Fourier transform infrared spectroscopy evaluation of low density lipoprotein oxidation in the presence of quercetin,catechin, and α-tocopherol

We investigated the changes in human LDL primary and secondary lipid oxidation products and modification of the apolipoprotein B-100 (apoB-100) secondary structures during Cu²⁺-mediated oxidation by FTIR spectroscopy in the presence of catechin, quercetin, and α-tocopherol at physiological concentrations. Catechin- and quercetin-containing samples had slower rates and longer lag phases for conjugated diene hydroperoxide (CD) formation than α-tocopherol-containing samples; however, all antioxidant-treated LDL samples generated similar CD levels (P<0.05). A lower maximum (98.4 nmol/mg LDL protein) of carbonyl compounds was produced in the quercetin- and catechin-treated samples than in α-tocopherol samples. Modification of the apoB-100 secondary structures corresponded closely to the formation of carbonyls and was hampered by the presence of antioxidants. Physiological concentrations of catechin and quercetin offered similar levels of protection against modification by carbonyls of the apoB-100 at advanced stages (carbonyls ∼96.0 nmol/mg LDL protein) but not at the intermediate stages (carbonyls ∼58.0 nmol/mg LDL protein) of LDL oxidation probably owing to differences in the protein-binding mechanisms of catechin and quercetin. Relationships between peroxide formation, carbonyl products, and LDL protein denaturation were shown by the FTIR approach. The FTIR technique provided a simple new tool for a comprehensive evaluation of antioxidant performance in protecting LDL during in vitro oxidation.     

An investigation of vinyl–ester?styrene bulk copolymerization cure kinetics using Fourier transform infrared spectroscopy

A Fourier transform infrared (FTIR) spectroscopy technique was developed to investigate the effects of reaction temperature and reactant composition on the isothermal curing kinetics of commercial vinyl nester resins comprised of vinyl–ester monomer (dimethacrylate of diglycidyl ether of bisphenol A DGEBA) and styrene. This technique enables a more complete evaluation of the bulk copolymerization reaction of vinyl–ester styrene systems by monitoring the depletion of vinyl–ester and styrene double bonds independently. The results indicate that the rate of fractional conversion of styrene double bonds is initially less than that of vinyl–ester vinyl groups. However, styrene monomer continues to react after conversion of vinyl–ester double bonds has ceased. In addition, the overall extent of conversion was found to increase with increasing isothermal cure temperature, and it was observed that higher styrene concentration enhances final conversion of vinyl–ester double bonds and not styrene double bonds. Increasing styrene monomer concentration also resulted in lowering the apparent activation energy for the reaction of vinyl groups from both monomers as characterized by an empirical autocatalytic model used to fit the conversion results for styrene and vinyl–ester double bonds independently. The results of this work demonstrate that reaction temperature and resin composition significantly affect the cure behavior of vinyl–ester resins and provide insight into the development of the resulting network structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1572–1582, 2000     

Calcium silicate hydrate—in-situ development of the silicate structure followed by infrared spectroscopy

In the current study, the development of the silicate structure of synthetic calcium silicate hydrates with different calcium contents was followed by in-situ infrared (IR) spectroscopy and correlated to the in-situ phase development evaluated by X-ray diffraction (XRD). A baseline correction method initially developed for X-ray diffractograms was successfully adapted for the complex background of the fingerprint region in in-situ IR, which significantly contributed to signal quality and reproducibility. The development of separate silicate infrared bands could be monitored over 24 h of reaction. These bands could be assigned to oligomeric and dimeric species based on their time and stoichiometry-dependent development. It was clearly shown that the main peak of the dimeric silicate species was overlooked in the literature. The correlation of time-dependent events to in-situ XRD revealed that changes in the unit cell of calcium silicate hydrate are related to silicate polymerization. The results were compared to ²⁹Si-MAS-NMR, which highlighted the benefits of in-situ IR spectroscopy.     

How the infrared radiation affects the film formation process from latexes?

In this study, the effect of the infrared radiative heating (IRH) was investigated on the film formation from composites of polystyrene (PS) latex particles and poly vinyl alcohol (PVA). The films were prepared as a pure PS and a mixture of PS and PVA particles at equal compositions at room temperature and they were annealed at elevated temperatures above the glass transition temperature (T_g) of PS for 10 min by using IRH technique. Identical experiments were performed by using standard convectional heating technique in oven as comparison. It was shown that the activation energy for the film formation from PS latex particles decreased considerably in IRH annealing technique. Photon transmission (PT) and steady state fluorescence (SSF) techniques were used to monitor the film formation process at each sintering step. Minimum film formation temperature, T_o, and healing temperature, T_h, were determined by the data obtained from the SSF and the PT measurements for each heating processes. The film formation was modeled as a void closure and as an interdiffusion stage below and above T_h, respectively. Scanning electron microscopy (SEM) was used to examine the variation in morphological structure of annealed composite films. It was observed that IRH heating causes more homogenous and more flat film surface than films annealed in the oven. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43289.     

Interface,thermal, and Fourier transform—infrared spectroscopy investigation on polylactic acid/polyhydroxyalkanoate composites with silane-treated aluminum particles and intercalated montmorillonite inclusions for semiconductor devices

In this investigation, the dielectric properties of silane-influenced aluminum conductive particles in polylactic acid, polyhydroxyalkanoates, and intercalated montmorillonite (MMT) composite were assessed for enhancing the dielectric constant, dielectric loss, and AC conductivities. Eight different sets of samples were fabricated with untreated and silane-treated batches of biopolymer composites where the highest recorded dielectric constant was 3.98 at relaxation frequency of 10 kHz. One of the notable observations in the dielectric loss was with PLA/PHA/iMMT/Al (10 wt%) (silane-treated) composites exhibited the lowest losses past relaxation frequencies. Furthermore, FT-IR spectra were conducted on the samples to identify stretching and bonds created by silane and aluminum particles. The IR spectra confirm the formation of the Si O Al bond when treated with 3-glycidyloxypropyl-trimethoxysilane (GPTMS) solution and confirm the bond of Al OH hydroxyl bonds in the untreated composite samples. Other IR spectra information that was gathered would include carbonyl group stretching at 1750 cm⁻¹ and absorption bands of hydroxy acids, between 3511 and 3640 cm⁻¹, respectively. Scanning electron microscopy was performed on the sample to observe the formation of matrix cracks and exfoliation. A rough surface can be seen on PLA/PHA blends and the crystallization of these polymer blends regions can be vividly seen from the micrographs. Lastly, thermogravimetry analysis on the composite samples shows a predominant mass loss at 300°C before complete degradation and the notable composite with the lowest mass loss would be PLA/PHA/iMMT/Al (10 wt%) (ST) composite samples and with the inclusion of a constant 5 wt% organoclay MMT fillers imposed a high-onset degradation temperature, which was remarkable for composites that were fabricated through standard hot-press compression molding and cooling procedures.     

Preparation and study of the mechanical and optical properties of infrared transparent Y2O3–MgO composite ceramics

In this study, fine Y₂O₃–MgO composite nanopowders were synthesized via the sol–gel method. Dense Y₂O₃–MgO composite ceramics were fabricated by pre-sintering the green body in air at different temperatures for 1 h and then subjecting the sintered bodies to hot isostatic pressing at 1300°C for 1 h. The effects of pre-sintering temperature on the microstructural, mechanical, and optical properties of the resulting ceramics were studied. The average grain size of the ceramics was increased, whereas their hardness and fracture toughness were decreased with increasing pre-sintering temperature. A maximum fracture toughness of 1.42 MPa·m^1/2 and Vickers hardness of 10.4 GPa were obtained. The average flexural strength of the ceramics was 411 MPa at room temperature and reached 361 MPa at 600°C. A transmittance of 84% in the 3–5 µm region was obtained when the composite ceramics were sintered at 1400°C. Moreover, a transmittance of 76% in the 3–5 µm region was obtained at 500°C.     

Physicochemical,adsorption, and catalytic properties of high-silica zeolites of the MFI type in the conversion of the propane–butane fraction into aromatic hydrocarbons

The complex of physicochemical properties of high-silica zeolites of the MFI-type obtained using organic templates, including hexamethylenediamine, POD-oils, and pentaerythritol, has been investigated. It was shown that zeolites produced using different templates demonstrated different activity and selectivity in the process of converting the propane–butane fraction into aromatic hydrocarbons.     

Real time monitoring of bioreactor mAb IgG3 cell culture process dynamics via Fourier transform infrared spectroscopy: Implications for enabling cell culture process analytical technologyŽ 

Compared to small molecule process analytical technology (PAT) applications, biotechnology product PAT applications have certain unique challenges and opportunities. Understanding process dynamics of bioreactor cell culture process is essential to establish an appropriate process control strategy for biotechnology product PAT applications. Inline spectroscopic techniques for real time monitoring of bioreactor cell culture process have the distinct potential to develop PAT approaches in manufacturing biotechnology drug products. However, the use of inline Fourier transform infrared (FTIR) spectroscopic techniques for bioreactor cell culture process monitoring has not been reported. In this work, real time inline FTIR Spectroscopy was applied to a lab scale bioreactor mAb IgG3 cell culture fluid biomolecular dynamic model. The technical feasibility of using FTIR Spectroscopy for real time tracking and monitoring four key cell culture metabolites (including glucose, glutamine, lactate, and ammonia) and protein yield at increasing levels of complexity (simple binary system, fully formulated media, actual bioreactor cell culture process) was evaluated via a stepwise approach. The FTIR fingerprints of the key metabolites were identified. The multivariate partial least squares (PLS) calibration models were established to correlate the process FTIR spectra with the concentrations of key metabolites and protein yield of in-process samples, either individually for each metabolite and protein or globally for all four metabolites simultaneously. Applying the 2^nd derivative pre-processing algorithm to the FTIR spectra helps to reduce the number of PLS latent variables needed significantly and thus simplify the interpretation of the PLS models. The validated PLS models show promise in predicting the concentration profiles of glucose, glutamine, lactate, and ammonia and protein yield over the course of the bioreactor cell culture process. Therefore, this work demonstrated the technical feasibility of real time monitoring of the bioreactor cell culture process via FTIR spectroscopy. Its implications for enabling cell culture PAT were discussed.     

Fourier-transform infrared spectra of fatty acid salts—Kinetics of high-oleic sunflower oil saponification

Sodium, lithium, and calcium soaps obtained by saponification of high-oleic sunflower oil were studied by Fourier-transform infrared spectroscopy. Spectra of crude mixtures containing soap, glycerin, residual alkali, and triacylglycerols were compared to those of pure soaps obtained from fatty acids. The infrared spectra of crude soaps showed the same characteristic bands as pure ones. The absorption bands of asymmetric (ω₂) and symmetric (ω₁) stretching vibrations of the carboxylate group indicated that the metal-oxygen bonds of these soaps had an ionic character whose strength differed from one cationic counterion to another. Once the characteristic absorption bands of the soaps were assigned, a kinetics study of saponification was performed. Saponification by sodium, anhydrous lithium, and calcium hydroxides was an autocatalytic reaction, characterized by an S-shaped kinetics curve, whereas saponification by aqueous lithium hydroxide was stoichiometric. The structure of the metal-oxygen bond played a role in the kinetic mechanisms.     

Comparison of the structural properties of compounds containing the XSSX moiety (X = H,Me, R,Cl, Br,F, OR)

A comparison of the structural parameters of a wide variety of compounds containing the S–S bond is summarized.     

Sol–gel synthesis and infrared radiation property of Li-substituted cordierite

The Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (0.1≤x≤1) ceramics with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ were synthesized by the sol–gel method. The characterization of the modified cordierite included X-ray diffraction, SEM, EDS and infrared radiation. The crystal structure of Mg₂Al₄Si₅O₁₈ with the substitution of (Li_1/2Al_1/2)²⁺ for Mg²⁺ changed and the amount of secondary phase increased with increasing the x value from 0.1 to 1. High infrared emissivity over 0.9 in the band of 8–14 μm at room temperature was obtained in Mg_2?xAl_4+1/2xLi_1/2xSi₅O₁₈ (x=0.1). The material based on cordierite with x=0.1 sintered at 1200 °C maintained a single phase, compact microstructure and good infrared emissivity with potential use in infrared heating.     

The impact of the discovery of the polymerization of the α-olefins on the development of the stereospecific polymerization of vinyl monomers

After a short survey of the first indications on the existence of stereoregularity in the main chains of the vinyl polymers, the first syntheses of stereoregular poly(vinylethers) and polystyrene are briefly summarized. The difficulties encountered in the early investigations of the propylene polymerization by the CoO/MoO₃/Al₂O₃ and CrO₃/SiO₂/Al₂O₃ catalysts are considered and the isolation and identification of a crystalline component in the mixture of diastereomeric macromolecules thus obtained, are discussed. The results obtained by different research groups, independently investigating the stereospecific polymerization of vinyl monomers, are compared and finally an attempt is made to explore the origin of the very rapid progress made in this field by Natta and coworkers in connection with their discovery of the stereospecific polymerization of α-olefins with the ‘Ziegler-Natta catalysts’.     

Uncertainty Budget of the SMPS–APS System in the Measurement of PM1, PM2.5, and PM10

The effects of particulate matter on environment and public health have been widely studied in recent years. In spite of the presence of numerous studies about this topic there is no agreement on the relative importance of the particles' size and origin with respect to health effects among researchers. Nevertheless, air quality standards are moving, as the epidemiological attention, towards greater focus on the smaller particles. The most reliable method used in measuring particulate matter (PM) is the gravimetric method since it directly measures PM concentration, guaranteeing an effective traceability to international standards. This technique, however, neglects the possibility to correlate short term intraday atmospheric parameter variations that can influence ambient particle concentration and size distribution as well as human activity patterns. Besides, a continuous method to determine PM concentrations through the measurement of the number size distribution is the system constituted by a Scanning Mobility Particle Sizer (SMPS) and an Aerodynamic Particle Sizer (APS). In this article, the evaluation of the uncertainty budget in measuring PM through the SMPS–APS system, as well as a metrological comparison with the gravimetric reference method in order to analyze the compatibility, was carried out and applied with reference to an experimental campaign developed in a rural site. This choice allowed to assume the hypothesis of spherical particle morphology. The average PM₁₀, PM_2.5, and PM₁ uncertainties obtained for the SMPS–APS system are equal to 27%, 29%, and 31%, respectively. Here the principle influence parameter is the particle density that has to be directly measured with low uncertainty in order to reduce the PM uncertainty.     

A Polymorphism at the 3′-UTR Region of the Aromatase Gene Is Associated with the Efficacy of the Aromatase Inhibitor,Anastrozole, in Metastatic Breast Carcinoma

Estrogen-related genes and the fat mass and obesity-associated (FTO) gene play a critical role in estrogen metabolism, and those polymorphisms are associated with a poor prognosis in breast cancer. However, little is known about the association between these polymorphisms and the efficacy of anastrozole. The aim was to investigate the impact of the genetic polymorphisms, CYP19A1, 17-β-HSD-1 and FTO, on the response to anastrozole in metastatic breast carcinoma (MBC) and to evaluate the impact of those polymorphisms on various clinicopathologic features. Two-hundred seventy-two women with hormone receptor-positive MBC treated with anastrozole were identified retrospectively. DNA was extracted from peripheral blood and genotyped for five variants in three candidate genes. Time to progression was improved in patients carrying the variant alleles of rs4646 when compared to patients with the wild-type allele (16.40 months versus 13.52 months; p = 0.049). The rs4646 variant alleles were significantly associated with longer overall survival (37.3 months versus 31.6 months; p = 0.007). This relationship was not observed with the rs10046, rs2830, rs9926298 and rs9939609 polymorphisms. The findings of this study indicate that rs4646 polymorphism in the CYP19A1 gene may serve as a prognostic maker of the response to anastrozole in patients with MBC who are treated with anastrozole.