全文获取类型
收费全文 | 479篇 |
免费 | 25篇 |
国内免费 | 12篇 |
专业分类
化学 | 380篇 |
晶体学 | 4篇 |
力学 | 13篇 |
数学 | 56篇 |
物理学 | 63篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 14篇 |
2020年 | 28篇 |
2019年 | 18篇 |
2018年 | 27篇 |
2017年 | 16篇 |
2016年 | 21篇 |
2015年 | 26篇 |
2014年 | 28篇 |
2013年 | 56篇 |
2012年 | 27篇 |
2011年 | 30篇 |
2010年 | 29篇 |
2009年 | 21篇 |
2008年 | 28篇 |
2007年 | 18篇 |
2006年 | 20篇 |
2005年 | 24篇 |
2004年 | 14篇 |
2003年 | 8篇 |
2002年 | 9篇 |
2001年 | 1篇 |
1999年 | 2篇 |
1998年 | 1篇 |
1997年 | 1篇 |
1996年 | 1篇 |
1994年 | 1篇 |
1993年 | 1篇 |
1992年 | 3篇 |
1991年 | 1篇 |
1988年 | 2篇 |
1987年 | 2篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1981年 | 1篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1973年 | 1篇 |
1934年 | 1篇 |
排序方式: 共有516条查询结果,搜索用时 31 毫秒
151.
152.
Ring‐opening polymerization of cyclic esters by pincer complexes derived from alkaline earth metals
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)
We report the synthesis and characterization of new Ca(II) and Mg(II) complexes of the type [Ph―PPP]MR (M = Ca, R = N(SiMe3)2 ( 1 ); M = Mg, R = nBu ( 2 )) where Ph―PPP? is a tridentate monoanionic ligand (Ph―PPP―H = bis(2‐diphenylphosphinophenyl)phosphine). Reaction of the opportune metal precursor (Ca[N(SiMe3)2]2.THF2 or MgnBu2) with 1 equiv. of the pro‐ligand Ph―PPP―H produces the corresponding calcium amido ( 1 ) or magnesium butyl ( 2 ) complex in high yield. Solution NMR studies show monomeric and kinetically stable structures for both species. The obtained complexes efficiently mediate the ring‐opening polymerization of ?‐caprolactone showing a turnover frequency of 40 000 h?1. In the presence of a hexogen alcohol, up to 2000 equiv. of monomer are converted by using a low loading of catalyst (5 µmol). Kinetic studies show a first‐order reaction in monomer concentration. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
153.
154.
Ilaria D'auria Mina Mazzeo Daniela Pappalardo Marina Lamberti Claudio Pellecchia 《Journal of polymer science. Part A, Polymer chemistry》2011,49(2):403-413
Phosphido‐diphosphine Group 3 metal complexes 1–4 [(o‐C6H4PR2)2P‐M(CH2SiMe3)2; R = Ph, 1 : M = Y, 2 : M = Sc; R = iPr, 3 : M = Y, 4 : M = Sc] are very efficient catalysts for the ring‐opening polymerization (ROP) of cyclic esters such as ε‐caprolactone (ε‐CL), L ‐lactide, and δ‐valerolactone under mild polymerization conditions. In the ROP of ε‐CL, complexes 1–4 promote quantitative conversion of high amount of monomer (up to 3000 equiv) with very high turnover frequencies (TOF) (~4 × 104 molCL/molI h) showing a catalytic activity among the highest reported in the literature. The immortal and living ROP of ε‐CL and L ‐lactide is feasible by combining complexes 1–4 with 5 equiv of 2‐propanol. Polymers with controlled molecular parameters (Mn, end groups) and low polydispersities (Mw/Mn = 1.05–1.09) are formed as a result of fast alkoxide/alcohol exchange. In the ROP of δ‐valerolactone, complexes 1–4 showed the same activity observed for lactide (L ‐ and D ,L ‐lactide) producing high molecular weight polymers with narrow distribution of molar masses. Complexes 1–4 also promote the ROP of rac‐β butyrolactone affording atactic low molecular weight poly(hydroxybutyrate) bearing unsaturated end groups probably generated by elimination reactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
155.
156.
Vitamin B12 supported on graphene oxide: As a bio‐based catalyst for selective aerobic oxidation of alcohols
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)
Ahmad Shaabani Adina Rashidi Vahid Shabnam Shaabani Reza Mohammadian Mohammad Taghi Nazeri Mina Keramati Nejad 《应用有机金属化学》2018,32(10)
The environmental impact of chemical processes has now opened new windows of opportunity for bio‐based catalysts. In this paper a highly active bio‐based catalyst of vitamin B12 supported on graphene oxide nanosheets is reported for the selective aerobic oxidation of alcohols to the corresponding carbonyl compounds. Operational simplicity, mild reaction conditions, high yield and selectivity, non‐hazardous nature, commercial availability and affordability are the main advantages of this novel catalytic system. 相似文献
157.
Hamid Moghimi Amir Moradi Javad Hamedi Mina Basiri 《Applied biochemistry and biotechnology》2016,178(6):1207-1219
158.
Assembly of an Achiral Chromophore into Light‐Responsive Helical Nanostructures in the Absence of Chiral Components
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Prof. Dr. Mina Han Prof. Dr. Sung June Cho Dr. Yasuo Norikane Prof. Dr. Masaki Shimizu Prof. Dr. Takahiro Seki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(12):3971-3975
The chirality found in living organisms is one of unsolved mysteries on Earth. It is crucial to understand the manner in which small achiral molecules evolve into helical superstructures in the absence of chiral components because this process can provide important insights regarding the origin of chirality in nature. 1) the uncommon helical assembly of an achiral trigonal chromophore into helical nanostructures with aggregation‐induced emission enhancement (AIEE) characteristics and 2) the tunability of the helical pitch and fluorescence intensity in response to light is reported. The Rietveld refinement of X‐ray diffraction (XRD) patterns and the growth process suggest that a striking transformation from an achiral to an asymmetric molecule can occur as a result of specific interactions with certain solvents, presumably leading to the unique helical assembly. More importantly, exposure to UV or visible light promoted not only the formation of irregular helical structures with a wide range of pitch lengths but also an increase in fluorescence intensity. 相似文献
159.
Youssef Z. Boutros Mina B. Abd-el-Malek Nagwa A. Badran Hossam S. Hassan 《Meccanica》2006,41(6):681-691
The boundary-layer equations for two-dimensional steady flow of an incompressible, viscous fluid near a stagnation point at
a heated stretching sheet placed in a porous medium are considered. We apply Lie-group method for determining symmetry reductions
of partial differential equations. Lie-group method starts out with a general infinitesimal group of transformations under
which the given partial differential equations are invariant. The determining equations are a set of linear differential equations,
the solution of which gives the transformation function or the infinitesimals of the dependent and independent variables.
After the group has been determined, a solution to the given partial differential equations may be found from the invariant
surface condition such that its solution leads to similarity variables that reduce the number of independent variables of
the system. The effect of the velocity parameter λ, which is the ratio of the external free stream velocity to the stretching
surface velocity, permeability parameter of the porous medium k
1, and Prandtl number Pr on the horizontal and transverse velocities, temperature profiles, surface heat flux and the wall
shear stress, has been studied. 相似文献
160.
This paper is concerned with the initial boundary value problem for the p‐system with nonlinear damping and fixed boundary condition. We show that the corresponding problem admits a unique global solution, and such a solution tends time asymptotically to the corresponding nonlinear diffusion wave governed by the classical Darcy's law provided that the corresponding prescribed initial error function is sufficiently small. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献