Control of polymerization processes of 10,12-pentacosadiynoic acid LB films

Studies have been carried out on KrF excimer laser light (EX), X-ray or electron beam (EB) induced polymerization of 10,12-pentacosadiynoic acid (PDA) Langmuir-Blodgett (LB) films in relation to molecular density or molecular arrangement of the films using X-ray diffraction analysis, infrared (IR) spectroscopy and Raman spectroscopy. The molecular arrangement or density of the PDA LB films was controlled by subphase conditions when the films were built up, such as pH, temperature of a subphase or salt concentration in the subphase. Polymerization sensitivity of the PDA LB film was affected by the arrangement or molecular density. On low density (A type) films the polymerization occurred by irradiation with EX, X-ray or EB, but on high density (B type) films the polymerization occurred only when the irradiation was carried out by high energy beams such as X-ray or EB. Decomposition of polymerized films was observed further by excessive irradiation of EX or X-ray, but not on the B type films. It was revealed by X-ray diffraction analysis that in the A type film, the PDA molecules bent to a larger extent than those in the B type film and the polymerization proceeded topochemically, that is, the thickness decreased little after EB irradiation in a helium atmosphere. On the other hand, in the B type film, the thickness decreased by about 10% as a result of EB irradiation. By IR reflection-absorption (RA) and Raman measurements, it was confirmed that conjugated diacetylenic bonds disappeared and conjugated double and new conjugated triple bonds appeared after high energy beam irradiations. These results support the supposition that 1,4-polymerization, i.e. polydiacetylene type polymerization, occurs easily in the A type film and 1,2- or 3,4-polymerization, i.e. polyacetylene type polymerization, occurs in the B type film, and that the polymerized A type film was decomposed at the polydiacetylenic bond when the irradiation continued further. It was also shown that the polyacetylene type polymer was obtained only when the B type film was irradiated with the high energy beam.     

低维聚合物PDCH的低温热膨胀与介电性质

研究了准一维聚合物单晶ＰＤＣＨ在８０～３００Ｋ温区内的热膨胀与个电性质。利用高精度的三端电容电桥法测量了沿不同方向的线膨胀系数和介电常数，在该温区内ＰＤＣＨ的热膨胀系数和个电常数均表现出很大的奇异性．结果还表明，ＰＤＣＨ在１７５Ｋ附近发生二级相变，在１３０Ｋ附近出现自发极化。     

A Colorimetric Hydrocarbon Sensor Employing a Swelling‐Induced Mechanochromic Polydiacetylene

Exceptional challenges have confronted the rational design of colorimetric sensors for saturated aliphatic hydrocarbons (SAHCs). The main reasons for this difficulty are the extremely nonpolar nature of these targets and their lack of functional groups that can interact with probes. By taking advantage of a mechanochromic conjugated polydiacetylene (PDA) and the hydrocarbon‐induced swelling properties of polydimethylsiloxane (PDMS), a sensor film that enables simple, colorimetric differentiation between a variety of C5 to C14 aliphatic hydrocarbons is fabricated. The unprecedented PDA–PDMS composite sensor undergoes a blue‐to‐red colorimetric transition on a timescale that is dependent on the chain length of the hydrocarbon target. In addition, the development of the red color is directly proportional to the swelling ratio of the film. This straightforward approach enables naked‐eye differentiation between n‐pentane and n‐heptane. The versatility of the sensor system is demonstrated by using it for the colorimetric determination of kerosene in adulterated diesel oil. Finally, the observation that a PDA microcrystal in the film undergoes significant expansion and tearing in concert with a blue‐to‐red colorimetric transition during the swelling process provides direct evidence for the mechanism for the mechanochromic behavior of the PDA.     

5－（2－硫甲基－4－甲基－5－嘧啶基）－2，4－戊二炔－1－醇α甲基丙烯酸酯非线性光学材料

聚二乙炔（ＰＤＡ）类化合物在超快全光开关、逻辑门和远距离通讯系统的多路传输等方面有着潜在的应用前景。但并不是所有的ＰＤＡ都能用于这些方面，它的选择应当考虑聚合性能、链密度、共轭度、溶解性、热稳定性及可加工性等多方面的因素。本文首次报道了５－（２－硫甲基－４－甲基－５－嘧啶基）－２，４－戊二炔－１－醇甲基丙烯酸酯（ＰＤＭＡ）的合成，该物质极易聚合、链密度高、聚合物可溶、单体热稳定性好，在许多方面可与当前最好的化合物ＰＴＳ及ｐｏｌｙ－４ＢＣＭＵ相媲美。     

Detection of Foot‐and‐Mouth Disease Virus Using a Polydiacetylene Immunosensor on Solid‐Liquid Phase

The rapid detection of foot‐and‐mouth disease virus (FMDV) is vital for the prevention of foot‐and‐mouth disease outbreaks. In this study, a polyvinylidene difluoride (PVDF)‐supported polydiacetylene (PDA) immunosensor is developed to detect FMDV, in which a polyclonal antibody against the FMDV VP1 antigen is conjugated as a specific virus‐binding module without a linker. First, a liposome‐based immunosensor is generated for the FMDV VP1 protein in the form of photopolymerized PDA colloids. Then, the VP1‐specific PDA immunosensors are modified onto PVDF strip to enable the rapid and portable detection of FMDV. Detailed analyses are performed using ultraviolet‐visible spectroscopy, dynamic light scattering, transmission electron microscopy, and scanning electron microscopy. A blue‐to‐red color transition is observed in the presence of FMDV particles, indicating the potential applications of FMDV‐specific PDA immunosensors for use in solid‐phase detection as well as via liquid‐phase liposome platforms. Thus, this work provides a rapid and simple detection for FMDV.     

Systemized organic functional group controls in polydiacetylenes and their effects on color changes

A variety of organic functional groups have been successfully installed into polydiacetylenes (PDAs) and applied to the color change‐controlled system of PDA sensors. Ten diacetylene compounds possessing different functionalities and lengths were systemically synthesized and fully characterized using spectroscopic methods. The polymerized vesicle solution with these compounds showed different temperatures required to induce a color change (from blue to red) depending on the functionalities installed on 10,12‐pentacosadiynoic acid (PCDA) molecules. In addition, the results reported here reveal that the intermolecular interactions of PCDA molecules and the intermolecular distance play a key role to the color of PDA system. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45011.     

A polydiacetylene microchip based on a biotin-streptavidin interaction for the diagnosis of pathogen infections

A micropatterned polydiacetylene (PDA) chip, utilizing the unique fluorogenic property of PDA and a specific biotin-streptavidin (STA) interaction, is constructed to detect pathogen infections. To construct the PDA chip, biotin-modified diacetylene liposomes are immobilized on aldehyde glass and conjugated with STA, followed by UV irradiation to polymerize the STA-functionalized diacetylene liposomes. Genomic DNA of a model pathogen, Chlamydia trachomatis, is isolated from human samples and biotin-labeled target DNA is obtained through PCR amplification using biotin-11-dUTP. Owing to the stimulus caused by the biotin-STA interaction, the biotinylated DNA induces an intense fluorescence signal on the immobilized PDA. By using this strategy, it is possible to diagnose Chlamydia infections by applying DNA samples from several nonhealthy humans to a single PDA chip. The results of this study serve as the basis for a new strategy for fluorogenic PDA microarray-based diagnosis of pathogen infections.