Structure of Cytochromec and Its Platinum-modified Derivatives by Fourier Transform Infrared Spectroscopy

ＳｔｒｕｃｔｕｒｅｏｆＣｙｔｏｃｈｒｏｍｅｃａｎｄＩｔｓＰｌａｔｉｎｕｍ┐ｍｏｄｉｆｉｅｄＤｅｒｉｖａｔｉｖｅｓｂｙＦｏｕｒｉｅｒＴｒａｎｓｆｏｒｍＩｎｆｒａｒｅｄＳｐｅｃｔｒｏｓｃｏｐｙＪＩＡＮＧＬｉ－ｊｕａｎａ，ＳＵＮＷｅｉ－ｙｉｎａ，ＦＡＮＧＪ...     

Reduction of the shrinkage of thermosets by the cationic curing of mixtures of diglycidyl ether of bisphenol A and 6,6‐dimethyl‐(4,8‐dioxaspiro[2.5]octane‐5,7‐dione)

Ytterbium and lanthanum triflates were used as initiators to cure mixtures of diglycidyl ether of bisphenol A and 6,6‐dimethyl‐(4,8‐dioxaspiro[2.5]octane‐5,7‐dione) in several proportions. The evolution of the epoxy and 6,6‐dimethyl‐(4,8‐dioxaspiro[2.5]octane‐5,7‐dione) bands during curing and the linear ester groups in the final materials were evaluated with Fourier transform infrared in the attenuated‐total‐reflection mode. The use of a conventional cationic initiator, boron trifluoride monoethylamine, was also studied to test the advantages of lanthanide triflates. The shrinkage after curing and the thermal degradability of the materials with variations in the comonomer ratio and the initiator were evaluated and related to the chemical structure of the final network. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6869–6879, 2006     

Stability of polyaniline in air and acidic water

Polyaniline is a member of the class of electrically conducting polymers, having possible commercial applications such as coatings. Aqueous‐based polyaniline coatings are preferred over organic solvent or concentrated strong acid based coatings because water is not a pollutant. The overall goal of this study was to further the development of water‐based polyaniline coatings by an examination of the effect of acidic water (pH 1.18) and air on polyaniline. Knowledge of the effect of water on the structure, molecular weight, electrical conductivity, and diffusion of the dopant assisted in ascertaining whether polyaniline degraded with water exposure. Knowledge of how Fourier transform infrared (FTIR) spectra would be affected by dry air was important for determining if polyaniline was chemically stable with time. The results showed that the molecular weight, ultraviolet–visible and FTIR spectra, and carbon‐to‐nitrogen molar ratio in the polymer backbone all remained unchanged during acidic water immersion. The constant nature of these physical parameters showed a high degree of water stability. A chloride ion diffusion coefficient of 2.8 to 85 × 10^?9 cm²/h, the chloride concentration, and the electrical conductivity were also measured with the water immersion time. Aging polyaniline powders in a desiccator for 5 years showed no effect on the molecular structure, as indicated by the FTIR spectrum. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 807–822, 2003     

The disorder-longitudinal acoustic mode of oligo (ethylene glycol)-lithium trifluoromethane sulfonate solutions as studied by FT Raman spectroscopy

This work presents the results of Fourier transform Raman spectroscopy investigations of the disorder-longitudinal acoustic mode (D-LAM) of oligo(ethylene glycol) dimethyl ether-lithium trifluoromethane sulfonate solutions in dependence on oligomer chain length, temperature and salt concentration. The peak position and the bandwidth of this mode depend on the long-range conformational disorder of oligo(ethylene glycol) chains. The addition of salt causes a marked increase of the long-range conformational disorder. The frequency shift of the D-LAM combined with changes in the asymmetric CH₂ stretching bands indicate that the increasing long-range conformational disorder is connected with an increasing short-range conformational disorder of oligomer chains in a linear relationship.     

Spectroscopic studies of structural changes in irradiated LDPE and its blends

The low temperature glass transition occurring at low temperature in polyethylene samples was studied using Fourier transform infrared, FT‐Raman spectroscopic techniques, which are known to be sensitive to any structural changes in the investigated samples. Anomalous behavior was obtained in the temperature range (98 K → 383 K) indicating the existence of phase transition occurring at about 98 K and disappearing at about 323 K while heating for unirradiated virgin low density polyethylene (VPE) sample with or without crosslinking agent (trimethylol propane triacrylate, TMPTA). Addition of TMPTA monomer caused severe changes in the temperature dependence of both unirradiated and irradiated polyethylene samples. The results given indicated the occurrence of abnormal temperature dependence, which is thought to be related with low temperature structural change resulting from local crosslinking in scrapped polyethylene (SPE) sample already suffering from high degree of crosslinking. Differential scanning calorimetry (DSC) thermograms confirmed the observed new phase transition observed in both unirradiated and irradiated TMPTA loaded VPE/SPE (50/50 wt %) blend. Irradiation, addition of TMPTA as a crosslinking agent, and blending VPE with SPE were found to affect remarkably the variation of the vibration spectrum of LDPE and consequently the resulting structural changes. The experimental results obtained were discussed and correlated with reorientational disorders of the molecular segments (local crosslinking). © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 850–859, 2007     

酞菁铜固态薄膜的红外光谱

利用红外透射光谱，偏振透射光谱、掠角反射光谱研究了三－２，４－二特戊基苯氧基８－喹啉氧基酞菁铜ＬＢ膜和蒸镀膜的结构。确认在ＬＢ膜中，（１）取代基的碳链是以六方晶系或假六方晶系方式堆积的；（２）用偏振红外可以区别苯环上的两个ＣＨ２的伸缩振动带。在蒸镀膜中分子基本呈现无序状态。     

夜视像增强器(蓝光延伸与近红外延伸光阴极)的近期进展

２０世纪９０年代以来，夜视像增强器的研究主要朝着两个方向发展：一是研究对于探测、识别与确认沙漠地带或沙地景物有贡献的蓝光延伸（＜５５０ｎｍ）ＧａＡｓ负电子亲和势（ＮＥＡ）光阴极，光谱响应向短波长延伸，使光阴极灵敏度、光增益与鉴别率等性能大大优于标准三代管，从而形成“加强三代管”或所谓“四代管”，其探测性能较标准三代管高一倍；二是研究与夜天空辐射较为匹配、对１．０６μｍ激光有较高响应的光阴极，包括研究ＩｎＧａＡｓ、ＮＥＡ光阴极（１．０～１．３μｍ和１．５～２．０μｍ）和多碱光阴极（１．０～１．１μｍ）这三类近红外（ＮＩＲ）像管，可用于主被动夜视。本文综述了这几个方面的进展及其在夜视中的实际应用。     

CONFORMATIONAL ANALYSIS AND MOLECULAR MODELING OF CHOLESTERIC LIQUID CRYSTAL POLYESTERS BASED ON XRD,RAMAN, AND TRANSITION THERMAL ANALYSIS

Molecular modeling of the cholesteric liquid crystal polyester poly[oxy(1,2 - dodecane)oxycarbonyl-1,4-phenyleneoxycarbonyl-1,4-phenylenecarbonyloxy-1,4-phenylenecarbonyl] (PTOBDME), [C₃₄H₃₆O₈] _n , synthesized in our laboratory and thermally characterized by differential scanning calorimetry (DSC), was performed to explain both its cholesteric mesophase and 3D crystalline structure. Conformational analysis (CA) was run for the monomer both by systematic search and with molecular dynamics (MD) simulations. Minima energy conformers were “polymerized” with Cerius² and helical, cholesteric molecules were obtained in all cases. Our models agree with the chiral behavior observed by X-ray diffraction (XRD), thermooptical analysis (TOA) and circular dichroism (CD) experiments. Crystal packing of the polymer molecules were simulated in cells with parameters a and b obtained from experimental powder X-ray diffraction patterns and c calculated from the translational repetitive unit during the theoretical polymerization. Recalculated X-ray powder diffraction patterns of our models matched the observed ones. Morphology simulation from those crystal models is in good agreement with the crystals observed by optical microscopy. We have also modeled the self-associating nature of those polyesters when dispersed in aqueous media. Simulation of our models surrounded by different solvents, such as water and chloroform, were performed by calculating their interaction energies, coordination numbers, and mixing energies, applying Monte Carlo simulation techniques based on the Flory-Huggins theory. These results were compared with their experimental vibrational Fourier transform (FT)–Raman spectra in the regions in which structural marker bands of the polymer appear.     

A Review of Online Real-Time Process Analyses of Melt-State Polymer Using the Near-Infrared Spectroscopy and Chemometrics

Abstract

This review describes the online process monitoring of the melt-state polymer by near-infrared (NIR) spectroscopy and chemometrics. The spectra of linear low-density polyethylene (LLDPE), random polypropylene (RPP), block polypropylene (BPP), and ethylene-vinylacetate (EVA) copolymer in melt states measured by an online monitoring system with a Fourier transform near-infrared spectrometer are discussed. The calibration models for the density of LLDPE, the content of ethylene copolymers in RPP and BPP, and vinylacetate concentration (VA) in EVA copolymers using partial least squares regression are reported. The continuous monitoring of the LLDPE density at the real plant is described as an example of online monitoring using NIR spectroscopy and chemometrics. For the precise prediction of VA in EVA, a combination method using regression and discrimination was inducted. Three compensation methods for the effect of the temperature change in the RPP and BPP samples are shown. Conventional calibration transfer methods are introduced, and a practical calibration transfer method using two samples and its performance are reported using BPP and RPP spectra. Moreover, the possibility of a calibration correction method using one sample for the realization of long-term traceability is indicated by the example of the relocation.