首页 | 本学科首页   官方微博 | 高级检索  
文章检索
  按 检索   检索词:      
出版年份:   被引次数:   他引次数: 提示:输入*表示无穷大
  收费全文   1030篇
  免费   70篇
  国内免费   74篇
化学   743篇
晶体学   4篇
力学   46篇
综合类   25篇
数学   100篇
物理学   256篇
  2024年   2篇
  2023年   111篇
  2022年   42篇
  2021年   49篇
  2020年   85篇
  2019年   49篇
  2018年   32篇
  2017年   58篇
  2016年   51篇
  2015年   54篇
  2014年   47篇
  2013年   54篇
  2012年   65篇
  2011年   52篇
  2010年   43篇
  2009年   63篇
  2008年   20篇
  2007年   33篇
  2006年   37篇
  2005年   21篇
  2004年   13篇
  2003年   20篇
  2002年   18篇
  2001年   29篇
  2000年   8篇
  1999年   31篇
  1998年   17篇
  1997年   16篇
  1996年   5篇
  1995年   6篇
  1994年   6篇
  1993年   2篇
  1992年   6篇
  1991年   9篇
  1990年   7篇
  1989年   5篇
  1988年   5篇
  1986年   1篇
  1959年   2篇
排序方式: 共有1174条查询结果,搜索用时 15 毫秒
131.
将油性剂油酸(OA)填充进多壁碳纳米管(MWCNTs)的空腔内制备复合物,再以复合物为添加剂制备一种纳米流体,考察了复合物的质量分数、MWCNTs的酸处理时间以及摩擦测试条件等对纳米流体摩擦学性能的影响,并分析了复合物的润滑机理. 结果表明:油酸被成功填充到经酸处理的MWCNTs管内,填充率约20%;摩擦过程中,复合物制备的纳米流体的摩擦系数有不断减小趋势,其减摩效果甚至优于同等含量的油酸乳化液;当复合物的质量分数为0.1%左右时,纳米流体可获得最佳的减摩、抗磨效果;随着酸化处理时间的增加,复合物制备的纳米流体的减摩、抗磨性能会有所提高. 摩擦过程中,复合物可释放出油酸并形成润滑膜,MWCNTs则能够在油酸形成的润滑膜上发挥“微轴承”的作用,从而使复合物获得更加优良的减摩、抗磨效果.   相似文献   
132.
Tomography phase microscopy (TPM) is a new microscopic method that can quantitatively yield the volumetric 3D distribution of a sample׳s refractive index (RI), which is significant for cell biology research. In this paper, a controllable TPM system is introduced. In this system a circulatory phase-shifting method and piezoelectric ceramic are used which enable the TPM system to record the 3D RI distribution at a more controllable speed, from 1 to 40 fps, than in the other TPM systems reported. The resolution of the RI distribution obtained by this controllable TPM is much better than that in images recorded by phase contrast microscopy and interference tomography microscopy. The realization of controllable TPM not only allows for the application of TPM to the measurement of kinds of RI sample, but also contributes to academic and technological support for the practical use of TPM.  相似文献   
133.
A chiral random grain boundary (RGB) phase was recently observed in a hockey-stick biphenyl-substituted 1,3,4-oxadiazole derivative. In the RGB phase, achiral molecules self-assemble into randomly oriented blocks of chiral smectic layers and the motif of the unique microstructure is attributed to the similarity of hockey-stick molecules both to bent-core and to rod-like molecules. In order to explore the effect of molecular structure on the RGB phase in detail, we systematically change the molecular design. When the flexible tail decreases, the high-temperature Smectic A (SmA) phase is replaced by a nematic phase, showing a phase sequence of Iso-N-SmA-RGB-Cryst in 2-(4-dodecyloxyphenyl)-5-biphenyl-1,3,4-oxadiazole. However, when we replace the 1,3,4-oxadiazole group by the 1,3,4-thiadiazole group, the bending angle increases in the 1,3,4-thiadiazole derivatives and the RGB phase disappears. Or when the length of the arm becomes short in naphthalene-substituted 1,3,4-oxadiazole, these molecules exhibited only normal rod-like molecules’ mesomorphism. These results will provide deep insights on the relationship of molecular structure and mesophase structural property.  相似文献   
134.
随着社会经济的快速发展,含氯有机物,特别是含氯苯系物,在农业、化工和医药等领域的使用量逐年增多,而使用过程中不合理的排放和控制致使含氯苯系物对生态环境,特别是水体环境的污染日趋严重.含氯苯系物具有高致毒致癌性,易生物富集,且很难被完全降解矿化,已被国家环保局认定为优先控制污染物.常规的废水处理工艺,如吸附、氧化及生物降解等,效率不高,且具有二次污染风险.电催化氢化脱氯技术是一种新型特别针对废水中含氯有机污染物的处理工艺,是通过在阴极电解还原水,原位生成原子态氢,以进攻苯环上C.Cl键,通过C.Cl键断裂H原子取代,使含氯苯系物完全转化为苯系物,达到去毒去害化的目的,近年来越来越受到研究者的关注.在整个电催化氢化脱氯技术中,高效稳定的电催化剂合成是关键,决定着脱氯效率、脱氯动力学、产物选择性及能量的利用率.本文报道了一种简易、无需添加任何表面活性剂的湿式还原法制备金属钯/氮化钛(Pd/TiN)和金属钯/碳(Pd/C)复合材料.在该复合材料中,金属钯颗粒具有均一的纳米尺寸(约5.0 nm)和球状形貌,且均匀分布在TiN和C载体上.作为针对水体中代表性含氯苯系物2,4-二氯苯酚的电催化氢化脱氯反应催化剂,Pd/TiN所展现的活性和稳定性均优于TiN和Pd/C,这源于TiN载体的促进作用.当TiN与Pd复合时,相应形成的Pd-TiN界面可改变Pd表面的电子结构,进一步优化Pd产活性氢及其吸附活化2,4-二氯苯酚的性能,因而其催化氢化脱氯活性增加.阴极工作电压是该催化反应中一个重要操作参数,决定了电催化氢化脱氯的效率和最终产物的构成.实验表明,.0.80 V vs Ag/AgCl是最佳操作电压,此时2,4-二氯苯酚的电催化氢化脱氯效率最高,可达到93.27%,且可实现最大程度的2,4-二氯苯酚向苯酚转化.脱氯反应路径研究发现,在Pd/TiN催化剂上2,4-二氯苯酚脱氯反应路径为2,4-二氯苯酚→对位一氯苯酚,邻位一氯苯酚→苯酚,但Pd/TiN对邻位和对位的C.Cl键断裂基本没有选择性.本文提供了一种新的有效调控Pd材料电催化氢化脱氯性能的方法,可望用于其他氢化反应体系的高效催化剂的设计合成,同时可推动电催化氢化脱氯技术在环境污染修复中的应用.  相似文献   
135.
A novel fluorescent probe was developed by integrating chlorinated coumarin and benzothiazolylacetonitrile and exploited for simultaneous detection of cysteine (Cys), homocysteine (Hcy), and glutathione (GSH). Featuring four binding sites and different reaction mechanisms for different biothiols, this probe exhibited rapid fluorescence turn‐on for distinguishing Cys, Hcy, and GSH with 108‐, 128‐, 30‐fold fluorescence increases at 457, 559, 529 nm, respectively, across different excitation wavelengths. Furthermore, the probe was successfully applied to the fluorescence imaging of endogenous Cys and GSH and exogenous Cys, Hcy, and GSH in living cells.  相似文献   
136.
《中国化学快报》2023,34(3):107639
The development of out-of-equilibrium self-assembly systems using light as input fuel is highly desirable and promising for the fabrication of smart supramolecular materials. Herein, we report the construction of new artificial light-fueled dissipative molecular and macroscopic self-assembly systems based on a visible-light-responsive transient quadruple H-bonding array, which consists of an azobenzene-modified ureidopyrimidinone (UPy) module (Azo-O-UPy) and a nonphotoactive diamidonaphthyridine (DAN) derived competitive binder (Napy-1). The visible light (410 nm) irradiation can induce the E to Z isomerization of the azobenzene unit of E-Azo-O-UPy to produce Z-Azo-O-UPy with an opened UPy binding site, which can complex with Napy-1 to form a quadruply H-bonded heterodimer. The heterodimer is metastable and can be quickly disassembled in dark, owing to the fast thermal relaxation of Z-Azo-O-UPy to E-Azo-O-UPy. While introducing such transient quadruple H-bonding interaction into a linear polymer system or a polymeric gel system, light-fueled out-of-equilibrium polymeric assembly both at molecular and macro-scale can be achieved.  相似文献   
137.
《中国化学快报》2023,34(6):107997
Levofloxacin (LVFX) as a representative drug of quinolone antibiotics is widely used in clinical, and its residues enriched in water bodies and sideline products seriously damage human health. It is imperative to develop a real-time/on-site sensing method for monitoring residual antibiotics. Here, we report a portable sensing platform by utilizing a composite fluorescent nanoprobe constructed by the cerium ions (Ce3+) coordination functionalized CdTe quantum dots (QDs) for the visual and quantitative detection of LVFX residues. This fluorescent probe provides a distinct color variation from red to green, which shows a good linear relationship to LVFX residues concentrations in the range of 0-6.0 µmol/L with a sensitive limit of detection (LOD) of 16.3 nmol/L. The smartphone platform with Color Analyzer App installed, which could accomplish quantified detection of LVFX in water, milk, and raw pork with a LOD of 27.9 nmol/L. The facile sensing method we proposed realizes rapid visualization of antibiotics residual in the environment and provides a practical application pathway in food safety and human health.  相似文献   
138.
《中国化学快报》2023,34(9):108156-51
Hydrogen evolution from water electrolysis has become an important reaction for the green energy revolution. Traditional precious metals and their compounds are excellent catalysts for producing hydrogen; however, their high cost limits their large-scale practical application. Therefore, the development of affordable electrocatalysts to replace these precious metals is important. Transition metal phosphides(TMPs) have shown remarkable performance for hydrogen evolution and garnered considerable ...  相似文献   
139.
《中国化学快报》2023,34(9):108157
This work reported the lanthanide ion (Gd3+) doped tungsten trioxide (Gd-WO3) nanocrystal for remarkable promoted photocatalytic degradation of organic pollutants and simultaneous in-situ H2O2 production. With doped lanthanide ion (Gd3+), Gd-WO3 showed a much broad and enhanced solar light absorption, which not only promoted the photocatalytic degradation efficiency of organic compounds, but also provided a suitable bandgap for direct reduction of oxygen to H2O2. Additionally, the isolated Gd3+ on WO3 surface can efficiently weaken the *OOH binding energy, increasing the activity and selectivity of direct reduction of oxygen to H2O2, with a rate of 0.58 mmol L−1 g−1 h−1. The in-situ generated H2O2 can be subsequently converted to OH based on Fenton reaction, further contributed to the overall removal of organic pollutants. Our results demonstrate a cascade photocatalytic oxidation-Fenton reaction which can efficiently utilize photo-generated electrons and holes for organic pollutants treatment.  相似文献   
140.
《中国化学快报》2023,34(7):108036
The first example of TBAI/H2O cooperative electrocatalytic coupling-annulation of quinoxalin-2(1H)-ones with N-arylglycines was developed. A broad range of tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones were obtained in good to excellent yields with exclusive chemoselectivities and excellent regioselectivities. The H-hydrogen bond served as a key factor for the electrocatalytic production of aminomethyl radical at lower oxidative potential.  相似文献   
设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号