Quantitative analysis of polyethylene blends by Fourier transform infrared spectroscopy

The quantitative analysis of binary polyethylene (PE) blends by Fourier transform infrared (FT-IR) spectroscopy has been achieved based on the ratio of two absorbance peaks in an FT-IR spectrum. The frequencies for the absorbance ratio are selected based on structural entities of the PE components in the blend. A linear relationship between the absorbance ratio and the blend composition was found to exist if one of the absorbance peaks is distinct to one of the components and the other peak is common to both components. It was also found that any peak resulting from short-chain branching in copolymers (such as linear low-density polyethylene (LLDPE) or metallocene-catalyzed LLDPE (mLLDPE)), is suitable for use as the peak that is designated as being distinct to that component. In order to optimize the linearity of the equation, however, the selection of the second common peak is the most important and depends on the blend system studied. Indeed, under certain circumstances peaks that are not spectrally distinct can be used successfully to apply the method. The method exhibits potential for the routine analysis of PE blends that have been calibrated prior to its application.     

Macromolecular concentrations in bovine nasal cartilage by Fourier transform infrared imaging and principal component regression

Fourier transform infrared imaging (FT-IRI) and principal component regression (PCR) were used to quantitatively determine collagen and proteoglycan concentrations in bovine nasal cartilage (BNC). An infrared spectral library was first established by obtaining eleven infrared spectra from a series of collagen and chondroitin 6-sulfate mixed in different ratios. FT-IR images were obtained from 6-μm-thick sections of BNC specimens at 6.25-μm pixel size. The spectra from the FT-IR images were imported into a PCR program to obtain the relative concentrations of collagen and proteoglycan in BNC, based on the spectral library of pure chemicals. These PCR-determined concentrations agreed with the molecular concentrations determined biochemically using an enzyme digestion assay. Use of the imaging approach revealed that proteoglycan loss in the specimens occurs first at the surface of the tissue block when compared with the middle portion of the tissue block. The quantitative correlation of collagen and proteoglycan revealed that their infrared absorption peak areas at 1338 and 1072-855 cm(-1) can only be used as qualitative indicators of the molecular contents. The use of PCR with FT-IRI offers an accurate tool to spatially determine the distributions of macromolecular concentration in cartilage.     

Interaction between a capacitor electrolyte and gamma-aluminum oxide studied by Fourier transform infrared spectroscopy

The interaction between y-aluminum oxide and an ethylene glycol (EG) based capacitor electrolyte was investigated by Fourier transform infrared (FT-IR) spectroscopy. It was found that only a few ingredients of the electrolyte react with the oxide (azelaic acid, poly(1-vinyl-2-pyrrolidone) (PVP), and phosphoric acid); the others act as pH or conductivity buffers (boric acid, ammonia, and water). The adsorption of azelaic acid and PVP from the electrolyte was studied as a function of temperature, pH, and time, and the result was compared to the adsorption from model solutions of simpler composition. The influence of other components such as phosphoric acid both in the electrolyte and on the aluminum oxide was also investigated, as was the presence of water. At low pH and high temperature (T > or = 105 degrees C) the acid formed an ester with EG and this product adsorbed on the oxide surface. The PVP was attached to the adsorbed azelaic acid by hydrophobic interaction, which is pH independent. Ester formation was found to be catalyzed by other electrolyte ingredients like boric acid. At high pH, surface adsorption of azelaic acid occurs through a deprotonated species, which is mainly coordinated through outer-sphere complexation. At high temperature or after a long equilibration time, the surface of the alumina changed, resulting in less adsorption of the organic substances, independent of pH. This change is due to a selective adsorption of phosphate species from the electrolyte, which block active surface sites.     

Study of dilution of Spin-On Glass by Fourier transform infrared spectroscopy

In this work, we study the dilution of Spin-On Glass (SOG) in order to obtain high quality SiO₂ films at 200 °C, with optical and electrical characteristics similar to those of the thermally grown SiO₂. For the production of SiO₂ films we used 2-propanol and deionized water (DI) as diluents for the SOG and we compared the electrical and optical film properties with those of the films obtained from undiluted SOG. From Fourier transform infrared spectroscopy we observed a considerable reduction of SiOH (920 cm^− 1), OH (3490 cm^− 1) and CH, CO bonds (1139 cm^− 1) in the films produced from SOG diluted with DI. Besides the above, the insulator breakdown field was approximately 21 MV/cm, the refractive index and the dielectric constant were close to those of the thermally grown SiO₂. Our results suggest that the film produced from SOG diluted with DI and cured at 200 °C is an excellent candidate to be used as insulator on flexible and large-area electronics.     

Fourier transform infrared (FT-IR) spectroscopy and improved principal component regression (PCR) for quantification of solid analytes in microalgae and bacteria

In bioanalytical chemistry, a detailed chemical understanding of biomaterials is often difficult to obtain due to the sheer number of analytes contained in a sample along with the samples' generally low reproducibility. This study presents a Fourier transform infrared (FT-IR) spectroscopic technique in conjunction with innovations in sample preparation and chemometric data preprocessing to overcome these limitations. These methodologies were applied to quantitative analyses of 31 representative compounds commonly found in biomaterial, which have been incorporated into a spectroscopic calibration database, that is, albumin (protein); D-alanine, glycine, histidine, valine, arginine, cysteine, phenylalanine, tyrosine, methionine, L-glutamine, and glutamic acid, (amino acids); glucose, fructose, galactose, mannose, sucrose, lactose, glycogen, agarose, and starch (carbohydrates); DNA (salmon sperm), sulphonoquinovosyl diglyceride ( sulpho-lipid ), and 1,2-diacyl-sn-glycero-3-phospho-L-serine ( phospho-lipid ); succinic acid and malic acid ( carboxylic acids ); glycolic acid (a -hydroxy acid), sodium pyruvate, b -carotene, frustules (microalgae silica-shells), and ammonium formate. Two proof-of-principle applications were based on calibration models incorporating these solids, i.e., characterization of E. coli and microalgae. The former aims for detection of bacterial contamination and the latter to enable investigations of changes in chemical composition of microalgae cells in response to shifting environmental conditions. Chemometric preprocessing steps have been developed for handling sample-to-sample fluctuations of absorption path lengths and baselines; the former incorporated mass normalization while the latter utilized a novel baseline correction method that requires no a priori information. Data preprocessing, chemometric calibration, and evaluation algorithms have been combined, together with an extensive spectral database of the aforementioned compounds (～1500 samples), for quantitative calibration purposes through the remotely accessible Virtual Chemometrics Lab , which can be utilized for a multitude of applications through a graphical user interface.     

Fourier transform infrared (FT-IR) imaging coupled with principal component analysis (PCA) for the study of photooxidation of polypropylene

Fourier transform infrared (FT-IR) imaging coupled with principal component analysis (PCA) is used to characterize the photooxidation of polypropylene (PP) and identify the photooxidative products at different oxidation times. PP slices were exposed to ultraviolet (UV) irradiation for times up to 60 hours and spatially resolved spectra were acquired with a transmission FT-IR imaging system in order to view the steric inhomogeneity of the photooxidation process of PP. The evolution of the oxidized products with irradiation time is shown through the application of PCA. Carboxylic acid is the major oxidized product in the initial period from 0 h to 8 h while ketone becomes the major product with the increase of irradiation time. Carboxylic anhydride is identified for the first time to our knowledge in oxidized PP after 16 h irradiation. Carboxylate ester is also observed in the oxidized PP after 32 h irradiation. Possible mechanisms forming these products have been discussed.     

Detection of albumin unfolding preceding proteolysis using Fourier transform infrared spectroscopy and chemometric data analysis

The hydrolysis of bovine serum albumin with protease K at 60 degrees C has been studied by means of infrared spectroscopy. Two-dimensional correlation spectroscopy (2DCoS) has been used to study spectral changes in the reaction. The use of the multivariate curve resolution-alternating least-squares method applied to infrared measurements allowed the recovery of pure infrared spectra and concentration profiles of the different species involved in the reaction. Special attention was paid to the careful inspection of residuals again using 2DCoS. In this way, a heat-induced unfolding step previous to protein hydrolysis was identified. The infrared spectra of the intermediate species showed a more disordered structure than native albumin, the decrease in alpha-helix conformation being especially noticeable. The formation of beta-sheet aggregates due to heating was detected too.     

Analysis of texture and microstructure of anatase thin films by Fourier transform infrared spectroscopy

This work provides the basis for a “fingerprint” analysis of the microstructure and the texture of anatase thin films by using Fourier transform infrared spectroscopy. For this, a formalism that reproduces the experimental spectra has been developed and its applicability is analysed for anatase thin films with different microstructure (columnar and porous, with varying degrees of compactness) and texture. The rather good agreement between calculated and experimental spectra observed in all cases demonstrated that a systematic use of this non-destructive technique can be very useful for the characterization of thin films.     

Determination of acid number and base number in lubricants by Fourier transform infrared spectroscopy

This paper describes the development of practical Fourier transform infrared (FT-IR) methods for the determination of acid number (AN) and base number (BN) in lubricants through the combined use of signal transduction via stoichiometric reactions and differential spectroscopy to circumvent matrix effects. Trifluoroacetic acid and potassium phthalimide were used as stoichiometric reactants to provide infrared (IR) signals proportional to the basic and acidic constituents present in oils. Samples were initially diluted with 1-propanol, then split, with one half treated with the stoichiometric reactant and the other half with a blank reagent, their spectra collected, and a differential spectrum obtained to ratio out the invariant spectral contributions from the sample. Quantitation for AN and BN was based on measurement of the peak height of the v(C = O) or v(COO) absorptions, respectively, of the products of the corresponding stoichiometric reactions, yielding a standard error of calibration of < 0.1 mg KOH/g oil. The AN/BN FT-IR methods were validated by the analysis of a wide range of new and used oils supplied by third parties, which had been analyzed by ASTM methods. Good correlations were obtained between the chemical and FT-IR methods, indicating that the measures are on the whole comparable. From a practical perspective, these new FT-IR methods have significant advantages over ASTM titrimetric methods in terms of environmental considerations, sample size, and speed of analysis, as well as the variety of oil types that can be handled. FT-IR analysis combining stoichiometric signal transduction with differential spectroscopy may be of wider utility as an alternative to titration in the determination of acid or basic constituents in complex nonaqueous systems.     

基于主成分分析的护听器优选方法研究

为了探究不同护听器对抽水蓄能电站内不同工作场所的降噪效果及适用情况,以便于工作人员根据不同需要选择合适的护听器,根据112种护听器的插入损失测试结果,应用主成分分析(Principal Component Analysis, PCA)对数据进行分析。结合某抽水蓄能电站10个工作场所的现场测试结果,得出文中所测试的112种护听器大部分适用于该蓄水电站中1#发电机隔声罩内、1#水车室外、1#水车室内、2#尾水锥管室外、2#尾水锥管检修门、3#尾水锥管室外和3#尾水锥管检修门7个工作场所,其他场所需要有针对性地选择适合的护听器。该文同时可以为其他不同工作场所情况下护听器的选择提供借鉴。     

结合主分量分析与DOA估计的语音盲分离

在欠定语音盲分离中,W-分离正交性假设通常使问题简化,但这种简化是以降低分离性能为代价。在语音信号满足近似W-分离正交性的假设下,提出利用主分量分析（PCA）检测只有一个源信号存在的时频点,检测出的时频点均满足W-分离正交性,因此提高了混合矩阵的估计精度。通过从混合矩阵中估计源信号的波达方向,可以较好地解决置换模糊问题。仿真结果表明,提出的方法与经典的DUET方法相比具有更优的性能,平均信干比提高了2.77dB。     

Fourier transform infrared attenuated total reflection and transmission spectra studied by dispersion analysis

Fourier transform infrared transmission (FT-IR) and attenuated total reflection (ATR) spectra of water-ethanol mixtures are recorded and reconstructed thanks to a causal dispersion analysis technique. As expected, the Beer's law technique is an empirical approximate method that cannot account for complex spectral features. On the other hand, a rigorous analysis performed by using the theoretical optical paths for both experimental techniques and Gaussian dispersion analysis (GDA) allows the dielectric functions of the pure liquids to be calculated. Simulations of the whole mid-infrared spectra in the range 500-4000 cm(-1) match the experimental data very well, whatever the water-ethanol mixtures. This method is a powerful tool to quantify such model mixtures and more generally could be the first step toward software for assistance to the FT-IR spectrum analysis.     

Structural analysis of triacylglycerols and edible oils by near-infrared Fourier transform Raman spectroscopy

Fourier transform Raman spectroscopy was employed for structural analysis of triacylglycerols and edible oils. Raman spectra sensitively reflected structural changes in oils. Even slight structural fluctuation between triacylglycerols and free fatty acids led to obvious differences in Raman bands as shown by C-O-C stretching from 800 to 1000 cm(-1) and the band at 1742 cm(-1). Structural difference in geometric isomers was easily distinguished as proved by C = C stretching at 1655 cm(-1) (cis) shifting to 1668 cm(-1) (trans) and by =C-H in-plane bending at 1266 cm(-1) in cis disappearing in the trans isomer. Raman intensity at 1266, 1302, and 1655 cm(-1) changed concomitantly with the change of double-bond content in oils. It showed that FT-Raman was capable of precisly reflecting the content of double bonds in oils. A linear correlation with high consistency between the Raman intensity ratio (v1655/v1444) and the iodine value was obtained for commercial oils. Based on the results, FT-Raman spectroscopy proved itself a simple and rapid technique for oil analysis since each measurement could be directly completed in 3 min without any sample modifications.     

Evaluation of model compounds–polypropylene film interactions by Fourier transformed infrared spectroscopy (FTIR) method

The interactions of methyl esters, methyl ketones and aldehyde compounds with polypropylene (PP) film were investigated. PP film, placed on a glass vial, was immersed in aqueous solution containing a model flavour compound. After a determined time at 45°C, the PP film was analysed by Fourier transform infrared spectroscopy (FTIR), allowing us to follow the speed of sorption and to quantify its relative rate. For PP films, we observed that the sorption strongly depended on the structure of sorbed molecules. For each functional group of flavour compounds, the sorption increased as the carbon chain number increased. A linear chain of 12–14 carbons favours the sorption more than a linear chain of eight carbons. Concerning functions, the rate of sorption usually decreases from esters to ketones and to aldehydes. High sorption was observed for flavour compounds with a low difference of solubility parameter (SP) value between the film and flavour [(δ_polymer ? δ_flavour)² value]. Furthermore, by using the proposed thermodynamic affinity concept, represented as the contribution of three interactive molecular forces [dispersion (d_d), polar (d_p) and hydrogen bonding (d_h)] between two SP values of film and flavour, packaging materials with high flavour preservation against sorption can be designed. We have a good correlation between the kinetic sorption by FTIR and the SP concept. Copyright © 2007 John Wiley & Sons, Ltd.     

Two-dimensional infrared spectroscopy and principal component analysis studies on a new azobenzene derivative supramolecular system based on hydrogen bonds

Infrared (IR) spectra of a supramolecular assembly with an azobenzene derivative and intermolecular hydrogen bonds have been measured in the temperature range from 30 to 200 degrees C to investigate heat-induced structural changes and thermal stability. Principal component analysis (PCA) and two kinds of two-dimensional (2D) correlation spectroscopy, variable-variable (VV) 2D and sample-sample (SS) 2D spectroscopy, have been employed to analyze the observed temperature-dependent spectral variations. The PCA and SS 2D correlation analyses have demonstrated that the complete decoupling of hydrogen bonds in the supramolecular assembly occurs between 110 and 115 degrees C, which is in good agreement with the results of a differential scanning calorimetry (DSC) study for the heating process. The PCA of the IR spectra in the region of 3600-3100 cm(-1) has illustrated that there are at least four principal components for the different NH2 and CONH species in the present supramolecular system. The VV 2D correlation spectroscopy study has provided information about the structure and strength of hydrogen bonds of NH2 and CONH groups and their temperature-dependent variations. The different species of hydrogen-bonded NH2 and CONH groups in the supramolecular system can be clarified by the VV 2D correlation analysis. The VV 2D correlation analysis has also revealed the specific order of the temperature-induced changes in the hydrogen bonds of NH2 and CONH groups.     

Connections between multiple co-inertia analysis and consensus principal component analysis

Consensus Principal Component Analysis is a multiblock method which is designed to reveal covariant patterns between and within several multivariate data sets. The computation of the parameters of this method namely, block scores, block loadings, global loadings and global scores are based on an iterative procedure. However, very few properties are known regarding the convergence of this iterative procedure. The paper discloses a monotony property of CPCA and exhibits an optimisation criterion for which CPCA algorithm provides a monotonic convergent solution. This makes it possible to highlight new properties of this method of analysis and pinpoint its connection to existing methods such as Generalized Canonical Correlation Analysis and Multiple Co-inertia Analysis.