全文获取类型
收费全文 | 4531篇 |
免费 | 481篇 |
国内免费 | 436篇 |
专业分类
化学 | 2954篇 |
晶体学 | 79篇 |
力学 | 166篇 |
综合类 | 30篇 |
数学 | 662篇 |
物理学 | 1557篇 |
出版年
2023年 | 91篇 |
2022年 | 109篇 |
2021年 | 140篇 |
2020年 | 168篇 |
2019年 | 137篇 |
2018年 | 131篇 |
2017年 | 139篇 |
2016年 | 187篇 |
2015年 | 162篇 |
2014年 | 189篇 |
2013年 | 273篇 |
2012年 | 330篇 |
2011年 | 330篇 |
2010年 | 208篇 |
2009年 | 248篇 |
2008年 | 264篇 |
2007年 | 239篇 |
2006年 | 191篇 |
2005年 | 190篇 |
2004年 | 124篇 |
2003年 | 114篇 |
2002年 | 111篇 |
2001年 | 88篇 |
2000年 | 75篇 |
1999年 | 71篇 |
1998年 | 52篇 |
1997年 | 47篇 |
1996年 | 72篇 |
1995年 | 71篇 |
1994年 | 60篇 |
1993年 | 62篇 |
1992年 | 64篇 |
1991年 | 59篇 |
1990年 | 54篇 |
1989年 | 45篇 |
1988年 | 36篇 |
1987年 | 36篇 |
1986年 | 34篇 |
1985年 | 40篇 |
1984年 | 43篇 |
1983年 | 29篇 |
1982年 | 23篇 |
1981年 | 17篇 |
1980年 | 18篇 |
1979年 | 24篇 |
1977年 | 15篇 |
1976年 | 17篇 |
1975年 | 15篇 |
1974年 | 17篇 |
1973年 | 25篇 |
排序方式: 共有5448条查询结果,搜索用时 15 毫秒
1.
We investigate the possibility of phantom crossing in the dark energy sector and the solution for the Hubble tension between early and late universe observations. We use robust combinations of different cosmological observations, namely the Cosmic Microwave Background (CMB), local measurement of Hubble constant (), Baryon Acoustic Oscillation (BAO) and SnIa for this purpose. For a combination of CMB+BAO data that is related to early universe physics, phantom crossing in the dark energy sector was confirmed at a 95% confidence level and we obtained the constraint km/s/Mpc at a 68% confidence level, which is in perfect agreement with the local measurement by Riess et al. We show that constraints from different combinations of data are consistent with each other and all of them are consistent with phantom crossing in the dark energy sector. For the combination of all data considered, we obtained the constraint km/s/Mpc at a 68% confidence level and the phantom crossing happening at the scale factor at a 68% confidence level. 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.
Single Crystal to Single Crystal (SC‐to‐SC) Transformation from a Nonporous to Porous Metal–Organic Framework and Its Application Potential in Gas Adsorption and Suzuki Coupling Reaction through Postmodification
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)
Dr. Rupam Sen Debraj Saha Dr. Subratanath Koner Dr. Paula Brandão Dr. Zhi Lin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(15):5962-5971
A new amino‐functionalized strontium–carboxylate‐based metal–organic framework (MOF) has been synthesized that undergoes single crystal to single crystal (SC‐to‐SC) transformation upon desolvation. Both structures have been characterized by single‐crystal X‐ray analysis. The desolvated structure shows an interesting 3D porous structure with pendent ?NH2 groups inside the pore wall, whereas the solvated compound possesses a nonporous structure with DMF molecules on the metal centers. The amino group was postmodified through Schiff base condensation by pyridine‐2‐carboxaldehyde and palladium was anchored on that site. The modified framework has been utilized for the Suzuki cross‐coupling reaction. The compound shows high activity towards the C?C cross‐coupling reaction with good yields and turnover frequencies. Gas adsorption studies showed that the desolvated compound had permanent porosity and was microporous in nature with a BET surface area of 2052 m2 g?1. The material also possesses good CO2 (8 wt %) and H2 (1.87 wt %) adsorption capabilities. 相似文献
4.
5.
5-Perfluorophenyl 4,5-dihydro-1H-pyrazoles were synthesized from 1,3-dipolar cycloaddition reaction of perfluorobenyl 2,4,6-triisopropylbenzenesulfonylhydrazone and α,β-unsaturated carbonyl compounds or acrylonitrile in THF or water. It was worthy to note that better results were obtained when water was employed as the solvent, which was considered as an effective, economic and environmentally friendly method to synthesize these pyrazole derivatives. 相似文献
6.
研究了γ-辐照前后纯Y2SiO5和Eu3+掺杂的Y2SiO5晶体吸收光谱的变化,辐照后,未退火和氢气退火的纯Y2SiO5晶体在260~270 nm和320 nm波段产生了附加吸收峰,分别是由F心和O-心的吸收引起的;经过空气退火的纯YSO晶体中,由于消除了氧空位,因此辐照后没有出现色心吸收峰。在Eu3+∶Y2SiO5晶体中,不但有相同的F心和O-心吸收峰,而且还有Eu2+离子在300 nm和390 nm的吸收峰。随着辐照剂量的增加,色心附加吸收峰增强。空气退火能减少Eu3+∶Y2SiO5晶体中的色心,而氢气退火能增加色心。 相似文献
7.
Liang Liao Yi Pang Liming Ding Frank E. Karasz 《Journal of polymer science. Part A, Polymer chemistry》2003,41(20):3149-3158
A soluble cyano‐substituted poly[(1,3‐phenylene vinylene)‐alt‐(1,4‐phenylene vinylene)] derivative ( 9 ) was synthesized and characterized. Comparison between 9 and its model compound ( 10 ) showed that the chromophore in 9 remained to be well defined as a result of a π‐conjugation interruption at adjacent m‐phenylene units. The attachment of a cyano substituent only at the β position of the vinylene allowed the maximum electronic impact of the cyano group on the optical properties of the poly(p‐phenylene vinylene) material. At a low temperature (?108 or ?198 °C), the vibronic structures of 9 and 10 were partially resolved. The absorption and emission spectra of a film of 9 were less temperature‐dependent than those of a film of 10 , indicating that the former had a lower tendency to aggregate. A light‐emitting diode (LED) based on 9 emitted yellow light (λmax ≈ 578 nm) with an external quantum efficiency of 0.03%. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3149–3158, 2003 相似文献
8.
关于Banach空间中凸泛函的广义次梯度不等式 总被引:2,自引:0,他引:2
本文在前人^[1,2]的基础之上,以凸泛函的次梯度不等式为工具,将Jensen不等式推广到Banach空间中的凸泛函,导出了Banach空间中的Bochner积分型的广义Jensen不等式,给出其在Banach空间概率论中某些应用,从而推广了文献[3—6]的工作. 相似文献
9.
Richard Kotek Kyeong Pang Ben Schmidt Alan Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(23):4247-4254
Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by 1H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO2 gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004 相似文献
10.
Quan Sen JIU Department of Mathematics Capital Normal University Beijing P.R.China Cheng HE Institute of Applied Mathematics Academy of Mathematics System Sciences Chinese Academy of Sciences Beijing P.R.China 《应用数学学报(英文版)》2004,(4)
In this paper we are interested in the sufficient conditions which guarantee the regularityof solutions of 3-D ideal magnetohydrodynamic equations in the arbitrary time interval [0,T].Fivesufficient conditions are given.Our results are motivated by two main ideas:one is to control theaccumulation of vorticity alone;the other is to generalize the corresponding geometric conditions of3-D Euler equations to 3-D ideal magnetohydrodynamic equations. 相似文献