全文获取类型
收费全文 | 1991篇 |
免费 | 189篇 |
国内免费 | 149篇 |
专业分类
化学 | 1620篇 |
晶体学 | 19篇 |
力学 | 71篇 |
综合类 | 12篇 |
数学 | 155篇 |
物理学 | 452篇 |
出版年
2023年 | 15篇 |
2022年 | 34篇 |
2021年 | 42篇 |
2020年 | 48篇 |
2019年 | 59篇 |
2018年 | 61篇 |
2017年 | 44篇 |
2016年 | 67篇 |
2015年 | 81篇 |
2014年 | 86篇 |
2013年 | 142篇 |
2012年 | 139篇 |
2011年 | 172篇 |
2010年 | 85篇 |
2009年 | 107篇 |
2008年 | 110篇 |
2007年 | 92篇 |
2006年 | 104篇 |
2005年 | 92篇 |
2004年 | 79篇 |
2003年 | 74篇 |
2002年 | 113篇 |
2001年 | 80篇 |
2000年 | 53篇 |
1999年 | 52篇 |
1998年 | 26篇 |
1997年 | 19篇 |
1996年 | 17篇 |
1995年 | 14篇 |
1994年 | 23篇 |
1993年 | 14篇 |
1992年 | 13篇 |
1991年 | 17篇 |
1990年 | 11篇 |
1989年 | 6篇 |
1988年 | 5篇 |
1987年 | 14篇 |
1986年 | 8篇 |
1985年 | 12篇 |
1984年 | 14篇 |
1983年 | 5篇 |
1982年 | 8篇 |
1980年 | 8篇 |
1979年 | 9篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1976年 | 6篇 |
1975年 | 7篇 |
1974年 | 4篇 |
1967年 | 7篇 |
排序方式: 共有2329条查询结果,搜索用时 15 毫秒
101.
Tetsuyuki Taniai Sachiko Wakasugi Susumu Hashimoto Ai Shimada Tatsuya Urabe Kazuya Takahashi 《International journal of environmental analytical chemistry》2013,93(5):601-612
To obtain information on the environmental impact of materials eluted from volcanic ashes of Mt. Oyama, Miyake Island, which erupted in July 2000, the dissolution behaviours of heavy metals and rare-earth elements from the volcanic ashes were examined. The most important characteristic of the Mt. Oyama eruption is that sulphur dioxide (SO2) gas has been continuously released, and all persons living on Miyake Island have been required to evacuate. To estimate in terms of the volcanic eruption using SO2 gas, the ash nature in Mt. Usu, Hokkaido, was also examined and compared with that in Mt. Oyama. When rain water mixed the ashes, the water from the ashes of Mt. Oyama became acidic because of the sulphuric acid. Therefore, SO2 gas in Mt. Oyama can accelerate the dissolution of protons and heavy metals in the ashes, whereas the rain water in Mt. Usu was not acidic and the dissolution of the heavy metals was not so evident compared with that in the case of Mt. Oyama. With this sulphuric acid, heavy metals such as As, Cd, Pb and Hg in the ashes in Mt. Oyama easily dissolved owing to the low pH. The ashes in Mt. Oyama had been released for eight years and the amount of fallen ashes was estimated to be 33 billion tons. The weights of the harmful heavy metals in the volcanic ashes, such as As, Cd, Pb and Hg, were estimated to be 3.8?×?102, 1.3?×?103, 1.1?×?103 and 29?kg, respectively, and these heavy metals were dissolved and diluted in seawater. Therefore, the concentration and species (chemical form) of these metals should be carefully monitored in the future. Moreover, SO2 gas, which has a direct effect on human health and has been monitored continuously, causes other effects, such as facilitation of metal ion elution and rock aeration. 相似文献
102.
Nicolas Zigon Manabu Hoshino Shota Yoshioka Yasuhide Inokuma Makoto Fujita 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(31):9161-9165
Crystal structures of α‐humulene, a cyclic sesquiterpene, and its oxidized subproducts, were analyzed by the crystalline sponge method. Regio‐ and stereochemistry, including absolute configuration when a chiral oxidant was applied, and the stable conformations of all the scaffold‐related compounds were successfully determined for samples on a 5–50 μg scale. 相似文献
103.
Yoshihiro Kon Toshiyuki Yokoi Masato Yoshioka Shinji Tanaka Yumiko Uesaka Takehisa Mochizuki Kazuhiko Sato Takashi Tatsumi 《Tetrahedron》2014
Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions. 相似文献
104.
The photoactivity of CdS nanorods was greatly improved by amino functionalized accordion-like MXene and spherical ZnSnO3. MXene possesses good electron transfer capability and ZnSnO3 presents matched energy band with CdS, which deeply accelerate the electron transfer and prevent the recombination of photogenerated electron-hole pair, leading to a strong photoelectrochemical (PEC) response. Taking the merit of the improved photoactivity of CdS nanorods, a novel PEC biosensor was constructed for DNA hydromethylation detection based on immune recognition of target molecule, where 5-hydroxymethyl-2′-deoxycytidine triphosphate (5hmdCTP) was employed as detect target, CdS/MXene was used as photoactive material, and ZnSnO3 was adopted as signal amplification unit. Under enzymatic covalent reaction of –CH2OH of 5hmdCTP with –NH2 of MXene, 5hmdCTP was specifically recognized and captured. Then, taking advantages of the covalent reaction between phosphate group of 5hmdCTP and ZnSnO3, the signal amplification unit was captured. Under the optimum conditions, this PEC biosensor presents wide linear range of 0.008–100 nM and low detection limit of 4.21 pM (3σ). The applicability of the developed method was evaluated by investigating the effect of Cd2+ and perfluorohexane compound pollutant on 5-hydroxymethylcytosine content in the genomic DNA of the roots and leaves of wheat seedlings. 相似文献
105.
Nanomaterials with localized surface plasmon resonance (LSPR) locating in the near-infrared region have broad application prospects in the field of biomedicine. However, the biggest problem that limits the biomedical application of such nanomaterials lies in two aspects: First, the potential long-term in vivo toxicity caused by the metabolism of many nanomaterials with LSPR effect; Second, most of current nanomaterials with LSPR effect are difficult to achieve LSPR wavelength tunability in the near-infrared region to adapt to different biomedical applications. Copper selenide nanomaterials are composed of selenium and copper, which are necessary nutrient elements for human life. Because of the active and flexible chemical properties of selenium and copper, copper selenide nanomaterials can not only be effectively degraded and utilized in human body, but also be endowed with various physicochemical properties by chemical modification or doping. Recently, copper selenide nanomaterials have shown unique properties such as LSPR in the near-infrared region, making them attractive for near-infrared thermal ablation, photoacoustic imaging, disease marker detection, multimode imaging, and so on. Currently, to the best of our knowledge, there is no review on the LSPR properties of copper selenide nanomaterials and its biomedical applications. This review first discusses the relationship between the physicochemical properties and the LSPR of copper selenide nanomaterials and then summarizes the latest progress in the application of copper selenide nanomaterials in biological detection, diagnosis, and treatment of diseases. In addition, the advantages, and prospects of copper selenide nanomaterials in biomedicine are also highlighted. 相似文献
106.
Dr. Yuki Kishimoto Dr. Osamu Nakagawa Akane Fujii Dr. Kotaro Yoshioka Dr. Tetsuya Nagata Prof. Dr. Takanori Yokota Prof. Dr. Yoshiyuki Hari Prof. Dr. Satoshi Obika 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2427-2438
Artificial nucleic acids are widely used in various technologies, such as nucleic acid therapeutics and DNA nanotechnologies requiring excellent duplex-forming abilities and enhanced nuclease resistance. 2′-O,4′-C-Methylene-bridged nucleic acid/locked nucleic acid (2′,4′-BNA/LNA) with 1,3-diaza-2-oxophenoxazine (BNAP ( BH )) was previously reported. Herein, a novel BH analogue, 2′,4′-BNA/LNA with 9-(2-aminoethoxy)-1,3-diaza-2-oxophenoxazine (G-clamp), named BNAP-AEO ( BAEO ), was designed. The BAEO nucleoside was successfully synthesized and incorporated into oligodeoxynucleotides (ODNs). ODNs containing BAEO possessed up to 104-, 152-, and 11-fold higher binding affinities for complementary (c) RNA than those of ODNs containing 2′-deoxycytidine ( C ), 2′,4′-BNA/LNA with 5-methylcytosine ( L ), or 2′-deoxyribonucleoside with G-clamp ( PAEO ), respectively. Moreover, duplexes formed by ODN bearing BAEO with cDNA and cRNA were thermally stable, even under molecular crowding conditions induced by the addition of polyethylene glycol. Furthermore, ODN bearing BAEO was more resistant to 3′-exonuclease than ODNs with phosphorothioate linkages. 相似文献
107.
108.
Sarah E. Walker Dr. James A. Jordan‐Hore Dr. David G. Johnson Prof. Dr. Stuart A. Macgregor Dr. Ai‐Lan Lee 《Angewandte Chemie (International ed. in English)》2014,53(50):13876-13879
A direct Pd‐catalyzed C? H functionalization of benzoquinone (BQ) can be controlled to give either mono‐ or disubstituted BQ, including the installation of two different groups in a one‐pot procedure. BQ can now be directly functionalized with aryl, heteroaryl, cycloalkyl, and cycloalkene groups and, moreover, the reaction is conducted in environmentally benign water or acetone as solvents. 相似文献
109.
New 6-(pyrazol-1-yl)pyrazolo[3,4-b]pyridin-3-ol compounds were synthesized by cyclization reaction from 2,6-dichloro-4-methylnicotinonitrile. Their derivatives exist as the 3-hydroxy tautomer. The structure of the compound 1a of one of the resulting compounds was studied in detail by X-ray diffraction. 相似文献
110.
Ming‐Shui Yao Jia‐Jia Zheng Ai‐Qian Wu Gang Xu Sanjog S. Nagarkar Gen Zhang Masahiko Tsujimoto Shigeyoshi Sakaki Satoshi Horike Kenichi Otake Susumu Kitagawa 《Angewandte Chemie (International ed. in English)》2020,59(1):172-176
Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu3(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10?5 S cm?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m2 g?1) of the Cu3(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor. 相似文献