Name: total internal reflection absorption spectroscopy (tiras) for the detection of solvated electrons at a plasma-liquid interface
Uploaded: 2018-01-24T14:30:00
Description: Watch this Scientific Journal Video about Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface at JoVE.com

这项工作得到了美国陆军研究办公室的 W911NF-14-1-0241 和 W911NF-17-1-0119 奖的支持。DMB 是由美国能源部科学办公室, 基础能源科学办公室在奖编号 DE-FC02-04ER1553。

1. 搭建实验装置
注: 要运行这个实验, 组装一个由等离子体反应器组成的系统, 其中的反应将发生, 光学元件的吸光度测量, 和电子锁定放大系统处理信号。
<ol><li>
构造等离子体电化学电池。
	<ol>
<li>制造一个由透明的玻璃容器组成的反应器单元, 直径50.8 毫米 (2), 两个光学窗口的角度近似°从正常平面向下。</li>
		<li>构造一个含有四孔的非渗透性盖子, 用于介绍等?...

<ol>
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结果表明, 在等离子体-液界面上测量光的吸光度是检测和测量水溶液中等离子体-溶剂电子浓度的有效方法。随后在不同波长上的测量结果在吸收谱的测量。虽然这个实验是在一个水次氯酸的4溶液中进行的, 但如果电子能在液体中化, 那么这种方法应该对其他种类的液体有效。
次氯酸4解决方案的一个有用的实验特性是, 次氯酸4与溶剂电子无反应。了解?...

等离子体-液体相互作用是等离子体科学和工程界越来越感兴趣的领域。等离子体与液体之间的复杂界面, 含有多种高活性自由基, 在分析化学、等离子体医学、水和废水处理、纳米材料合成等领域有广泛的应用.1,2,3,4,5,6。虽然有各种配置, 可以用来带来与液体7接触的等离子体, 也许最简单的是电解电池的等离子模拟, 其中一个标准金属电极被等离子体或气体放电所取代8. 等离子体电化学电池由反应堆容器、浸入式金属电极和等离子体放电组成, 它可以作为阴极或阳极 (或两者) 的作用。当等离子体放电被用作阴极时, 等离子体中产生的气相电子被注入溶液中。电子进入溶液后, 它们的动能在飞9,10,11的时间尺度上消散, 主要通过非弹性散射的溶剂分子。一旦电子达到了接近热的动能, 它们就会在周围的溶剂分子形成的空穴中捕获和化。根据溶剂和温度, 这些 "溶剂" 电子可能是稳定的, 直到他们与一些可还原的物种在解决方案或与另一个溶剂电子的反应。在水溶液中, 溶剂电子也被称为水合电子12。
这种溶剂的过程早已为人所知, 并从二十世纪六十年代13,14,15, 研究了由脉冲辐或闪光光解等过程产生的水合电子的检测。在传统的辐和光解中, 溶剂电子通过溶剂分子的电离产生;然而, 电子溶剂在血浆-液体接口被注射从气体血浆16。先前的实验已经确定水合电子吸收红光近 700 nm13,14,17, 这使得它们可以通过光学吸收光谱进行实验研究。其他的实验已经测量了它们的扩散常数, 它们的反应速率与数以百计的化学种类, 它们的回转半径, 以及它们的电荷移动性, 以及其他感兴趣的属性12,18。
在文献中, 报告了几种检测溶剂电子的方法, 主要分为两类: 体积剂量法, 其中溶剂电子存在是从其反应产物的大宗化学分析中推断出来的,直接瞬态吸收光谱法, 当反应发生时, 电子的吸收量被测量。后一类, 这里提出的方法是基于, 具有直接和即时证据的优势, 以及监测中间反应的能力。
全内反射吸收谱 (拉斯) 方法的发展背后的基本原理是直接研究溶剂电子在等离子体-液体界面上的作用。反射几何的选择, 因为生产溶剂电子使用等离子体放电, 而不是方法, 如辐或光解, 发生在界面之间的等离子体和液体。当探针激光在入射的浅角度吃表面时, 它被完全反射回溶液中, 并输出到探测器中, 减少了电子吸收的少量光。由于没有光进入等离子体, 实验技术只测量液相中的自由基, 就在界面下方, 因此是一种高度敏感的界面检测技术。此外, 总的内部反射现象具有消除噪声的优点, 即由于表面起伏而引起的部分反射的变化, 从而导致信号的控制。
本文概述的拉斯协议具有三基本特性。第一种是等离子体电化学电池, 它由一个透明的玻璃烧杯组成, 它由两个光学窗口构成, 在大约°朝下的角度和氩气的控制顶部。第二个特性是光学测量系统, 它包括二极管激光器、光笼和光电二极管探测器。激光器提供被溶剂电子吸收的光, 并安装在一个可调节的虹膜和一个光学笼中的 50 mm 透镜上。这种安排是安装在一个测, 使它可以旋转到一个预期的入射角。然后由光电探测器测量透射光的强度, 它由在反向偏置泄漏电路中有线的大面积光电二极管组成。最后, 由于他们的高反应性, 溶剂电子只击穿 ~ 10 毫微米入解答, 产生极小的光学吸收信号的 ~ 10-5光学密度。为了保证一个足够高的信噪比, 第三要素是一个锁定放大系统, 其中包括一个等离子开关电路和一个锁定放大器。在开关电路中, 固态继电器电路在由函数发生器设定的20赫的载波频率上调节高和低值之间的等离子体电流。这反过来也调节了界面的溶剂电子浓度及其光学吸收。锁在放大器然后采取信号从光电探测器并且过滤所有噪声在载波频率外面。
在等离子体-液体实验中, 特别是在等离子体电化学中, 拉斯方法有很大的潜力来揭示重要的化学过程。还原和氧化途径主要是由在等离子体-液体界面上的各种短寿命的自由基驱动的, 而对这些物种的检测对于了解界面化学是极其重要的。拉斯的原位监视功能将有助于建立对等离子体-液体界面所涉及的重要电子驱动反应的更深入的了解。拉斯, 例如, 使测量的反应率可能存在的电子清道夫。以前的研究重点是减少没有2-(蒽醌), 没有3-(蒽醌)和 H2O2 (蒽醌)清除剂溶解在水溶液16, 以及减少溶解CO2 (蒽醌)19。其他研究的重点是等离子体载体气体对等离子体-溶剂电子化学的影响20。

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			<td style="width:144px;">Ultra-high purity</td>
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</table>

total internal reflection absorption spectroscopy (tiras) for the detection of solvated electrons at a plasma-liquid interface

本文提出的全内反射吸收光谱法 (拉斯) 方法采用廉价的二极管激光器, 检测与水溶液接触的低温等离子体产生的溶剂电子。溶剂电子是一种强大的还原剂, 它被认为在气体等离子体或放电和导电液体之间的界面化学中起着重要的作用。然而, 由于在界面上的反应物种的高度局部浓度, 他们有一个短的平均寿命 (〜1µs), 这使得他们极其难以检测。拉斯技术使用独特的全内反射几何结合振幅调制锁定放大, 以区分溶剂电子的吸光度信号从其他杂散噪声源。这使得原位检测界面区域中的短寿命中间体, 而不是溶液中的稳定产品的批量测量。这种方法对于等离子体电化学领域尤其有吸引力, 因为在那里, 许多重要的化学物质都是由短寿命自由基驱动的。本实验方法用于分析亚硝酸盐的还原 (无2-(蒽醌)), 硝酸盐 (没有3-(蒽醌)), 过氧化氢 (H2O2 (蒽醌)) 和溶解的二氧化碳 (CO2 (蒽醌)) 通过等离子体溶剂电子, 并推断出有效速率常数。这种方法的局限性可能出现在非预期的平行反应中, 例如等离子体中的空气污染, 而减少的电化学产品的沉淀也会阻碍吸光度的测量。总的来说, 拉斯法可以成为研究等离子体-液体界面的有力工具, 但其有效性取决于所研究的特定系统和反应化学。

如步骤5所述, 本实验测量吸收信号的余弦和正弦分量、它们之间的相角和信号的大小。在图 4中显示了信号的大小及其两个分量的图。
有时, 将有可能不是最佳或甚至无法使用的测量。这可能是由于激光与等离子束的失调或引入噪声进入系统。一个好的和坏的测量的例子可以在图 5?...

Watch this Scientific Journal Video about Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface at JoVE.com

Total Internal Reflection Absorption Spectroscopy TIRAS for the Detection of Solvated Electrons at a Plasma-liquid Interface

本文提出了一种全内反射吸收光谱法 (拉斯) 测量等离子体-液体界面的短活自由基。特别是, 拉斯是用来识别溶剂电子的基础上, 其光学吸收的红光近700纳米。

全内反射吸收光谱法 (拉斯) 在等离子体-液体界面上检测溶剂电子

The total internal reflection absorption spectroscopy (TIRAS) method presented in this article uses an inexpensive diode laser to detect solvated ...

Research

JoVE Journal

Chemistry

Total Internal Reflection Absorption Spectroscopy (TIRAS) for the Detection of Solvated Electrons at a Plasma-liquid Interface

Isolation and Chemical Characterization of Lipid A from Gram-negative Bacteria

隔离和脂质A的化学表征革兰氏阴性菌

Lipopolysaccharide (LPS) is the major cell surface molecule of gram-negative bacteria, deposited on the outer leaflet of the outer membrane bilayer. LPS ...

科研

化学

1,3,5-Triphenylbenzene and Corannulene as Electron Receptors for Lithium Solvated Electron Solutions

1,3,5-三苯和碗烯作为电子受体锂溶剂化电子解决方案

The authors report on conductivity studies carried out on lithium solvated electron solutions (LiSES) prepared using two types of polyaromatic ...

Insights into the Interactions of Amino Acids and Peptides with Inorganic Materials Using Single-Molecule Force Spectroscopy

洞察氨基酸和多肽与无机材料的使用相互作用的单分子力谱

The interactions between proteins or peptides and inorganic materials lead to several interesting processes. For example, combining proteins with minerals ...

NMR Spectroscopy as a Robust Tool for the Rapid Evaluation of the Lipid Profile of Fish Oil Supplements

核磁共振作为鱼油补充剂的血脂的快速评价一个强大的工具

The western diet is poor in n-3 fatty acids, therefore the consumption of fish oil supplements is recommended to increase the intake of these essential ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

电化学阻抗谱作为电化学速率常数估计的一种工具

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Detection and Quantification of Plasmodium falciparum in Aqueous Red Blood Cells by Attenuated Total Reflection Infrared Spectroscopy and Multivariate Data Analysis

Detection and Quantification of Plasmodium falciparum in Aqueous Red Blood Cells by Attenuated Total Reflection Infrared Spectroscopy and Multivariate Data Analysis

衰减全反射红外光谱和多变量数据分析检测和定量水红血球中恶性疟原虫

We demonstrate a method of quantification and detection of parasites in aqueous red blood cells (RBCs) by using a simple benchtop Attenuated Total ...

Elemental-sensitive Detection of the Chemistry in Batteries through Soft X-ray Absorption Spectroscopy and Resonant Inelastic X-ray Scattering

软 x 射线吸收光谱和共振非弹性 x 射线散射法检测电池化学成分的元素敏感度

Energy storage has become more and more a limiting factor of today's sustainable energy applications, including electric vehicles and green electric grid ...

Imaging Corrosion at the Metal-Paint Interface Using Time-of-Flight Secondary Ion Mass Spectrometry

利用飞行时二次离子质谱法成像金属颜料界面的腐蚀

Corrosion developed at the paint and aluminum (Al) metal-paint interface of an aluminum alloy is analyzed using time-of-flight secondary ion mass ...

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

N719-色光/钛合金界面的振动光谱，来自经验-电位分子动力学模拟，由室温离子液体解低

The accurate molecular simulation prediction of vibrational spectra, and other structural, energetic and spectral characteristics, of photo-active ...

Biological Samples Preparation for Speciation at Cryogenic Temperature using High-Resolution  X-Ray Absorption Spectroscopy

使用高分辨率X射线吸收光谱在低温下制备生物样品以进行形态分析

The study of elements with X-ray absorption spectroscopy (XAS) is of particular interest when studying the role of metals in biological systems. Sample ...