Crystallization behaviors of poly(3-hydroxybutyrate) and poly(l-lactic acid) in their immiscible and miscible blends

By adjusting the molecular weight of the poly(l-lactic acid) (PLLA) component in poly(3-hydroxybutyrate) (PHB)/PLLA blends, we investigated the crystallization behaviors of the two components in their immiscible and miscible 50:50 blends by real time infrared (IR) spectroscopy. In the immiscible PHB/PLLA blend, the stepwise crystallization of PHB and PLLA was realized at different crystallization temperatures. PLLA crystallizes first at a higher temperature (120 degrees C). Its crystallization mechanism from the immiscible PHB/PLLA melt is not affected by the presence of the PHB component, while its crystallization rate is substantially depressed. Subsequently, in the presence of crystallized PLLA, the isothermal melt-crystallization of PHB takes place at a lower temperature (90 degrees C). It is interesting to find that there are two growth stages for PHB. At the early stage of the growth period, the Avrami exponent is 5.0, which is unusually high, while in the late stage, it is 2.5, which is very close to the reported value (n approximately 2.5) for the neat PHB system. In contrast to the stepwise crystallization of PHB and PLLA in the immiscible blends, the almost simultaneous crystallization of PHB and PLLA in the miscible 50:50 blend was observed at the same crystallization temperature (110 degrees C). Detailed dynamic analysis by IR spectroscopy has disclosed that, even in such apparently simultaneous crystallization, the crystallization of PLLA actually occurs faster than that of PHB. It has been found that, both in the immiscible and miscible blends, the crystallization dynamics of PHB are heavily affected by the presence of crystallized PLLA.     

1,6-Stannatropic strategy: effective generation and cyclization of 1,5-dipoles from o-stannylmethylated thioanilides or phenyl isothiocyanates

[reaction: see text] A new method for the generation of 1,5-dipoles from o-stannylmethylated thioanilides via 1,6-stannatropy under neutral conditions was developed. Cyclization of the 1,5-dipoles afforded indole derivatives effectively. The strategy has potential for application to the generation of alternative 1,5-dipoles from o-stannylmethylated aryl isothiocyanates leading to indole derivatives having a stannylthio group that was readily converted to other functional groups.     

Electrophoretic analysis of proteins and enantiomers using capillaries modified by a successive multiple ionic-polymer layer (SMIL) coating technique

The applicability of three-layer coatings consisting of three different polymers (A⁺-B⁻-C⁺ coating) prepared by a successive multiple ionic-polymer layer (SMIL) coating technique to the immobilization of polypeptides and/or proteins onto the inner surface of the capillaries was investigated to provide a high-performance separation medium for proteins and enantiomers in capillary electrophoresis (CE). To obtain a stable protein-coated capillary, high molecular mass poly(ethyleneimine) (PEI) was employed as the first layer in the A⁺-B⁻-C⁺ coating, and then a cationic protein was immobilized as the third layer. Comparisons of analytical performances between the A⁺-B⁻-C⁺ coating and the conventional SMIL-coated (A⁺-B⁻-A⁺ coating) capillary were conducted. The CE separation of cationic proteins was successfully achieved with the prepared capillaries. In addition, the polypeptide- and protein-coated capillaries were applied to the chiral separation of a binaphthyl compound. It should be noted that the chiral separation efficiency was strongly dependent on the second anionic polymer layer of the coating. Effects of the interaction between oppositely charged ionic polymer layers on the separation efficiency are discussed.     

Crystallization Behavior of Poly(3-hydroxybutyrate) (PHB), Poly(ε-caprolactone) (PCL) and Their Blend (50:50 wt.%) Studied by 2D FT-IR Correlation Spectroscopy

Variable-temperature FT-IR spectra of poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL) and a PHB/PCL (50:50 wt.%) blend were analyzed by two-dimensional correlation spectroscopy (2DCOS). For this purpose the ν(CO) region was employed to characterize in some detail the crystallization behavior of the investigated polymer systems during cooling from the melt. The asynchronous 2D correlation spectra clearly captured the existence of three components in the crystallinity-sensitive region of the CO stretching mode for PHB and PCL, respectively: a well-ordered, an inter-mediate and a less ordered crystalline state. Furthermore, by 2DCOS application a sequential order of the observed structural changes could be proposed for the whole temperature range during the crystallization of both polymers. In the case of the PHB/PCL (50:50 wt.%) polymer blend, we have split up the spectral data set in the sub-sets between 200–120 °C and 70–30 °C for a more detailed 2DCOS analysis. In this way we could separate the crystallization process of PHB and PCL in the polymer blend.     

Surface-enhanced Raman scattering: realization of localized surface plasmon resonance using unique substrates and methods

Surface-enhanced Raman scattering (SERS) enhancement and the reproducibility of the SERS signal strongly reflect the quality and nature of the SERS substrates because of diverse localized surface plasmon resonance (LSPR) excitations excited at interstitials or sharp edges. LSPR excitations are the most important ingredients for achieving huge enhancements in the SERS process. In this report, we introduce several gold and silver nanoparticle-based SERS-active substrates developed solely by us and use these substrates to investigate the influence of LSPR excitations on SERS. SERS-active gold substrates were fabricated by immobilizing colloidal gold nanoparticles on glass slides without using any surfactants or electrolytes, whereas most of the SERS-active substrates that use colloidal gold/silver nanoparticles are not free of surfactant. Isolated aggregates, chain-like elongated aggregates and two-dimensional (2D) nanostructures were found to consist mostly of monolayers rather than agglomerations. With reference to correlated LSPR and SERS, combined experiments were carried out on a single platform at the same spatial position. The isolated aggregates mostly show a broadened and shifted SPR peak, whereas a weak blue-shifted peak is observed near 430 nm in addition to broadened peaks centered at 635 and 720 nm in the red spectral region in the chain-like elongated aggregates. In the case of 2D nanostructures, several SPR peaks are observed in diverse frequency regions. The characteristics of LSPR and SERS for the same gold nanoaggregates lead to a good correlation between SPR and SERS images. The elongated gold nanostructures show a higher enhancement of the Raman signal than the the isolated and 2D samples. In the case of SERS-active silver substrates for protein detection, a new approach has been adopted, in contrast to the conventional fabrication method. Colloidal silver nanoparticles are immobilized on the protein functionalized glass slides, and further SERS measurements are carried out based on LSPR excitations. A new strategy for the detection of biomolecules, particularly glutathione, under aqueous conditions is proposed. Finally, supramolecular J-aggregates of ionic dyes incorporated with silver colloidal aggregates are characterized by SERS measurements and correlated to finite-difference time-domain analysis with reference to LSPR excitations. Figure SPR and SERS images for isolated, elongated and two-dimensional gold nanostructures     

Relationships between the anisotropy of longitudinal wave velocity and hydroxyapatite crystallite orientation in bovine cortical bone

Quantitative ultrasound (QUS) is now widely used for evaluating bone in vivo, because obtained ultrasonic wave properties directly reflect the visco-elasticity. Bone tissue is composed of minerals like hydroxyapatite (HAp) and a collagen matrix. HAp crystallites orientation is thus one parameter of bone elasticity. In this study, we experimentally investigated the anisotropy of ultrasonic wave velocity and the HAp crystallites orientation in the axial-radial and axial-tangential planes in detail, using cylindrical specimens obtained from the cortical bone of three bovine femurs. Longitudinal bulk wave propagation was investigated by using a conventional ultrasonic pulse system. We used the one cycle of sinusoidal pulse which was emitted from wide band transmitter. The nominal frequency of the pulse was 1 MHz. First, we investigated the anisotropy of longitudinal wave velocity, measuring the anisotropy of velocity in two planes using cylindrical specimens obtained from identical bone areas. The wave velocity changed due to the rotation angle, showing the maximum value in the direction a little off the bone axis. Moreover, X-ray pole figure measurements also indicated that there were small tilts in the HAp crystallites orientation from the bone axis. The tilt angles were similar to those of the highest velocity direction. There were good correlations between velocity and HAp crystallites orientation obtained in different directions. However, a comparatively low correlation was found in posterior bone areas, which shows the stronger effects of bone microstructure. In the radial-tangential plane, where the HAp crystallites hardly ever align, weak anisotropy of velocity was found which seemed to depend on the bone microstructure.     

Computer-generated hologram fabricated by electron-beam lithography for noise reduction

A Lohmann-type computer-generated hologram (CGH) is fabricated using an electron-beam lithographic system. A high-resolution groove width of 0.2 μm is attained in relief gratings by changing the e-beam exposures. A diffraction efficiency close to ∼30.4% is obtained by using resist-on-silicon recording materials and cell-structural apertures in a CGH. The reconstructed images exhibit fewer phase noises owing to the incorporation of a non-overflow cell structure into a CGH. The CGH is designed for reconstruction-noise reduction by using an iterative error-reduction algorithm. The designed CGH exhibits fewer reconstruction noises such that the performance function in the convergence is smaller by a factor of 1/3 than that in the first iteration. Experiments demonstrating the performance of CGHs obtained by electron-beam lithography are presented.     

Ultrasound activates ataxia telangiectasia mutated- and rad3-related (ATR)-checkpoint kinase 1 (Chk1) pathway in human leukemia Jurkat cells

Low-intensity ultrasound (US) has been shown to induce death of cancer cells; however, the underlying mechanism remains unclarified. Here, we provide novel evidence that the inhibition of checkpoint kinase 1 (Chk1) by a selective inhibitor or small interfering RNA (siRNA) enhances US-induced apoptosis in Jurkat cells. Jurkat cells showed insignificant lysis immediately after US at any applied intensity, whereas approximately 70% of the cells were γH2AX-positive 30min after US at 0.4W/cm(2). Regarding DNA damage response (DDR), Chk1, known as a target of ataxia telangiectasia mutated (ATM) and rad3-related (ATR), was phosphorylated in cells after US exposure. An ATM inhibitor showed nearly no effect on Chk1 phosphorylation, whereas chemicals showing the ATR inhibitory effect markedly abrogated the phosphorylation, indicating that Chk1 phosphorylation is preferentially more dependent on ATR than on ATM in cells exposed to US. The pharmacological inhibition of Chk1 promoted caspase-3 cleavage and increased the percentage of cells in SubG1 after US exposure. siRNA targeting Chk1 abrogated approximately 55% of Chk1 expression and also promoted apoptosis, suggesting that Chk1 plays anti-apoptotic roles in response to US. These findings revealed, for the first time, that US activates Chk1 dependently on ATR and the activated Chk1 is involved in apoptosis of cells exposed to US. Moreover, we propose that Chk1 may be a promising target in US-aided therapy.     

In situ Raman and optical microscopy of the relaxation behavior of amorphous ices under pressure

The transformation of low‐density amorphous (LDA) ice produced from high‐density amorphous (HDA) ice was studied up to 400 MPa as a function of temperature by in situ Raman spectroscopy and optical microscopy. Changes in these amorphous states of H₂O were directly tracked without using emulsions to just above the crystallization temperature T_x. The spectra show significant changes occurring above ∼125 K. The results are compared with data reported for the relaxation behavior of HDA, to form what we call relaxed HDA, or rHDA. We find a close connection with expanded HDA (eHDA), which is reported to exist as another metastable form in this P–T region. The observation of this temperature‐induced LDA transition under pressure complements the previously observed pressure‐induced reversible transition between LDA and HDA at 120–140 K. Copyright © 2009 John Wiley & Sons, Ltd.     

A Significant Two-Dimensional Structural Transformation in a Coordination Polymer that Changes Its Electronic and Protonic Behavior

A 2D-to-2D (2D: two-dimensional) structural transformation accompanying significant bond rearrangement and coordination environment change is demonstrated in a coordination polymer (CP) comprised of copper(II) ions and terephthalate (BDC²⁻) ligands for the first time. When immersed in water, a free-standing membrane of 2D Cu(BDC)(DMF) ( Cu-1 ; DMF: N,N-dimethylformamide) transforms into 2D Cu(BDC)(H₂O)₂ ( Cu-2 ) while maintaining its highly oriented layered structure. In the 2D sheet, paddlewheel-type Cu^II dimers coordinated with four bidentate BDC ligands in a square-planar array in Cu-1 were released to form uniform aqua-bridged Cu^II chains, which are cross-linked with each other by unidentate BDC ligands, in Cu-2 . The present facile approach to implement the 2D-to-2D transformation accompanied by bond rearrangement, which is characteristic of CPs, leads to a marked increase in in-plane magnetic susceptibility and proton conductivity. In situ experiments in support of theoretical calculations unveiled the energy diagram that governs the unique structural transformation.