全文获取类型
收费全文 | 1034篇 |
免费 | 29篇 |
国内免费 | 7篇 |
专业分类
化学 | 772篇 |
晶体学 | 12篇 |
力学 | 19篇 |
数学 | 91篇 |
物理学 | 176篇 |
出版年
2023年 | 8篇 |
2022年 | 9篇 |
2021年 | 10篇 |
2020年 | 8篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 10篇 |
2016年 | 16篇 |
2015年 | 19篇 |
2014年 | 22篇 |
2013年 | 65篇 |
2012年 | 56篇 |
2011年 | 58篇 |
2010年 | 38篇 |
2009年 | 27篇 |
2008年 | 61篇 |
2007年 | 79篇 |
2006年 | 62篇 |
2005年 | 73篇 |
2004年 | 49篇 |
2003年 | 58篇 |
2002年 | 54篇 |
2001年 | 12篇 |
2000年 | 16篇 |
1999年 | 20篇 |
1998年 | 12篇 |
1997年 | 12篇 |
1996年 | 15篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 8篇 |
1992年 | 5篇 |
1991年 | 8篇 |
1989年 | 7篇 |
1988年 | 5篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 22篇 |
1983年 | 7篇 |
1982年 | 11篇 |
1981年 | 16篇 |
1980年 | 11篇 |
1979年 | 9篇 |
1978年 | 4篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1973年 | 4篇 |
1972年 | 3篇 |
排序方式: 共有1070条查询结果,搜索用时 31 毫秒
991.
syn‐9,9′‐Bibenzonorbornenylidene sulfoxide 8b underwent pinacol‐type rearrangement to form 9 , together with a mixture of thiiranes 4a and 4b by reaction with TMSOTf in CH2Cl2 at room temperature. The rearrangement of anti‐sulfoxide 8a proceeded more slowly giving a mixture of 9, 4a , and 4b . © 2009 Wiley Periodicals, Inc. Heteroatom Chem 20:29–34, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20507 相似文献
992.
Yoshiaki Obara Mike E. N. Majerus 《Proceedings of the Japan Academy. Series B, Physical and biological sciences》2009,85(6):198-203
Heterosubspecific mating experiments were carried out between two subspecies of cabbage butterflies, British Pieris rapae rapae and Japanese P. rapae crucivora, to examine how accurately males recognize the mates. The two subspecies are different in that the wings of female P. rapae rapae reflect little UV light, whereas those of female P. rapae crucivora are strongly UV-reflective. The wing colouration of P. rapae crucivora involving UV is believed to be critical in mate recognition. The results showed that males of both subspecies displayed mating behaviours, to and copulated with, females of both subspecies. Furthermore, P. rapae crucivora males exhibited mating behaviours and attempted to copulate with females of Pieris melete with low UV reflectance which are critically different from P. rapae crucivora females with high UV reflectance. Based on these findings, we propose the “pioneer male” hypothesis, which argues that such inaccurate mate recognition may sometimes be selectively beneficial for males and thus an adaptive mating strategy. The “pioneer male” was discussed in terms of its possible role in the evolution. 相似文献
993.
Kazuya Ikoma Hisatake Takamiya Yoshiaki Kusaka Yoshiteru Seo 《Magnetic resonance imaging》2001,19(10):1287-1296
The 1H double-quantum filtered (DQF) NMR and DQF MRI is applied to the joint tissues of rabbits for selective visualization of tendons, menisci and articular cartilage. The 1H DQF NMR selectively filters double-quantum coherence arising from the 1H dipolar interaction of the “bound” water in these tissues. The double-quantum creation time dependency of the DQF signal intensity is determined by the molecular environment of the “bound” water. Therefore, each tissue has a unique creation time at which the DQF signal reaches its maximum intensity, τmax (Achilles tendon: 0.46 ± 0.02 ms, patella: 0.55 ± 0.8 ms, anterior cruciate ligament: 0.60 ± 0.05 ms, meniscus: 0.78 ± 0.02 ms, skin: 0.81 ± 0.07 ms). We have presented the creation-time-contrasted DQF images of the meniscus, patella, foot, and knee joint. Compared with conventional T2*-weighted gradient-echo (GRE) MR images, tendons, ligaments, menisci, and articular cartilage were more clearly seen in the DQF MR images. All these tissues were distinctly discriminated from each other by their creation times. DQF MR images of foot and knee joints can selectively demonstrated tendons, ligaments, and cartilage, which make it easier to understand the complicated anatomic structure of joints. Because the DQF NMR signal intensity and τmax are sensitive to the order structure of the “bound” water, it might be possible to introduce the creation-time dependent-contrast of 1H DQF MR images as a new tool for analyzing the changes in the ordered structure of the tissue. 相似文献
994.
995.
In this review, cross-coupling reactions by cooperative Pd/Cu or Ni/Cu catalysis based on catalytically generated organocopper nucleophiles are summarized. Compared to conventional methods based on the use of stoichiometric amounts of pre-synthesized organometallic reagents, these methods are powerful tools for the alkynylation, arylation, alkenylation, and alkylation of organic electrophiles, especially as they can be carried out in a highly step-economical manner with readily available starting materials based on simple arenes, carboxylic acids, alkenes, and alkynes as pre-nucleophiles. 相似文献
996.
Takaya Murakami Yoshiaki Iwamuro Reiko Ishimaru Satoshi Chinaka Noriyuki Kato Yuki Sakamoto Natsuhiko Sugimura Hiroshi Hasegawa 《Journal of mass spectrometry : JMS》2019,54(3):205-212
A reliable method for structural analysis is crucial for the forensic investigation of new psychoactive substances (NPSs). Towards this end, mass spectrometry is one of the most efficient and facile methods for the identification of NPSs. However, the differentiation among 2‐, 3‐, and 4‐fluoromethcathinones (o‐, m‐, and p‐FMCs), which are ring‐fluorinated positional isomers part of the major class of NPSs referred to as synthetic cathinones, remains a challenge. This is mostly due to their similar retention properties and nearly identical full scan mass spectra, which hinder their identification. In this study, we describe a novel and practical method for differentiating the fluorine substitution position on the phenyl ring of FMCs, based on energy‐resolved mass spectrometry (ERMS) using an electron ionization‐triple quadrupole mass spectrometer. ERMS measurements showed that the three FMC positional isomers exhibited differences in relative abundances of both the fluorophenyl cation (m/z 95) and the fluorobenzoyl cation (m/z 123). The logarithmic plots of the abundance ratio of these two cations (m/z 95 to m/z 123) as a function of the collision energy (CE) followed the order of o‐FMC < p‐FMC < m‐FMC at each CE, which allowed the three isomers to be unambiguously and reliably differentiated. The theoretical dissociation energy calculations confirmed the relationship obtained by ERMS analyses, and additional ERMS measurements of methylmethcathinone positional isomers showed that the differences in abundance among the FMCs were attributed to the differences in their collision‐induced dissociation reactivities arising from the halogen‐induced resonance effects on the phenyl ring. Moreover, the method for differentiation described herein was successfully applied to the actual samples containing seized drugs. We expect that the described methodology will also contribute significantly to the reliable and accurate structural identification of NPSs in the fields of therapeutic, clinical, and forensic toxicology. 相似文献
997.
Takahiro Kojima Takahiro Nakae Zhen Xu Chinnusamy Saravanan Kentaro Watanabe Yoshiaki Nakamura Hiroshi Sakaguchi 《化学:亚洲杂志》2019,14(23):4400-4407
Graphene, the one‐atom‐thick two‐dimensional (2D) carbon material, has attracted tremendous interest in both academia and industry due to its outstanding electrical, mechanical, and thermal properties. For electronic applications, the challenging task is to make it as a semiconductor. The bottom‐up synthesis of semiconducting one‐dimensional (1D) nanometer‐wide graphene strips, namely, graphene nanoribbons (GNRs), has attracted much attention owing to its promising electronic, optical, and magnetic properties. In this regard, we report the fabrication of cove‐type 2D GNR networks (GNNs) via the interconnection of 1D self‐assembled GNRs on the surface of Au(111). The cove‐type 2D GNRs networks (GNNs) were fabricated from the GNR, 5‐CGNR‐1‐1 , synthesized using the precursor of DBSP . Annealing of high‐density self‐assembled GNRs on the surface of Au(111) through two‐zone chemical vapour deposition (2Z CVD) successfully generated a 2D interconnected structure with high yield via the fusion and ladder coupling reactions of GNR chains. In order to validate the later fusion reaction, we have also synthesized the GNR, 7‐AGNR‐1‐1 , using the precursor of DBBA . The GNNs, which consist of hybridized metallic‐like and semiconducting GNRs, are a new class of carbon‐based materials. Further, we applied this material for thermoelectric (TE) applications and found a very low cross‐plane thermal conductivity of 0.11 Wm?1 K?1, which is one of the lowest value among the carbon‐based materials as well as inorganic semiconductors, while maintaining the cross‐plane electrical conductivity of 188 S m?1. 相似文献
998.
Ab initio configuration interaction study on electronically excited 4-dimethylamino-4′-cyanostilbene
Yoshiaki Amatatsu 《Theoretical chemistry accounts》2000,103(6):445-450
Ab initio configuration interaction calculations have been performed to examine the electronic structures of both trans-4-dimethylamino-4′-cyanostilbene (DCS) and four types of perpendicularly twisted DCSs, trans-DCS is predominantly excited into the S1 state out of low-lying excited states. The S1 state is an intramolecular charge-transfer (ICT) state in which the dipole moment is about twice as large as that in S0. The excited DCS at the 4-dimethylanilino twisted conformation, which becomes S1 in polar solvents, has a very much larger dipole moment than that in S1 to trans-DCS. This means that the geometrical structure of the twisted ICT (TICT) is the 4-dimethylanilino twisted form, not the dimethylamino
twisted one which is well know from the TICT structure of 4-dimethylaminobenzonitrile.
Received: 16 December 1998 / Accepted: 19 March 1999 / Published online: 9 September 1999 相似文献
999.
Taniguchi A Sohma Y Kimura M Okada T Ikeda K Hayashi Y Kimura T Hirota S Matsuzaki K Kiso Y 《Journal of the American Chemical Society》2006,128(3):696-697
A clear understanding of the dynamic events of amyloid beta peptide (Abeta) 1-42, such as the folding, self-assembly, and aggregation processes, would be of great significance in Alzheimer's disease (AD) research. However, elucidation of these Abeta1-42 dynamic events is a difficult issue due to uncontrolled polymerization, which also poses a significant obstacle for establishing an experimental system that clarifies the pathological function of Abeta1-42. On the basis of the O-acyl isopeptide method, we herein developed a novel photo-triggered "click peptide" of Abeta1-42, for example, 26-N-Nvoc-26-AIAbeta42, in which the photocleavable 6-nitroveratryloxycarbonyl (Nvoc) group was introduced at the alpha-amino group of Ser26 in 26-O-acyl isoAbeta1-42 (26-AIAbeta42). From the results, (1) the click peptide did not exhibit the self-assembling nature under physiological conditions due to one single modified ester; (2) photoirradiation of the click peptide and subsequent O-N intramolecular acyl migration afforded the intact Abeta1-42 with a quick and one-way conversion reaction (so-called "click"), while the click peptide was stable under nonphotolytic or storage conditions. In addition, it is advantageous that no additional fibril inhibitory auxiliaries were released during conversion to Abeta1-42. This method provides a novel system useful for investigating the dynamic biological functions of Abeta1-42 in AD by inducible activation of Abeta1-42 self-assembly. 相似文献
1000.
A Ni/PMe2Ph catalyst is found to effect regioselective addition of cyanoformate esters across 1,2-dienes, giving rise to 3-alkoxycarbonyl-3-butenenitriles. Functional groups such as cyano, protected hydroxyl, and amino groups in the 1,2-diene substrates are tolerated. Isomerization of the initial products to thermodynamically more stable isomers takes place possibly through further oxidative addition of the C-CN bond of 3-alkoxycarbonyl-3-butenenitriles to Ni(0) followed by reductive elimination. The cyanoesterification products undergo further addition across alkynes in the presence of a Ni/P(4-CF3-C6H4)3 catalyst. 相似文献