Phase transition of layer structure of poly(p-benzenedithiol-co-p-diethynylbenzene) by heat or photon mode

Phase transition of the layer structure of poly(p-benzenedithiol-co-p-diethylbenzene) obtained in solid state polymerization was studied by a thermal treatment or UV irradiation under a nitrogen atmosphere. The peak intensities in the X-ray diffraction diagram of polymers gradually decreased with the thermal treatment time above 55°C. Below 50°C the layer structure of polymers hardly changed. The apparent activation energy for the phase transition was about 15 Kcal/mol [63 KJ/mol] at the initial stage and gradually decreased to a few Kcal/mol [ca. 2 KJ/mol]. UV light from a high-pressure mercury lamp also gradually induced the phase transition from the layer structure to an amorphous one. The pristine polymer possesses phase transition points at 75, 95 and 130°C. The exothermic transition at 75°C can be understood as the thermal destruction of the semistable layer structure. The exothermic transition at 95°C may be correspond to the cis → trans thermal isomerization of the C?°C bond in the polymer main chain. The diffuse reflectance spectrum of the pristine polymer differed from that of the amorphous polymer obtained by the thermal treatment of the pristine polymer. SEM photographs of the pristine polymer showed a particular surface structure, i.e. entangled fibrous material. TEM photographs of the pristine polymer exhibited a bright valley-and-hill structure, whereas that of the amorphous polymer obtained by thermal treatment exhibited a plain surface.     

Analog vision chip for motion detection of an approaching object against a moving background based on the insect visual system

A network for motion detection of an approaching object without influence of the moving background was proposed based on the insect visual system. The two-dimensional array of the analog complementary metal oxide semiconductor (CMOS) circuits for extracting the edge signals of the approaching object without outputting those of the moving background was inserted at the first stage of the network. At the next stage, analog CMOS circuits for detection of approaching velocity and direction, which accept the extracted edge signals, were inserted based on the locust vision system. A chip of the proposed network was fabricated with the 1.2 mm CMOS process. It was clarified from the measured results and the simulation results with the simulation program with integrated circuit emphasis (SPICE) that the two-dimensional circuits of the first stage can only generate the signals of target edges. The measured results showed that the chip can detect the approaching velocity and direction of the target in the image which contains the moving background.     

High-speed monitoring of the crystallinity change in poly(lactic acid) during photodegradation by using a newly developed wide area NIR imaging system (Compovision)

We aimed to achieve wide area rapid monitoring of the crystallinity change in poly(lactic acid) (PLA) during photodegradation caused by ultraviolet (UV) light by using a newly developed near-infrared (NIR) camera (Compovison). Several kinds of PLA samples with different crystallinities and their blends with poly[(3)-(R)-hydroxybutyrate] were prepared. Their two-dimensional NIR spectra in the 1,000–2,350-nm region were measured by Compovision at a 5-min interval during photolysis. An intensity decrease of the band in the 1,900-1,925-nm region due to the second overtone of the C = O stretching vibration of PLA was observed during photolysis. This suggests that an anhydride carbonyl is produced during photolysis. The NIR image of the crystallinity change monitored by the band at 1,917 nm in the standard normal variate spectra clearly shows the inhomogeneity of crystal evolution. A logarithmic increase was observed for all identified areas in the PLA film; however, the time to reach the maximum crystallinity was slightly different according to the initial crystallinity of the sample. It is likely that the initial crystallinity of the sample influences the degradation speed more than the degradation amount. These imaging results have provided fundamental chemical insights into the photolytic process for PLA, and at the same time they have demonstrated that the two-dimensional spectral data obtained by Compovision are useful for process monitoring of polymers.     

Water revealed as molecular mirror when measuring low concentrations of sugar with near infrared light

Near infrared spectroscopy is an overtone spectroscopy regarded as a quick and non-destructive method that provides analytical solutions for components that represent approximately 1% or more of the total mass of the investigated composite samples. Aquaphotomics offers the possibility for disentanglement of information remaining hidden in the spectra when conventional data evaluation methods are used, since this concept utilizes changes of the water structure induced by the measured solute as specific molecular vibrations at water bands. Here, near infrared technique and aquaphotomics are applied for non-destructive identification and quantification of mono- and di-saccharide solutes at 100–0.02 mM concentration that is accepted as unachievable with near infrared spectroscopy. The results presented in this study support the aquaphotomics' water molecular mirror concept that explores spectral changes related to water molecular rearrangements caused by minute changes of the solutes in the aqueous systems. The method provides quick and accurate alternative for classical analytical measurements of saccharides even at millimolar concentration levels.     

HPLC for Separation and Quantification of Deoxyribonucleic Acid Fragments and Measurement of Deoxyribonucleic Acid Degradation

DNA quantification has made its mark in pharmaceutical analysis and the life sciences. In particular, in the quality control of nucleic acid drugs and the detection and quantification of genetically modified organisms, evaluation of the DNA degradation rate has become imperative. In this study, by using high-performance liquid chromatography with an anion-exchange column, we established a method for the separation and quantification of DNA fragments in mixed DNA samples. By using a NaCl concentration gradient, DNA fragments in mixed DNA sample were separated well. A calibration curve from 0.05 to 12.4 ng μL^?1 was obtained with high linearity and the correlation coefficient was 0.9999. The limit of detection was 0.02 ng μL^?1 and the limit of quantification was 0.06 ng μL^?1 for S/N = 3 or S/N = 10, respectively. The relative standard deviation was less than 2 % in the measurement of peak area repeatability. The recovery of approximately 1 ng μL^?1 of a specific DNA spiked in a mixed DNA sample was 99.9 ± 3.6 %. The method was able to measure the degradation rate of 600 bp DNA with a variation of approximately 1 %.     

Supported lipid bilayer composition microarray fabricated by pattern-guided self-spreading

We report on the fabrication of a microarray of supported lipid bilayers (SLBs) with different chemical compositions and demonstrate its biosensing application. The technique utilizes the phenomenon of lipid self-spreading on a patterned surface, which offers complete positional selectivity for a supported lipid bilayer. We describe the fabrication of parallel 10-μm-wide lines, each filled with an SLB with a unique composition, at 5 μm intervals. Structures obtained with our new technique are finer and more highly integrated than previously reported structures that employ the vesicle fusion technique on patterned surfaces. We also detected specific binding between biotin and streptavidin with high contrast, indicating that the microarray is valuable for biosensing applications.     

Effect of void structure on the toughness of double network hydrogels

Introduction of soft filler in a hard body, which is one of the common toughening methods of hard polymeric materials, was applied for further toughening of robust double network (DN) hydrogels composed of poly(2‐acrylamido‐2‐methylpropanesulfonic acid) gels (PAMPS gels) as the first component and polyacrylamide (PAAm) as the second component. The fracture energy of the DN gels with the void structure (called void‐DN gels) became twice when the volume fraction of void was 1–3 vol % and the void diameter was much larger than the Flory radius of the PAAm chains. Such toughening was induced by wider range of internal fracture of the PAMPS network derived from partial stress concentration near void structure. Considering the mechanical tests and the dynamic light scattering results, it is implied that the absence of the load‐bearing PAAm structure inside the void is important for the toughening. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1246–1254, 2011     

MOF-on-MOF heteroepitaxy: perfectly oriented [Zn2(ndc)2(dabco)]n grown on [Cu2(ndc)2(dabco)]n thin films

We report the successful heteroepitaxial growth of perfectly oriented hybrid MOF thin films. By employing step-by-step liquid-phase epitaxy (LPE), [Zn(2)(ndc)(2)(dabco)](n) was grown on [Cu(2)(ndc)(2)(dabco)](n), thus demonstrating that the MOF-on-MOF deposition scheme developed for powdered microcrystalline MOF materials can also be applied in connection with LPE for MOF thin films or multilayers. The deposition was monitored by surface plasmon resonance (SPR) spectroscopy, the resulting MOF heterostructures were characterized using IR spectroscopy and different types of X-ray diffraction (XRD)-based techniques. The results suggest that the LPE method is a promising way to fabricate and grow MOF heterostructures, and also demonstrates the potential of [Cu(2)(ndc)(2)(dabco)](n) MOF thin films as substrates for the LPE-based growth of different MOFs on top.     

Cu-mediated chemoselective trifluoromethylation of benzyl bromides using shelf-stable electrophilic trifluoromethylating reagents

Copper-mediated chemoselective trifluoromethylation at the benzylic position by the use of shelf-stable electrophilic trifluoromethylating reagents 3 in good to high yields under mild conditions is described for the first time. The generality of this trifluoromethylation for a wide variety of benzyl bromides facilitates the rapid creation of structural diversity of medicinal candidates in drug discovery.