全文获取类型
收费全文 | 5706篇 |
免费 | 1043篇 |
国内免费 | 596篇 |
专业分类
化学 | 3707篇 |
晶体学 | 49篇 |
力学 | 255篇 |
综合类 | 36篇 |
数学 | 786篇 |
物理学 | 2512篇 |
出版年
2024年 | 3篇 |
2023年 | 138篇 |
2022年 | 109篇 |
2021年 | 170篇 |
2020年 | 239篇 |
2019年 | 201篇 |
2018年 | 190篇 |
2017年 | 181篇 |
2016年 | 294篇 |
2015年 | 246篇 |
2014年 | 318篇 |
2013年 | 385篇 |
2012年 | 491篇 |
2011年 | 565篇 |
2010年 | 345篇 |
2009年 | 339篇 |
2008年 | 366篇 |
2007年 | 334篇 |
2006年 | 323篇 |
2005年 | 269篇 |
2004年 | 203篇 |
2003年 | 174篇 |
2002年 | 190篇 |
2001年 | 152篇 |
2000年 | 128篇 |
1999年 | 163篇 |
1998年 | 136篇 |
1997年 | 114篇 |
1996年 | 113篇 |
1995年 | 77篇 |
1994年 | 57篇 |
1993年 | 53篇 |
1992年 | 48篇 |
1991年 | 57篇 |
1990年 | 32篇 |
1989年 | 30篇 |
1988年 | 25篇 |
1987年 | 17篇 |
1986年 | 22篇 |
1985年 | 17篇 |
1984年 | 5篇 |
1983年 | 5篇 |
1982年 | 5篇 |
1981年 | 6篇 |
1980年 | 1篇 |
1979年 | 2篇 |
1978年 | 4篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有7345条查询结果,搜索用时 31 毫秒
61.
62.
Zhi-Qiang Hou Rui-Zhe Zhang Li-Gang Luo Jing Yang Chun-Ze Liu Yuan-Yuan Wang Li-Yi Dai 《Chemical Papers》2015,69(3):490-494
The reaction of phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water was studied. The effects of various operating conditions, such as reaction temperature, reaction time, the mole ratio of phenylacetonitrile/water/methanol or ethanol on the product yield were systematically investigated. The optimal yield of methyl phenylacetate for phenylacetonitrile in supercritical methanol in a system containing a small volume of water was 70 % at 583 K and 2.5 h. The optimal yield of ethyl phenylacetate for phenylacetonitrile in supercritical ethanol with a small volume of water was 80 % at 583 K and 1.0 h. At the same time, a feasible mechanism was proposed for phenylacetonitrile in supercritical methanol and ethanol in a system containing a small volume of water. 相似文献
63.
In this study, the poly(L-lactide)/poly(D-lactide)(PLLA/PDLA) blends with different optical purities of PLLA and various molecular weights of PDLA are prepared by solution mixing, and the stereocomplex formation and phase separation behaviors of these blends are investigated. Results reveal that optical purity and molecular weight do not vary the crystal structure of PLA stereocomplex(sc) and homochiral crystallites(hc). As the optical purity increasing in the blends, the melting temperature of sc(Tsc) and the content of sc(ΔHsc) increased, while the melting temperature of hc(Thm) hardly changes, although the content of hc(ΔHhm) decreased gradually. The Tsc and ΔHsc are also enhanced as the molecular weight of PDLA reduces, and the ΔHhm reduces rapidly even though the Thm does not vary apparently. With lower optical purities of PLLA and higher molecular weights of PDLA, three types of crystals form in the blends, i.e., PLA sc, PLLA hc and PDLA hc. As molecular weight decreases and optical purity enhances, the crystal phase decreases to two(sc and PDLA hc), and one(sc) finally. This investigation indicates that the phase separation behavior between PLLA and PDLA in the PLLA/PDLA blends not only depends on molecular weights, but also relies on the optical purities of polymers. 相似文献
64.
Enhanced Photocatalytic Reduction of CO2 to CO through TiO2 Passivation of InP in Ionic Liquids 下载免费PDF全文
Guangtong Zeng Jing Qiu Bingya Hou Haotian Shi Dr. Yongjing Lin Mark Hettick Prof. Ali Javey Prof. Stephen B. Cronin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(39):13502-13507
A robust and reliable method for improving the photocatalytic performance of InP, which is one of the best known materials for solar photoconversion (i.e., solar cells). In this article, we report substantial improvements (up to 18×) in the photocatalytic yields for CO2 reduction to CO through the surface passivation of InP with TiO2 deposited by atomic layer deposition (ALD). Here, the main mechanisms of enhancement are the introduction of catalytically active sites and the formation of a pn‐junction. Photoelectrochemical reactions were carried out in a nonaqueous solution consisting of ionic liquid, 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([EMIM]BF4), dissolved in acetonitrile, which enables CO2 reduction with a Faradaic efficiency of 99 % at an underpotential of +0.78 V. While the photocatalytic yield increases with the addition of the TiO2 layer, a corresponding drop in the photoluminescence intensity indicates the presence of catalytically active sites, which cause an increase in the electron‐hole pair recombination rate. NMR spectra show that the [EMIM]+ ions in solution form an intermediate complex with CO2?, thus lowering the energy barrier of this reaction. 相似文献
65.
66.
Acid‐Labile Thermoresponsive Copolymers That Combine Fast pH‐Triggered Hydrolysis and High Stability under Neutral Conditions 下载免费PDF全文
Dr. Qilu Zhang Zhanyao Hou Benoit Louage Dr. Dingying Zhou Nane Vanparijs Prof. Dr. Bruno G. De Geest Prof. Dr. Richard Hoogenboom 《Angewandte Chemie (International ed. in English)》2015,54(37):10879-10883
Biodegradable polymeric materials are intensively used in biomedical applications. Of particular interest for drug‐delivery applications are polymers that are stable at pH 7.4, that is, in the blood stream, but rapidly hydrolyze under acidic conditions, such as those encountered in the endo/lysosome or the tumor microenvironment. However, an increase in the acidic‐degradation rate of acid‐labile groups goes hand in hand with higher instability of the polymer at pH 7.4 or during storage, thus posing an intrinsic limitation on fast degradation under acidic conditions. Herein, we report that a combination of acid‐labile dimethyldioxolane side chains and hydroxyethyl side chains leads to acid‐degradable thermoresponsive polymers that are quickly hydrolyzed under slightly acidic conditions but stable at pH 7.4 or during storage. We ascribe these properties to high hydration of the hydroxy‐containing collapsed polymer globules in conjunction with autocatalytic acceleration of the hydrolysis reactions by the hydroxy groups. 相似文献
67.
In this paper, we presented a novel, rapid and highly sensitive sensor for glutathione (GSH), cysteine (Cys) and histidine (His) based on the recovered fluorescence of the carbon quantum dots (CQDs)–Hg(II) system. The CQDs were synthesized by microwave-assisted approach in one pot according to our previous report. The fluorescence of CQDs could be quenched in the presence of Hg(II) due to the coordination occurring between Hg(II) and functional groups on the surface of CQDs. Subsequently, the fluorescence of the CQDs–Hg(II) system was recovered gradually with the addition of GSH, Cys or His due to their stronger affinity with Hg(II). A good linear relationship was obtained from 0.10 to 20 μmol L−1 for GSH, from 0.20 to 45 μmol L−1 for Cys and from 0.50 to 60 μmol L−1 for His, respectively. This method has been successfully applied to the trace detection of GSH, Cys or His in human serum samples with satisfactory results. The proposed method was simple in design and fast in operation, which demonstrated great potential in bio-sensing fields. 相似文献
68.
69.
70.
Structures and Fluorescent Properties of Cadmium(II) Complexes with 1D and 2D Structures Based on Tridentate Benzimidazole Ligands 下载免费PDF全文
The cadmium(II) complexes [CdL1(m‐nba)2] ( 1 ), [CdL1(p‐nba)2] · C2H5OH ( 2 ), [CdL2(p‐nba)2] · CH3OH ( 3 ), and [CdL2(p‐nbat)2] ( 4 ) containing the ligands L1 and L2 [L1 = 2,6‐bis(benzimidazol‐2‐yl)pyridine, L2 = bis(2‐benzimidazolylmethyl)amine] were synthesized and characterized (m‐nba, p‐nba, and p‐nbat are the anions of p‐nitrobenzoic acid, m‐nitrobenzoic acid, and p‐nitrobenzeneacetic acid, respectively). The complexes were investigated by X‐ray single crystal diffraction, elemental analysis as well as IR and fluorescence spectroscopy. Compounds 1 – 3 contain a distorted pentagonal bipyramidal coordination sphere with CdII coordinated by two carboxylate ligands in bidentate‐chelating mode, whereas complex 4 exhibits a distorted octahedral arrangement with one carboxylate ligand in bidentate‐chelating and the other in monodentate coordination mode. 1 and 2 form a 1D chain interplayed by hydrogen bonding and strong π–π stacking interactions. 3 and 4 vary from 1D chain into 2D single‐layer and double‐layer networks because of more extensive hydrogen bonding interactions. The complexes show emission maxima in the blue region in the solid state and emission bands are red‐shifted compared to those of the free ligands. 相似文献