Structural interconversion and regulation of optical properties of stable hypercoordinate dipyrrin-silicon complexes

Novel pentacoordinate dipyrrin-silicon complexes showed efficient red or near-IR fluorescence, and the structural interconversion between silanol and siloxane derivatives resulted in significant changes in the optical properties.     

Use of tube radial distribution of ternary mixed carrier solvents for introduction of absorption reagent for metal ion separation and online detection into capillary

When ternary mixed solvents consisting of water-hydrophilic/hydrophobic organic solvents are fed into a micro-space under laminar flow conditions, the solvent molecules are radially distributed in the micro-space. The specific fluidic behavior of the solvents is called the "tube radial distribution phenomenon (TRDP)". A novel capillary chromatography method was developed based on the TRDP that creates the inner major and outer minor phases in a tube, where the outer phase acts as a pseudo-stationary phase. This is called "tube radial distribution chromatography (TRDC)". In this study, Chrome Azurol S as an absorption reagent was introduced into the TRDC system for metal ion separation and online detection. The fused-silica capillary tube (75 μm id and 110 cm length) and water-acetonitrile-ethyl acetate mixture (3:8:4 volume ratio) including 20 mM Chrome Azurol S as a carrier solution were used. Metal ions, i.e. Co(II), Cu(II), Ni(II), Al(III), and Fe(III), as models were injected into the present TRDC system. Characteristic individual absorption characteristics and elution times were obtained as the result of complex formation between the metal ions and Chrome Azurol S in the water-acetonitrile-ethyl acetate mixture solution. The elution times of the metal ions were examined based on their absorption behavior; Co(II), Ni(II), Al(III), Fe(III), and Cu(II) were eluted in this order over the elution times of 4.7-6.8 min. The elution orders were determined from the molar ratios of metal ion to Chrome Azurol S and Irving-Williams series for bivalent metal ions.     

Effects of Temperature and Mobile Phase Condition on Chiral Recognition of Poly(l-phenylalanine) Chiral Stationary Phase

Characteristics of the chiral stationary phase with poly(l-phenylalanine) peptide selector, which was in ??-helical state, was reported. Since environmental factors affect peptide conformation, the changes in enantioselectivity were examined depending on column temperature and mobile phase conditions (ionic strength, pH, mobile phase composition). Column temperature and pH drastically affected the enantioselectivity. Based on these changes, the relation between chiral recognition and secondary structure of the peptide selector was discussed. The column stability during sequential analysis under different separation conditions was also evaluated.     

Experimental demonstration and stochastic modeling of autonomous formation of nanophotonic droplets

We have previously demonstrated a novel technique for autonomously forming a nanophotonic droplet, which is micro-scale spherical polymer structure that contains paired heterogeneous nanometric components. The sort-selectivity and alignment accuracy of the nanometric components in each nanophotonic droplet, and the related homogeneity of the optical function, are due to a characteristic pairing process based on a phonon-assisted photo-curing method. The proposed method requires irradiating a mixture of components with light to induce optical near-field interactions between each component, and subsequent processes based on these interactions. The pairing yield of components via the interactions is considered to mainly depend on the frequency of their encounters and the size-resonance effect between encountered components. In this paper, we model these two factors by individual stochastic procedures and construct a numerical model to describe the pairing process. Agreement between the results of numerical and experimental demonstrations shows the validity of our stochastic modeling.     

Altered posttranslational modification on U1 small nuclear ribonucleoprotein 68k in systemic autoimmune diseases detected by 2D Western blot

Anti-ribonucleoprotein (anti-RNP) antibodies are one of the representative autoantibodies detectable in patients with systemic lupus erythematosus (SLE) and mixed connective tissue disease (MCTD). Generally, posttranslational modifications (PTMs) on autoantigens are proposed to be involved in the production of autoantibodies. In this study, we tried to detect the alteration in PTMs on a U1 small nuclear RNP 68k subunit (U1-68k), a major antigen of anti-RNP antibodies. Peripheral blood mononuclear cells (PBMCs) were obtained from patients with MCTD, SLE, and rheumatoid arthritis (RA), and from healthy donors. U1-68ks in the PBMCs were detected by 2D Western blot (WB), where extracted nuclear proteins were separated by 2DE, followed by the detection of U1-68k using WB. More than 20 PTM isoforms were detected with different molecular weights of 65.0 , 66.5, and 68.0kDa, and different pIs between 6.0 and 8.5. Importantly, the relative intensity of the spot with 66.5 kDa and pI 7.5 was significantly increased in the MCTD and SLE groups compared to the RA and healthy groups. Further, this U1-68k isoform, in particular, in its RS domain, was found to have significantly decreased phosphorylation compared to the other isoforms. The PTM alternation may be one of the steps to generate the anti-RNP antibodies.     

Ultrafast Encapsulation of Metal Nanoclusters into MFI Zeolite in the Course of Its Crystallization: Catalytic Application for Propane Dehydrogenation

Encapsulating metal nanoclusters into zeolites combines the superior catalytic activity of the nanoclusters with high stability and unique shape selectivity of the crystalline microporous materials. The preparation of such bifunctional catalysts, however, is often restricted by the mismatching in time scale between the fast formation of nanoclusters and the slow crystallization of zeolites. We herein demonstrate a novel strategy to overcome the mismatching issue, in which the crystallization of zeolites is expedited so as to synchronize it with the rapid formation of nanoclusters. The concept was demonstrated by confining Pt and Sn nanoclusters into a ZSM-5 (MFI) zeolite in the course of its crystallization, leading to an ultrafast, in situ encapsulation within just 5 min. The Pt/Sn-ZSM-5 exhibited exceptional activity and selectivity with stability in the dehydrogenation of propane to propene. This method of ultrafast encapsulation opens up a new avenue for designing and synthesizing composite zeolitic materials with structural and compositional complexity.     

Validated method using liquid chromatography-electrospray ionization tandem mass spectrometry for the determination of contamination of the exterior surface of vials containing platinum anticancer drugs

Contamination of the exterior surface of vials of cytostatic drugs by the drugs themselves is a potential hazard to human health. This study developed a validated method using liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS) for the determination of contamination of the exteriors of vials of cisplatin and carboplatin. Large Alpha^® sampling swabs were employed to wipe the vial exterior. Cisplatin or carboplatin and gold(III) as an internal standard were derivatized by N,N-diethyldithiocarbamate (DDTC). Pt(DDTC)₃⁺ and Au(DDTC)₂⁺ were monitored by the respective transitions of m/z 639.3-490.9 and 493.0-345.0, respectively. Each separation was completed within 9 min using a 3 μm particle ODS-column. Calibration curves for cisplatin and carboplatin were linear over concentration ranges of 30-10,000 and 30-30,000 pg vial⁻¹, respectively. The accuracies and precisions were 96.1-102.5% and within 8.2% for intra-assay and 99.6-103.3% and within 7.6% for inter-assay, respectively. Their lower limit of quantification was 30 pg vial⁻¹. Amounts of 0.17-17.0 ng vial⁻¹ as cisplatin and 0.48-794 ng vial⁻¹ as carboplatin were detected from the exterior surface of the vials. This validated method using LC-ESI-MS/MS for the determination of platinum anticancer drugs is helpful for monitoring contamination of the exterior surface of drug vials.     

Numerical simulations of the ignition of n-heptane droplets in the transition diameter range from heterogeneous to homogeneous ignition

Spontaneous ignition of single n-heptane droplets in a constant volume filled with air is numerically simulated with the spherical symmetry. The volume is closed against mass, species, and energy transfer. The numerical model is fully transient. It continues calculation even after the droplet has completely vaporized, and therefore can predict pre-vaporized ignition. Initial pressure and initial air temperature are fixed at 3 MPa and 773 K, respectively. The droplet is initially at room temperature, and its diameter is between 1 and 100 μm. When the overall equivalence ratio is fixed to be sufficiently large, there exists no ignition limit in terms of initial droplet diameter d₀, and the ignition delay takes a minimum value at certain d₀. In such a case, transition from the heterogeneous ignition to the homogeneous ignition with decreasing d₀ is observed. When d₀ is fixed to be so small that the ignition would not occur in an infinite volume of air, the ignition delay takes a minimum value at certain , which is less than unity. Two-stage ignition behavior is investigated with this model. Ignition delay of a cool flame has the dependence on d₀ that is similar to that of ignition delay of a hot flame when is unity. When is almost zero, the ignition limit for cool flame in terms of d₀ is not identified unlike that for hot flame.     

Sliding acceleration of water droplets on a surface coated with fluoroalkylsilane and octadecyltrimethoxysilane

Both fluoroalkylsilane (FAS) and octadecyltrimethoxysilane (ODS) were coated on oxidized silicon wafers using soaking and CVD method. Smooth coatings with Ra values of less than 1 nm were attained. The slope of the sliding acceleration against the inverse of the droplet mass showed an inflection point. That point shifted to the direction of smaller droplets with decreasing FAS ratio to ODS. The water droplets’ length was increased when the sliding velocity was increased. Fluoroalkylsilane addition to ODS increases the interaction between water and the hydrophobic surface. Results showed that the sliding acceleration of a water droplet depends strongly on the surface ratio of these silanes.