全文获取类型
收费全文 | 2783篇 |
免费 | 115篇 |
国内免费 | 9篇 |
专业分类
化学 | 2150篇 |
晶体学 | 33篇 |
力学 | 75篇 |
数学 | 134篇 |
物理学 | 515篇 |
出版年
2024年 | 3篇 |
2023年 | 20篇 |
2022年 | 52篇 |
2021年 | 54篇 |
2020年 | 56篇 |
2019年 | 49篇 |
2018年 | 37篇 |
2017年 | 32篇 |
2016年 | 91篇 |
2015年 | 81篇 |
2014年 | 88篇 |
2013年 | 155篇 |
2012年 | 218篇 |
2011年 | 248篇 |
2010年 | 161篇 |
2009年 | 133篇 |
2008年 | 218篇 |
2007年 | 194篇 |
2006年 | 169篇 |
2005年 | 167篇 |
2004年 | 112篇 |
2003年 | 93篇 |
2002年 | 99篇 |
2001年 | 57篇 |
2000年 | 42篇 |
1999年 | 48篇 |
1998年 | 22篇 |
1997年 | 19篇 |
1996年 | 28篇 |
1995年 | 26篇 |
1994年 | 22篇 |
1993年 | 22篇 |
1992年 | 12篇 |
1991年 | 11篇 |
1990年 | 11篇 |
1989年 | 6篇 |
1988年 | 7篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1982年 | 4篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 5篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1974年 | 5篇 |
1973年 | 1篇 |
1972年 | 1篇 |
排序方式: 共有2907条查询结果,搜索用时 15 毫秒
991.
Single-molecule spectroscopic investigation of energy migration processes in cyclic porphyrin arrays
Park M Yoon MC Yoon ZS Hori T Peng X Aratani N Hotta J Uji-I H Sliwa M Hofkens J Osuka A Kim D 《Journal of the American Chemical Society》2007,129(12):3539-3544
Covalently linked cyclic porphyrin arrays have been synthesized to mimic natural light-harvesting apparatuses and to investigate the highly efficient energy migration processes occurring in these systems for future applications in molecular photonics. To avoid an ensemble-averaged picture, we performed a single-molecule spectroscopic study on the energy migration processes of cyclic porphyrin arrays and a linear model compound embedded in a rigid polymer matrix by recording fluorescence intensity trajectories, by performing coincidence measurements, and by doing wide-field defocused imaging. Our study demonstrates efficient energy migration within the cyclic porphyrin arrays at the single-molecule level. By comparison with the data of the linear model compound, we could pinpoint the role of the dipole-dipole coupling between diporphyrin subunits and the rigidity of the cyclic structures on the energy transfer processes. 相似文献
992.
993.
994.
The capillary burst microvalve offers an attractive means to regulate microliquid flow owing to its simple structure and operation process. However, there existed no rigorous theoretical work to elucidate how the valve works and consequently to predict the valve-bursting condition. Therefore, here we report the theoretical investigation of how the capillary burst valve can stop the advancing liquid meniscus and when it bursts. We confirm our theory with experiments using a centrifugal microfluidic valve system fabricated by soft lithography. 相似文献
995.
Reported herein is a novel approach to the total syntheses of (-)-alpha-kainic acid and (+)-alpha-allokainic acid, where the stereochemistries on C(2), C(3), and C(4) of the pyrrolidine core were introduced efficiently and selectively. A regio- and stereoselective C-H insertion reaction was utilized to prepare the gamma-lactam as an intermediate. A Michael-type cyclization of phenylsulfone with a conjugated acetylenic ketone was developed to prepare the tricyclic ketone as a key intermediate for (-)-alpha-kainic acid. Subsequently, a stereoselective dephenylsulfonylation was carried out successfully to secure the cis relationship at C(3) and C(4) centers. An unprecedented acetylation on the phenylsulfone, followed by a stereoselective dephenylsulfonylation, secured the trans relationship at C(3) and C(4) centers in (+)-alpha-allokainic acid. 相似文献
996.
Sung NK Cho DW Choi JH Choi KW Yoon UC Maeda H Mariano PS 《The Journal of organic chemistry》2007,72(23):8831-8837
A novel methodology for the synthesis of bis-crown ethers has been developed. The preparative route takes advantage of an efficient single electron transfer promoted photomacrocyclization reaction of polyether branched bisphthalimides which contain alpha-trimethylsilylmethyl groups at terminal positions. The generality of the methodology was demonstrated by its application to the synthesis of symmetric and unsymmetric bis-crown ethers of various ring sizes. Finally, the metal cation binding and fluorescence emission properties of the bis-crowns, prepared by using the developed procedure, were briefly explored. 相似文献
997.
Lee SJ Lee JR Kim YH Park YS Park SI Park HS Kim KP 《Rapid communications in mass spectrometry : RCM》2007,21(17):2797-2804
Protein tyrosine nitration is one of the important regulatory mechanisms in various cellular phenomena such as cell adhesion, endo/exo-cytosis of cellular materials, and signal transduction. In the present study, electrospray ionization tandem mass spectrometry (ESI-MS/MS) with a linear ion-trap mass spectrometer was applied for identification of nitrated proteins and localization of the modified tyrosine residues. When angiotensin II(DRVYIHPF) was nitrated in vitro with tetranitromethane (TNM), the mass spectrum showed a shift of +45 Da which corresponded to tyrosine nitration. An additional +29 Da mass shift was also detected by ESI-MS. This differed from nitrated peptide analysis with matrix-associated laser desorption/ionization mass spectrometry (MALDI-MS), which showed oxygen neutral loss from the nitrated tyrosine residues upon laser irradiation. Hence the +29 Da mass shift of the nitrated peptide observed by ESI-MS suggested the introduction of an NO group for nitrosylation of tyrosine residues. To confirm this in vitro nitrosylation on the protein level, bovine serum albumin was in vitro nitrated with TNM and analyzed by ESI-MS/MS. As expected, +29 as well as +45 Da mass shifts were detected, and the +29 Da mass shift was found to correspond to the modification on tyrosine residues by NO. Although the chemical mechanism by which this occurs in ESI-MS is not clear, the +29 Da mass shift could be a new potential marker of nitrosylated peptides. 相似文献
998.
Hyung-Seok Yoo Yo-Sep Yang Soo Lim Kim Seung Hwan Son Yoon Hu Jang Jeong-Won Shin Prof. Nam-Jung Kim 《化学:亚洲杂志》2021,16(21):3469-3475
Aromatic N-heterocycle-fused scaffolds such as indoles and quinolines are important core structures found in various bioactive natural products and synthetic compounds. Recently, various dehydrogenation methods with the help of alkoxides, known to significantly promote dihydro- or tetrahydro-heterocycles to be oxidized, were developed for the heterocycle synthesis. However, these approaches are sometimes unsuitable due to resulting undesired side reactions such as reductive dehalogenation. Herein, expedient syntheses of 1H-indoles, quinolines, and 6-membered N-heterocycle-fused scaffolds from their hydrogenated forms through palladium(II)-catalyzed aerobic dehydrogenation under alkoxide-free conditions are reported. A total of 48 compounds were successfully synthesized with a wide range of functional groups including halogens (up to 99% yield). These methodologies provide facile routes for various privileged structures possessing aromatic N-heterocycles without the help of alkoxides, in highly efficient manners. 相似文献
999.
Nitroreductases belong to a member of flavin-containing enzymes that can reduce nitroaromatic compounds to amino derivatives with NADH as an electron donor. NTR activity is known to be elevated in the cancerous environment and is considered an advantageous target in therapeutic prodrugs for the treatment of cancer. Here, we developed a ratiometric fluorescent molecule for observing NTR activity in living cells. This can provide a selective and sensitive response to NTR with a distinct increase in fluorescence ratio (FI530/FI630) as well as color changes. We also found a significant increase in NTR activity in cervical cancer HeLa and lung cancer A549 cells compared to non-cancerous NIH3T3. We proposed that this new ratiometric fluorescent molecule could potentially be used as a NTR-sensitive molecular probe in the field of cancer diagnosis and treatment development related to NTR activity. 相似文献
1000.
Taehoon Lee Joong-Ho Won Johan Lim Sungroh Yoon 《Journal of computational and graphical statistics》2017,26(4):851-864
We present a massively parallel algorithm for the fused lasso, powered by a multiple number of graphics processing units (GPUs). Our method is suitable for a class of large-scale sparse regression problems on which a two-dimensional lattice structure among the coefficients is imposed. This structure is important in many statistical applications, including image-based regression in which a set of images are used to locate image regions predictive of a response variable such as human behavior. Such large datasets are increasingly common. In our study, we employ the split Bregman method and the fast Fourier transform, which jointly have a high data-level parallelism that is distinct in a two-dimensional setting. Our multi-GPU parallelization achieves remarkably improved speed. Specifically, we obtained as much as 433 times improved speed over that of the reference CPU implementation. We demonstrate the speed and scalability of the algorithm using several datasets, including 8100 samples of 512 × 512 images. Compared to the single GPU counterpart, our method also showed improved computing speed as well as high scalability. We describe the various elements of our study as well as our experience with the subtleties in selecting an existing algorithm for parallelization. It is critical that memory bandwidth be carefully considered for multi-GPU algorithms. Supplementary material for this article is available online. 相似文献