全文获取类型
收费全文 | 22409篇 |
免费 | 3520篇 |
国内免费 | 4385篇 |
专业分类
化学 | 22966篇 |
晶体学 | 260篇 |
力学 | 544篇 |
综合类 | 185篇 |
数学 | 538篇 |
物理学 | 5821篇 |
出版年
2024年 | 61篇 |
2023年 | 322篇 |
2022年 | 769篇 |
2021年 | 820篇 |
2020年 | 1052篇 |
2019年 | 840篇 |
2018年 | 733篇 |
2017年 | 893篇 |
2016年 | 1101篇 |
2015年 | 1045篇 |
2014年 | 1225篇 |
2013年 | 1867篇 |
2012年 | 1975篇 |
2011年 | 1556篇 |
2010年 | 1356篇 |
2009年 | 1462篇 |
2008年 | 1488篇 |
2007年 | 1556篇 |
2006年 | 1398篇 |
2005年 | 1303篇 |
2004年 | 1265篇 |
2003年 | 986篇 |
2002年 | 738篇 |
2001年 | 635篇 |
2000年 | 531篇 |
1999年 | 444篇 |
1998年 | 433篇 |
1997年 | 395篇 |
1996年 | 298篇 |
1995年 | 324篇 |
1994年 | 250篇 |
1993年 | 257篇 |
1992年 | 186篇 |
1991年 | 186篇 |
1990年 | 155篇 |
1989年 | 96篇 |
1988年 | 83篇 |
1987年 | 39篇 |
1986年 | 34篇 |
1985年 | 23篇 |
1984年 | 25篇 |
1983年 | 15篇 |
1982年 | 19篇 |
1981年 | 14篇 |
1980年 | 11篇 |
1979年 | 14篇 |
1978年 | 6篇 |
1976年 | 6篇 |
1974年 | 6篇 |
1972年 | 5篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
11.
Leila Torkian Mostafa M. Amini Tayebeh Gorji Omid Sadeghi 《Arabian Journal of Chemistry》2019,12(7):1315-1321
In this study, multiwalled carbon nanotube (MWCNT) was modified by the pyridine group using a silane agent and characterized by infrared spectroscopy (IR), thermal analysis (TG/DTA), and elemental analysis (CHN) and scanning electron microscopy (SEM). The application of this sorbent was investigated in determination of lead ions in aqueous samples, using flame atomic absorption spectrometry (FAAS). Through this study, different parameters such as pH and sample flow rate on adsorption process and eluent concentration, volume and flow rate were optimized. The limit of detection (LOD), the relative standard deviation and the recovery of the method were 2 ng mL?1, 1.3% and 99.7%, respectively. Two standard reference materials (NIST 1571 and NIST 1572) were used to verify accuracy of this method. Finally, the sorbent was successfully applied for extraction and determination of low levels of Pb(II) ions in aqueous samples. 相似文献
12.
Pu Duan Bo Zhi Luke Coburn Christy L. Haynes Klaus Schmidt-Rohr 《Magnetic resonance in chemistry : MRC》2020,58(11):1130-1138
The composition of fluorescent polymer nanoparticles, commonly referred to as carbon dots, synthesized by microwave-assisted reaction of citric acid and ethylenediamine was investigated by 13C, 13C{1H}, 1H─13C, 13C{14N}, and 15N solid-state nuclear magnetic resonance (NMR) experiments. 13C NMR with spectral editing provided no evidence for significant condensed aromatic or diamondoid carbon phases. 15N NMR showed that the nanoparticle matrix has been polymerized by amide and some imide formation. Five small, resolved 13C NMR peaks, including an unusual ═CH signal at 84 ppm (1H chemical shift of 5.8 ppm) and ═CN2 at 155 ppm, and two distinctive 15N NMR resonances near 80 and 160 ppm proved the presence of 5-oxo-1,2,3,5-tetrahydroimidazo[1,2-a]pyridine-7-carboxylic acid (IPCA) or its derivatives. This molecular fluorophore with conjugated double bonds, formed by a double cyclization reaction of citric acid and ethylenediamine as first shown by Y. Song, B. Yang, and coworkers in 2015, accounts for the fluorescence of the carbon dots. Cross-peaks in a 1H─13C HETCOR spectrum with brief 1H spin diffusion proved that IPCA is finely dispersed in the polyamide matrix. From quantitative 13C and 15N NMR spectra, a high concentration (18 ± 2 wt%) of IPCA in the carbon dots was determined. A pronounced gradient in 13C chemical-shift perturbations and peak widths, with the broadest lines near the COO group of IPCA, indicated at least partial transformation of the carboxylic acid of IPCA by amide or ester formation. 相似文献
13.
14.
New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers
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. Rinaldo Poli 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(19):6988-7001
The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed. 相似文献
15.
Zinc polyoxometalate on activated carbon: an efficient catalyst for selective oxidation of alcohols with hydrogen peroxide
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)
[PW11ZnO39]5? was immobilized on activated carbon and characterized using Fourier transform infrared, X‐ray diffraction, Brunauer–Emmett–Teller and elemental analysis techniques. Effective oxidation of various alcohols with hydrogen peroxide was performed in the presence of this catalyst. Easy separation of the catalyst from the reaction mixture, cheapness, high activity and selectivity, stability as well as retained activity in subsequent catalytic cycles make this supported catalyst suitable for small‐scale synthesis. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
16.
分析学生对二氧化碳的3个典型学科认知障碍,以“二氧化碳的捕捉”为情境,通过“尝试捕捉二氧化碳”“谁在捕捉二氧化碳”“捕捉背后的原理”等3个主要环节,实现对学科认知障碍的突破,展示了一种新的中考复习教学思路。 相似文献
17.
《Comptes Rendus Chimie》2015,18(9):993-1000
The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism. 相似文献
18.
G.E. Farr 《Discrete Mathematics》2019,342(5):1510-1519
This paper continues the study of combinatorial properties of binary functions — that is, functions such that , where is a finite set. Binary functions have previously been shown to admit families of transforms that generalise duality, including a trinity transform, and families of associated minor operations that generalise deletion and contraction, with both these families parameterised by the complex numbers. Binary function representations exist for graphs (via the indicator functions of their cutset spaces) and indeed arbitrary matroids (as shown by the author previously). In this paper, we characterise degenerate elements – analogues of loops and coloops – in binary functions, with respect to any set of minor operations from our complex-parameterised family. We then apply this to study the relationship between binary functions and Tutte’s alternating dimaps, which also support a trinity transform and three associated minor operations. It is shown that only the simplest alternating dimaps have binary representations of the form we consider, which seems to be the most direct type of representation. The question of whether there exist other, more sophisticated types of binary function representations for alternating dimaps is left open. 相似文献
19.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
20.
Guangrui Chen Yuxing Yan Dr. Jie Wang Prof. Yong Sik Ok Guiyuan Zhong Prof. Bu Yuan Guan Prof. Yusuke Yamauchi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(44):19831-19836
Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition. 相似文献