全文获取类型
收费全文 | 973篇 |
免费 | 31篇 |
国内免费 | 6篇 |
专业分类
化学 | 749篇 |
晶体学 | 6篇 |
力学 | 5篇 |
数学 | 64篇 |
物理学 | 186篇 |
出版年
2023年 | 3篇 |
2022年 | 6篇 |
2021年 | 6篇 |
2020年 | 9篇 |
2019年 | 10篇 |
2018年 | 8篇 |
2017年 | 5篇 |
2016年 | 15篇 |
2015年 | 16篇 |
2014年 | 32篇 |
2013年 | 55篇 |
2012年 | 60篇 |
2011年 | 72篇 |
2010年 | 39篇 |
2009年 | 47篇 |
2008年 | 60篇 |
2007年 | 63篇 |
2006年 | 57篇 |
2005年 | 50篇 |
2004年 | 41篇 |
2003年 | 30篇 |
2002年 | 41篇 |
2001年 | 18篇 |
2000年 | 18篇 |
1999年 | 17篇 |
1998年 | 12篇 |
1997年 | 14篇 |
1996年 | 8篇 |
1995年 | 3篇 |
1994年 | 10篇 |
1993年 | 12篇 |
1992年 | 18篇 |
1991年 | 17篇 |
1990年 | 12篇 |
1989年 | 10篇 |
1988年 | 11篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 14篇 |
1984年 | 10篇 |
1983年 | 7篇 |
1982年 | 6篇 |
1979年 | 6篇 |
1977年 | 5篇 |
1976年 | 4篇 |
1975年 | 6篇 |
1974年 | 5篇 |
1972年 | 5篇 |
1970年 | 3篇 |
1967年 | 4篇 |
排序方式: 共有1010条查询结果,搜索用时 15 毫秒
41.
Yanting Song Katsuya Takatsuki Muneki Isokawa Tetsushi Sekiguchi Jun Mizuno Takashi Funatsu Shuichi Shoji Makoto Tsunoda 《Analytical and bioanalytical chemistry》2013,405(25):7993-7999
In this study, a fast and quantitative determination method for branched-chain amino acids (BCAAs), namely leucine, isoleucine, and valine, was developed using a pillar array column. A pillar array column with low-dispersion turns was fabricated on a 20?×?20-mm2 microchip using multistep ultraviolet photolithography and deep reactive ion etching. The BCAAs were fluorescently labeled with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), followed by reversed-phase separation on the pillar array column. The NBD derivatives of the three BCAAs and an internal standard (6-aminocaproic acid) were separated in 100 s. The calibration curves for the NBD-BCAAs had good linearity in the range of 0.4–20 μM, using an internal standard. The intra- and interday precisions were found to be in the ranges of 1.42–3.80 and 2.74–6.97 %, respectively. The accuracies for the NBD-BCAA were from 90.2 to 99.1 %. The method was used for the analysis of sports drink and human plasma samples. The concentrations of BCAAs determined by the developed method showed good agreements with those determined using a conventional high-performance liquid chromatography system. As BCAAs are important biomarkers of some diseases, these results showed that the developed method could be a potential diagnostic tool in clinical research. 相似文献
42.
Unsymmetrical oxamides are conveniently synthesized in good yields by a new trapping reaction of unstable carbamoyl lithiums with isocyanates. 相似文献
43.
Sulfonylurea derivatives including useful antidiabetics (Tolbutamide, Chlorpropamide) were synthesized in good yields from benzene-sulfonamides with thiocarbamates in the presence of DBU. Thiocarbamates were prepared by the selenium-assisted carbonylation of primary amines with carbon monoxide, sulfur, and methyl iodide under mild conditions. 相似文献
44.
Yutaka Kubota Yuri Kaneda Kazuhiro Haraguchi Mirei Mizuno Hiroshi Abe Satoshi Shuto Takayuki Hamasaki Masanori Baba Hiromichi Tanaka 《Tetrahedron》2013
The key glycosyl donor for the target molecule 12 was prepared by two-step sequences; (1) acetalization of tert-butyldimethylsilyloxyacetaldehyde with 3-bromopropanediol, (2) DBN-initiated β-elimination of the resulting 2-(tert-butyldimethylsilyloxy)methyl-4-bromomethyl-1,3-dioxolane 11. Electrophilic glycosidation between 12 and silylated pyrimidine nucleobase proceeded efficiently to provide a mixture of β- and α-anomers of the respective glycosides 14 and 15. Tin radical-mediated reduction of the bromomethyl functional group of 14 and 15 gave protected 4′-C-methyl-dioxorane uracil- 16 and thymine nucleoside 17. The respective cytosine nucleoside 18 was synthesized from 16. De-silylation of 4′-methyl-1′,3′-dioxolane pyrimidine nucleosides 16–18 gave the target molecules. Evaluation of the anti-HIV-1 activity of the β- and α-anomers of the novel 4′-C-methyl-1′,3′-dioxolane nucleosides 22β,α–24β,α revealed that none of the nucleoside derivatives possess anti-viral activity against HIV-1 and show cytotoxicity against MT-4 cells at 100 μM. 相似文献
45.
The synthesis of glycosyl bromides from 1-O-acetyl sugars using a photo-irradiative phase-vanishing method involving molecular bromine was achieved. A bottom phase of molecular bromine was overlaid first with perfluorohexanes (FC-72), followed by overlaying with ethyl acetate containing a 1-O-acetyl sugar. Upon irradiation, the bromine layer gradually disappeared, leaving two phases. Glycosyl bromide was obtained in good yield from the ethyl acetate phase. 相似文献
46.
Rinta Sato Dr. Kosuke Suzuki Midori Sugawa Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(39):12982-12990
Polyoxometalates (POMs) with heterodinuclear lanthanoid cores, TBA8H4[{Ln(μ2‐OH)2Ln′}(γ‐SiW10O36)2] ( LnLn′ ; Ln=Gd, Dy; Ln′=Eu, Yb, Lu; TBA=tetra‐n‐butylammonium), were successfully synthesized through the stepwise incorporation of two types of lanthanoid cations into the vacant sites of lacunary [γ‐SiW10O36]8? units without the use of templating cations. The incorporation of a Ln3+ ion into the vacant site between two [γ‐SiW10O36]8? units afforded mononuclear Ln3+‐containing sandwich‐type POMs with vacant sites ( Ln1 ; TBA8H5[{Ln(H2O)4}(γ‐SiW10O36)2]; Ln=Dy, Gd, La). The vacant sites in Ln1 were surrounded by coordinating W? O and Ln? O oxygen atoms. On the addition of one equivalent of [Ln′(acac)3] to solutions of Dy1 or Gd1 in 1,2‐dichloroethane (DCE), heterodinuclear lanthanoid cores with bis(μ2‐OH) bridging ligands, [Dy(μ2‐OH)2Ln′]4+, were selectively synthesized ( LnLn′ ; Ln=Dy, Gd; Ln′=Eu, Yb, Lu). On the other hand, La1 , which contained the largest lanthanoid cation, could not accommodate a second Ln′3+ ion. DyLn′ showed single‐molecule magnet behavior and their energy barriers for magnetization reversal (ΔE/kB) could be manipulated by adjusting the coordination geometry and anisotropy of the Dy3+ ion by tuning the adjacent Ln′3+ ion in the heterodinuclear [Dy(μ2‐OH)2Ln′]4+ cores. The energy barriers increased in the order: DyLu (ΔE/kB=48 K)< DyYb (53 K)< DyDy (66 K)< DyEu (73 K), with an increase in the ionic radii of Ln′3+; DyEu showed the highest energy barrier. 相似文献
47.
Synthesis of α‐Dawson‐Type Silicotungstate [α‐Si2W18O62]8− and Protonation and Deprotonation Inside the Aperture through Intramolecular Hydrogen Bonds 下载免费PDF全文
Takuo Minato Dr. Kosuke Suzuki Dr. Keigo Kamata Prof. Dr. Noritaka Mizuno 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(20):5946-5952
The design of structurally well‐defined anionic molecular metal–oxygen clusters, polyoxometalates (POMs), leads to inorganic receptors with unique and tunable properties. Herein, an α‐Dawson‐type silicotungstate, TBA8[α‐Si2W18O62] ? 3 H2O ( II ) that possesses a ?8 charge was successfully synthesized by dimerization of a trivacant lacunary α‐Keggin‐type silicotungstate TBA4H6[α‐SiW9O34] ? 2 H2O ( I ) in an organic solvent. POM II could be reversibly protonated (in the presence of acid) and deprotonated (in the presence of base) inside the aperture by means of intramolecular hydrogen bonds with retention of the POM structure. In contrast, the aperture of phosphorus‐centered POM TBA6[α‐P2W18O62]?H2O ( III ) was not protonated inside the aperture. The density functional theory (DFT) calculations revealed that the basicities and charges of internal μ3‐oxygen atoms were increased by changing the central heteroatoms from P5+ to Si4+, thereby supporting the protonation of II . Additionally, II showed much higher catalytic performance for the Knoevenagel condensation of ethyl cyanoacetate with benzaldehyde than I and III . 相似文献
48.
Mapping Platinum Species in Polymer Electrolyte Fuel Cells by Spatially Resolved XAFS Techniques 下载免费PDF全文
Dr. Shinobu Takao Dr. Oki Sekizawa Dr. Shin‐ichi Nagamatsu Dr. Takuma Kaneko Dr. Takashi Yamamoto Dr. Gabor Samjeské Dr. Kotaro Higashi Dr. Kensaku Nagasawa Dr. Takuya Tsuji Dr. Motohiro Suzuki Dr. Naomi Kawamura Dr. Masaichiro Mizumaki Prof. Dr. Tomoya Uruga Prof. Dr. Yasuhiro Iwasawa 《Angewandte Chemie (International ed. in English)》2014,53(51):14110-14114
There is limited information on the mechanism for platinum oxidation and dissolution in Pt/C cathode catalyst layers of polymer electrolyte fuel cells (PEFCs) under the operating conditions though these issues should be uncovered for the development of next‐generation PEFCs. Pt species in Pt/C cathode catalyst layers are mapped by a XAFS (X‐ray absorption fine structure) method and by a quick‐XAFS(QXAFS) method. Information on the site‐preferential oxidation and leaching of Pt cathode nanoparticles around the cathode boundary and the micro‐crack in degraded PEFCs is provided, which is relevant to the origin and mechanism of PEFC degradation. 相似文献
49.
Optical Review - We demonstrate distributed measurement of the polarization beat length along single-mode optical fibers (SMFs) using slope-assisted Brillouin optical correlation-domain... 相似文献
50.
Prof. Makoto Tadokoro Masaki Itoh Ryota Nishimura Kensuke Sekiguchi Dr. Norihisa Hoshino Dr. Hajime Kamebuchi Prof. Jun Miyazaki Dr. Fumiya Kobayashi Prof. Motohiro Mizuno Prof. Tomoyuki Akutagawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(47):e202201397
A new H-bonded crystal [RuIII(Him)3(Im)3] with three imidazole (Him) and three imidazolate (Im−) groups was prepared to obtain a higher-temperature proton conductor than a Nafion membrane with water driving. The crystal is constructed by complementary N−H⋅⋅⋅N H-bonds between the RuIII complexes and has a rare Icy-c* cubic network topology with a twofold interpenetration without crystal anisotropy. The crystals show a proton conductivity of 3.08×10−5 S cm−1 at 450 K and a faster conductivity than those formed by only HIms. The high proton conductivity is attributed to not only molecular rotations and hopping motions of HIm frameworks that are activated at ∼113 K, but also isotropic whole-molecule rotation of [RuIII(Him)3(Im)3] at temperatures greater than 420 K. The latter rotation was confirmed by solid-state 2H NMR spectroscopy; probable proton conduction routes were predicted and theoretically considered. 相似文献