全文获取类型
收费全文 | 5161篇 |
免费 | 514篇 |
国内免费 | 945篇 |
专业分类
化学 | 4283篇 |
晶体学 | 74篇 |
力学 | 278篇 |
综合类 | 91篇 |
数学 | 1306篇 |
物理学 | 588篇 |
出版年
2024年 | 5篇 |
2023年 | 74篇 |
2022年 | 111篇 |
2021年 | 117篇 |
2020年 | 223篇 |
2019年 | 220篇 |
2018年 | 220篇 |
2017年 | 223篇 |
2016年 | 249篇 |
2015年 | 199篇 |
2014年 | 243篇 |
2013年 | 498篇 |
2012年 | 492篇 |
2011年 | 283篇 |
2010年 | 222篇 |
2009年 | 258篇 |
2008年 | 326篇 |
2007年 | 325篇 |
2006年 | 298篇 |
2005年 | 270篇 |
2004年 | 228篇 |
2003年 | 197篇 |
2002年 | 196篇 |
2001年 | 125篇 |
2000年 | 163篇 |
1999年 | 138篇 |
1998年 | 113篇 |
1997年 | 99篇 |
1996年 | 93篇 |
1995年 | 62篇 |
1994年 | 55篇 |
1993年 | 42篇 |
1992年 | 49篇 |
1991年 | 33篇 |
1990年 | 28篇 |
1989年 | 26篇 |
1988年 | 25篇 |
1987年 | 16篇 |
1986年 | 15篇 |
1985年 | 8篇 |
1984年 | 13篇 |
1983年 | 4篇 |
1982年 | 7篇 |
1981年 | 5篇 |
1980年 | 4篇 |
1979年 | 3篇 |
1978年 | 6篇 |
1977年 | 3篇 |
1974年 | 2篇 |
1973年 | 2篇 |
排序方式: 共有6620条查询结果,搜索用时 15 毫秒
1.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
2.
Functional zinc(II) phthalocyanines bearing Schiff base complexes as oxidation catalysts for bleaching systems
下载免费PDF全文
![点击此处可从《应用有机金属化学》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Oxidation catalysis is used to increase the performance of hydrogen peroxide in laundry bleach applications. Bleach catalysts provide cost‐effective, energy‐saving and environmentally friendly bleach systems yielding perfect stain removal at lower temperatures. This comparative study is based on the synthesis of bis[bis(salicylhydrazonephenoxy)manganese(III)] phthalocyaninatozinc(II) ( 2 ), bis[bis(salicylhydrazonephenoxy)cobalt(III)] phthalocyaninatozinc(II) ( 3 ) and bis[bis(salicylhydrazonephenoxy)iron(III)] phthalocyaninatozinc(II) ( 4 ) as tri‐nuclear complexes consisting of two Schiff base complexes substituting a zinc phthalocyanine. Complexion on the periphery to obtain complexes 2 , 3 , 4 was performed through the reaction of a Schiff base‐substituted phthalocyanine using MnCl2?4H2O, CoCl2?6H2O or FeCl3?6H2O salts in basic condition in dimethylformamide. Fourier transform infrared, 1H NMR, 13C NMR, UV–visible, inductively coupled plasma optical emission and mass spectra were applied to characterize the prepared compounds. The bleach performances of the three phthalocyanine compounds 2 , 3 , 4 were examined by the degradation of morin as hydrophilic dye. The degradation progress in the presence of catalysts 2 , 3 , 4 /H2O2 combination in aqueous solution was investigated using an online spectrophotometric method. It was found that the catalysts 2 , 3 , 4 exhibited better bleaching performance at 25 °C than tetraactylethylethylenediamine as bleach activator used in powder detergent formulations for stain removal. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
3.
Dr. Sebastian Lars Müller Xinglong Zhou Dr. Peter Leonard Oxana Korzhenko Dr. Constantin Daniliuc Prof. Dr. Frank Seela 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3077-3090
Silver-mediated α-dC–Ag+–β-dC hybrid base pairs decorated with 5-iodo- or 5-octadiynyl residues are well accommodated in duplex DNA. A strong Tm increase and favorable thermodynamic data for duplex DNA were observed after addition of silver ions. The phenomenon is particularly obvious when both nucleobases of the base pairs are functionalized. Neither the position of the base pair, nor the type of 5-substituent had a negative influence. On the contrary, functionalization of conventional silver-mediated β-dC–Ag+–β-dC homo base pairs showed a negative impact induced by the bulky substituents. To this end, cytosine modified 12-mer oligodeoxynucleotides were prepared by solid-phase synthesis employing new α-anomeric 2′-deoxycytidine phosphoramidites. A multigram scale synthesis was developed for 5-iodo-α-d -2′-deoxycytidine ( 1 ) employing the direct glycosylation of cytosine with Hoffer's α-d -halogenose followed by separation of anomeric DMT nucleosides. Regarding base-pair stability and functionalization silver-mediated α/β-dC hybrid base pairs were found to be superior to β/β-dC homo pairs. According to their extraordinary properties, they might find applications in DNA diagnostics, material science, or nanotechnology. 相似文献
4.
Minoru Koyama Dr. Takafumi Kawakami Dr. Takashi Okazoe Prof. Dr. Kyoko Nozaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10913-10917
Methacrylic esters, represented by methyl methacrylate (MMA), are widely used as commodity chemicals. Here, the one-pot synthesis of methacrylic esters from acetone, a haloform and alcohols in the presence of an organic base is described. Using DBU as the organic base for the reaction of acetone, chloroform and methanol in acetonitrile afforded MMA in 66 % yield. When the solvent was replaced by benzonitrile, the product MMA was successfully purified by distillation. Applicability of this process to various alcohols was also investigated to show ethyl, phenyl, CF3CH2, and n-C6F13CH2CH2 esters were obtained in moderate yields. The use of bromoform instead of chloroform resulted in the improvement of the yield, for example, methyl and n-C6F13CH2CH2 esters up to 81 and 70 %, respectively. The reaction with deuterated starting materials acetone-d6 and MeOH-d4, with DBU in acetonitrile afforded deuterated MMA (MMA-d8) in 70 % yield. 相似文献
5.
R. J. Vanderbei 《Mathematical Programming》1989,43(1-3):31-44
The affine-scaling modification of Karmarkar's algorithm is extended to solve problems with free variables. This extended primal algorithm is used to prove two important results. First the geometrically elegant feasibility algorithm proposed by Chandru and Kochar is the same algorithm as the one obtained by appending a single column of residuals to the constraint matrix. Second the dual algorithm as first described by Adler et al., is the same as the extended primal algorithm applied to the dual. 相似文献
6.
7.
通过分析计算,设计了一种大口径宽视场折射式红外相机光学系统。该系统设计用于超长线阵扫描红外相机的地面演示成像,它能同时对短波2μm—3μm、中波3μm—4.5μm双波段成像,且同时具有24°的大视场和150mm的宽口径,成像质量接近衍射极限。该系统在航天遥感领域应用广泛。 相似文献
8.
关新民 《新疆大学学报(理工版)》2002,19(1):95-99
介绍了采用MATLAB V5.2提供的模糊逻辑工具箱来设计研究电孤纺电极调节系统中的模糊--PD控制器,讨论了在SIMULINK环境下模糊-PD控制器的参数自调速原理、结构、建立模糊控制规则库和模糊推论方法,并给出仿真结果与结论。 相似文献
9.
Nobuhiro Honda 《Mathematische Nachrichten》2003,256(1):48-57
In a previous paper of the same title the author gave a generalization of the constrution of Donaldson–Friedman, to prove the existence of twistor spaces of n CP 2 with a special kind of divisors. In the present paper, we consider its equivariant version. When n = 3, this gives another proof of the existence of degenerate double solid with C *–action, and we show that the branch quartic surface is birational to an elliptic ruled surface. In case n ≥ 4, this yields new Moishezon twistor spaces with C *–action, which is shown to be the most degenerate ones among twistor spaces studied by Campana and Kreußler. 相似文献
10.
Marcelino Maneiro Manuel R. Bermejo M. Isabel Fernndez Ana M. Gonzlez‐Noya Alexei M. Tyryshkin Robin G. Pritchard 《无机化学与普通化学杂志》2003,629(2):285-290
A new MnIII‐Schiff base complex, [MnL(OH2)](ClO4) ( 1 ) (H2L = N, N′‐bis‐(3‐Br‐5‐Cl‐salicylidene)‐1, 2‐diimino‐2‐methylethane), an inorganic model of the catalytic center (OEC, Oxygen Evolving Complex) in photosystem II (PSII), has been synthesized and characterized by elemental analysis, IR and EPR spectroscopy, mass spectrometry, magnetic susceptibility measurement and the study of its redox properties by cyclic and normal pulse voltammetry. This complex mimics reactivity (showing a relevant photolytic activity), and also some structural characteristics (parallel‐mode MnIII EPR signal from partially assembled OEC cluster) of the natural OEC. The complex 1 was found to rearrange in solution into a crystallographically solved square‐pyramidal complex, [MnLL′] ( 2 ) (HL′ = 6‐bromo‐4‐chloro‐2‐cyanophenol), through a process, which probably liberates radical species (detected by EPR), and provokes a C—N bond cleavage in the ligand. A photo‐radical mechanism is discussed to explain this rearrangement. 相似文献