Raman and surface-enhanced Raman spectra of chrysin,apigenin and luteolin

The FT-Raman and surface-enhanced Raman (SER) spectra of three flavonoids, namely chrysin, apigenin and luteolin, have been obtained. The SERS spectra were obtained on citrate reduced Ag colloids. Assignments of the experimentally obtained normal vibrational modes were aided by density functional theory (DFT) calculations using the B3LYP functional and the 6-31+G* basis set. Excellent fits were obtained for the observed spectra with little or no scaling. The most intense lines in the three flavonoids SERS spectra are those in the CO stretching region and around 1250 cm^?1. The first ones are often weakened by proximity of the metal surface, whereas the latter are not affected by the Ag. On the other hand, the lines at lower wavenumbers, assigned to in-plane ring deformation, are strongly enhanced by the surface, indicating a perpendicular orientation of the flavonoids on the Ag surface. The spectra of the flavonoids are compared, and a case study of application to detect weld, a mixture of apigenin and luteolin, in a textile is presented.     

Negative thermal expansion of poly(vinylidene fluoride) and polyethylene tie molecules: A molecular dynamics study

The mechanism of thermal actuation for poly(vinylidene fluoride) (PVDF) and polyethylene (PE) tie molecules has been investigated using molecular dynamics simulations. Tie molecules are found in semicrystalline polymers and are polymer chains that link two (or more) crystalline lamellae, allowing for the transfer of force between these regions. A novel simulation technique has been developed to enable measurement of changes in the tie molecule length upon heating. We investigate the dependence of the percentage actuation observed upon heating, on the external applied force that stretches the tie molecules, the temperature range used for heating as well as the length and the number of tie molecules. Two molecular level mechanisms for actuation are identified. An entropically driven mechanism occurs at low applied forces and is applicable to all flexible polymers. A second mechanism due to conformational changes is observed for PVDF but not for PE at intermediate applied forces. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2223–2232     

Saponins Extracted from Tea (Camellia Sinensis) Flowers Induces Autophagy in Ovarian Cancer Cells

Tea flower saponins (TFS) possess effective anticancer properties. The diversity and complexity of TFS increases the difficulty of their extraction and purification from tea flowers. Here, multiple methods including solvent extraction, microporous resin separation and preparative HPLC separation were used to obtain TFS with a yield of 0.34%. Furthermore, we revealed that TFS induced autophagy—as evidenced by an increase in MDC-positive cell populations and mCherry-LC3B-labeled autolysosomes and an upregulation of LC3II protein levels. 3-MA reversed the decrease in cell viability induced by TFS, showing that TFS induced autophagic cell death. TFS-induced autophagy was not dependent on the Akt/mTOR/p70S6K signaling pathway. TFS-induced autophagy in OVCAR-3 cells was accompanied by ERK pathway activation and reactive oxygen species (ROS) generation. This paper is the first report of TFS-mediated autophagy of ovarian cancer cells. These results provide new insights for future studies of the anti-cancer effects of TFS.     

(P,C) Cyclometalated Gold(III) Complexes: Highly Active Catalysts for the Hydroarylation of Alkynes

The first catalytic application of well‐defined (P,C) cyclometalated gold(III) complexes is reported. The bench‐stable bis(trifluoroacetyl) complexes 2 a , b perform very well in the intermolecular hydroarylation of alkynes. The reaction is broad in scope, it proceeds within few hours at 25 °C at catalytic loadings of 0.1–5 mol %. The electron‐rich arene adds across the C≡C bond with complete regio‐ and stereo‐selectivity. The significance of well‐defined gold(III) complexes and ligand design are highlighted in a powerful but challenging catalytic transformation.     

A weak‐derivative form for linear hyperbolic systems

Difference schemes for linear hyperbolic systems are considered. As a main result, a weak derivative form (WDF) of the governing equations is derived, which is also valid near flow discontinuities. The occurrence of one‐sided derivatives in the WDF structure indicated how to difference near discontinuities. When first‐order differencing is applied to the WDF result, the (linearly identical) schemes by Godunov, Roe, and Steger‐Warming are reproduced. The extension to nonlinear systems is via a local linearization. Choosing Roe's averaging reduces the WDF algorithm to Roe's scheme, whereas other nonlinear WDF schemes are possible. The suitability of various kinds of averaging is numerically investigated. For weak shocks a surprising lack of sensitivity of the method to a particular averaging is exhibited. However, for strong shocks and where the ordinary arithmetic average is used, a slightly more pronounced difference in performance exists between Roe's scheme and WDF. © 2004 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq, 2004     

Polarization and spatial-mode behavior of short-wavelength VCSELs

We have investigated the packaging introduced feedback and resulting variations in the characteristics of Vertical-cavity surface-emitting lasers (VCSELs). An integrated test and characterization method was developed for both the packaged and bare dies as well as on-wafers chips. Using an ‘integrated test bench (ITB)’ for characterization, packaged and ‘un-packaged’ VCSELs from multiple sources were studied. ITB was used to monitor and measure simultaneously several beam-parameters under various bias conditions including both dc and high-speed pulsed pumping at room-temperature, or at higher-/lower-temperatures that are thermo-electrically controlled. Typical beam parameters included state of polarization (SOP), transverse (spatial) modes, wavelength spectra, and output power. A common observation was that majority of devices are affected by the presence of optical windows capping the package. A shift in longitudinal mode was noticeable in packaged versus ‘un-packaged’ (window-removed) devices. But, SOP and transverse modes in various devices are affected severely and in an unpredictable fashion.     

Misfolding of a polyalanine variant due to lack of electrostatic polarization effects

Folding of a polyalanine variant (A-AQ12 with the sequence Ac-[AAQAA]₂-GY-NH₂) in pure water is studied with molecular dynamics (MD) simulation using AMBER fixed charge model and AHBC charge variation model, respectively. The results show that AMBER ostensibly misfolds A-AQ12 into a well-defined α-helix, while A-AQ12 remains a random coil in AHBC agreeing better with the experimental predication of low fractional helical content. The difference is most likely due to the different backbone solvation with and without the incorporation of electrostatic polarization in the simulations, which highlights the importance of electrostatic polarization in H-bonds dynamics of α-helix in water.     

Exponential amplification by redox cross-catalysis and unmasking of doubly protected molecular probes

The strength of autocatalytic reactions lies in their ability to provide a powerful means of molecular amplification, which can be very useful for improving the analytical performances of a multitude of analytical and bioanalytical methods. However, one of the major difficulties in designing an efficient autocatalytic amplification system is the requirement for reactants that are both highly reactive and chemically stable in order to avoid limitations imposed by undesirable background amplifications. In the present work, we devised a reaction network based on a redox cross-catalysis principle, in which two catalytic loops activate each other. The first loop, catalyzed by H₂O₂, involves the oxidative deprotection of a naphthylboronate ester probe into a redox-active naphthohydroquinone, which in turn catalyzes the production of H₂O₂ by redox cycling in the presence of a reducing enzyme/substrate couple. We present here a set of new molecular probes with improved reactivity and stability, resulting in particularly steep sigmoidal kinetic traces and enhanced discrimination between specific and nonspecific responses. This translates into the sensitive detection of H₂O₂ down to a few nM in less than 10 minutes or a redox cycling compound such as the 2-amino-3-chloro-1,4-naphthoquinone down to 50 pM in less than 30 minutes. The critical reason leading to these remarkably good performances is the extended stability stemming from the double masking of the naphthohydroquinone core by two boronate groups, a counterintuitive strategy if we consider the need for two equivalents of H₂O₂ for full deprotection. An in-depth study of the mechanism and dynamics of this complex reaction network is conducted in order to better understand, predict and optimize its functioning. From this investigation, the time response as well as detection limit are found to be highly dependent on pH, nature of the buffer, and concentration of the reducing enzyme.

Reduction of the non-specific background in autocatalytic molecular amplifications by a double masking strategy.     

A hybrid numerical method for the shallow water equations with source term

In coastal oceanography there is interest in problems modeled by the shallow water equations, where variations in channel depth are accounted for by the presence of source terms. A numerical treatment for the solution of such problems is presented here, in terms of a hybrid approach, which combines a second-order TVD scheme for conservation law equations (assuming no source terms) with an eigenvector projection scheme that incorporates the effects of nonzero source terms (in regions where the bottom is not flat). For the case where an initially sharp wave profile is assumed, the progress of a wave as it traverses an estuary whose channel depth varies is calculated. Excellent numerical results are obtained. © 1996 John Wiley & Sons, Inc.