全文获取类型
收费全文 | 1438篇 |
免费 | 54篇 |
国内免费 | 12篇 |
专业分类
化学 | 1097篇 |
晶体学 | 27篇 |
力学 | 12篇 |
数学 | 76篇 |
物理学 | 292篇 |
出版年
2023年 | 6篇 |
2022年 | 9篇 |
2021年 | 16篇 |
2020年 | 21篇 |
2019年 | 26篇 |
2018年 | 17篇 |
2017年 | 8篇 |
2016年 | 34篇 |
2015年 | 35篇 |
2014年 | 25篇 |
2013年 | 58篇 |
2012年 | 65篇 |
2011年 | 100篇 |
2010年 | 46篇 |
2009年 | 44篇 |
2008年 | 80篇 |
2007年 | 82篇 |
2006年 | 89篇 |
2005年 | 66篇 |
2004年 | 82篇 |
2003年 | 63篇 |
2002年 | 48篇 |
2001年 | 52篇 |
2000年 | 31篇 |
1999年 | 33篇 |
1998年 | 18篇 |
1997年 | 13篇 |
1996年 | 22篇 |
1995年 | 14篇 |
1994年 | 14篇 |
1993年 | 12篇 |
1992年 | 13篇 |
1991年 | 15篇 |
1990年 | 18篇 |
1989年 | 11篇 |
1988年 | 13篇 |
1987年 | 22篇 |
1986年 | 15篇 |
1985年 | 25篇 |
1984年 | 16篇 |
1983年 | 15篇 |
1982年 | 9篇 |
1981年 | 11篇 |
1980年 | 12篇 |
1979年 | 17篇 |
1977年 | 7篇 |
1976年 | 9篇 |
1975年 | 10篇 |
1972年 | 5篇 |
1967年 | 5篇 |
排序方式: 共有1504条查询结果,搜索用时 0 毫秒
61.
Makoto Kunisada Taro Masaki Ryusuke Ono Hironobu Morinaga Eiji Nakano Flandiana Yogianti Kunihiro Okunishi Hiroshi Sugiyama Chikako Nishigori 《Photochemistry and photobiology》2013,89(3):649-654
The UVA is currently thought to be carcinogenic because, similar to UVB, it induces the formation of cyclobutane pyrimidine dimers (CPDs). Various drugs have been reported to cause photosensitive drug eruptions as an adverse effect. Although the precise mechanism of photosensitive drug eruption remains to be elucidated, it is generally accepted that free radicals and other reactive molecules generated via UV‐irradiated drugs play important roles in the pathogenesis of photosensitive drug eruptions. The waveband of concern for photo‐reactive drugs is UVA‐visible light, but some extend into the UVB region. We tested whether photosensitive drugs could enhance CPD formation after UVA exposure by using isolated DNA in the presence of several reported photosensitive drugs using high‐performance liquid chromatography. We found that the diuretic agent hydrochlorothiazide (HCT) significantly enhanced the production of TT dimers over a wide range of UVA. Furthermore, we investigated whether UVA plus HCT could enhance CPD production in xeroderma pigmentosum model mice defective in nucleotide excision repair. Immunofluorescence studies showed that CPD formation in the skin significantly increased after 365 nm narrow‐band UVA irradiation in the presence of HCT, compared with that in wild‐type mice. HCT could be used with caution because of its enhancement of UVA‐induced DNA damage. 相似文献
62.
Yuta Suzuki Tetsuhiro NemotoShun-ichi Nakano Zengduo ZhaoYuta Yoshimatsu Yasumasa Hamada 《Tetrahedron letters》2014
A novel method for synthesizing 4,5-fused tricyclic quinoline derivatives based on an acid-promoted intramolecular Friedel–Crafts allenylation of anilines. Using aryl group-substituted propargyl alcohol derivatives with a meta-substituted N-Boc aniline unit as substrates, a four-step reaction sequence involving an acid-promoted intramolecular Friedel–Crafts allenylation of anilines, an acid-promoted intramolecular C–N bond formation, deprotection of the Boc group, and air oxidation proceeded in a single pot, producing the corresponding 4,5-fused tricyclic quinoline derivatives in 31–84% yield. 相似文献
63.
Katsuya Sako Toshiaki Kakehi Shota Nakano Hiroyuki Oku Xu Feng Shen Tetsuo Iwanaga Manami Yoshikawa Kouta Sugahara Shinji Toyota Hiroyuki Takemura Teruo Shinmyozu Michito Shiotsuka Hitoshi Tatemitsu 《Tetrahedron letters》2014
Two novel redox-active 1,3-dithiole (DT) ring-fused 4,5-diazafluorene ligands with crown ether moieties (L1 and L2) were synthesized and characterized. The crystal structure of L1 was studied. The electrochemical and spectroscopic properties of these new ligands, as well as the corresponding bis(bipyridine)ruthenium(II) complexes [4: Ru L1(bpy)2 and 5: Ru L2(bpy)2], were also been investigated. 相似文献
64.
On the induced‐fit mechanism of substrate‐enzyme binding structures of nylon‐oligomer hydrolase
下载免费PDF全文
![点击此处可从《Journal of computational chemistry》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Takeshi Baba Ryuhei Harada Masayoshi Nakano Yasuteru Shigeta 《Journal of computational chemistry》2014,35(16):1240-1247
We present a detailed computational investigation of the induced‐fit motion in a nylon‐oligomer hydrolase (NylB) upon substrate binding. To this aim, we resort on the recently introduced parallel cascade selection molecular dynamics approach, allowing for an accelerated access to the set of conformational changes from an open‐ to a closed‐state structure to form the enzyme‐substrate complex in a specific induce‐fit mechanism. The structural investigation is quantitatively complemented by free energy analyses within the umbrella sampling algorithm accompanied by weighted histogram analysis. We find that the stabilization free energy is about 1.4 kcal/mol, whereas the highest free energy barrier to be overcome is about 2.3 kcal/mol. Conversely, the energetic contribution for the substrate binding is about 20 kcal/mol, as estimated from Generalized Born/Surface Area. This means that the open‐close induced‐fit motion could occur frequently once the substrate binds to the open state of NylB. © 2014 Wiley Periodicals, Inc. 相似文献
65.
66.
Dr. Neil J. Stewart Hitomi Nakano Shuto Sugai Mitsushi Tomohiro Yuki Kase Yoshiki Uchio Dr. Toru Yamaguchi Yujirou Matsuo Dr. Tatsuya Naganuma Dr. Norihiko Takeda Dr. Ikuya Nishimura Dr. Hiroshi Hirata Dr. Takuya Hashimoto Dr. Shingo Matsumoto 《Chemphyschem》2021,22(10):915-923
Hyperpolarized [1-13C]fumarate is a promising magnetic resonance imaging (MRI) biomarker for cellular necrosis, which plays an important role in various disease and cancerous pathological processes. To demonstrate the feasibility of MRI of [1-13C]fumarate metabolism using parahydrogen-induced polarization (PHIP), a low-cost alternative to dissolution dynamic nuclear polarization (dDNP), a cost-effective and high-yield synthetic pathway of hydrogenation precursor [1-13C]acetylenedicarboxylate (ADC) was developed. The trans-selectivity of the hydrogenation reaction of ADC using a ruthenium-based catalyst was elucidated employing density functional theory (DFT) simulations. A simple PHIP set-up was used to generate hyperpolarized [1-13C]fumarate at sufficient 13C polarization for ex vivo detection of hyperpolarized 13C malate metabolized from fumarate in murine liver tissue homogenates, and in vivo 13C MR spectroscopy and imaging in a murine model of acetaminophen-induced hepatitis. 相似文献
67.
We study the temperature evolution of aluminum nanoparticles generated by femtosecond laser ablation with spatiotemporally resolved x-ray-absorption fine-structure spectroscopy. We successfully identify the nanoparticles based on the L-edge absorption fine structure of the ablation plume in combination with the dependence of the edge structure on the irradiation intensity and the expansion velocity of the plume. In particular, we show that the lattice temperature of the nanoparticles is estimated from the L-edge slope, and that its spatial dependence reflects the cooling of the nanoparticles during plume expansion. The results reveal that the emitted nanoparticles travel in a vacuum as a condensed liquid phase with a lattice temperature of about 2500 to 4200 K in the early stage of plume expansion. 相似文献
68.
Kakuyanagi K Meno T Saito S Nakano H Semba K Takayanagi H Deppe F Shnirman A 《Physical review letters》2007,98(4):047004
In order to gain a better understanding of the origin of decoherence in superconducting flux qubits, we have measured the magnetic field dependence of the characteristic energy relaxation time (T(1)) and echo phase relaxation time (T(2)(echo)) near the optimal operating point of a flux qubit. We have measured T(2)(echo) by means of the phase cycling method. At the optimal point, we found the relation T(2)(echo) approximately 2T(1). This means that the echo decay time is limited by the energy relaxation (T(1) process). Moving away from the optimal point, we observe a linear increase of the phase relaxation rate (1/T(2)(echo)) with the applied external magnetic flux. This behavior can be well explained by the influence of magnetic flux noise with a 1/f spectrum on the qubit. 相似文献
69.
70.
Tailoring D‐Amino Acid Oxidase from the Pig Kidney to R‐Stereoselective Amine Oxidase and its Use in the Deracemization of α‐Methylbenzylamine
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Kazuyuki Yasukawa Dr. Shogo Nakano Prof. Dr. Yasuhisa Asano 《Angewandte Chemie (International ed. in English)》2014,53(17):4428-4431
The deracemization of racemic amines to yield enantioenriched amines using S‐stereoselective amine oxidases (AOx) has recently been attracting attention. However, R‐stereoselective AOx that are suitable for deracemization have not yet been identified. An R‐stereoselective AOx was now evolved from porcine kidney D ‐amino acid oxidase (pkDAO) and subsequently use for the deracemization of racemic amines. The engineered pkDAO, which was obtained by directed evolution, displayed a markedly changed substrate specificity towards R amines. The mutant enzyme exhibited a high preference towards the substrate α‐methylbenzylamine and was used to synthesize the S amine through deracemization. The findings of this study indicate that further investigations on the structure–activity relationship of AOx are warranted and also provide a new method for biotransformations in organic synthesis. 相似文献