全文获取类型
收费全文 | 402篇 |
免费 | 92篇 |
国内免费 | 36篇 |
专业分类
化学 | 157篇 |
晶体学 | 6篇 |
力学 | 18篇 |
综合类 | 2篇 |
数学 | 23篇 |
物理学 | 324篇 |
出版年
2024年 | 1篇 |
2023年 | 6篇 |
2022年 | 15篇 |
2021年 | 13篇 |
2020年 | 16篇 |
2019年 | 19篇 |
2018年 | 20篇 |
2017年 | 21篇 |
2016年 | 19篇 |
2015年 | 15篇 |
2014年 | 25篇 |
2013年 | 37篇 |
2012年 | 21篇 |
2011年 | 25篇 |
2010年 | 21篇 |
2009年 | 27篇 |
2008年 | 25篇 |
2007年 | 19篇 |
2006年 | 21篇 |
2005年 | 17篇 |
2004年 | 15篇 |
2003年 | 18篇 |
2002年 | 17篇 |
2001年 | 13篇 |
2000年 | 15篇 |
1999年 | 8篇 |
1998年 | 17篇 |
1997年 | 2篇 |
1996年 | 4篇 |
1995年 | 4篇 |
1994年 | 7篇 |
1993年 | 4篇 |
1992年 | 2篇 |
1990年 | 3篇 |
1989年 | 1篇 |
1988年 | 1篇 |
1987年 | 4篇 |
1986年 | 2篇 |
1985年 | 4篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1979年 | 2篇 |
排序方式: 共有530条查询结果,搜索用时 15 毫秒
1.
Saqib Kamal Arif I. Inamdar Kuan-Ru Chiou Batjargal Sainbileg Muhammad Usman Jenq-Wei Chen Tzuoo-Tsair Luo Michitoshi Hayashi Chen-Hsiung Hung Wen-Feng Liaw Kuang-Lieh Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(30):e202103905
The dielectric properties of coordination polymers has been a topic of recent interest, but the role of different functional groups on the dielectric properties of these polymers has not yet been fully addressed. Herein, the effects of electron-donating (R=NH2) and electron-withdrawing (R=NO2) groups on the dielectric behavior of such materials were investigated for two thermally stable and guest-free Zn-based coordination polymers, [Zn(L1)(L2)]n ( 1 ) and [Zn(L1)(L3)]n ( 2 ) [L1=2-(2-pyridyl) benzimidazole (Pbim), L2=5-aminoisophthalate (Aip), and L3=5-nitroisophthalate (Nip)]. The results of dielectric studies of 1 revealed that it possesses a high dielectric constant (κ=65.5 at 1 kHz), while compound 2 displayed an even higher dielectric constant (κ=110.3 at 1 kHz). The electron donating and withdrawing effects of the NH2 and NO2 substituents induce changes in the polarity of the polymers, which is due to the inductive effect from the aryl ring for both NO2 and NH2. Theoretical results from density functional theory (DFT) calculations, which also support the experimental findings, show that both compounds have a distinct electronic behavior with diverse wide bandgaps. The significance of the current work is to provide information about the structure-dielectric property relationships. So, this study promises to pave the way for further research on the effects of different functional groups on coordination polymers on their dielectric properties. 相似文献
2.
对石英音叉增强型光声光谱(QEPAS)系统中常用的石英音叉进行了有限元模态计算,获得石英音叉前6阶振型与模态频率,认知了第4阶对称摆动振型为有效振动,利用单因素法分析了石英音叉的音臂长度l1、音臂宽度w1、音臂厚度t、音臂切角θ、音臂圆孔直径d及音臂圆孔高度h对低阶有效共振频率(Fre)的影响,敏感度依次为: l1> w1>d>θ>t>h,考虑实际设计情形,筛选出了l1,w1,d与h四个石英音叉设计变量,采用Box-Behnken实验设计方案与RSM(response surface methodology)方法,以Fre为函数目标,建立l1,w1,d与h的二次回归响应面模型,得到了参数之间的交互作用,利用Design-Expert软件对响应面模型进行设计参数反求,结果表明,在15 000 Hz≤Fre≤25 000 Hz计算区域内误差较小,基本满足QEPAS系统的计算需求,所提出的研究与设计方法具有一定通用性,可为QEPAS系统中石英音叉结构参数设计提供参考。 相似文献
3.
4.
Metalation of CH2OH-substituted triazolium salts with CoCl2 under basic conditions affords C,O-bidentate chelating carbene Co(III) complexes ( 3a , 3b ), while analogous phenyl-substituted triazolium salts produce monodentate carbene Co(II) complexes ( 3c , 3d ). The distinct substituent-induced properties of the metal centers were demonstrated by electrochemical measurements and catalytic activities in two specific processes. The complexes showed appreciable activity in the reduction of C=O bonds through hydrosilylation, with methoxybenzene-functionalized triazolylidene Co(III) complex 3a achieving a high selectivity towards aldehydes vs. ketones with turnover frequencies (TOFs) up to 200 h−1. The C,O-chelate systems were also active catalysts in the Biginelli process, a one-step three-component reaction for efficient dihydropyrimidinone synthesis. Optimization of reaction conditions provides high activity with complex 3a , reaching TOFs of 800 h−1, the highest activity known for cobalt NHC complexes to date. 相似文献
5.
Jos Renato Guimares Letícia Passos Miranda Roberto Fernandez-Lafuente Paulo Waldir Tardioli 《Molecules (Basel, Switzerland)》2021,26(1)
The performance of the previously optimized magnetic cross-linked enzyme aggregate of Eversa (Eversa-mCLEA) in the enzymatic synthesis of biolubricants by transesterification of waste cooking oil (WCO) with different alcohols has been evaluated. Eversa-mCLEA showed good activities using these alcohols, reaching a transesterification activity with isoamyl alcohol around 10-fold higher than with methanol. Yields of isoamyl fatty acid ester synthesis were similar using WCO or refined oil, confirming that this biocatalyst could be utilized to transform this residue into a valuable product. The effects of WCO/isoamyl alcohol molar ratio and enzyme load on the synthesis of biolubricant were also investigated. A maximum yield of around 90 wt.% was reached after 72 h of reaction using an enzyme load of 12 esterification units/g oil and a WCO/alcohol molar ratio of 1:6 in a solvent-free system. At the same conditions, the liquid Eversa yielded a maximum ester yield of only 34%. This study demonstrated the great changes in the enzyme properties that can be derived from a proper immobilization system. Moreover, it also shows the potential of WCO as a feedstock for the production of isoamyl fatty acid esters, which are potential candidates as biolubricants. 相似文献
6.
给出了硅微机械谐振陀螺仪的结构,介绍了硅微机械谐振陀螺仪的工作原理,详细推导并给出了陀螺仪的输出频率和标度因数非线性的计算公式;基于影响谐振陀螺仪标度因数的参数,分析了由谐振器的振幅和梳齿静电驱动力引起的硅微机械谐振陀螺仪的非线性特性,给出了振动幅度与谐振频率关系的表达式.实验结果表明,陀螺仪的整体性能主要取决于谐振器振动幅度的稳定性. 相似文献
7.
报道了基于掺氧化镁准周期极化铌酸锂(MgO:QPLN)的多光参量振荡器电场调谐特性理论与实验研究. 通过对电场调谐能力与极化结构参数间关联性的理论分析, 确定了高正负晶畴比MgO:QPLN电场调谐的可行性, 并模拟得到跨周期参量光输出波长与加载电压的关系曲线. 实验中通过对MgO:QPLN有效的电场加载, 实现了3.84 μm波段参量光的电场调谐, 频谱调谐带宽约6 nm, 调谐速率接近1 nm/kV, 进一步结合温度调谐, 实现了参量光宽谱段高精度的连续调谐. 所获得实验结果与理论模拟结果基本符合, 电场调谐在精度控制、快速响应方面相比于传统温度调谐更具技术优势. 相似文献
8.
Ytterbium, erbium, aluminum tri-doped zinc oxide crystal was synthesized, which can turn color from red to green up-conversion luminescence through adjusting aluminum content. When the aluminum concentration reached 4?mol%, the color of up-conversion emission first turn from red to green. Meanwhile, the ratio of red to green emission reduced from 25.32 to 0.26, and the coordinates of chromaticity coordinate calculation changes from (0.5749, 0.3378) to (0.2190, 0.7169) with aluminum concentration range from 0 to 4?mol%. The up-conversion emission peaks at 521, 542, and 660?nm of sample originate from the transitions of 2H11/2 → 4I15/2, 4S3/2 → 4I15/2, and 4F9/2 → 4I15/2 of erbium ions, respectively. X-ray diffraction patterns perform the better crystallization degree with increasing aluminum concentration. The scanning electron microscopy images show the porous and lamellar structures with different aluminum concentrations. A convenient but effective design to obtain ytterbium, erbium, aluminum tri-doped zinc oxide up-conversion luminescence is reported, which can turn color from red to green. 相似文献
9.
10.
D.C. LiL. Fang S.K. DengK.Y. Kang L.X. ShenW.H. Wei H.B. Ruan 《Physica B: Condensed Matter》2012,407(8):1238-1243
The total energy and electronic structures for type-I (β phase) and type-VIII (α phase) Ba8Ga16Sn30 clathrates under hydrostatic pressure have been investigated using density functional theory (DFT) calculations. It was found that the type-VIII phase is more stable than the type-I one at ambient conditions and that β→α phase transition can not occur under hydrostatic pressure. The band structures show that the type-I and type-VIII Ba8Ga16Sn30 are indirect semiconductors with band gaps of 0.24 eV and 0.19 eV, respectively. The results suggested that type-I clathrate Ba8Ga16Sn30 has a larger value of the thermoelectric (TE) power than that of type-VIII clathrate. We found that pressure tuning changes the k-point of conduction band minimum (CBM) in the Brillouin zone for β-phase, but it is not the case for α-phase. Furthermore, the results show that the pressure can change the interaction between guest atoms and the host lattice, and consequently results in the decrease of the band gap of β-phase and the increase of the band gap of α-phase, indicating that the pressure effect can play an important role in the magnitude of the TE power. 相似文献