Synthesis and Properties of Polycarbosilanes Having Lactose‐Derived Structures

A polycarbosilane having lactose‐derived structures was synthesized, and its thermal property, cytotoxicity, chemical crosslinking, and protein adsorption properties were investigated. The polycarbosilane (PSB‐Lac) was prepared by a thiol‐ene reaction between precursor poly(1‐(3‐butenyl)‐1‐methylsilacyclubane) (PSB) and heptaacetyl lactose that carried a thiol group at the anomeric position, and the successive deprotection of the acetyl groups. The lactose introduction efficiency determined by ¹H NMR measurement was 75%. TGA and DSC revealed that the polymer had a 5 wt% decomposition temperature of 260 °C and glass transition temperature (T_g) of 84 °C, which indicated that PSB‐Lac was a thermally stable polymer. PSB‐Lac had no significant cytotoxicity, which was evaluated by human liver cancer cell line HepG2 cultivation on the polystyrene dishes coated with the polymer. Urethane‐crosslinked PSB‐Lac films were prepared by casting solutions of PSB‐Lac and hexamethylene diisocyanate and heating at 120 °C after evaporation of the solvent. The crosslinked PSB‐Lac showed higher adsorption of bovine serum albumin than the similarly crosslinked polycarbosilane that had a glucose structure (PSB‐Glc). © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 2420–2425     

Synthesis of Anthracene Derivatives with Azaacene-Containing Iptycene Wings and the Utilization as a Dopant for Solution-Processed Organic Light-Emitting Diodes

Substituted acene derivatives are regarded as promising materials for organic electronic devices such as organic light-emitting diodes (OLEDs). In particular, anthracene derivatives are known to exhibit good fluorescence property, with the air stability and solubility in common organic solvents expected to give advantages for solution-processed device fabrication. In this study, a series of bistriisopropylsilyl(TIPS)ethynyl anthracene derivatives with azaacene-containing iptycene wings have been synthesized by using condensation reactions. Effects of size of azaacenes on optical properties and packing structures were investigated. UV/Vis absorption and fluorescence spectra indicate that the π-elongation of iptycene units has small effects on the overall π-system, which is also supported by electrochemical measurements. Secondly, single-crystal X-ray analysis implies that the molecules likely have interactions with the iptycene units of adjacent molecules, while the iptycene wings and TIPSethynyl groups can prevent the central anthracene unit from undesirable non-radiative energy loss. Finally, the most emissive derivative was used as a dopant for solution-processed OLEDs, showing obvious electroluminescence with a luminance of over 920 cd m⁻².     

Fluorescence Properties and Exciplex Formation of Emissive Naphthyridine Derivatives: Application as Sensors for Amines

Water-soluble donor–acceptor-type fluorophore 15Nap-Cl having two trifluoromethyl groups and a Cl group on a 1,5-aminonaphthyridine framework was prepared. Fluorophore 15Nap-Cl showed strong solvatochromic fluorescence, and, as the solvent polarity increased, a bathochromic shift was observed accompanied by an increase in the fluorescence quantum yield. In addition, in the presence of amines such as ethylamine, diethylamine, and aniline, further considerable bathochromic shifts in the fluorescence were observed. Density functional calculations identified the source of the fluorescence behavior as exciplex formation between 15-Nap-Cl and the corresponding amine. The fluorescence behavior was exploited to fabricate a sensor that can identify various primary, secondary, and tertiary amines.     

Synthesis of thermally stable aromatic poly(spiroorthocarbonate)s having a Cardo or bent structure

Novel poly(spiroorthocarbonate)s [poly(SOC)]s having a Cardo or bent structure were synthesized by polycondensation of several bis‐catechols having fluorene (BCFL), spirobisindane (BCSPI), or spirobischromane (BCSPC) in the structure with 2,2,6,6‐tetrachlorobenzo[1,2‐d:4,5‐d’]bis[1,3]dioxole (4ClBD). Synthesis of poly(SOC)s was confirmed by NMR and IR spectrometry. The poly(SOC)s obtained from BCFL or BCSPC were soluble in common organic solvents. The glass transition temperature of the poly(SOC)s was not detected by differential scanning calorimetry (DSC) in the range of 50–300 °C. The 10 wt % decomposition temperature of the poly(SOC)s was found to be above 400 °C. These results indicated the high thermal stability of the poly(SOC)s. Soluble poly(SOC)s could be possessed to form a film on a glass plate by the spin coat method. The obtained polymer films were 0.2 μm in thickness with 95% light transmission in the optical wavelength range. These results suggested that the Cardo or bent structure may block the packing of the main‐chain of the structure, which improves the solubility of the polymers, increases transparency, and enhances the thermal stability of SOCs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1409‐1416     

Triply Linked Corrole Dimers

The oxidation of 10–10′ singly linked corrole dimers with DDQ at low concentration in CHCl₃ afforded meso–meso, β–β, β–β triply linked 2H‐corrole dimers (with two inner NH groups in each corrole unit), which exhibited characteristic ¹H NMR and absorption spectra attributable to their nonaromatic electronic networks. These 2H‐corrole dimers were reduced with NaBH₄ to aromatic 3H‐corrole dimers, which were unstable and easily oxidized back to the 2H‐corrole dimers upon exposure to air. Bis(zinc(II)) complexes of the 2H‐corrole dimers were synthesized and characterized as rare examples of nonaromatic zinc(II) corrole complexes.     

A novel method for determination of inorganic oxyanions by electrospray ionization mass spectrometry using dehydration reactions

Novel methods for the determination of inorganic oxyanions by electrospray (ES) ionization mass spectrometry have been developed using dehydration reactions between oxyanions and carboxylic acids at the ES interface. Twelve oxyanions (VO₃^?, CrO₄^2?, MoO₄^2?, WO₄^2?, BO₃^3?, SiO₃^2?, SiO₄^4?, AsO₄^4?, AsO₂^?, SeO₄^2?, SeO₃^2? and NO₂^?), out of 16 tested, reacted with at least one of four aminopolycarboxylic acids, i.e. iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), trans‐1,2‐diaminocyclohexane‐N,N,N′,N′‐tetraacetic acid and triethylenetetramine‐N,N,N′,N″,N′″,N′″‐hexaacetic acid, at the ES interface to produce the dehydration products that gave intense mass ion responses, sufficient for trace analysis. As examples, trace determinations of Cr^VI and silica in water samples were achieved after online ion exchange chromatography, where the dehydration product of CrO₄^2? and NTA (m/z 290) and that of SiO₄^4? and IDA (m/z 192) were measured. The limits of detection of the respective methods were 17 nM (0.83 ng Cr/ml) for Cr^VI and 0.17 μM (4.8 ng Si/mL) for SiO₄^4?. Copyright © 2016 John Wiley & Sons, Ltd.     

Path to achieving molecular dispersion in a dense reactive mixture

A uniform dispersion of reactants is necessary to achieve a complete reaction involving multicomponents. In this study, we have examined the role of plasticizer in the reaction of two seemingly unlikely reactants: a highly crystalline hexamethylenetetramine (HMTA) and a strongly hydrogen bonded phenol formaldehyde resin. By combining information from NMR, infrared spectroscopy and differential scanning calorimetry, we were able to determine the role of specific intermolecular interactions necessary for the plasticizer to dissolve the highly crystalline HMTA and to plasticize the phenol formaldehyde resin in this crosslinking reaction. The presence of the plasticizer increased the segmental mobility, disrupted the hydrogen bonded matrix, and freed the hydroxyl units, which further increased the solubility of the HMTA. Both the endothermic and exothermic transitions are accounted for in the calorimetric data obtained. For the first time, it is possible to obtain the effective molar ratio of each component needed to complete the crosslinking reaction efficiently. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1519–1526     

Aromaticity Relocation in Perylene Derivatives upon Two‐Electron Oxidation To Form Anthracene and Phenanthrene

We prepared perylene dications 1 ²⁺ and 2 ²⁺ by using “capped” perylene derivatives, and for the first time, successfully obtained single crystals of a perylene dication 1 ²⁺ that enabled us to perform its structural analysis. We realized that the substituted aryl groups on perylene control the positions of positive charges, thus the remaining electronic system satisfies Clar's sextet rule toward the highest number of localized sextets. Experimental and theoretical evidence proved that Clar's aromatic π‐sextet rule could be applied even for the dicationic perylenes in a very simple way.