全文获取类型
收费全文 | 10885篇 |
免费 | 1192篇 |
国内免费 | 1360篇 |
专业分类
化学 | 9177篇 |
晶体学 | 78篇 |
力学 | 244篇 |
综合类 | 133篇 |
数学 | 302篇 |
物理学 | 3503篇 |
出版年
2024年 | 18篇 |
2023年 | 195篇 |
2022年 | 342篇 |
2021年 | 531篇 |
2020年 | 500篇 |
2019年 | 412篇 |
2018年 | 332篇 |
2017年 | 503篇 |
2016年 | 569篇 |
2015年 | 539篇 |
2014年 | 721篇 |
2013年 | 784篇 |
2012年 | 830篇 |
2011年 | 647篇 |
2010年 | 582篇 |
2009年 | 723篇 |
2008年 | 637篇 |
2007年 | 681篇 |
2006年 | 583篇 |
2005年 | 573篇 |
2004年 | 491篇 |
2003年 | 338篇 |
2002年 | 271篇 |
2001年 | 172篇 |
2000年 | 165篇 |
1999年 | 164篇 |
1998年 | 133篇 |
1997年 | 128篇 |
1996年 | 92篇 |
1995年 | 125篇 |
1994年 | 81篇 |
1993年 | 84篇 |
1992年 | 77篇 |
1991年 | 40篇 |
1990年 | 59篇 |
1989年 | 48篇 |
1988年 | 55篇 |
1987年 | 43篇 |
1986年 | 34篇 |
1985年 | 29篇 |
1984年 | 18篇 |
1983年 | 16篇 |
1982年 | 32篇 |
1981年 | 14篇 |
1980年 | 5篇 |
1979年 | 12篇 |
1978年 | 3篇 |
1971年 | 2篇 |
1969年 | 1篇 |
1959年 | 1篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
101.
研制了一种新型微电流放大器系统,用于检测琢-Hemolysin生物蛋白纳米通道在单分子检测实验中所产生的微弱电流信号(<100 pA)。在1 mol/L KCl、10 mmol/L Tris-HCl,1 mmol/L EDTA的缓冲液(pH 8.0)中测定了DNA-PEG-DNA交联物与纳米通道的穿越和碰撞信号。实验中使用3 kHz贝塞尔滤波器和100 kHz模数转换器来对电流进行采样。结果表明,此放大器系统能够有效降低电流记录过程中的噪音,有利于分辨待测物分子与纳米通道作用所产生的较小阻断的电流信号(<10 pA)。 相似文献
102.
电化学还原氧化石墨烯用于四环素电催化检测 总被引:1,自引:0,他引:1
四环素(TTC)因其广泛的抗菌性和低生产成本等特点而成为应用最广泛的兽医药物. TTC的大量使用不可避免地导致其进入地表水、地下水和污水处理厂.迄今,已有许多方法用于TTC检测,包括免疫测定法、微生物检测法和化学-物理法等.然而,这些方法费用高,耗时长或需要复杂的样品预处理过程,不适合现场测量或常规分析.电化学分析法具有操作简单、成本低廉、选择性和灵敏度较高、易实现在线检测等特点,在检测领域具有重要优势.石墨烯在电化学传感器领域表现出优越的应用性能,但有关石墨烯材料应用于电分析和电催化方面的报道仍然有限.石墨烯的前驱体氧化石墨烯(GO)片层底面上具有各种类型的含氧官能团和层状边缘,导致其绝缘并具有很多缺陷,使GO包含了sp2和sp3杂化碳原子,为GO提供了独特的具有化学功能的异构电子结构.通过对GO进行还原,可以生成新的sp2域或者改变含氧官能团的数量和类型,从而为GO提供更多的特殊性质.研究表明,电化学还原是一种绿色快速的还原方法,可以控制GO的还原程度和还原过程.本文利用电化学还原法来调整GO表面的官能团和缺陷度,利用在–0.8 V还原电位下得到的电化学还原氧化石墨烯(ERGO-0.8V)修饰玻碳电极(GC)为工作电极(GC/ERGO-0.8V),采用循环伏安法对溶解在pH=3的缓冲溶液中的TTC进行电化学检测,发现ERGO-0.8V对TTC具有电催化性能.利用红外光谱(FT-IR)、X射线光电子能谱(XPS)和拉曼光谱对ERGO-0.8V, ERGO-1.2V, GO及化学还原得到的石墨烯(CRGO)表面官能团和缺陷程度进行了表征,考察了TTC在ERGO-0.8V/GC上的电化学行为,对其电催化还原机理进行了推测.结果表明,与GO, ERGO-1.2V及CRGO修饰电极相比, GC/ERGO-0.8V修饰电极的催化还原峰在0–0.5 V,对TTC表现出独特的电催化性能, GC/ERGO-0.8V电极对浓度为0.1–120 mg/L的TTC溶液具有良好的检测性能,在不同浓度范围内其氧化峰峰电流与峰电位的线性关系不同. FT-IR和XPS结果显示,在–0.8 V还原电位下得到的ERGO-0.8V,其官能团类型和数量发生变化,但仍存在大量官能团,主要是羧基、羟基和环氧基.同时,拉曼表征显示ERGO-0.8V的缺陷密度增大,同时新生成的sp2域减小而使得ERGO的sp2域减小.对比GO等其他材料的表征结果推测,官能团变化是影响ERGO独特电催化性质的主要因素,除此之外还有材料的缺陷度和sp2域.推测GC/ERGO-0.8V修饰电极对TTC可能的催化机理为: TTC在GC/ERGO电极上的还原与氢醌和醌之间的转换有关;而对于ERGO,则可能对应于羧基和羟基之间的转化.然而,同样具有羧基和羟基的ERGO-1.2V则对TTC没有产生电催化作用.其原因可能是在–0.8到–1.2 V还原电位下,形成的羧基位于石墨烯片层内部,而片层内的电子传递较慢. 相似文献
103.
104.
Graphene Oxide Nanosheets Modified with Single‐Domain Antibodies for Rapid and Efficient Capture of Cells 下载免费PDF全文
Dr. Christopher S. Theile Neelkanth M. Bardhan Dr. Priyank V. Kumar Joao N. Duarte Dr. Takeshi Maruyama Ali Rashidfarrokh Dr. Angela M. Belcher Dr. Hidde L. Ploegh 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(48):17178-17183
Peripheral blood can provide valuable information on an individual’s immune status. Cell‐based assays typically target leukocytes and their products. Characterization of leukocytes from whole blood requires their separation from the far more numerous red blood cells. 1 Current methods to classify leukocytes, such as recovery on antibody‐coated beads or fluorescence‐activated cell sorting require long sample preparation times and relatively large sample volumes. 2 A simple method that enables the characterization of cells from a small peripheral whole blood sample could overcome limitations of current analytical techniques. We describe the development of a simple graphene oxide surface coated with single‐domain antibody fragments. This format allows quick and efficient capture of distinct WBC subpopulations from small samples (~30 μL) of whole blood in a geometry that does not require any specialized equipment such as cell sorters or microfluidic devices. 相似文献
105.
High Sensitive Microsensor Based on Organic‐Inorganic Composite for Two‐Dimensional Mapping of H2O2 by SECM 下载免费PDF全文
Danielle Diniz Justino Isabel Lourenço Torres Rita de Cássia Silva Luz Flavio Santos Damos 《Electroanalysis》2015,27(5):1202-1209
The present work describes the development of a selective, sensitive and stable sensing microsensor for scanning electrochemical microscopy (SECM) to measure H2O2 during electrochemical reduction of oxygen. The microsensor is based on graphene and Poly(3,4‐ethylenedioxythiophene) composite as support to iron (III) hexacyanoferrate (II) (PEDOT/graphene/FeIII4[FeII(CN)6]3 microsensor). The electrochemical properties of the PEDOT/graphene/FeIII4[FeII(CN)6]3 microsensor were investigated by cyclic voltammetry (CV) and scanning electrochemical microscopy (SECM). The PEDOT/graphene/FeIII4[FeII(CN)6]3 microsensor showed an excellent electrocatalytic activity toward hydrogen peroxide (H2O2) reduction with a diminution of the overpotential of about 500 mV in comparison to the process at a bare gold microelectrode. The microsensor presented excellent performance for two dimensional mapping of H2O2 by SECM in 0.1 mol L?1 phosphate buffer solution (pH 7.0). Under optimized conditions, a linear response range from 1 up to 1000 µmol L?1 was obtained with a sensitivity of 0.08 nA L µmol?1 and limit of detection of 0.5 µmol L?1. 相似文献
106.
Synthesis of Carbon/Sulfur Nanolaminates by Electrochemical Extraction of Titanium from Ti2SC 下载免费PDF全文
Dr. Meng‐Qiang Zhao Morgane Sedran Zheng Ling Maria R. Lukatskaya Olha Mashtalir Michael Ghidiu Boris Dyatkin Darin J. Tallman Prof. Thierry Djenizian Prof. Michel W. Barsoum Prof. Yury Gogotsi 《Angewandte Chemie (International ed. in English)》2015,54(16):4810-4814
Herein we electrochemically and selectively extract Ti from the MAX phase Ti2SC to form carbon/sulfur (C/S) nanolaminates at room temperature. The products are composed of multi‐layers of C/S flakes, with predominantly amorphous and some graphene‐like structures. Covalent bonding between C and S is observed in the nanolaminates, which render the latter promising candidates as electrode materials for Li‐S batteries. We also show that it is possible to extract Ti from other MAX phases, such as Ti3AlC2 , Ti3SnC2 , and Ti2GeC, suggesting that electrochemical etching can be a powerful method to selectively extract the “M” elements from the MAX phases, to produce “AX” layered structures, that cannot be made otherwise. The latter hold promise for a variety of applications, such as energy storage, catalysis, etc. 相似文献
107.
An Efficient Labelling Approach to Harness Backbone and Side‐Chain Protons in 1H‐Detected Solid‐State NMR Spectroscopy 下载免费PDF全文
Deni Mance Dr. Tessa Sinnige Mohammed Kaplan Siddarth Narasimhan Mark Daniëls Dr. Klaartje Houben Prof. Marc Baldus Dr. Markus Weingarth 《Angewandte Chemie (International ed. in English)》2015,54(52):15799-15803
1H‐detection can greatly improve spectral sensitivity in biological solid‐state NMR (ssNMR), thus allowing the study of larger and more complex proteins. However, the general requirement to perdeuterate proteins critically curtails the potential of 1H‐detection by the loss of aliphatic side‐chain protons, which are important probes for protein structure and function. Introduced herein is a labelling scheme for 1H‐detected ssNMR, and it gives high quality spectra for both side‐chain and backbone protons, and allows quantitative assignments and aids in probing interresidual contacts. Excellent 1H resolution in membrane proteins is obtained, the topology and dynamics of an ion channel were studied. This labelling scheme will open new avenues for the study of challenging proteins by ssNMR. 相似文献
108.
Ran Chen Dr. Nikoloz Nioradze Dr. Padmanabhan Santhosh Dr. Zhiting Li Dr. Sumedh P. Surwade Ganesh J. Shenoy David G. Parobek Min A. Kim Prof. Haitao Liu Prof. Shigeru Amemiya 《Angewandte Chemie (International ed. in English)》2015,54(50):15134-15137
High electrochemical reactivity is required for various energy and sensing applications of graphene grown by chemical vapor deposition (CVD). Herein, we report that heterogeneous electron transfer can be remarkably fast at CVD‐grown graphene electrodes that are fabricated without using the conventional poly(methyl methacrylate) (PMMA) for graphene transfer from a growth substrate. We use nanogap voltammetry based on scanning electrochemical microscopy to obtain very high standard rate constants k0≥25 cm s?1 for ferrocenemethanol oxidation at polystyrene‐supported graphene. The rate constants are at least 2–3 orders of magnitude higher than those at PMMA‐transferred graphene, which demonstrates an anomalously weak dependence of electron‐transfer rates on the potential. Slow kinetics at PMMA‐transferred graphene is attributed to the presence of residual PMMA. This unprecedentedly high reactivity of PMMA‐free CVD‐grown graphene electrodes is fundamentally and practically important. 相似文献
109.
Photocatalytically Renewable Micro‐electrochemical Sensor for Real‐Time Monitoring of Cells 下载免费PDF全文
Jia‐Quan Xu Yan‐Ling Liu Qian Wang Huan‐Huan Duo Xin‐Wei Zhang Dr. Yu‐Tao Li Prof. Wei‐Hua Huang 《Angewandte Chemie (International ed. in English)》2015,54(48):14402-14406
Electrode fouling and passivation is a substantial and inevitable limitation in electrochemical biosensing, and it is a great challenge to efficiently remove the contaminant without changing the surface structure and electrochemical performance. Herein, we propose a versatile and efficient strategy based on photocatalytic cleaning to construct renewable electrochemical sensors for cell analysis. This kind of sensor was fabricated by controllable assembly of reduced graphene oxide (RGO) and TiO2 to form a sandwiching RGO@TiO2 structure, followed by deposition of Au nanoparticles (NPs) onto the RGO shell. The Au NPs‐RGO composite shell provides high electrochemical performance. Meanwhile, the encapsulated TiO2 ensures an excellent photocatalytic cleaning property. Application of this renewable microsensor for detection of nitric oxide (NO) release from cells demonstrates the great potential of this strategy in electrode regeneration and biosensing. 相似文献
110.
Recent advance in liquid crystal (LqC) based immunoassays enables label-free detection of antibody, but manual preparation of LqC cells and injection of LqC are required. In this work, we developed a new format of LqC-based immunoassay which is hosted in a microfluidic device. In this format, the orientations of LqC are strongly influenced by four channel walls surrounding the LqC. When the aspect ratio (depth/width) of the channel is smaller than 0.38, LqC orients homeotropically inside the microchannel and appears dark. After antigens bind to immobilized antibodies on the channel walls, a shift of the LqC appearance from dark to bright (due to the disruption of LqC orientation) can be visualized directly. To streamline the immunoassay process, a tubing cartridge loaded with a sample solution, washing buffers and a plug of LqC is connected to the microfluidic device. By using pressure-driven flow, the cartridge allows antigen/antibody binding, washing and optical detection to be accomplished in a sequential order. We demonstrate that this microfluidic immunoassay is able to detect anti-rabbit IgG with a naked-eye detection limit down to 1 μg mL−1. This new format of immunoassay provides a simple and robust approach to perform LqC-based label-free immunodetection in microfluidic devices. 相似文献