全文获取类型
收费全文 | 1684篇 |
免费 | 199篇 |
国内免费 | 177篇 |
专业分类
化学 | 1278篇 |
晶体学 | 36篇 |
力学 | 70篇 |
综合类 | 16篇 |
数学 | 192篇 |
物理学 | 468篇 |
出版年
2024年 | 2篇 |
2023年 | 28篇 |
2022年 | 29篇 |
2021年 | 49篇 |
2020年 | 49篇 |
2019年 | 57篇 |
2018年 | 47篇 |
2017年 | 40篇 |
2016年 | 59篇 |
2015年 | 75篇 |
2014年 | 84篇 |
2013年 | 121篇 |
2012年 | 131篇 |
2011年 | 145篇 |
2010年 | 80篇 |
2009年 | 77篇 |
2008年 | 111篇 |
2007年 | 93篇 |
2006年 | 80篇 |
2005年 | 87篇 |
2004年 | 82篇 |
2003年 | 54篇 |
2002年 | 53篇 |
2001年 | 51篇 |
2000年 | 55篇 |
1999年 | 36篇 |
1998年 | 22篇 |
1997年 | 23篇 |
1996年 | 31篇 |
1995年 | 20篇 |
1994年 | 20篇 |
1993年 | 26篇 |
1992年 | 26篇 |
1991年 | 23篇 |
1990年 | 22篇 |
1989年 | 12篇 |
1988年 | 8篇 |
1987年 | 10篇 |
1986年 | 6篇 |
1985年 | 9篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1979年 | 1篇 |
1978年 | 1篇 |
1977年 | 2篇 |
1973年 | 1篇 |
1970年 | 2篇 |
排序方式: 共有2060条查询结果,搜索用时 15 毫秒
101.
102.
103.
Prussian blue nanoparticles (PBNPs) have peroxidase-like activity for H2O2. However, PB alone have poor electrochemical performances. Herein, a strategy was proposed by direct in-situ growth PBNPs onto gold nanowires (AuNWs) surface to obtain the peroxidase-like activity with about 4.05 times higher than that of PBNPs alone. PBNPs@AuNWs was employed to construct a non - enzymatic electrochemical H2O2 sensor with the detection limit of 5.3×10−9 mol/L (S/N=3). The sensor was successfully used to detect H2O2 in human serum samples or secreted from living HeLa cells. It may be a competitive candidate for H2O2 assaying in biological samples or cellular investigation. 相似文献
104.
Efficient cross polarization with simultaneous adiabatic frequency sweep on the source and target channels 总被引:2,自引:2,他引:0
In this work, we propose a new and efficient heteronuclear cross polarization scheme, in which adiabatic frequency sweeps from far off-resonance toward on-resonance are applied simultaneously on both the source and target spins. This technique, which we call as Simultaneous ADIabatic Spin-locking Cross Polarization (SADIS CP), is capable of efficiently locking both the source and target spins with moderate power even in the presence of large spectral distribution and fast relaxation. It is shown that by keeping the time-dependent Hartmann-Hahn mismatch minimal throughout the mixing period, polarization transfer can be accelerated. Experiments are demonstrated in a powder sample of L-alanine. 相似文献
105.
费米子符号在费米液体理论中至关重要. 然而, 在Mott绝缘体中, 很强的电子Coulomb相互作用抑制了体系的电荷涨落并消除了电子交换带来的费米子符号问题. 本文首先回顾二分晶格上Hubbard模型的相位弦理论, 从弱关联的费米液体到强关联的反铁磁Mott绝缘体的转变可以由此得到统一理解. 在任意Coulomb作用强度U下, 我们首先导出Hubbard模型的严格的符号结构. 在小U极限下, 它回到通常的费米子符号; 在大U极限下, 它给出了t-J模型的相位弦符号. 在半满情形下, 我们构造了一种电子分数化的表象, 其中, 电荷子与自旋子通过演生的交互Chern-Simons规范场相互耦合. 由此导出的基态波函数拟设与低能有效理论可以定性刻画Hubbard模型的基态相图. 在弱关联区域, 费米液体的准粒子由电荷子与自旋子的束缚态构成, 其长程相位相干性取决于背景自旋的关联性质. 体系的Mott转变可以通过电荷子打开能隙或是通过自旋子玻色凝聚来实现. 相似文献
106.
Shang-Hao Liu Yen-Pin Yu Yu-Chi Lin Sheng-Yi Weng Tung-Feng Hsieh Hung-Yi Hou 《Journal of Thermal Analysis and Calorimetry》2014,116(3):1361-1367
Azo compounds are widely used in dyes, pigments, blowing agents, and initiators. Unfortunately, these compounds contain the bivalent –N–N– composition which might be cleavaged readily even under high ambient temperature. The self-accelerating decomposition might cause a runaway reaction and lead to a fire or explosion when the cooling system fails or other upsets occur. To investigate the thermal stability parameters of 2,2′-azobis(isobutyronitrile) with thermal hazard and mechanism, differential scanning calorimetry and thermal activity monitor III were applied with non-isothermal method and isothermal method to obtain onset temperature (T 0), maximum temperature (T max), and heat of decomposition (ΔH d). Thermal stability parameters play a pivotal role in thermal analysis, leading particularly to complex evaluation of the inherently safer design during preparation, processing, transport, or storage. The results provide sufficient thermokinetic parameters for process safety in terms of proactive loss prevention program. 相似文献
107.
Synthesis of CuI Trifluoromethylselenates for Trifluoromethylselenolation of Aryl and Alkyl Halides 下载免费PDF全文
Chaohuang Chen Li Ouyang Quanfu Lin Yanpin Liu Chuanqi Hou Prof. Dr. Yaofeng Yuan Prof. Dr. Zhiqiang Weng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):657-661
The development of new strategies for synthesis of trifluoromethylthiolate compounds is of considerable importance in pharmaceuticals, agrochemicals, and advanced materials. Accordingly, currently much attention is being devoted to the development of effective methods and reagents for their synthesis. In contrast, considerably less effort has been afforded to the development of preparing C?SeCF3 bonds. Herein we report a concise route to synthesize a family of copper(I) trifluoromethylselenolate reagents by the reaction of CuI with the Ruppert’s reagent (Me3SiCF3), KF, and elemental selenium in the presence of dinitrogen ligands in CH3CN at room temperature. The reagent [Cu(bpy)(SeCF3)]2 was proven to be air‐stable and highly efficient for nucleophilic trifluoromethylthselenolation of a broad range of (hetero)aryl halides and alkyl halides. This method represents a powerful protocol for the construction trifluoromethylselenolate compounds. 相似文献
108.
Cellulosic nanocomposite membranes from hydroxypropyl cellulose reinforced by cellulose nanocrystals 总被引:1,自引:0,他引:1
Lin Ma Lili Wang Lixin Wu Dongxian Zhuo Zixiang Weng Rongrong Ren 《Cellulose (London, England)》2014,21(6):4443-4454
Cellulosic nanocomposite membranes were prepared by incorporation of cellulose nanocrystals (CNCs) into a hydroxypropyl cellulose (HPC) matrix using a mixing/evaporation technique. CNCs were obtained from filter paper using the sulfuric acid hydrolysis method with the aid of ultrasonication. The relationship between the microstructure and mechanical properties of the CNCs/HPC nanocomposite membranes was studied. Scanning electron microscopy showed that the CNCs were well dispersed in the HPC matrix, and the fracture surface demonstrated a fibrous characteristic. With increasing CNCs content, the tensile strength and Young’s modulus of the CNCs/HPC nanocomposite membranes gradually increased. At 5 wt% content of CNCs, the strength was increased by 525 % and the Young’s modulus by 124 % compared with pure HPC membrane. Moreover, the effect of the phase change of HPC on the mechanical properties of the CNCs5wt%/HPC nanocomposite membranes and the corresponding mechanism were also studied. 相似文献
109.
X‐Ray Emission Spectroscopy: A Spectroscopic Measure for the Determination of NO Oxidation States in Fe–NO Complexes 下载免费PDF全文
Prof. Tsai‐Te Lu Dr. Tsu‐Chien Weng Prof. Wen‐Feng Liaw 《Angewandte Chemie (International ed. in English)》2014,53(43):11562-11566
Extensive study of the electronic structure of Fe‐NO complexes using a variety of spectroscopic methods was attempted to understand how iron controls the binding and release of nitric oxide. The comparable energy levels of NO π* orbitals and Fe 3d orbitals complicate the bonding interaction within Fe? NO complexes and puzzle the quantitative assignment of NO oxidation state. Enemark–Feltham notation, {Fe(NO)x}n, was devised to circumvent this puzzle. This 40‐year puzzle is revisited using valence‐to‐core X‐ray emission spectroscopy (V2C XES) in combination with computational study. DFT calculation establishes a linear relationship between ΔEσ2s*‐σ2p of NO and its oxidation state. V2C Fe XES study of Fe? NO complexes reveals the ΔEσ2s*‐σ2p of NO derived from NO σ2s*/σ2p→Fe1s transitions and determines NO oxidation state in Fe? NO complexes. Quantitative assignment of NO oxidation state will correlate the feasible redox process of nitric oxide and Fe‐nitrosylation biology. 相似文献
110.
Hua Chyn Lee Kah Weng Siew Maksudur R.Khan Sim Yee Chin Jolius Gimbun Chin Kui Cheng 《天然气化学杂志》2014,(5):645-656
The paper reports the development of cement clinker-supported nickel (with metal loadings of 5 wt%, 10 wt%, 15 wt% and 20 wt%) catalysts for glycerol dry (CO2) reforming reaction. XRF results showed that CaO constituted 62.0% of cement clinker. The physicochemical characterization of the catalysts revealed 32-folds increment of BET surface area (SBET) with the addition of nickel metal into the cement clinker, which was also corroborated by FESEM images. Significantly, XRD results suggested different types of Ni oxides formation with Ni loading, whilst Ca3SiO5 and Ca2Al0.67Mn0.33FeO5 were the main crystallite species for pure cement clinker. Temperature-programmed reduction analysis yielded three domains of H2 reduction peaks, viz. centered at approximately 750 K referred to as type-Ⅰ peaks, another peaks at 820 K denoted as type-Ⅱ peaks and the highest reduction peaks, type-Ⅲ recorded at above 1000 K. 20 wt% Ni was found to be the best loading with the highest XG and H2 yield, whilst the lowest methanation activity. Syngas with lower H2/CO ratios (0.6 to 1.5) were readily produced from glycerol dry reforming at CO2-to-Glycerol feed ratio (CGR) of unity. Nonetheless, carbon deposit comprised of whisker type (Cv) and graphitic-like type (Cc) species were found to be in majority on 20 wt%Ni/CC catalysts. 相似文献