全文获取类型
收费全文 | 1340篇 |
免费 | 61篇 |
国内免费 | 4篇 |
专业分类
化学 | 1112篇 |
晶体学 | 13篇 |
力学 | 10篇 |
数学 | 65篇 |
物理学 | 205篇 |
出版年
2023年 | 9篇 |
2022年 | 8篇 |
2021年 | 16篇 |
2020年 | 24篇 |
2019年 | 33篇 |
2018年 | 21篇 |
2017年 | 15篇 |
2016年 | 34篇 |
2015年 | 36篇 |
2014年 | 40篇 |
2013年 | 56篇 |
2012年 | 93篇 |
2011年 | 112篇 |
2010年 | 66篇 |
2009年 | 51篇 |
2008年 | 59篇 |
2007年 | 93篇 |
2006年 | 92篇 |
2005年 | 79篇 |
2004年 | 56篇 |
2003年 | 83篇 |
2002年 | 62篇 |
2001年 | 26篇 |
2000年 | 20篇 |
1999年 | 21篇 |
1998年 | 12篇 |
1997年 | 16篇 |
1996年 | 16篇 |
1995年 | 13篇 |
1994年 | 16篇 |
1993年 | 8篇 |
1992年 | 12篇 |
1991年 | 8篇 |
1990年 | 5篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 6篇 |
1986年 | 7篇 |
1985年 | 8篇 |
1984年 | 14篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 6篇 |
1980年 | 6篇 |
1979年 | 3篇 |
1978年 | 10篇 |
1977年 | 4篇 |
1974年 | 2篇 |
1971年 | 2篇 |
1968年 | 2篇 |
排序方式: 共有1405条查询结果,搜索用时 15 毫秒
71.
Syota Shimizu Akihiro Aoki Takuya Takahashi Fumiki Harano 《Photochemistry and photobiology》2020,96(5):1105-1115
Infrared-A (IRA), which can penetrate deeply into the human skin, is a major component of solar radiation and is recognized to promote photoaging of human dermis. To our knowledge, however, the cellular and molecular consequences of human epidermis exposure to IRA have not been clarified. Thus, we investigated whether IRA inhibits the proliferation of normal human epidermal keratinocytes (NHEKs). IRA irradiation ed in cell cycle arrest at G1 and a dose-dependent reduction in the proliferation of NHEKs. We found that mechanistic target of rapamycin complex 1 (mTORC1) was initially inactivated during IRA irradiation due to the formation of stress granules (SGs), and this inactivation was maintained for at least 6 h after irradiation due to Akt dephosphorylation. Furthermore, repeated exposure of human skin equivalents to IRA led to marked thinning of the epidermal cell layer. In conclusion, IRA irradiation inhibits mTORC1 activity possibly through two molecular mechanisms involving SG formation in the early-phase and subsequent Akt dephosphorylation. This sequential mechanism seems to cause G1 cell cycle arrest and a reduction in cell proliferation, supporting the hypothesis that the decreased proliferation of basal keratinocytes that occurs during skin aging might be partly attributable to IRA radiation. 相似文献
72.
We investigated the fluorescent properties, including the excited-state intermolecular proton transfer, of urea derivatives comprising a coumarin ring, which is a widely used fluorophore. We prepared two different coumarin–urea derivatives, 6CU and 7CU, which bear a urea-based substituent at the 6 and 7 positions of a coumarin ring, respectively. In the presence of the acetate ion, 7CU showed additional tautomer fluorescence emission with respect to 6CU, indicating that tautomer formation depends on the positions of the urea-based substituent on the coumarin ring. Thus, the resonance structures of urea derivatives might play an important role in the behavior of dual fluorescence, which is an important phenomenon applicable to photochemical anion sensing. Moreover, in order to further improve the fluorescence properties of the mentioned derivatives, a CF3 group was introduced in a phenyl ring opposite to a coumarin ring. The fluorescence quantum yield of 7CUCF3 thus synthesized was 65 times as large as that of 7CU, an observation that renders 7CUCF3 a suitable anion sensor candidate. The results of this study will contribute to the development of new molecular designs for highly fluorescent sensing. 相似文献
73.
Microbial biosynthesis of hydrocarbon from CO2 reduction driven by electron uptake process from the cathodic electrode has gained intensive attention in terms of potential industrial application. However, a lack of a model system for detailed studies on the mechanism of the CO2 reduction hinders the improvement in efficiency for microbial electrosynthesis. Here, we examined the mechanism of microbial CO2 reduction at the cathode by a well‐described microbe for extracellular electron uptake, Shewanella oneidensis MR‐1, capable of reducing gaseous CO2 to produce formic acid. Using whole‐cell electrochemical assay, we observed stable cathodic current production at ?0.65 V vs Ag/AgCl KCl sat. associated with the introduction of CO2. The observed cathodic current was enhanced by the addition of 4 μM riboflavin, which specifically accelerates the electron uptake process of MR‐1 by the interaction to its outer‐membrane c‐type cytochromes. The significant impact of an uncoupler agent and a mutant strain of MR‐1 lacking sole F‐type ATPase suggested the importance of proton import to the cytoplasm for the cathodic CO2 reduction. The present data suggest that MR‐1 potentially serves as a model system for microbial electrosynthesis from CO2. 相似文献
74.
Akihiro Kitashoji Kosei Kitagawa Dr. Akimasa Fujihara Prof. Dr. Tomoyuki Yatsuhashi 《Chemphyschem》2020,21(9):847-852
A multiply charged molecule expands the range of a mass window and is utilized as a precursor to provide rich sequence coverage; however, reflectron time-of-flight mass spectrometer has not been well applied to the product ion analysis of multiply charged precursor ions. Here, we demonstrate that the range of the mass-to-charge ratio of measurable product ions is limited in the cases of multiply charged precursor ions. We choose C6F6 as a model molecule to investigate the reactions of multiply charged molecular cations formed in intense femtosecond laser fields. Measurements of the time-of-flight spectrum of C6F6 by changing the potential applied to the reflectron, combined with simulation of the ion trajectory, can identify the species detected behind the reflectron as the neutral species and/or ions formed by the collisional charge transfer. Moreover, the metastable ion dissociations of doubly and triply charged C6F6 are identified. The detection of product ions in this manner can diminish interference by the precursor ion. Moreover, it does not need precursor ion separation before product ion analysis. These advantages would expand the capability of mass spectrometry to obtain information about metastable ion dissociation of multiply charged species. 相似文献
75.
Keiko Takahashi Hiroshi Narita Megumi Oh-Hashi Akihiro Yokoyama Tsutomu Yokozawa 《Journal of inclusion phenomena and macrocyclic chemistry》2004,50(1-2):121-127
A complete assignment of proton resonances for N(N-formyl d-phenylalanyl)-deoxyamino--cyclodextrin (1d) was performed by means of 1D and 2D NMR,1H–^1H-COSY, 1H–^13C-COSY, TOCSYand NOESY spectroscopy. Based on 2D-NMR ROESY and circular dichroism spectroscopy, the conformation of 1d was determined; the phenyl group stays inside the distorted cyclodextrin (CyD) cavity forming a self-inclusion complex, which is almost the same as N(N-formyl l-phenylalanyl)-deoxyamino--CyD (1l). The remarkable diastereomeric difference was observed in the chemical shifts of H(5) and H(6) protons at the narrow rim of the CyD cavity and induced circular dichroism spectra. These results suggest the existence of hydrogen bonds between the hydroxyl group on CyD and the amide groups on the arms, which provides the difference in the molecular recognition properties. 相似文献
76.
77.
78.
Hydrothermal formation of tobermorite studied by in situ X‐ray diffraction under autoclave condition
Jun Kikuma Masamichi Tsunashima Tetsuji Ishikawa Shin‐ya Matsuno Akihiro Ogawa Kunio Matsui Masugu Sato 《Journal of synchrotron radiation》2009,16(5):683-686
Hydrothermal formation of tobermorite from a pre‐cured cake has been investigated by transmission X‐ray diffraction (XRD) using high‐energy X‐rays from a synchrotron radiation source in combination with a newly designed autoclave cell. The autoclave cell has a large and thin beryllium window for wide‐angle X‐ray diffraction; nevertheless, it withstands a steam pressure of more than 1.2 MPa, which enables in situ XRD measurements in a temperature range of 373 to 463 K under a saturated steam pressure. Formation and/or decomposition of several components has been successfully observed during 7.5 h of reaction time. From the intensity changes of the intermediate materials, namely non‐crystalline C–S–H and hydroxylellestadite, two pathways for tobermorite formation have been confirmed. Thus, the newly developed autoclave cell can be used for the analyses of reaction mechanisms under specific atmospheres and temperatures. 相似文献
79.
We present the validity of in-line-type differential push-pull methods using segmented gratings with respect to arrangement
errors by numerical calculation for the first time. In these differential push-pull methods, the segmented gratings for generating
subspots are divided into more than two regions, each with a specific width and a specific phase value, and are ideally arranged
on the optical axis. We calculate tracking error signals in these methods with respect to the arrangement errors against the
optical axis under parameter conditions of the widths of the segmented regions of the gratings. The obtained results show
that the grating with a simpler configuration with two regions reveals good compatibility between DVD-recordable (DVD-R) and
DVD-random access memory (DVD-RAM) compared with those with three or four regions, when the arrangement error is less than
10% of the radius of the incident laser beam. 相似文献
80.
9,10‐Diaminoanthracenes Revisited: The Influence of N‐Substituents on Their Electronic States
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Masashi Uebe Prof. Dr. Tatsuhisa Kato Prof. Dr. Kazuyoshi Tanaka Dr. Akihiro Ito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(52):18923-18931
The electronic and molecular structures of 9,10‐diamino‐substituted anthracenes with different N‐substituents have been re‐examined. In particular, different N‐substituents influence both the electronic and molecular structures of the oxidized species of 9,10‐diaminoanthracenes. The anthrylene moiety of 9,10‐bis(N,N‐di(p‐anisyl)amino)anthracene retains its planarity during the course of two successive one‐electron oxidations, whereas 9,10‐bis(N,N‐dimethylamino)anthracene and 9,10‐bis(N‐p‐anisyl‐N‐methylamino)anthracene undergo a substantial structural change to a butterfly‐like structure through a two‐electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above‐mentioned three kinds of 9,10‐diaminoanthracenes due to different extents of mixing between the amine‐localized and anthrylene‐localized orbitals. 相似文献