全文获取类型
收费全文 | 433篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 297篇 |
晶体学 | 5篇 |
力学 | 7篇 |
数学 | 10篇 |
物理学 | 130篇 |
出版年
2023年 | 2篇 |
2022年 | 5篇 |
2021年 | 6篇 |
2020年 | 4篇 |
2019年 | 5篇 |
2018年 | 5篇 |
2016年 | 3篇 |
2015年 | 12篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 33篇 |
2011年 | 26篇 |
2010年 | 18篇 |
2009年 | 19篇 |
2008年 | 38篇 |
2007年 | 31篇 |
2006年 | 24篇 |
2005年 | 26篇 |
2004年 | 18篇 |
2003年 | 20篇 |
2002年 | 15篇 |
2001年 | 8篇 |
2000年 | 8篇 |
1999年 | 8篇 |
1998年 | 3篇 |
1996年 | 2篇 |
1995年 | 4篇 |
1994年 | 3篇 |
1993年 | 4篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 2篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1987年 | 3篇 |
1986年 | 6篇 |
1985年 | 10篇 |
1984年 | 4篇 |
1983年 | 7篇 |
1982年 | 5篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1975年 | 2篇 |
1968年 | 1篇 |
1942年 | 1篇 |
1932年 | 1篇 |
1930年 | 2篇 |
1928年 | 1篇 |
排序方式: 共有449条查询结果,搜索用时 46 毫秒
71.
Murai K Nakamura A Matsushita T Shimura M Fujioka H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(27):8448-8453
A method for conducting enantioselective bromolactonization reactions of trisubstituted alkenoic acids, using the C(3)-symmetric trisimidazoline 1 and 1,3-dibromo-5,5-dimethyl hydantoin as a bromine source, has been developed. The process generates chiral δ-lactones that contain a quaternary carbon. The results of studies probing geometrically different olefins show that (Z)-olefins rather than (E)-olefins are favorable substrates for the process. The method is not only applicable to acyclic olefin reactants but can also be employed to transform cyclic trisubstituted olefins into chiral spirocyclic lactones. Finally, the synthetic utility of the newly developed process is demonstrated by its application to a concise synthesis of tanikolide, an antifungal marine natural product. 相似文献
72.
Kumai R Horiuchi S Fujioka J Tokura Y 《Journal of the American Chemical Society》2012,134(2):1036-1046
Supramolecular ferroelectric cocrystals of phenazine (Phz) with chloranilic acid (H(2)ca), bromanilic acid (H(2)ba), and fluoranilic acid (H(2)fa) have been characterized by the interplay between their structural transformations and solid-state acid-base (proton transfer) reactions. At ambient pressure, the Phz-H(2)ca, Phz-H(2)ba, and their deuterated crystals exhibit incomplete proton displacement, which transforms the neutral molecules into semi-ionic at low temperatures below the Curie point (T(c)(IC) < T < T(c)(I)). For the cocrystal of the less acidic H(2)fa, the ferroelectric phase is induced only by applying hydrostatic pressure above ~0.6 GPa. According to the combined studies of temperature-dependent dielectric permittivity and synchrotron X-ray diffraction, it was proved that the ferroelectric (FE-I) phase is always accompanied at lower temperatures by successive phase transitions to the lattice modulated phases with incommensurate periodicities (IC phase, T(c)(II) < T < T(c)(IC)) and with commensurate (2- or 3-fold) periodicities (FE-II or FE-III phase, T < T(c)(II)). Whereas the ground-state structures at ambient pressure are different from one another among the Phz-H(2)ca (FE-II form), Phz-H(2)ba (FE-III form), and Phz-H(2)fa (paraelectric form), their systematic changes under pressure depict a universal pressure-temperature phase diagram. The possible origins of structural changes are assigned to the valence instability and the frustrated Coulomb interactions that induce the charge disproportionation (coexisting neutral ionic) states with the staging spatial orders. 相似文献
73.
Covering: up to 2011. This review focuses on the recent revealing of the immunostimulatory bacterial cell wall peptidoglycan (PGN) fragments as Nod1 ligands, especially a newly developed chemical synthesis of the partial structures, fragment structures in the environment and bacterial supernatant, and the immunostimulatory activities of the Nod1 ligands. 相似文献
74.
Uchida T Sekine Y Matsui T Ikeda-Saito M Ishimori K 《Chemical communications (Cambridge, England)》2012,48(53):6741-6743
HutZ, one of the crucial proteins of the iron uptake system in Vibrio cholerae, was purified, which binds to heme at a stoichiometry of 1 : 1. In the presence of ascorbic acid, the HutZ-bound heme degrades via the same intermediates observed in heme oxygenase, suggesting that HutZ works as a heme degradation enzyme. 相似文献
75.
A novel method for the synthesis of 4-phenylquinazolinones via a palladium-catalyzed domino reaction of o-aminobenzamides with benzyl alcohols is developed. This protocol involves N-benzylation, benzylic C-H amidation, and dehydrogenation in water, which may play an important role in the smooth generation of the (η(3)-benzyl)palladium species by activation of the hydroxyl group of the benzyl alcohol. 相似文献
76.
Eiichi Masumoto Hiroshi Maruoka Fumi Okabe Sho Nishida Ryoko Tomita Toshihiro Fujioka Kenji Yamagata 《Journal of heterocyclic chemistry》2012,49(4):893-899
A novel synthetic route to 4‐pyridazineacetic acids 10 – 12 has been achieved by the ring‐expansion reaction of N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 – 9 . 1H‐Pyrazole‐4‐acetic acids 1 – 3 were reacted with iodoacetonitrile in the presence of triethylamine in refluxing acetonitrile to give the corresponding C‐cyanomethylated 1H‐pyrazole‐4‐acetic acids 4 – 6 as major products together with N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 8 as minor products. On the other hand, reactions of 1 and 3 with chloroacetonitrile in the presence of triethylamine in refluxing chloroform afforded the corresponding N‐cyanomethylated 3‐pyrazoline‐4‐acetic acids 7 and 9 as major products. Thermal treatment of 7 – 9 with sodium hydride in N,N‐dimethylformamide caused ring expansion to yield the corresponding 4‐pyridazineacetic acids 10 – 12 . 相似文献
77.
Dr. Tokuhisa Kawawaki Yukari Imai Daiki Suzuki Shun Kato Ibuki Kobayashi Taiyo Suzuki Ryo Kaneko Dr. Sakiat Hossain Prof. Yuichi Negishi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16150-16193
Metal nanoclusters (NCs) have a particle size of about one nanometer, which makes them the smallest unit that can give a function to a substance. In addition, metal NCs possess physical and chemical properties that are different from those of the corresponding bulk metals. Metal NCs with such characteristics are expected to be important for use in nanotechnology. Research on the precise synthesis of metal NCs and elucidation of their physical/chemical properties and functions is being actively conducted. When metal NCs are alloyed, it is possible to obtain further various electronic and geometrical structures and functions. Thus, research on alloy NCs has become a hot topic in the study of metal NCs and the number of publications on alloy NCs has increased explosively in recent years. Such publications have provided much insight into the effects of alloying on the electronic structure and function of metal NCs. However, the rapid increase in knowledge has made it difficult for researchers (especially those new to the field) to grasp all of it. Therefore, in this review, we summarize the reported chemical composition, geometrical structure, electronic structure, and physical and chemical properties of Aun−xMx(SR)m, Agn−xMx(SR)m, Aun−xMx(PR3)l(SR)m, and Agn−xMx(PR3)l(SR)m (Au=gold, Ag=silver, M=heteroatom, PR3=phosphine, and SR=thiolate) NCs. This review is expected to help researchers understand the characteristics of alloy NCs and lead to clear design guidelines to develop new alloy NCs with intended functions. 相似文献
78.
Prof. Takahisa Omata Aman Sharma Prof. Issei Suzuki Tomohiro Ishiyama Shinji Kohara Koji Ohara Prof. Madoka Ono Prof. Yang Ren Khurelbaatar Zagarzusem Prof. Masaya Fujioka Prof. Gaoyang Zhao Prof. Junji Nishii 《Chemphyschem》2022,23(3):e202100840
Anhydrous silicophosphoric acid glass with an approximate composition of H5Si2P9O29 was synthesized and its thermal and proton-conducting properties were characterized. Despite exhibiting a glass transition at 192 °C, the supercooled liquid could be handled as a solid up to 280 °C owing to its high viscosity. The glass and its melt exhibited proton conduction with a proton transport number of ∼1. Although covalent O−H bonds were weakened by relatively strong hydrogen bonding, the proton conductivity (4×10−4 S cm−1 at 276 °C) was considerably lower than that of phosphoric acid. The high viscosity of the melt was due to the tight cross-linking of phosphate ion chains by six-fold-coordinated Si atoms. The low proton conductivity was attributed to the trapping of positively charged proton carriers around anionic SiO6 units (expressed as (SiO6/2)2−) to compensate for the negative charges. 相似文献
79.
Naoto HayashiHiroki Nakashima Yukari TakayamaHiroyuki Higuchi 《Tetrahedron letters》2003,44(29):5423-5426
Octaethylporphyrin (OEP) was combined with 2-substituted 3-hexylthiophenes (HTh) by diacetylene linkage to afford the highly extended conjugation system (HTh-OEP). Their absorption spectral properties were examined, proving that the electronic structure of OEP is affected by the more electron-withdrawing substituents through the diacetylene linkage more dramatically. The substituent effect on the HTh-OEP conjugation system is much outstanding, as compared with that on the corresponding benzene system (Bzn-OEP). 相似文献
80.
Kenji Mori Takeshi Sugai Yukari Maeda Tomomi Okazaki Tadashi Noguchi Hiroshi Naito 《Tetrahedron》1985,41(22):5307-5311
The racemate and both the (R)- and (S)-forms of gizzerosine [2-amino-9-(4-imidazolyl)-7-azanonanoic acid] were synthesised, and the (S)-isomer was identified as the toxic substance in fish meal causing severe gizzard erosion (black vomit) in chicks. 相似文献