全文获取类型
收费全文 | 11005篇 |
免费 | 990篇 |
国内免费 | 1413篇 |
学科分类
数理化 | 13408篇 |
出版年
2024年 | 12篇 |
2023年 | 119篇 |
2022年 | 113篇 |
2021年 | 160篇 |
2020年 | 303篇 |
2019年 | 318篇 |
2018年 | 328篇 |
2017年 | 372篇 |
2016年 | 344篇 |
2015年 | 295篇 |
2014年 | 514篇 |
2013年 | 903篇 |
2012年 | 728篇 |
2011年 | 727篇 |
2010年 | 537篇 |
2009年 | 629篇 |
2008年 | 725篇 |
2007年 | 710篇 |
2006年 | 656篇 |
2005年 | 584篇 |
2004年 | 488篇 |
2003年 | 513篇 |
2002年 | 457篇 |
2001年 | 332篇 |
2000年 | 350篇 |
1999年 | 335篇 |
1998年 | 324篇 |
1997年 | 266篇 |
1996年 | 203篇 |
1995年 | 159篇 |
1994年 | 152篇 |
1993年 | 103篇 |
1992年 | 107篇 |
1991年 | 75篇 |
1990年 | 68篇 |
1989年 | 51篇 |
1988年 | 47篇 |
1987年 | 40篇 |
1986年 | 35篇 |
1985年 | 26篇 |
1984年 | 32篇 |
1983年 | 17篇 |
1982年 | 33篇 |
1981年 | 28篇 |
1980年 | 18篇 |
1979年 | 13篇 |
1978年 | 17篇 |
1977年 | 7篇 |
1976年 | 7篇 |
1973年 | 9篇 |
排序方式: 共有10000条查询结果,搜索用时 31 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
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.
三维位势问题的边界元分析中,关于坐标变量的边界位势梯度的计算是一个困难的问题. 已有一些方法着手解决这个问题,然而,这些方法需要复杂的理论推导和大量的数值计算. 本文提出求解一般边界位势梯度边界积分方程的辅助边值问题法. 该方法构造了与原边界值问题具有相同解域的辅助边值问题,该辅助边值问题具有已知解,因此通过求解此辅助边值问题,可获得梯度边界积分方程对应的系统矩阵,然后将此系统矩阵应用于求解原边值问题,求解过程非常简单,只需求解一个线性系统即可获得原边值问题的解. 值得注意的是,在求解原边值问题时,不再需要重新计算系统矩阵,因此辅助边值问题法的效率并不很差. 辅助边值问题法避免了强奇异积分的计算,具有数学理论简单、程序设计容易、计算精度高等优点,为坐标变量梯度边界积分方程的求解提供了一个新的途径. 3个标准的数值算例验证了方法的有效性. 相似文献
4.
Theoretical study on the mechanism for the excited-state double proton transfer process of an asymmetric Schiff base ligand 下载免费PDF全文
Zhengran Wang 《中国物理 B》2022,31(4):48202-048202
Excited-state double proton transfer (ESDPT) in the 1-[(2-hydroxy-3-methoxy-benzylidene)-hydrazonomethyl]-naphthalen-2-ol (HYDRAVH2) ligand was studied by the density functional theory and time-dependent density functional theory method. The analysis of frontier molecular orbitals, infrared spectra, and non-covalent interactions have cross-validated that the asymmetric structure has an influence on the proton transfer, which makes the proton transfer ability of the two hydrogen protons different. The potential energy surfaces in both S0 and S1 states were scanned with varying O-H bond lengths. The results of potential energy surface analysis adequately proved that the HYDRAVH2 can undergo the ESDPT process in the S1 state and the double proton transfer process is a stepwise proton transfer mechanism. Our work can pave the way towards the design and synthesis of new molecules. 相似文献
5.
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
6.
In this paper, the deformation of the Heisenberg algebra, consistent with both the generalized uncertainty principle and doubly special relativity, has been analyzed. It has been observed that, though this algebra can give rise to fractional derivative terms in the corresponding quantum mechanical Hamiltonian, a formal meaning can be given to them by using the theory of harmonic extensions of function. Depending on this argument, the expression of the propagator of the path integral corresponding to the deformed Heisenberg algebra, has been obtained. In particular, the consistent expression of the one dimensional free particle propagator has been evaluated explicitly. With this propagator in hand, it has been shown that, even in free particle case, normal generalized uncertainty principle and doubly special relativity show very much different result. 相似文献
7.
假设纤维方向角沿层合板的长度方向线性变化,研究了变角度纤维复合材料层合斜板的颤振.通过坐标变换将斜板变换为正方形板,采用层合板表面连续变化的速度环量来模拟空气对其的作用,速度环量分布利用Cauchy积分公式计算.建立了系统的Lagrange方程并采用Ritz法得到了层合板的自振频率和颤振/不稳定性分离临界速度.通过数值算例验证了本文模型和方法的正确性和收敛性,分析了各个铺层内纤维方向角的变化对自振频率和颤振/不稳定性分离临界速度的影响.研究结果表明,通过纤维的变角度铺设,可有效地提高层合板的基频和颤振/不稳定性分离临界速度.经合理设计的变角度复合材料层合板具有抑制颤振的作用. 相似文献
8.
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
9.
10.
Boundedness of commutators on homogeneous Herz spaces 总被引:9,自引:0,他引:9
The boundedness on homogeneous Herz spaces is established for a large class of linear commutators generated by BMO(R
n
) functions and linear operators of rough kernels which include the Calderón-Zygmund operators and the Ricci-Stein oRfiUatory
singular integrals with rough kernels.
Project supponed in pan by the National h’atural Science Foundation of China (Grant No. 19131080) and the NEDF of China. 相似文献