高分子 Vol.73 No.6
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特集  高分子を支える分析技術の進歩:表面・分子構造・反応を分析する最新分光技術
トピックス COVER STORY: Topics and Products
テラヘルツ・低波数ラマン分光法で見る高分子
Terahertz and Low-Frequency Raman Spectroscopy of Polymers
佐藤 春実
Harumi SATO
<要旨> Infrared, Raman, and near-infrared spectroscopy are well known as vibrational spectroscopy methods, and recently, in addition to these methods, terahertz (THz) and low-frequency Raman spectroscopy have been used in a variety of fields. THz and low-frequency Raman spectroscopy mainly deal with the region below 300 cm-1. Since molecular skeletal and intermolecular vibrations are observed, and the spectra observed in these regions are very sensitive to the higher-order structure of polymer compounds and intermolecular interactions. Recently, authors have attempted to study the higher-order structures and intermolecular interactions of semi-crystalline polymers and biodegradable polymers as well as low-frequency imaging and marine degradation processes of polymers. Here, we present some applications of these vibrational spectroscopic techniques to polymers.
Keywords: Terahertz Spectroscopy / Low-Frequency Raman Spectroscopy / Intermolecular Hydrogen Bonding
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和周波発生分光による界面分析
Evaluation of the Surface/Interface by Sum-Frequency Generation (SFG) Spectroscopy
宮前 孝行
Takayuki MIYAMAE
<要旨> Sum frequency generation (SFG) spectroscopy is widely recognized as a surface and interface specific vibrational spectroscopic technique. Various physical and chemical properties at the polymers and liquid interfaces are strongly correlated with the molecular behavior at the surfaces and interfaces, and it is essential to observe their behavior in-situ. In this paper, we present (1) the analysis of buried epoxy polymer/metal interfaces, (2) charged polymer surfaces and their charged mapping, (3) molecular orientation of saponin aqueous interfaces, and (4) the relationship between molecular orientation of isohumulones on beer surface and the foam stability.
Keywords: Sum Frequency Generation / Interface / Polymer / Liquid Interfaces / Electrification
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バイオハイブリッド光合成アンテナにおけるエネルギー移動の過渡吸収スペクトル測定
Energy Transfer in Biohybrid Photosynthetic Antenna Studied by Transient Absorption Spectroscopy
長澤 裕
Yutaka NAGASAWA
<要旨> LH2 is the periferal light-harvesting antenna complex of the photosynthetic purple bacteria. It contains two types of bacteriochlorophyll groups called B800 and B850 that absorbs light at 800 nm and 850 nm. While the light around 500 nm could be absorbed by the carotenoids, absorbance of LH2 is weak around 650 nm. Hence, biohybrid antenna (LH2-Alexa) with an artificial dye, Alexa 647 (Alexa), attached to LH2 was developed. In order to investigate the energy transfer dynamics of the biohybrid, femtosecond time-resolved transient absorption spectroscopy was performed. As a result, the energy transfer from Alexa to LH2 occurred multiexponentially with four major components with time constants ranging from 440 fs to 23 ps. The multiexponentiality of the energy transfer is due to the heterogeneous attachment of Alexa to the cystein residue of LH2.
Keywords: Ultrafast Spectroscopy / Transient Absorption Spectroscopy / Photosynthesis / Light-Harvesting Anntena Complex / Biohybrid / Energy Transfer / Förster Theory
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分光と機械学習を組み合わせたプラスチック劣化診断技術
Aging of Polypropylene Probed by Near Infrared Spectroscopy
新澤 英之
Hideyuki SHINZAWA
<要旨> This paper describes the attempt to characterize thermally induced aging of polypropylene (PP) samples by near infrared (NIR) spectroscopy. Significant levels of variation in NIR bands associated with short (amorphous-dominated) and long (crystalline-dominated) helices was readily captured when PP samples were subjected to thermal aging treatment. A regression model derived from the NIR spectra indicated a significant level of correlation between the actual and predicted elongations of the samples. Thus, by utilizing the NIR spectra, it becomes possible to predict the change in the elongation property of the aged PP sample without conventional mechanical testing.
Keywords: NIR Spectroscopy / Polymer / PP / Aging
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分子選択的動的光散乱:動的ラマン散乱
Dynamic Light Scattering: Molecular-Selective Dynamic Light Scattering
廣井 卓思
Takashi HIROI
<要旨> Dynamic light scattering (DLS) is a technique that has been widely used for the characterization of diffusion dynamics for polymer solutions and soft materials. In DLS measurement, the fluctuation of Rayleigh scattering is recorded as a form of the time correlation function. One of the major disadvantages of DLS is the absence of molecular selectivity, which limits the application of DLS to multi-component materials. To solve this problem, we have conceived a new measurement technique combining DLS and Raman scattering. Raman scattering is a scattering process whose wavelength is shifted depending on the molecular vibrational frequency of the target molecule. A simple combination of DLS and Raman scattering is the measurement of the fluctuation of Raman scattering from the target species. However, this strategy does not work because the intensity of Raman scattering does not fluctuate at all since conventional Raman scattering is an incoherent process. We solved this problem by utilizing coherent anti-Stokes Raman scattering.
Keywords: Dynamic Light Scattering / Raman Scattering / Molecular Selectivity
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固体NMR法で眺める高分子のミクロな世界
Polymer Strucutres As Explored by State-of-The-Art Solid-state NMR Spectroscopy
折内 俊哉・三好 利一
Shunya ORIUCHI, Toshikazu MIYOSHI
<要旨> Combined use of state-of-the-art solid state NMR spectroscopy with 13C isotope labeling enable ones to detect unique polymer strucutre such as chain folding strucutre of semicrystalline polymers (intramolecular packing) after crystalization as well as to separately observe intramolecular and intermolecular chemical reactions of solid polymers. Here, we in triduce two examples of i) chain folding strucutre of isotacitc-poly(1-butene) solution-grown crystals as a function of kinetics and ii) chemical reactions of polyacrylonitrile during stabilization process.
Keywords: Solid-State NMR / Isotope Labeling / Intermolecular and Intermolecular Intereaction / Polymer Crystallization / Chemica Reaction / Carbon Fiber / Polyacrylonitrile
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次世代の超高速赤外分光と超解像赤外顕微鏡
Next-Generation High-Speed Infrared Spectrosocpy and Super-Resolution Infrared Microscopy
井手口 拓郎
Takuro IDEGUCHI
<要旨> In the field of laser physics, we have recently witnessed remarkable developments in lasers and optical technologies in the infrared spectral region. These advancements have led to the creation of innovative spectroscopic and microscopic measurement techniques. This paper introduces our recently developed technologies on high-speed infrared spectroscopy and super-resolution infrared microscopy. We anticipate that the high-performance vibrational spectroscopy and microscopy will pioneer new trends in polymer chemistry.
Keywords: Laser / Infrared / Spectroscopy / Microscopy
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温度可変赤外分光法でみた高分子中の水構造
Water Structure in Polymers Observed by Thermal Analysis via Variable-Temperature Mid-Infrared Spectroscopy
源明 誠・加賀谷 重浩
Makoto GEMMEI-IDE, Shigehiro KAGAYA
<要旨> The water structure in polymer-water systems was observed based on heat flux measurements such as differential scanning calorimetry,DSC, has been discussed on the assumption that the heat flux is a state change between liquid water and ice, that is, freezing of water and melting of ice. However, variable-temperature mid-infrared spectroscopy, VT-mid-IR method, has revealed that water in polymer solids can undergo not only freezing and melting, but also state changes including condensation, deposition, sublimation, and evaporation, as well as deposition during heating (re-deposition). The combination of DSC and VT-mid-IR methods to study the water structure in polymer solids is currently limited, but it is expected to contribute to a deeper understanding of the relationship between function of polymers and the water structure.
Keywords: Free Water / Intermediate Water / Non-Freezing Water / State Changes / Polymer Solids
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グローイングポリマー Polymer Science and I: A Personal Account
環境を変えることで得られること
What Can Be Gained by Changing Environments
土肥 侑也
Yuya DOI
<要旨> I have learned a lot in my life as a researcher (especially after obtaining my Ph.D.) by changing my environment. In this article, I introduce some of my experiences so far.
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高分子科学最近の進歩 Front-Line Polymer Science
界面を利用するコロイド粒子の集積と機能発現
Assembly and Functionalization of Colloidal Particles Using Interfaces
前島 結衣・桑折 道済
Yui MAEJIMA, Michinari KOHRI
<要旨> This topic summarizes recent trends in the fabrication of colloidal particle assemblies using interfaces and their functions, focusing on research from the past few years. Particle assemblies have many attractive and unique features not found in other materials, and coupled with advances in particle fabrication methods, research in this area is progressing rapidly. The particle-assembling process at the interface is dynamic, and advances in analytical techniques are essential to understanding the process. We look forward to further developing this field through interdisciplinary research.
Keywords: Colloidal Particles / Interface / Assembly / Colloidal Crystals
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