Ring closure reaction dynamics of diarylethene derivatives in solution

Photochromic ring closure reaction dynamics of 1,2-bis(2-methylbenzo[b]thiophen-3-yl)hexafluoro cyclopentene and its derivatives in solution has been studied by femtosecond time-resolved fluorescence. Time-resolved spontaneous fluorescence of the open isomer reveals a fast component of around 1 ps and a slow component on the order of 100 ps. Fluorescence time profiles, reaction quantum yields, and relative populations of the parallel (C(s) symmetry) and antiparallel (C(2) symmetry) conformations indicate that both time components are attributable mostly to the C(2) conformer that undergoes the ring closure reaction. The fast component is assigned to the direct ring closure reaction, and the slow component is assigned to the reaction through conformation change. Time constants of the slow component for the derivatives are inversely proportional to the reaction quantum yields, suggesting that the rate of the conformational dynamics is comparable to the rate of other population relaxation processes. The relative amplitude and exact time constant of the fast component depend on the detection wavelength displaying a higher relative amplitude with shorter time constant at longer wavelengths. The results allow us to propose a conformational inhomogeneity model, in which a broad distribution of conformations of the open isomers in the ground state is projected into two minima in the excited electronic potential surface to lead to the slow and the fast reaction pathways.     

Simultaneous Quantification of 3′- and 6′-Sialyllactose in Rat Plasma Using Liquid Chromatography-Tandem Mass Spectrometry and Its Application to a Pharmacokinetic Study

Sialyllactose (SL), an acidic oligosaccharide, has immune-protective effects against pathogens and helps with the development of the immune system and intestinal microorganisms. To elucidate the pharmacokinetic characterization after oral administration to rats, the simultaneous quantification method for 3′-SL and 6′-SL in rat plasma was validated, using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in an electrospray ionization (ESI) mode. Several types of columns [C18, amide, and hydrophilic interaction liquid chromatography (HILIC) phase] were used to separate the peaks of 3′-SL and 6′-SL, which improved chromatographic selectivity. Ultimately, the HILIC phase column had a good peak shape and quick resolution, with a mobile phase comprising ammonium acetate buffer and acetonitrile obtained by gradient elution. In addition, the simultaneous quantification of 3′-SL and 6′-SL in rat plasma samples were adequately applied to pharmacokinetic study.     

A colorimetric and fluorescent chemosensor for detection of Hg2+ using counterion exchange of cationic polydiacetylene

In this study, a colorimetric and fluorescent chemosensor for mercury ions (Hg²⁺) was developed. Cationic polydiacetylene (PDA) vesicles with a quaternary ammonium cation and iodide as a counterion show a blue-to-red color transition; the color change is accompanied by a fluorescence enhancement in selective response to Hg²⁺ ions because of a perturbation of the ene–yne conjugated backbone induced by counterion exchange. It allows for selective detection of Hg²⁺ with the naked eye and the sensor is used to determine Hg²⁺ concentrations in tap water samples.     

Fast and accurate group delay ripple measurement technique for ultralong chirped fiber Bragg gratings

A simple and very precise group delay ripple (GDR) measurement technique for linearly chirped fiber Bragg gratings (CFBGs) is proposed. It is based on real-time optical Fourier transformation of an ultrashort pulse directly induced by the CFBG dispersion. We have experimentally demonstrated highly accurate characterization of the GDR profile of a commercial 10-m-long CFBG with a dispersion of +2000 ps/nm, having achieved a remarkably small standard deviation in our measurements of about 4 ps over a bandwidth of 28 nm. The proposed method has the unique potential to provide real-time GDR monitoring (in the MHz range) by use of commercially available high-speed sampling electronics.     

A Hollow Foldecture with Truncated Trigonal Bipyramid Shape from the Self‐Assembly of an 11‐Helical Foldamer

The creation of self‐assembling microscale architectures that possess new and useful physical properties remains a significant challenge. Herein we report that an 11‐helical foldamer self‐assembles in a controlled manner to form a series of 3D foldectures with unusual three‐fold symmetrical shapes that are distinct from those generated from 12‐helical foldamers. The foldamer packing motif was revealed by powder X‐ray diffraction technique, and provides an important link between the molecular‐level symmetry and the microscale morphologies. The utility of foldectures with hollow interiors as robust and well‐defined supramolecular hosts was demonstrated for inorganic, organic, and even protein guests. This work will pave the way for the design of functional foldectures with greater 3D shape diversity and for the development of biocompatible delivery vehicles and containment vessels.     

A triazine compound S06 inhibits proinvasive crosstalk between carcinoma cells and stromal fibroblasts via binding to heat shock protein 90

Carcinoma-associated fibroblasts (CAFs) promote tumor invasion by secreting soluble factors. A tagged triazine library was screened in our novel transwell coculture model of CAF and oral squamous cell carcinoma (OSCC). We discovered compound S06, which reduced OSCC invasion by inhibiting secretion of CAF-derived proinvasive chemokines. The N-terminus of Hsp90 was found to be the cellular target of S06. Importantly, S06 did not induce hepatic toxicity, a side effect associated with well-known Hsp90 inhibitors. Moreover, S06 inhibited tumor cell migration in a zebrafish xenograft model. Our results demonstrate that Hsp90 is a novel target for stromal-based therapy to modulate proinvasive molecular crosstalk within the tumor microenvironment. Furthermore, S06 represents a new class of Hsp90 inhibitor and is an attractive candidate for anticancer drug development.     

Raman fingerprint of doping due to metal adsorbates on graphene

The properties of single-layer graphene are strongly affected by metal adsorbates and clusters on graphene. Here, we study the effect of a thin layer of chromium (Cr) and titanium (Ti) metals on chemical vapor deposition (CVD)-grown graphene by using Raman spectroscopy and transport measurements. The Raman spectra and transport measurements show that both Cr and Ti metals affect the structure as well as the electronic properties of the CVD-grown graphene. The shift of peak frequencies, intensities and widths of the Raman bands are analyzed after the deposition of metal films of different thickness on CVD-grown graphene. The shifts in G and 2D peak positions indicate the doping effect of graphene by Cr and Ti metals. While p-type doping was observed for Cr-coated graphene, n-type doping was observed for Ti-coated graphene. The doping effect is also confirmed by measuring the gate voltage dependent resistivity of graphene. We have also found that annealing in Ar atmosphere induces a p-type doping effect on Cr- or Ti-coated CVD-grown graphene.     

Ball lens based lensed patch cord probes for optical coherence tomography in the field of dentistry

A lensed patch cord probe has been made with a ball lens packaged in a metal cylinder. By simply placing a ball lens directly in front of a fiber patch cord, a compact and potentially disposable sampling probe for optical coherence tomography (OCT) could be implemented. To achieve a sufficiently long working distance and a good transverse resolution simultaneously, the proper ball lens diameter and the distance between the ball lens and the fiber patch cord were investigated. Experimentally, a working distance of up to 5.2 mm, 3 dB bandwidth of 2 mm, and transverse resolution of 16 μm were achieved. With the patch cord probe, a common path swept source OCT system was implemented and used to demonstrate the feasibility as the dedicated probe for dentistry.     

Single-shot electronic optical activity interferometry: power and phase fluctuation-free measurement

We demonstrate that a single-pulse characterization of electronic optical activity-free induction decay, which carries information on both circular dichroism and optical rotatory dispersion, is experimentally feasible. Employing a self-referencing scheme, we show that a highly reliable interferometric chiroptical measurement free from power and phase fluctuations is achievable on a shot-by-shot basis.     

Effect of changing data size on eigenvalues in the Korean and Japanese stock markets

In this study, we attempted to determine how eigenvalues change, according to random matrix theory (RMT), in stock market data as the number of stocks comprising the correlation matrix changes. Specifically, we tested for changes in the eigenvalue properties as a function of the number and type of stocks in the correlation matrix. We determined that the value of the eigenvalue increases in proportion with the number of stocks. Furthermore, we noted that the largest eigenvalue maintains its identical properties, regardless of the number and type, whereas other eigenvalues evidence different features.