全文获取类型
收费全文 | 3064篇 |
免费 | 82篇 |
国内免费 | 7篇 |
专业分类
化学 | 2333篇 |
晶体学 | 47篇 |
力学 | 22篇 |
数学 | 164篇 |
物理学 | 587篇 |
出版年
2023年 | 18篇 |
2022年 | 24篇 |
2021年 | 35篇 |
2020年 | 66篇 |
2019年 | 47篇 |
2018年 | 45篇 |
2017年 | 31篇 |
2016年 | 77篇 |
2015年 | 59篇 |
2014年 | 94篇 |
2013年 | 144篇 |
2012年 | 202篇 |
2011年 | 258篇 |
2010年 | 124篇 |
2009年 | 119篇 |
2008年 | 209篇 |
2007年 | 201篇 |
2006年 | 212篇 |
2005年 | 191篇 |
2004年 | 174篇 |
2003年 | 142篇 |
2002年 | 137篇 |
2001年 | 45篇 |
2000年 | 37篇 |
1999年 | 23篇 |
1998年 | 28篇 |
1997年 | 23篇 |
1996年 | 32篇 |
1995年 | 21篇 |
1994年 | 19篇 |
1993年 | 13篇 |
1992年 | 25篇 |
1991年 | 19篇 |
1990年 | 23篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 21篇 |
1984年 | 21篇 |
1983年 | 17篇 |
1982年 | 24篇 |
1981年 | 13篇 |
1980年 | 20篇 |
1979年 | 14篇 |
1978年 | 12篇 |
1977年 | 12篇 |
1976年 | 9篇 |
1975年 | 11篇 |
1973年 | 5篇 |
排序方式: 共有3153条查询结果,搜索用时 15 毫秒
101.
Hozumi A Kojima S Nagano S Seki T Shirahata N Kameyama T 《Langmuir : the ACS journal of surfaces and colloids》2007,23(6):3265-3272
A microfabrication technique is presented to fabricate a mesostructured inorganic/organic composite film, i.e., silica/cetyltrimethylammonium chloride (CTAC) film, with near-perfect site-selectivity on a large surface area based on a spatially regulated growth method. To precisely regulate the site-selective growth of this mesocomposite film at the solid/liquid interface, we designed a novel microtemplate consisting of a "dual-component" self-assembled monolayer (SAM) with alternating hydrophobic trifluorocarbon (CF3) and cationic amino (NH2) groups. First, (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trimethoxysilane (FAS)-SAM was formed onto Si substrate covered with native oxide (SiO2/Si) from vapor phase. The substrate was then photolithographically micropatterned using 172 nm vacuum UV light. Finally, the micropatterned FAS-SAM was immersed in a solution of 1 vol % (aminoethylaminomethyl)phenethyltrimethoxysilane (AEAMPS) in absolute toluene. Due to these treatments, a dual-SAM microtemplate with CF3- and NH2-terminated surfaces was fabricated, as evidenced by lateral force microscopy, ellipsometry, and X-ray photoelectron spectroscopy. Using this template, the microfabrication of a mesocomposite film was demonstrated. As a control, the micropatterned hydrophobic FAS-SAM template (composed of CF3- and OH-terminated surfaces) was also treated under the same conditions. Optical microscopy and atomic force microscopy confirmed that the formation of the continuous mesocomposite film proceeded only on the FAS-SAM-covered regions, while the AEAMPS-SAM-covered regions remained free of deposits. This shielding effect also remained constant regardless of the pattern's geometry, i.e., the interval distance between the FAS-SAM-covered areas in the pattern. Through this approach, we were able to obtain well-defined 5-, 10-, and 20-mum wide mesocomposite microlines over the entire 10 x 10 mm2 area with high area-selectivity. On the other hand, when the SiO2 regions were not terminated with the cationic NH2 groups, cluster formation proceeded not only on the hydrophobic CF3 regions but also on the SiO2 regions, particularly with an increase in the pattern interval distance, resulting in lower final pattern resolution. 相似文献
102.
Three-dimensional porous coordination polymer functionalized with amide groups based on tridentate ligand: selective sorption and catalysis 总被引:1,自引:0,他引:1
Hasegawa S Horike S Matsuda R Furukawa S Mochizuki K Kinoshita Y Kitagawa S 《Journal of the American Chemical Society》2007,129(9):2607-2614
To create a functionalized porous compound, amide group is used in porous framework to produce attractive interactions with guest molecules. To avoid hydrogen-bond formation between these amide groups our strategy was to build a three-dimensional (3D) coordination network using a tridentate amide ligand as the three-connector part. From Cd(NO3)2.4H2O and a three-connector ligand with amide groups a 3D porous coordination polymer (PCP) based on octahedral Cd(II) centers, {[Cd(4-btapa)2(NO3)2].6H2O.2DMF}n (1a), was obtained (4-btapa = 1,3,5-benzene tricarboxylic acid tris[N-(4-pyridyl)amide]). The amide groups, which act as guest interaction sites, occur on the surfaces of channels with dimensions of 4.7 x 7.3 A2. X-ray powder diffraction measurements showed that the desolvated compound (1b) selectively includes guests with a concurrent flexible structural (amorphous-to-crystalline) transformation. The highly ordered amide groups in the channels play an important role in the interaction with the guest molecules, which was confirmed by thermogravimetric analysis, adsorption/desorption measurements, and X-ray crystallography. We also performed a Knoevenagel condensation reaction catalyzed by 1a to demonstrate its selective heterogeneous base catalytic properties, which depend on the sizes of the reactants. The solid catalyst 1a maintains its crystalline framework after the reaction and is easily recycled. 相似文献
103.
Tanaka D Horike S Kitagawa S Ohba M Hasegawa M Ozawa Y Toriumi K 《Chemical communications (Cambridge, England)》2007,(30):3142-3144
Confinement of electron donor guests affords an efficient, photo-induced charge transfer (CT) with the anthracene moieties of a porous coordination polymer. 相似文献
104.
Okamoto K Sakagami M Feng F Togame H Takemoto H Ichikawa S Matsuda A 《The Journal of organic chemistry》2012,77(3):1367-1377
Full details of the total synthesis of pacidamycin D (4) and its 3'-hydroxy analogue 32 are described. The chemically labile Z-oxyacyl enamide moiety is the most challenging chemical structure found in uridylpeptide natural products. Key elements of our approach to the synthesis of 4 include the efficient and stereocontrolled construction of the Z-oxyvinyl halides 6 and 7 and their copper-catalyzed cross-coupling with the tetrapeptide carboxamide 5, a thermally unstable compound containing a number of potentially reactive functional groups. This synthetic route also allowed us to easily prepare 3'-hydroxy analogue 32. The assemblage by cross-coupling of the Z-oxyvinyl halide 6 and the carboxamide 5 at a late stage of the synthesis provided ready access to a range of uridylpeptide antibiotics and their analogues, despite their inherent labile nature with potential epimerization, simply by altering the tetrapeptide moiety. 相似文献
105.
The self-motion of a benzoquinone (BQ) disk on NADPH was investigated as the coupling of an autonomous motor and an enzyme reaction. In the absence of the enzyme reaction, features of motion changed depending on the concentration of NADPH, that is, continuous motion→ intermittent oscillatory motion→ no motion. When the reverse reaction from NADP(+) to NADPH was introduced into the system with the addition of an enzyme reaction, continuous motion changed to intermittent oscillatory motion with small amplitude. The mechanism of this mode change is discussed in relation to the surface tension as a driving force and the time course of UV spectra as a window to the progress of the reaction. Characteristic features of the mode change were qualitatively reproduced by a numerical calculation. 相似文献
106.
The reaction of allyltitanocenes with five- to seven-membered cyclic enones proceeded with good to high diastereoselectivity depending on the ring size of enones. The stereochemistry of the major isomers produced by the reaction of cinnamyltitanocene was opposite to that of crotyltitanocene. 相似文献
107.
K Iwasaki R Kanno T Morimoto T Yamashita S Yokoshima T Fukuyama 《Angewandte Chemie (International ed. in English)》2012,51(36):9160-9163
What a core-ker! The title synthesis was achieved using a route featuring an intramolecular Mitsunobu reaction of a nosyl amide, stereoselective construction of the β-lactam, and formation of an enamide moiety by selenoxide elimination. The stereochemistry of the alkylation for the formation of the β-lactam was controlled by a secondary hydroxy group on the ten-membered ring. SEM=2-(trimethylsilyl)ethoxymethyl; TBS=tert-butyldimethylsilyl. 相似文献
108.
Nagao S Hirai Y Suzuki A Yamamoto Y 《Journal of the American Chemical Society》2005,127(12):4146-4147
A 19F NMR study on the acid-alkaline transition in sperm whale myoglobin reconstituted with a perfluoromethyl heme, 13,17-bis(2-carboxylatoethyl)-3,8-diethyl-2,12,18-trimethyl-7-trifluoromethylporphyrinatoiron(III), demonstrated that the thermodynamics of the transition is predominantly controlled by the stability of acidic form. 相似文献
109.
Sayoko?Nagashima Satoshi?Kamiguchi Satoshi?Ohguchi Teiji?ChiharaEmail author 《Journal of Cluster Science》2011,22(4):647-660
Pyridine is allowed to react with methanol under a hydrogen stream in the presence of (H3O)2[(W6Cl8)Cl6]·6H2O supported on silica gel. When the temperature is raised above 200 °C, the catalytic activity of the cluster appears. Methylation of pyridine proceeds yielding 2-methylpyridine in 61% selectivity at 400 °C. The corresponding hexanuclear chloride clusters of niobium, molybdenum, and tantalum also catalyze the reaction. Ethanol affords the corresponding 2-ethylpyridine. When phenol is allowed to react with methanol in the presence of (H3O)2[(Mo6Cl8)Cl6]·6H2O supported on silica gel in the same manner, selective O-methylation proceeds yielding anisole in 57% selectivity at 150–200 °C. Above 250 °C, C-methylation predominates and provides o-cresol with 67% selectivity at 300 °C. The corresponding clusters of niobium, tantalum, and tungsten also catalyze the reaction. Ethanol and 1-propanol afford the corresponding 2-alkylphenols. Alkyl cations produced over weak Brønsted acid sites (H 0 ≈ +1.3) developed on the clusters are assumed as intermediates for both reactions. 相似文献
110.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献