Kuan Yen D. Prathyusha Varma Wei Mei Guo Dr. Vincent H. B. Ho Dr. Vimalan Vijayaragavan Dr. Parasuraman Padmanabhan Prof. Kishore Bhakoo Prof. Subramanian Tamil Selvan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(10):3914-3918
In this communication, we report the synthesis of small‐sized (<10 nm), water‐soluble, magnetic nanoparticles (MNPs) coated with polyhedral oligomeric silsesquioxanes (POSS), which contain either polyethylene glycol (PEG) or octa(tetramethylammonium) (OctaTMA) as functional groups. The POSS‐coated MNPs exhibit superparamagnetic behavior with saturation magnetic moments (51–53 emu g?1) comparable to silica‐coated MNPs. They also provide good colloidal stability at different pH and salt concentrations, and low cytotoxicity to MCF‐7 human breast epithelial cells. The relaxivity data and magnetic resonance (MR) phantom images demonstrate the potential application of these MNPs in bioimaging. 相似文献
57.
Close‐Packed Two‐Dimensional Silver Nanoparticle Arrays: Quadrupolar and Dipolar Surface Plasmon Resonance Coupling 下载免费PDF全文
Sukang Yun Soonchang Hong Jesus A. I. Acapulco Jr. Ho Young Jang Songyi Ham Kyungeun Lee Prof. Seong Kyu Kim Prof. Sungho Park 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(16):6165-6172
Silver nanoparticles (NPs) ranging in size from 40 to 100 nm were prepared in high yield by using an improved seed‐mediated method. The homogeneous Ag NPs were used as building blocks for 2D assembled Ag NP arrays by using an oil/water interface. A close‐packed 2D array of Ag NPs was fabricated by using packing molecules (3‐mercaptopropyltrimethoxysilane) to control the interparticle spacing. The homogeneous 2D Ag NP array exhibited a strong quadrupolar cooperative plasmon mode resonance and a dipolar red‐shift relative to individual Ag NPs suspended in solution. A well‐arranged 2D Ag NP array was embedded in polydimethylsiloxane film and, with biaxial stretching to control the interparticle distance, concomitant variations of the quadrupolar and dipolar couplings were observed. As the interparticle distance increased, the intensity of the quadrupolar cooperative plasmon mode resonance decreased and dipolar coupling completely disappeared. The local electric field of the 2D Ag NP array was calculated by using finite difference time domain simulation and qualitatively showed agreement with the experimental measurements. 相似文献
58.
Herein, we report an addition to the toolbox for the monitoring and quantification of the hydrolytic decay of pentose-1-phosphates, which are known to be elusive and difficult to quantify. This communication describes how apparent equilibrium shifts of a nucleoside phosphorolysis reaction can be employed to calculate hydrolytic loss of pentose-1-phosphates based on the measurement of post-hydrolysis equilibrium concentrations of a nucleoside and a nucleobase. To demonstrate this approach, we assessed the stability of the relatively stable ribose-1-phosphate at 98 °C and found half-lives of 1.8–11.7 h depending on the medium pH. This approach can be extended to other sugar phosphates and related reaction systems to quantify the stability of UV-inactive and hard-to-detect reaction products and intermediates. 相似文献
59.
We present the fabrication of core-shell-satellite Au@SiO2-Pt nanostructures and demonstrate that LSPR excitation of the core Au nanoparticle can induce plasmon coupling effect to initiate photocatalytic hydrogen generation from decomposition of formic acid. Further studies suggest that the plasmon coupling effect induces a strong local electric field between the Au core and Pt nanoparticles on the SiO2 shell, which enables creation of hot electrons on the non-plasmonic-active Pt nanoparticles to participate hydrogen evolution reaction on the Pt surface. In addition, small SiO2 shell thickness is required in order to obtain a strong plamon coupling effect and achieve efficient photocatalytic activities for hydrogen generation. 相似文献
60.
Yuwei Wang Jia-Jun Yan Shengnan Hu Prof. David James Young Prof. Hong-Xi Li Prof. Zhi-Gang Ren 《化学:亚洲杂志》2021,16(18):2681-2686
A photoluminescent bimetallic cluster [Ag10Cu6(bdppthi)2(C≡CPh)12(MeOH)2(H2O)](ClO4)4 ( 1 , bdppthi=N,N’-bis(diphenylphosphanylmethyl)-tetrahydroimidazole} was synthesized from the PNNP type ligand bdppthi generated in-situ. Upon excitation at 365 nm, 1 exhibited strong phosphorescent emission at 630 nm, which was selectively quenched by NH3 in air or water. The sensing of NH3 was rapid and recoverable, with detection limits of 53 ppm (v/v) in N2 and 21 μmol/L (0.36 ppm, w/w) for NH3 ⋅ H2O in water. Cluster 1 could potentially serve as a bifunctional chemical sensor for the efficient detection of ammonia in waste-gas and waste-water. 相似文献