全文获取类型
收费全文 | 426篇 |
免费 | 6篇 |
国内免费 | 7篇 |
专业分类
化学 | 311篇 |
晶体学 | 4篇 |
力学 | 5篇 |
数学 | 51篇 |
物理学 | 68篇 |
出版年
2024年 | 1篇 |
2021年 | 3篇 |
2020年 | 4篇 |
2019年 | 4篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 14篇 |
2013年 | 33篇 |
2012年 | 17篇 |
2011年 | 24篇 |
2010年 | 5篇 |
2009年 | 15篇 |
2008年 | 31篇 |
2007年 | 32篇 |
2006年 | 27篇 |
2005年 | 31篇 |
2004年 | 26篇 |
2003年 | 30篇 |
2002年 | 16篇 |
2001年 | 3篇 |
2000年 | 6篇 |
1999年 | 7篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 5篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 7篇 |
1989年 | 5篇 |
1988年 | 5篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 3篇 |
1982年 | 6篇 |
1981年 | 8篇 |
1980年 | 5篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1975年 | 1篇 |
1973年 | 4篇 |
1971年 | 1篇 |
1964年 | 1篇 |
排序方式: 共有439条查询结果,搜索用时 62 毫秒
61.
Catalytic SbF5 and the use of EtOH as an additive efficiently converted a mixture of phenylalkynes and aldehydes to indanone compounds in one pot, and the reaction stereoselectively afforded the corresponding 2,3-disubstituted indanones as a single trans-isomer. 相似文献
62.
In the presence of 0.5-1 mol % of FeCl(3) with lithium bromide as a crucial additive, alkynyl Grignard reagents, prepared from the corresponding alkynes and methylmagnesium bromide, react with alkenyl bromides or triflates to give the corresponding conjugated enynes in high to excellent yields. The reaction shows wide applicability to various terminal alkynes and alkenyl electrophiles. 相似文献
63.
T. Ishikawa S. Yamashita Y. Nakazawa A. Kawamoto M. Oguni 《Journal of Thermal Analysis and Calorimetry》2008,92(2):435-438
Thermodynamic investigation of an organic superconductor κ-(BEDT-TTF)2Ag(CN)2H2O in which the BEDT-TTF dimers are arranged in the κ-type structure in the donor layers is performed by the relaxation calorimetric
technique at low temperatures and under magnetic fields. A thermal anomaly related to the superconductive phase transition
was observed at 5 K. The existence of residual γ* in the superconductive state is about 18% of the normal state γ value, which is larger than those of κ-(BEDT-TTF)2Cu(NCS)2, and κ-(BEDT-TTF)2Cu[N(CN)2]Br salt. The lattice heat capacity reflected on the β-term in the low-temperature heat capacity was found to be affected
by the cooling rate. The disorder produced in the network structure constructed by hydrogen bond in the insulating layer is
considered to give low-energy phonon excitations reflected in the heat capacity. 相似文献
64.
A novel low-symmetry tetrabenzoporphine with D2h symmetry (1) and its zinc complex (2) were prepared via mixed condensation reaction of 5,6-dimethyl phthalimide and 4,5,6,7-tetraphenyl phthalimide with sodium acetate in the presence of zinc acetate. The zinc complex 2 exhibited a split Q band at 640 and 623 nm and a single Soret band at 435 nm. The absorption spectra of 1 and 2 were calculated and analyzed using Hartree-Fock theory based on INDO/S Hamiltonian. 相似文献
65.
Nagata M Kondo M Suemori Y Ochiai T Dewa T Ohtsuka T Nango M 《Colloids and surfaces. B, Biointerfaces》2008,64(1):16-21
Dialkyl disulfide-linked naphthoquinone, (NQ-Cn-S)2, and anthraquinone, (AQ-Cn-S)2, derivatives with different spacer alkyl chains (Cn: n = 2, 6, 12) were synthesized and these quinone derivatives were self-assembled on a gold electrode. The formation of self-assembled monolayers (SAMs) of these derivatives on a gold electrode was confirmed by infrared reflection-absorption spectroscopy (IR-RAS). Electron transfer between the derivatives and the gold electrode was studied by cyclic voltammetry. On the cyclic voltammogram a reversible redox reaction between quinone (Q) and hydroquinone (QH2) was clearly observed under an aqueous condition. The formal potentials for NQ and AQ derivatives were −0.48 and −0.58 V, respectively, that did not depend on the spacer length. The oxidation and reduction peak currents were strongly dependent on the spacer alkyl chain length. The redox behavior of quinone derivatives depended on the pH condition of the buffer solution. The pH dependence was in agreement with a theoretical value of E1/2 (mV) = E′ − 59pH for 2H+/2e− process in the pH range 3–11. In the range higher than pH 11, the value was estimated with E1/2 (mV) = E′ − 30pH , which may correspond to H+/2e− process. The tunneling barrier coefficients (β) for NQ and AQ SAMs were determined to be 0.12 and 0.73 per methylene group (CH2), respectively. Comparison of the structures and the alkyl chain length of quinones derivatives on these electron transfers on the electrode is made. 相似文献
66.
Qu J Morita R Satoh M Wada J Terakura F Mizoguchi K Ogata N Masuda T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(11):3250-3259
We report here the first example of organic radical battery with DNA. Though there is a growing interest in DNA/cationic-lipid complexes as promising gene delivery vehicles, few efforts have been focused on the use of such complexes as advanced materials for organic optoelectronic applications. The present article describes how substitution of the sodium counter cation of DNA with cationic amphiphilic lipid(1-4) provided novel DNA-lipid complexes that contain TEMPO radicals, in which the actual mole ratio of phosphate to lipid was 1:0.84 to 1:0.16. All the TEMPO-containing DNA-lipid complexes displayed reversible two-stage charge/discharge processes, the discharge capacities of which were 40.5-60.0 A h kg(-1). In particular, the capacity of a DNA-lipid(3)-based cell reached 60.0 A h kg(-1), which corresponds to 192 % relative to its theoretical value for the single-electron one-stage process, indicating a two-electron process. 相似文献
67.
Fujimoto T Endo K Tsuji H Nakamura M Nakamura E 《Journal of the American Chemical Society》2008,130(13):4492-4496
Construction of a nonracemic all-carbon quaternary stereocenter at the alpha-position of beta-ketoesters was achieved by way of an indium(III)-catalyzed diastereoselective alpha-alkenylation reaction of chiral enamines with 1-alkynes. The enamine bearing a chiral auxiliary derived from l-isoleucine was added to the alkyne to give an alpha-alkenylated product in excellent yield and with a stereoselectivity better than 90% ee. One can ascribe the high selectivity to a chelate intermediate involving the auxiliary and the metal atom and the high yield to efficient interactions between the indium(III) atom and the alkyne. The selectivity increased as the reaction temperature was raised to 120 degrees C and decreased at higher temperatures. 相似文献
68.
We have discovered the unprecedented catalytic use of In(0) for catalytic C-C bond transformations. Remarkably, these general catalytic allylations of ketones proceeded smoothly in water as a sole solvent under mild conditions, and water proved to be essential for these reactions. Both the displayed substrate scope and the functional group tolerance were excellent. Importantly, the In metal catalyst could be easily recovered and reused without loss of catalytic activity. Moreover, when an alpha-substituted allylboronate was used, an unusual constitutional selectivity was observed providing exclusively the formal alpha-adduct. Additionally, the resulting tertiary homoallylic alcohols were obtained with exceptionally high diastereoselectivities. The applicability of this concept to asymmetric catalysis in water by using In(0) combined with a chiral bis(oxazoline) ligand was demonstrated as well. 相似文献
69.
Prof. Dr. Katsuhiro Isozaki Tomoya Yokoi Ryota Yoshida Dr. Kazuki Ogata Dr. Daisuke Hashizume Dr. Nobuhiro Yasuda Prof. Dr. Koichiro Sadakane Prof. Dr. Hikaru Takaya Prof. Dr. Masaharu Nakamura 《化学:亚洲杂志》2016,11(7):1076-1091
Two (ONO pincer)ruthenium‐complex‐bound norvalines, Boc?[Ru(pydc)(terpy)]Nva?OMe ( 1 ; Boc=tert‐butyloxycarbonyl, terpy=terpyridyl, Nva=norvaline) and Boc?[Ru(pydc)(tBu‐terpy)]Nva?OMe ( 5 ), were successfully synthesized and their molecular structures and absolute configurations were unequivocally determined by single‐crystal X‐ray diffraction. The robustness of the pincer Ru complexes and norvaline scaffolds against acidic/basic, oxidizing, and high‐temperature conditions enabled us to perform selective transformations of the N‐Boc and C?OMe termini into various functional groups, such as alkyl amide, alkyl urea, and polyether groups, without the loss of the Ru center or enantiomeric purity. The resulting dialkylated Ru‐bound norvaline, n‐C11H23CO?l ‐[Ru(pydc)(terpy)]Nva?NH‐n‐C11H23 (l ‐ 4 ) was found to have excellent self‐assembly properties in organic solvents, thereby affording the corresponding supramolecular gels. Ru‐bound norvaline l ‐ 1 exhibited a higher catalytic activity for the oxidation of alcohols by H2O2 than parent complex [Ru(pydc)(terpy)] ( 11 a ). 相似文献
70.
Takanori Kiyokura Fumihiko MAEDA Yoshio Watanabe Yoshinori Iketaki Koumei Nagai Yoshiaki Horikawa Masaharu Oshima Eiji Shigemasa Akira Yagishita 《Optical Review》2000,7(6):576-578
The throughput of a Schwarzschild objective using undulator synchrotron radiation was measured. Conventionally, the throughput was estimated from the squared reflectivity of one multilayer mirror and from the obstruction ratio. However, we evaluated the transmission ratio from the input and output photon flux using a precisely calibrated monochromatic beam from an undulator light source. It was found that the objective has a maximum throughput of 8.5% at a wavelength of 13.9 nm. 相似文献