Attenuated Total Reflection Surface-Enhanced Infrared Absorption Spectroscopy: a Powerful Technique for Bioanalysis

Attenuated total reflection surface-enhanced infrared absorption spectroscopy(ATR-SEIRAS)has recently been proven to be a powerful tool for bioanalysis.It enables in situ and in real-time observation of dynamic processes occurring on specific interface,revealing rich structural and functional information of biomolecules at sub monolayer level.The aim of this general review was to give an overview of the cutting edge applications of ATRSEIRAS.We start with description of the basic configuration of the standard ATR-SEIRAS platform.The enhanced mechanisms and methods to fabricate enhanced substrates are then presented.We discuss the recent developments,challenges and applications of ATR-SEIRAS in bioanalysis,mainly focusing on DNA analysis,protein behavior and cell properties.Finally,further development of the ATRSEIRAS technique with enhanced sensitivity,improved time and spatial resolutions will be prospected.

In situ infrared, Raman and X-ray spectroscopy for the mechanistic understanding of hydrogen evolution reaction

Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.

Novel infrared differential optical absorption spectroscopy remote sensing system to measure carbon dioxide emission

A CO_2 infrared remote sensing system based on the algorithm of weighting function modified differential optical absorption spectroscopy(WFM-DOAS) is developed for measuring CO_2 emissions from pollution sources. The system is composed of a spectrometer with band from 900 nm to 1700 nm, a telescope with a field of view of 1.12?, a silica optical fiber, an automatic position adjuster, and the data acquisition and processing module. The performance is discussed,including the electronic noise of the charge-coupled device(CCD), the spectral shift, and detection limits. The resolution of the spectrometer is 0.4 nm, the detection limit is 8.5 × 10^(20)molecules·cm^(-2), and the relative retrieval error is < 1.5%.On May 26, 2018, a field experiment was performed to measure CO_2 emissions from the Feng-tai power plant, and a twodimensional distribution of CO_2 from the plume was obtained. The retrieved differential slant column densities(dSCDs)of CO_2 are around 2 × 10^(21) molecules·cm^(-2) in the unpolluted areas, 5.5 × 10^(21)molecules·cm^(-2) in the plume locations most strongly affected by local CO_2 emissions, and the fitting error is less than 2 × 10^(20)molecules·cm^(-2), which proves that the infrared remote sensing system has the characteristics of fast response and high precision, suitable for measuring CO_2 emission from the sources.

Label-free surface-enhanced infrared spectro-electro-chemical analysis of the Redox potential shift of cytochrome c complexed with a cardiolipin-containing lipid membrane of varied composition

In this study, a lipid membrane was fabricated by fusing cardiolipin-phosphatidylcholine（CL_PC, 1：4） vesicles onto a hydrophobic surface of 1-dodecanethiol（DT） preadsorbed on a nanostructured gold film. By changing the concentration of the DT adsorption solution, we constructed a series of CL PC-DT bilayers with different hydrophobicity to study the effects of lipid membrane characteristics on the adsorption conformation of cytochrome c（Cyt c）. Electrochemical analysis showed that the formal potential is 0.24 V for Cyt c-CL_PC-DT（10）, 0.2 V for Cyt c-CL_PC-DT（20）, and 0.16 V for Cyt c-CL_PC-DT（40） — a gradual positive shift with the decreasing DT concentration — relative to the potential of native cyt c（0.02 V）. Potential-induced surface-enhanced infrared adsorption difference spectroscopy revealed that the gradual positive shift of the formal potential of CL-bound cyt c is determined by the environment with the gradually lowered dielectric constant for the heme cofactor in CL-bound cyt c（Fe^3＋）.

Investigation of a Hot Filament Diamond Deposition by in situ Infrared Absorption

In situ infrared absorption spectroscopy has been measured for a hot filament diamondgrowth process.Absorption of CH4 and C2H2 species at 3050cm-1and 730cm-1were detectedrespectively.The absorption intensity of CH4 decreases while that of C2H2 increases as fila-ment temperature is raised.The correlation between infrared absorption intensity and dia-mond growth rate or diamond film quality was found.High C2H2 or low CH4 concentration inthe reaction region leads to high quality diamond film growth and high growth rate.

Investigation on N-doped FZ-Si Crystals by IR Absorption Spectrum

N-doped FZ-Si crystals and N-doped NTD FZ-Si crystals and their annealing behavior have been studied by IR spectrum. Two models of nitrogen configuration, nearly substitutional nitrogen and interstitial nitrogen pair, have been proposed and two nitrogen-related IR absorption peaks at 767cm-1 and 963cm-1 have been well explained.

Nanobridged rhombic antennas supporting both dipolar and high-order plasmonic modes with spatially superimposed hotspots in the mid-infrared

Mid-infrared antennas(MIRAs)support highly-efficient optical resonance in the infrared,enabling multiple applications,such as surface-enhanced infrared absorption(SEIRA)spectroscopy and ultrasensitive mid-infrared detection.However,most MIRAs such as dipolar-antenna structures support only narrow-band dipolar-mode resonances while high-order modes are usually too weak to be observed,severely limiting other useful applications that broadband resonances make possible.In this study,we report a multiscale nanobridged rhombic antenna(NBRA)that supports two dominant reson-ances in the MIR,including a charge-transfer plasmon(CTP)band and a bridged dipolar plasmon(BDP)band which looks like a quadruple resonance.These assignments are evidenced by scattering-type scanning near-field optical micro-scopy(s-SNOM)imaging and electromagnetic simulations.The high-order mode only occurs with nanometer-sized bridge(nanobridge)linked to the one end of the rhombic arm which mainly acts as the inductance and the resistance by the circuit analysis.Moreover,the main hotspots associated with the two resonant bands are spatially superimposed,en-abling boosting up the local field for both bands by multiscale coupling.With large field enhancements,multiband detec-tion with high sensitivity to a monolayer of molecules is achieved when using SEIRA.Our work provides a new strategy possible to activate high-order modes for designing multiband MIRAs with both nanobridges and nanogaps for such MIR applications as multiband SEIRAs,IR detectors,and beam-shaping of quantum cascade lasers in the future.

用于单片机实验教学的红外激光气体检测仪

为了实现科研反哺教学、促进教学与科研的深度融合,研制了一种基于嵌入式多核处理器和数字信号处理器的实验教学用红外激光气体检测仪。该检测仪包括光学系统和电学系统,其中电学系统包含光谱信息感知模块和嵌入式控制模块。利用研制的检测仪开展了氨制冷冷库现场的泄漏氨气浓度的检测应用。结果表明,与传统气体检测仪相比,该检测仪实现了检测仪的网络化与智能化,而且性能满足实验教学要求。

CO and CO_2 dual-gas detection based on mid-infrared wideband absorption spectroscopy

A dual-gas sensor system is developed for CO and CO_2 detection using a single broadband light source, pyroelectric detectors and time-division multiplexing(TDM) technique. A stepper motor based rotating system and a single-reflection spherical optical mirror are designed and adopted for realizing and enhancing dual-gas detection. Detailed measurements under static detection mode(without rotation) and dynamic mode(with rotation) are performed to study the performance of the sensor system for the two gas samples. The detection period is 7.9 s in one round of detection by scanning the two detectors. Based on an Allan deviation analysis, the 1σ detection limits under static operation are 3.0 parts per million(ppm) in volume and 2.6 ppm for CO and CO_2, respectively, and those under dynamic operation are 9.4 ppm and 10.8 ppm for CO and CO_2, respectively. The reported sensor has potential applications in various fields requiring CO and CO_2 detection such as in the coal mine.

小型化中红外直接吸收CO_(2)光谱仪

二氧化碳(Carbon Dioxide,CO_(2))是一种关键的温室气体,对地球气候和生态系统调节有重要作用,准确检测痕量CO_(2)浓度对评价温室效应意义重大。一般情况下,气体分子在中红外光谱范围存在强吸收,可以实现高灵敏探测,因此,以4.219μm中红外波段的带间级联激光器为光源结合可调谐半导体激光吸收光谱技术(Tunable Diode Laser Absorption Spectroscopy,TDLAS)设计了小型化CO_(2)监测仪器。在不同标气浓度下对仪器进行了标定,并通过分析Allan方差,得出积分时间在8.7 s时对应的最低检测限为16.6×10^(-9),满足温室效应研究对CO_(2)气体的高灵敏测量需求。采用仪器对大气CO_(2)连续监测8天,并与商用仪器LGR进行对比,充分验证了小型化CO_(2)监测仪器的可靠性,以及中红外光源与TDLAS技术相结合的气体浓度检测方法在大气CO_(2)准确测量方面的可行性。该系统具有结构简单、体积小、功耗低和质量轻的特点,为建设空基无人机平台的CO_(2)监测能力提供了技术支持。

海博麦布结构确证

本文采用紫外吸收光谱、红外吸收光谱、质谱、核磁共振波谱(包含^(1)HNMR、^(13)CNMR、DEPT、^(1)H-^(1)H COSY、^(1)H-^(1)HNOESY、^(1)H-^(13)CHSQC和^(1)H-^(13)CHMBC)以及单晶衍射等方法对海博麦布进行结构分析,对其所有的^(1)HNMR和^(13)CNMR谱信号进行了归属,还通过差示扫描量热法、热重分析及粉末X-射线衍射分析对海博麦布晶型进行研究.

Analysis of infrared spectra with narrow band absorption by a graphene/square-ring structure

A graphene covered on square-ring structure is designed and fabricated to achieve narrow band absorption of three peaks in the infrared band.The absorption rates of graphene/square-ring structures calculated by simulation are 90.49%,65.67%and 20.38%,respectively,and the experimentally measured absorption rates are 82.12%,53.13%,and 16.58%,respectively.Comparing the absorption rate of simulation calculation with experimental measurement,as well as the reasons for the differences are presented.The dynamic control characteristics of the graphene device are not observed with this structure in the experiment,which is different from the simulation.We analyzed the reason for this distinction and proposed three solutions based on the experimental design.The research results of this paper provide an important reference to the design and preparation of graphene devices.

Spectroscopy system based on a single quantum cascade laser for simultaneous detection of CO and CO_2

A quantum cascade laser（QCL） based system for simultaneous detection of CO and CO_2 is developed.The QCL can scan over two neighboring CO（2055.40 cm^（-1）） and CO_2（2055.16 cm^（-1）） lines with a single current scan.The wavelength modulation spectroscopy（ f = 20 k Hz） is utilized to enhance the signal-to-noise ratio.A white cell with an effective optical path length of 74 m is used.The calibration of the sensor is performed and minimum detection limits of 1.3 ppb（1 × 10^（-9））for CO and 0.44 ppm（1 × 10^（-6）） for CO_2 are achieved.

基于红外光谱成像的危险气体泄漏检测技术综述

危险气体检测技术是石化等企业安全生产的必要保障之一,在工业生产中有着重要的作用。首先比较了现有气体检测技术的优缺点,明确了基于分子吸收光谱的红外成像技术在危险气体检测中具有适用于远距离监测、维护成本低的优势,是理想的广域监控形式;其次介绍了红外光谱成像技术的检测原理与硬件构成;接下来列举并分析了泄漏气体图像可视化及气体浓度分析的相关研究;然后分析了基于红外图像分析技术的气体泄漏自动检测算法,并分别对传统的基于图像处理的方法与深度学习算法的发展现状及其存在的问题进行了深入的分析;最后对红外光谱成像技术难点与发展趋势进行了总结。

陶瓷助剂聚乙二醇分子结构及热变性研究

基于中红外(MIR)光谱原理开展了聚乙二醇的分子结构研究。试验发现,聚乙二醇分子的红外吸收模式主要包括ν_(sCH_(2-聚乙二醇))、ν_(OH_(-聚乙二醇))、δ_(CH_(2-聚乙二醇))、ω_(CH_(2-聚乙二醇))、ρ_(CH_(2-聚乙二醇))和ν_(C-O_(-聚乙二醇))。采用变温中红外(TD-MIR)光谱进一步开展了聚乙二醇分子热变性研究。结果表明,在303 K~473 K的温度范围内,随着测定温度的升高,聚乙二醇分子主要官能团对应的吸收频率及强度都有一定的改变,进一步进行了热变性机理研究。本项研究拓展了MIR及TD-MIR光谱在重要的陶瓷工业助剂(聚乙二醇)分子结构及热变性的研究范围。

麻醉气体的红外吸收光谱等效模拟方法

校准麻醉气体检测仪时需要使用标准麻醉气体,但标准麻醉气体制备成本高昂,配气过程费时费力。针对这一问题提出了一种麻醉气体等效模拟方法,采用红外滤光片模拟不同浓度麻醉气体对红外光的吸收,从而替代标准麻醉气体。建立了麻醉气体检测系统,制备了体积分数0.23%~8.50%的七氟醚气体和透过率为36%~95%的红外滤光片进行实验验证。结果表明:红外滤光片等效七氟醚气体浓度的重复性误差小于0.02%,温度效应引入的等效浓度最大变化量不大于0.02%+1.5%·c(c为被测气体体积分数),可实现对标准麻醉气体的等效模拟。

基于滤波器的动植物油光谱信号预处理方法比较及识别分类

为实现对动植物油的快速无损检验,探究滤波器在提高光谱分析模型区分能力方面的可行性,该研究借助衰减全反射-表面增强红外吸收光谱技术,采集了动物油(159份)和植物油(188份)共计347份样本的光谱信息数据,构建了Fisher判别分析、支持向量机和决策树3种分类模型。比较了希尔伯特变换、有限长单位脉冲响应滤波器、无限长冲激响应滤波器、快速傅里叶变换和小波变换5种滤波器对3种分类模型精度的影响,同时考察了滤波器窗函数(矩形窗、汉宁窗、海明窗、布莱克曼窗)、小波基函数(Morlet、Dgauss、Mexhat、Haar、Daubechies、Biorthogonal)、滤波方式(低通、高通、带通、带阻)在动植物油样本区分效果方面的差异性。结果发现,滤波器能显著提升光谱分析模型的准确性,低通和带阻滤波方式,矩形窗和布莱克曼窗函数能有效提升模型对样本的区分能力,相较于其他2种算法,支持向量机对各样本的识别区分能力最好。基于FIR低通/带阻滤波器处理后构建的SVM模型(RBF核函数)可作为动植物油样本识别的最佳模型,其对347份样本实现了100%的“类别-品牌”的两级准确区分。综上,滤波器可有效提升光谱分析模型的准确性,结合ATR-SEIRAS光谱信息数据,可准确区分不同的动植物油样本,这为包括动植物油在内的诸多样本的快速无损分析提供了一定参考,为滤波器在提升光谱分析模型方面的应用提供了一定借鉴。

中红外波长调制离轴积分腔输出光谱技术应用于OH自由基高灵敏度探测研究

将波长调制技术与离轴积分腔技术相结合,建立了波长调制离轴积分腔输出光谱实验装置,增加吸收光程,避免低频的1/f噪声和与波长无关的背景功率的影响,将其应用于OH自由基探测研究。探测激光器选择2.8μm中红外室温型连续波分布反馈式二极管激光器,OH自由基选择3568.52 cm^(-1)处Q(1.5e)跃迁谱线开展光谱探测,在512 m有效吸收光程和100 s采样时间下,实现了OH自由基1.2×10^(8)molecule/cm3的探测极限。实验研究发现,在弱透过光强下,激光器放大的自发辐射对吸收系数测量影响大,本实验装置下造成了约70倍的吸收低估,需要有效避免。

片上红外气体传感技术的研究进展(特邀)

片上集成的光波导气体传感器具有体积小、重量轻、功耗低、无需光路校准等优点,近年来光学气体传感器逐渐由体积较大的分立系统向片上集成系统演变。中红外波段的气体吸收系数大,但二氧化硅在中红外波段的损耗较大,所以常用的绝缘衬底上的硅材料体系不适用于中红外波段。因此,片上气体传感器需要采用硫系玻璃、锗等中红外透明材料来拓宽工作波段。同时,波导结构直接影响了气体对光的吸收,而且气体传感技术也会影响传感器性能。本文总结了基于红外吸收光谱的片上气体传感器的最新进展。介绍了片上气体传感方法、波导材料、波导结构、片上气体传感的理论和实验进展。阐述了矩形波导、狭缝波导、悬浮波导、微环谐振波导和光子晶体波导在片上气体传感领域的应用现状。最后对基于红外吸收光谱的片上气体传感器进行了展望。

中红外差分吸收激光雷达探测苯气体浓度

苯作为挥发性有机化合物(VOCs)的重要组成部分,其大气污染状况日益引起人们的关注,中红外波段通常是分子的基频指纹吸收区,已成为痕量气体检测的重要波段,而差分吸收激光雷达是探测大气痕量气体的重要手段,故针对区域性苯浓度实时遥感问题,提出基于中红外带间级联激光器(ICL)的探测大气苯浓度路径积分型差分吸收(IPDA)激光雷达系统。首先,在分析IPDA激光雷达的探测原理的基础上,构建了IPDA激光雷达的反演算法及其误差分析模型。其次,详细分析来自HITRAN数据库的中红外3100 cm^(-1)附近苯以及主要干扰气体(如HCl,CH_(4)和H_(2)O)的吸收光谱,结合HCl和CH_(4)着重考虑了H_(2)O对探测结果的影响,选择IPDA激光雷达的测量波长和参考波长分别为3090.89和3137.74 cm^(-1)。再次,基于两个连续波ICL,设计了探测大气苯浓度IPDA激光雷达系统,并可通过控制温度和驱动电流调谐激光器的输出波长,使其波长分别稳定在强吸收谱区和弱吸收谱区,并设计了基于中红外衍射光栅的光谱分光子系统,以实现双波长接收信号的同步探测。最后,基于标准大气模型,仿真分析了不同路径长度、能见度和水汽浓度情况下激光雷达的探测性能,并搭建中红外波段检测气体池开展了测试实验,以验证该IPDA激光雷达系统的可行性。仿真及实验结果分析表明,当大气能见度为5 km,水汽浓度低于0.4%时,苯的浓度路径积(CL)在0.1~24 mg·m^(-3)·km范围内探测的相对误差优于10%,而苯的CL为5 mg·m^(-3)·km时探测相对误差优于1%;初步实验测试了中外红波段差分吸收激光雷达探测的线性相关系数R^(2)约为98.7%。