全文获取类型
收费全文 | 1531篇 |
免费 | 127篇 |
国内免费 | 3篇 |
学科分类
数理化 | 1661篇 |
出版年
2023年 | 14篇 |
2022年 | 15篇 |
2021年 | 42篇 |
2020年 | 39篇 |
2019年 | 68篇 |
2018年 | 53篇 |
2017年 | 27篇 |
2016年 | 50篇 |
2015年 | 63篇 |
2014年 | 70篇 |
2013年 | 113篇 |
2012年 | 142篇 |
2011年 | 155篇 |
2010年 | 69篇 |
2009年 | 50篇 |
2008年 | 104篇 |
2007年 | 74篇 |
2006年 | 68篇 |
2005年 | 59篇 |
2004年 | 59篇 |
2003年 | 52篇 |
2002年 | 39篇 |
2001年 | 23篇 |
2000年 | 18篇 |
1999年 | 13篇 |
1998年 | 11篇 |
1997年 | 7篇 |
1996年 | 11篇 |
1995年 | 9篇 |
1994年 | 9篇 |
1993年 | 7篇 |
1992年 | 7篇 |
1990年 | 7篇 |
1989年 | 10篇 |
1988年 | 8篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 4篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 9篇 |
1978年 | 8篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 7篇 |
1974年 | 6篇 |
1969年 | 3篇 |
1967年 | 6篇 |
1966年 | 3篇 |
排序方式: 共有1661条查询结果,搜索用时 218 毫秒
1.
Yuki Shintani Taku Ohtomi Dr. Aya Shibata Dr. Yoshiaki Kitamura Koichiro M. Hirosawa Prof. Kenichi G. N. Suzuki Prof. Masato Ikeda 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(8):e202104421
Aqueous self-assembly of short peptides has attracted growing attention for the construction of supramolecular materials for various bioapplications. Herein, we describe how the thermolysin-assisted biocatalytic construction of a dipeptide hydrazide from an N-protected amino acid and an amino acid hydrazide leads to the formation of thermally stable supramolecular hydrogels. In addition, we demonstrate the post-assembly modification of the supramolecular architectures constructed in situ tethering hydrazide groups as a chemical handle by means of fluorescence imaging. 相似文献
2.
Recently, we developed a convenient microfluidic droplet generation device based on vacuum‐driven fluid manipulation with a piezoelectric diaphragm micropump. In the present study built on our previous work, we investigate the influence of settings applied to the piezoelectric pump, such as peak‐to‐peak drive voltage (Vp‐p) and wave frequency, on droplet generation characteristics. Stepwise adjustments to the drive voltage in ±10‐Vp‐p increments over the range of 200?250 Vp‐p during droplet creation revealed that the droplet generation rate could be reproducibly controlled at a specific drive voltage. The droplet generation rate switched within <0.5 s after the input of a new voltage. Although the droplet generation rate depended on the drive voltage, this setting had almost no influence on droplet size. The frequency over the selected range (50?60 Hz) did not markedly influence the droplet generation rate or droplet size. We show that the current fluid manipulation system can be conveniently used for both droplet generation and for rapid droplet reading, which is required in many microfluidic‐based applications. 相似文献
3.
D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity 下载免费PDF全文
Yohei Ohkoda Akane Asaishi Tomoya Namiki Tomoaki Hashimoto Midori Yamada Koichiro Shirai Yuta Katagami Dr. Tomoaki Sugaya Prof. Makoto Tadokoro Prof. Akiharu Satake 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(33):11745-11756
The one‐step synthesis of D3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η3‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η3‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands. 相似文献
4.
Mitsuki Yamashita Yuna Kawasumi Yuki Tachibana Dr. Shinnosuke Horiuchi Dr. Koji Yamamoto Prof. Tetsuro Murahashi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(5):1212-1216
Although small cyclic- and open-chain unsaturated hydrocarbon anions such as cyclopentadienide and open-chain pentadienide are used as the strongly electron-donating auxiliary ligands for metal complexes, more extended π-conjugated unsaturated hydrocarbon anions have rarely been used in coordination chemistry, despite their potential ability to serve as the multiply bridging π-ligands for metal clusters. This work reports isolation of metal chain clusters bearing the multi-dentate, open-chain extended unsaturated hydrocarbon anion ligands. The extended open-chain π-conjugated polyenyl ligands could effectively stabilize oxidized palladium chains, including an unprecedented [Pd4]4+ chain. 相似文献
5.
Masashi Ohkawa Yuki Shirai Takeshi Goto Seishi Sekine Takashi Sato 《Fiber and Integrated Optics》2002,21(2):105-113
In this paper, a silicon-based integrated optic pressure sensor using an intermodal interference between the fundamental TM-like and TE-like modes is described. The sensor consists of a micromachined rectangular diaphragm and a straight polystyrene optical waveguide passing over the diaphragm. Its sensitivity is theoretically known to be strongly dependent on the position of the waveguide over the diaphragm. To experimentally investigate such dependence, we fabricated a sensor with a 1.2 mm ×10 mm ×20 μm diaphragm, over which waveguides were placed at 50 μm intervals. The measured phase sensitivity was 98 mrad/kPa for the waveguide nearest to the diaphragm edge. The measurement was also carried out for the other waveguides. As theoretically expected, the largest sensitivity was obtained for the waveguide nearest to the edge. 相似文献
6.
A. Noda S. Nakamura Y. Iwashita S. Sakabe M. Hashida T. Shirai S. Shimizu H. Tongu H. Ito H. Souda A. Yamazaki M. Tanabe H. Daido M. Mori M. Kado A. Sagisaka K. Ogura M. Nishiuchi S. Orimo Y. Hayashi A. Yogo S. Bulanov T. Esirkepov A. Nagashima T. Kimura T. Tajima T. Takeuchi K. Matsukado A. Fukumi Z. Li 《Laser Physics》2006,16(4):647-653
In order to widely spread out particle beams utilized in cancer therapy, laser-produced ions are developed as the injection beam for an ion synchrotron dedicated for cancer therapy. Such a laser ion source is expected to contribute largely to the realization of compactness of the size and low cost of the cancer therapy accelerator. The energy spectrum of the laser-produced ions, however, has no peak, but their intensities decrease exponentially according to the increase of the energy. For the purpose of modifying such a situation, we have proposed a scheme to rotate the beam in the longitudinal phase space with the use of the RF electric field, which is phase-adjusted with the pulse laser. We aim for a reduction of the energy spread of ± 5% selected by an energy analyzer and slits to ±1% by such phase rotation. For this purpose, a quarter wavelength resonator with two gaps with the same resonant frequency as the source laser has already been fabricated, together with its RF power source. The above phase rotation system and its recent experimental realization are presented. 相似文献
7.
Joji Ohshita Ryosuke Taketsugu Yuki Nakahara Atsutaka Kunai 《Journal of organometallic chemistry》2004,689(20):3258-3264
Selective dehydrogenative coupling of di- and trihydrosilanes with alcohols catalyzed by PdCl2 or NiCl2 afforded alkoxyhydro- and dialkoxyhydrosilanes in good yield. Further treatment of the resulting alkoxyhydrosilanes with carbon tetrachloride or allyl bromide in the presence of the same catalyst led to the formation of alkoxychloro- and alkoxybromosilanes, respectively. Similar reactions of dialkoxyhydrosilanes with carbon tetrachloride afforded dialkoxychlorosilanes in good yield, although contamination of small amounts of trialkoxysilanes and alkoxydichlorosilanes was detected in the products. Selective substitution of the alkoxyhalosilanes with nucleophiles is also reported. 相似文献
8.
Recently, we have developed a new tight-binding quantum chemical molecular dynamics program “Colors” for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO2(111) support. Significant electron transfer from the Pt particle to the CeO2(111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO2 surface is a main reason for the strong interaction of the Pt particle and CeO2(111) support. 相似文献
9.
Hideyuki Yoshida Yuki Ohno Kenichiro Yoshikuni Kenichiro Todoroki Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2003,19(2):317-319
A simple and sensitive fluorometric high-performance liquid chromatographic method was developed for the determination of midodrine in human plasma. After liquid-liquid extraction from plasma, the drug and 2-phenylglycinol (internal standard) were convened into the corresponding fluorescent derivatives by reaction with 3,4-dihydro-6,7-dimethoxy-4-methyl-3-oxoquinoxaline-2-carbonyl chloride, a fluorescence derivatization reagent for amines. The derivatives were separated within 30 min on a reversed-phase column using isocratic elution with acetonitrile-methanol-water (10:30:60, v/v) and were detected spectrofluorometrically at 485 nm with excitation at 400 nm. The detection limit for midodrine was 0.3 pmol (76 pg) per mL plasma at a signal-to-noise ratio of 3. 相似文献
10.
Tomohiro Shirai 《Optical Review》2004,11(5):312-319
Spatial coherence of the field modified by low-order adaptive optics is analyzed to establish a theoretical basis for the recent idea of using adaptive optics as a spatial coherence modifier. In this context low-order adaptive optics has the ability to correct some of the low-order aberrations specified by Zernike polynomials. The initial field to be modified is assumed to be a spatially partially coherent one resulting from phase disturbance. It is demonstrated, as in the previous study, that low-order adaptive optics serves to enhance the spatial coherence of the resultant field and that the effect of the enhancement becomes stronger as the spatial coherence of the initially partially coherent field increases. Potential applications of low-order adaptive optics as a spatial coherence modifier are briefly discussed. 相似文献