Liquid crystal mixtures for potential infrared applications

Liquid crystals (LCs) with diazo linkages have high dielectric and optical anisotropy. Two newly synthesized liquid crystalline compounds were dissolved in room temperature LC hosts, E7 and PTTP-24/36, to assess their properties. It was found that these mixtures have higher birefringence, larger dielectric anisotropy, and better elastic properties than the hosts. Satisfactory viscoelastic coefficients were also obtained for these mixtures, showing that they are promising LC materials for applications in the near IR region.     

Towards a new class of ferroelectric liquid crystal molecules for nonlinear optical applications

The synthesis of a new molecule specifically designed to exhibit both ferroelectric and nonlinear optical properties is presented. This molecule possesses an optically active phenyl sulphinic group, which introduces a dipole moment directly linked to the chromophore group, with a nitro group in the meta -position. The rest of the molecule comprises a tolane and a benzoate group. Such a structure results in an enantiotropic smectic C*-smectic A phase sequence in its polymorphism. A first measurement of the spontaneous polarization shows a high value. The polymorphism of the racemic homologous molecule possessing the nitro group in the ortho-position is also presented, and also shows the smectic C-smectic A phase sequence.     

New insights into the role of hydrogen bonding on the liquid crystal behaviour of 4-alkoxybenzoic acids: a detailed IR spectroscopy study

ABSTRACT

Hydrogen bonding is an efficient alternative to covalent bonding as a way to stabilise liquid crystallinity, by yielding symmetric and non-symmetric complexes with increased molecular anisotropy. In designing new hydrogen-bonded liquid crystals, HBLCs, it is crucial to account for the competing hydrogen bonds that can lead to different supramolecular species coexisting in a temperature-dependent equilibrium. Thus, as part of a systematic development of this area, in the present work we study with detail the relationships between the phase behaviour and hydrogen bonding in a series of 4-n-alkoxybenzoic acids, nOBAs, which are widely used as components in HBLCs. Five acids with alkyl chain lengths of n = 1, 4, 5, 7 and 8 have been investigated using Fourier transform infrared spectroscopy, FTIR, in a broad range of temperatures under two different experimental configurations: sandwiched between potassium bromide, KBr, windows and dispersed in KBr discs. The nematic phase is correlated with the amounts of closed dimers between acid molecules, through the formation of strong hydrogen bonds. Moreover, high concentrations of open dimers are found in samples sandwiched between KBr slides, which are linked to the appearance of smectic-like aggregates that perturb the local order of the nematic phase. The results are interpreted in terms of the ability of the 4-alkoxybenzoic acids to align due to surface interactions, which are less acute in samples dispersed in the discs. These effects must be taken into account in order to correctly interpret the information about the supramolecular species present in the samples, and thus to better understand the relationships between hydrogen bond strength and mesomorphism in HBLCs.     

Liquid crystal parameters through image analysis

A technique which combines image analysis and polarising optical microscope (POM) is a useful tool for the physical investigation of discotic liquid crystals, such as hexabutoxytriphenylene and hexahexyloxytriphenylene. This investigation includes the phase transitions, optical properties and order parameter as a function of temperature. Textures of discotic liquid crystals are captured as a function of temperature using POM. These microscopic textures are analysed using MATLAB software to compute statistical parameters, Legendre moments, optical parameters and order parameters of discotic liquid crystal samples. Compared with other techniques in the literature, the proposed methodology is a reliable and very simple technique for the physical investigation of liquid crystals.     

Electrospray micro liquid chromatography – Fourier transform infrared micro spectrometry

Microcolumn liquid chromatography has been interfaced with infrared microspectrometry by means of a novel technique involving electrospray nebulization. The eluent from the LC column is subjected to a high positive potential relative to the surroundings and the electric field generated charges the surface of the emerging liquid causing it to disintegrate into charged droplets which are attracted to an earthed, infrared-transparent, zinc selenide deposition plate. Nitrogen sheath gas is used to evaporate the solvent in the droplets, and the separated components are deposited on the zinc selenide plate for subsequent analysis by means of a Fourier transform infrared microscope and spectrometer. Provided low flow rates (～4 μl/min) are used, total elimination of the solvent is achieved and easily identifiable infrared spectra can be measured from less than 500 pg of sample (caffeine).     

Fourier transform raman spectroscopy using a bench-top fourier transform infrared spectrometer

The use of a bench top FTIR spectrometer for near infrared Fourier transform Raman spectroscopy is demonstrated. The use of near infrared excitation results in fluorescence free Raman spectra allowing previously difficult samples to be measured.     

Comparative analysis of smokeless gunpowders by Fourier transform infrared and Raman spectroscopy

Fourier Transform Infrared (FTIR) and Raman spectroscopic techniques were used to perform a comparative study of the spectral profiles of single-base, double-base and triple-base smokeless gunpowders. Preliminary results based on visual comparison of the spectra point out that spectra obtained by both vibrational techniques were useful for a rapid identification of gunpowders containing dinitrotoluene as one of the major components and triple-base gunpowders. Additionally, the Raman spectra of gunpowders with diphenylamine in its primary composition showed a characteristic band, assigned to 2-nitro-diphenylamine, allowing the identification of this type of gunpowders.     

离子液体BMIMBF4中对甲氧基甲苯的电化学氧化

以离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)为电解质,采用循环伏安法(CV)、计时电流法(CP)、原位傅里叶变换红外光谱(in situ FTIRS)法等手段研究了对甲氧基甲苯(p-MT)在铂电极上的电氧化行为.实验结果表明:对甲氧基甲苯在离子液体中的电化学氧化反应是受扩散控制的四电子不可逆过程,估算了其扩散系数D=3.4×10-7cm2.s-1,主要电氧化产物为茴香醛,加入适量的水或适当提高温度有利于电氧化反应向生成相应醛的方向进行.     

TGA/FT-IR: Thermogravimetric analysis with fourier transform infrared detection of evolved gases

Thermogravimetric analysis (TGA) is a widely employed technique for measuring the change in weight of a sample as a function of temperature or time in a controlled atmosphere. FT-IR has been utilized with success in the identification of gases [1]. The combination of these two techniques permits a complete characterization of materials in terms of thermal stability and decomposition mechanisms [2]. A complete integrated system for TGA/FT-IR analysis is described.     

Electrochemical Reduction of Nitrobenzene in Ionic Liquid BMImAc

Ionic liquid,1-butyl-3-methylimidazolium acetate（BMImAc）,was used in the electrochemical reduction of nitrobenzene.The electro-reduction of nitrobenzene on platinum electrode was studied by cyclic voltammetry（CV）,in situ Fourier transform infrared（FTIR） spectroscopy and constant-potential electrolysis.The experimental results show that electrochemical reduction process of nitrobenzene was controlled by diffusion,the main reduction product was azobenzen at-1.45 V,and the influences of scan rate and temperature on the electrochemical behaviors were obviously.A reduction mechanism of nitrobenzene in an ionic liquid was a probable ‘nitrobenzene→nitrosobenzene→azobenzene→aniline＇ main reductive reaction route.     

Discrimination of extracted lipophilic constituents of Angelica with multi-steps infrared macro-fingerprint method

It is the most pressing task that fast and effective analysis methods monitor the inherent qualities of traditional Chinese medicine (TCM) and its corresponding extract products as a complicated mixture system. Owing to the unique fingerprint character and extensive applicability to test sample, infrared spectral method has been used in many research fields. In recent years, Fourier transform infrared spectroscopy (FT-IR), accompanied with the development of spectroscopic technology and combined with computer science, plays an important role in the TCM research. In this paper, we use FT-IR, second derivative infrared spectroscopy and two-dimensional correlation infrared spectroscopy (2D-IR) step by step to analyze the lipophilic constituents in Angelica extracted by two different extract crafts. As a result, all spectra can not only supply lots of structural information of main constituents in the complicated system, but also can differentiate the tiny differences between the similar systems according to the infrared macro-fingerprint characters. This is a very quick, effective and well repetitive method for monitoring the process of the TCM.     

Low loss liquid crystals for infrared applications

Seven fluorinated and chlorinated terphenyl compounds intended for mid-wave infrared (MWIR) applications are synthesised and two eutectic mixtures formulated, and their physical properties evaluated. In addition to low absorption, some desirable properties for MWIR applications include wide nematic range, high birefringence, large dielectric anisotropy and low viscosity. The fluorinated terphenyl mixture exhibits a relatively low absorption in the vicinities of λ ~ 3 μm, but a fairly strong overtone appears in the 4–5 μm region. To suppress these overtone absorptions, short-chain chlorinated terphenyl compounds are proven to be useful.     

Towards a practical Fourier transform infrared chemical imaging protocol for cancer histopathology

Fourier transform infrared (FTIR) chemical imaging is a strongly emerging technology that is being increasingly applied to examine tissues in a high-throughput manner. The resulting data quality and quantity have permitted several groups to provide evidence for applicability to cancer pathology. It is critical to understand, however, that an integrated approach with optimal data acquisition, classification, and validation is necessary to realize practical protocols that can be translated to the clinic. Here, we first review the development of technology relevant to clinical translation of FTIR imaging for cancer pathology. The role of each component in this approach is discussed separately by quantitative analysis of the effects of changing parameters on the classification results. We focus on the histology of prostate tissue to illustrate factors in developing a practical protocol for automated histopathology. Next, we demonstrate how these protocols can be used to analyze the effect of experimental parameters on prediction accuracy by analyzing the effects of varying spatial resolution, spectral resolution, and signal to noise ratio. Classification accuracy is shown to depend on the signal to noise ratio of recorded data, while depending only weakly on spectral resolution.     

An in situ Fourier transform infrared spectroscopy method for collecting real-time data for the liquid-phase reaction of CO2 and mono-ethanolamine in alcoholic solvent systems

A novel Fourier transform infrared (FTIR) spectroscopy method of analysis was developed to study the industrially important reaction of CO₂ with the primary amine, mono-ethanolamine (MEA), in n-propanol as representative alcoholic solvent. A semi-batch reactor with a piston like ‘floating’ head was specifically designed in order to study the reaction in the liquid phase, thereby eliminating the mass transfer limitations of a gas-liquid system. An attenuated total reflectance (ATR) probe was used to monitor the change in reagent and product concentrations in-situ. Successful spectral peak identification and calibrations were performed in order to collect real time, reaction kinetic data. Data analysis confirmed that the zwitterion reaction mechanism most accurately describes the reaction in non-aqueous systems.     

Photopolymerization of nematic liquid crystal monomers for structural applications: Linear viscoelastic behavior and cure effects

This article is concerned with molecular orientation in liquid crystal (LC) monomers and the retention of orientation in crosslinked network polymers formed from them by photopolymerization. This is of importance because anisotropic mechanical and physical properties can be beneficial in certain structural applications. To this end, linear viscoelastic behavior of liquid crystal photo-monomers was investigated with dynamic mechanical analysis, and molecular order was studied by infrared dichroism measured with Fourier transform infrared spectroscopy. Although the order parameter of the monomer could vary from 0.45 to 0.70, depending on temperature, the order parameters of the polymer samples varied only from 0.50 to 0.62 and depended on polymerization temperature and extent of cure. The mechanical anisotropy was found to be a complicated phenomenon that depended not only on the molecular order, but also on other factors such as free volume and network structure. The difference in the elastic modulus parallel and perpendicular to the alignment direction was as high as a factor of two in the glassy state, and a factor of three above T_g. In addition, different amounts of mechanical anisotropy could be induced by varying the cure conditions. Finally, different postcuring schemes could cause variations in mechanical behavior by advancing cure or by inducing secondary reactions. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 1081–1089, 1998     

Seafood freshness determination through vapour phase Fourier transform infrared spectroscopy

A new vapour-phase manifold has been developed to determine trimethylamine (TMA) in fish and cephalopod samples by Fourier transform infrared (FT-IR) spectroscopy. Samples were treated off-line for 1 h with trichloroacetic acid (TCA), filtered and washed. The obtained extracts were aspirated and alkalinized with NaOH 2.0 M, in an on-line system. TMA was separated from the solution in a gas phase separator and then transported by means of a nitrogen carrier into a home made 10 cm pathlength IR gas cell, where the corresponding FT-IR spectra were acquired by accumulating 30 scans per spectrum with 2 cm⁻¹ nominal resolution. The method was applied to the determination of TMA in natural samples providing concentration values statistically comparables with those obtained by a head space gas chromatography (HS-GC) reference procedure. The sample throughput by FT-IR is increased by a factor of 6 as compared with HS-GC.     

涂石蜡大米傅立叶变换红外吸收光谱识别分析

针对11种未涂石蜡大米和18个涂不同量石蜡的大米样品,以石油醚提取的油脂为试样,采用傅立叶变换红外光谱仪,扫描样品的傅立叶变换红外吸收光谱,并对光谱进行预处理,提取红外特征信息,将2855与1746、1462与1163 cm-1处特征峰的面积比值为坐标,采用Origín 6.0软件作识别分类图.结果表明:特征峰的面积比值与所涂石蜡量成线性变化,大米油脂的特征峰面积比值在一定的区域分布,涂以0.05%以上石蜡的大米,其油脂特征峰面积比值与未涂石蜡米油脂的值有一定区别.     

Determination of sucrose by flow injection analysis with fourier transform infrared detection

A new methodology for the determination of sucrose in complex aqueous matrices by flow injection analysis with FTIR detection is presented. The methodology based on the enzymatic hydrolytic cleavage of sucrose by means of invertase to -D-glucose and -D-fructose. A special manifold consisting of two internally coupled injection valves being switched simultaneously is applied to facilitate recording FTIR spectra of the sample before and after the enzymatic reaction. The analytical readout is taken from the resulting difference spectrum obtained by subtracting the FTIR spectra of the sample before and after the reaction. The developed methodology uses a GC-IR software to continuously record the FTIR spectra of the effluent from the manifold. The proposed method gives linear results in the range of 10 to 100 mmol/l and has been successfully applied to the analysis of sucrose in synthetic mixtures as well as in real samples such as soft drinks.     

Temperature‐Programmed Packed Capillary Liquid Chromatography Coupled to Fourier‐Transform Infrared Spectroscopy

Temperature‐programmed packed capillary liquid chromatography has been coupled off‐line to Fourier‐transform infrared spectroscopy, utilizing a commercially available interface with a pneumatic nebulizer rebuilt to handle low flow rates at elevated temperatures. The modified interface showed excellent performance with regard to non‐aqueous reversed phase separations of polymer additives, resulting in constructed Gram‐Schmidt chromatograms comparable to chromatograms obtained using UV detection. The spray of the in‐house constructed nebulizer was not influenced by temperature changes of the column effluent, and hence temperature‐programmed gradient separations could be used successfully. The relative standard deviation of peak height was 4.4% (n = 5) and the mass limit of detection was determined to be about 40 ng, using a polymer antioxidant as model compound. The present instrumental coupling has been used for characterization of the antioxidant Irgafos P‐EPQ.     

36种灵芝产品傅里叶变换红外光谱快速鉴别研究

利用傅里叶变换红外光谱法（FTIR）无损快速鉴别了36种灵芝类产品。灵芝、孢子粉和菌丝体的红外谱图差别较显著;不同厂家所生产的灵芝产品由于所选用灵芝的产地不同、所用辅料的种类以及辅料所添加的多少不同,均引起了谱图的相对峰强度和波数位置的改变。结果表明：36种灵芝产品均可以根据红外的特征谱图进行分类鉴别。该方法快速、不需对灵芝产品进行分离提取。