Chain-growth polycondensation for well-defined aramide. Synthesis of unprecedented block copolymer containing aramide with low polydispersity

Poly(p-benzamide) with a defined molecular weight and a low polydispersity and a block copolymer containing this well-defined aramide was synthesized. Phenyl 4-aminobenzoate, which would yield poly(p-benzamide), did not polymerize under the conditions of chain-growth polycondensation. However, phenyl 4-(4-octyloxybenzylamino)benzoate (1b) polymerized at room temperature in the presence of base and phenyl 4-nitrobenzoate (2) as an initiator in a chain-growth polycondensation manner to give well-defined aromatic polyamides having the 4-octyloxybenzyl groups as a protecting group on nitrogen in an amide. It was confirmed by a model reaction that deprotection of this protecting group proceeded completely with trifluoroacetic acid (TFA) without breaking the amide linkage. The utility of this approach to poly(p-benzamide) with a low polydispersity was demonstrated by the synthesis of block copolymers. Thus, phenyl 4-(octylamino)benzoate (1a) polymerized in the presence of 2 and base, followed by addition of 1b and base to the reaction mixture of the prepolymer to yield the block copolymer of 1a and 1b with a controlled molecular weight and a low polydispersity. The block copolymer was treated with TFA, resulting in a soluble block copolymer of poly(N-octyl-p-benzamide) and poly(p-benzamide). The SEM images of the supramolecular assemblies of the block copolymer showed mum-sized bundles and aggregates of flake structures.     

Oligothiophene-containing coumarin dyes for efficient dye-sensitized solar cells

We have developed oligothiophene-containing coumarin dyes fully functionalized for dye-sensitized nanocrystalline TiO(2) solar cells (DSSCs). DSSCs based on the dyes gave good performance in terms of incident photon-to-current conversion efficiency (IPCE) in the range of 400-800 nm. A solar energy-to-electricity conversion efficiency (eta) of 7.4% was obtained with a DSSC based on 2-cyano-3-[5'-(1,1,6,6-tetramethyl-10-oxo-2,3,5,6-tetrahydro-1H,4H,10H-11-oxa-3a-aza-benzo[de]anthracen-9-yl)-[2,2']bithiophenyl-5-yl]acrylic acid (NKX-2677) under simulated AM 1.5G irradiation (100 mW cm(-2)) with a mask: short-circuit current density (J(sc)) = 13.5 mA cm(-2); open-circuit voltage (V(oc)) = 0.71 V; fill factor (FF) = 0.77. Transient absorption spectroscopy measurements indicated that electron injection from NKX-2677 to the conduction band of TiO(2) is very rapid (<100 fs), which is much faster than the emission lifetime of the dye (1.0 ns), giving a highly efficient electron injection yield of near unity.     

An Efficient Method for the Conjugation of Hydrophilic and Hydrophobic Components by Solid‐Phase‐Assisted Disulfide Ligation

Chemical conjugation between hydrophilic and hydrophobic components is difficult because of their extremely different solubility. Herein, we report a new versatile method with a solid‐phase‐assisted disulfide ligation to overcome the difficulty of conjugation attributed to solubility. The method involves two steps in a one‐pot process: 1) loading of a hydrophobic molecule onto a resin in an organic solvent, and 2) release of the solid‐supported hydrophobic molecule as a conjugate with a hydrophilic molecule into an aqueous solvent. This strategy allows the use of a suitable solvent system for the substrates in each step. Conjugates of a water‐insoluble drug, plinabulin, with hydrophilic carriers that could not be prepared by solution‐phase reactions were obtained in moderate yields (29–45 %). This strategy is widely applicable to the conjugation of compounds with solubility problems.     

Heterocyclic effect for optical properties of naphthoquinone-based pigment: 2-methyl-3-heteroarylthio-1,4-naphthalenedione

Three novel naphthoquinone-based heterocyclic pigments, 2-methyl-3-[(1-methyl-1H-imidazol-2-yl)thio-1,4-naphthalenedione, (4-methyl-4H-1,2,4-triazol-3-yl)thio-1,4-naphthalenedione, and (1-methyl-1H-tetrazol-5-yl)thio]-1,4-naphthalenedione, are synthesized, and their optical properties in both solution and solid states are investigated. Depending on the heteroarylthio ring in the pigment, variation in optical properties is observed, e.g. characteristic colours for each pigment in the solution and solid states. The achiral pigment containing the 1-methyl-1H-tetrazol-5-yl ring exhibits a chiral space group and a CD signal in the solid state.     

Crystal growth and luminescent properties of Pr-doped K(Y,Lu)3F10 single crystal for scintillator application

Pr1%:K(Y_1−xLu_x)₃F₁₀ (x=0, 0.2, 0.4) single crystals were grown by the μ-PD method. All the grown crystals were greenish and perfectly transparent without any inclusions or cracks. Radioluminescence spectra and decay kinetics of the Pr1%:K(Y,Lu)₃F₁₀ crystals were measured. Emission from the Pr³⁺ 5d–4f transition, peaking around 260 nm and of the decay time of around 22 ns were observed. The 5d–4f emission intensities of the Pr1%:K(Y,Lu)₃F₁₀ crystals were higher than that of the standard BGO scintillator.     

9,10‐Diaminoanthracenes Revisited: The Influence of N‐Substituents on Their Electronic States

The electronic and molecular structures of 9,10‐diamino‐substituted anthracenes with different N‐substituents have been re‐examined. In particular, different N‐substituents influence both the electronic and molecular structures of the oxidized species of 9,10‐diaminoanthracenes. The anthrylene moiety of 9,10‐bis(N,N‐di(p‐anisyl)amino)anthracene retains its planarity during the course of two successive one‐electron oxidations, whereas 9,10‐bis(N,N‐dimethylamino)anthracene and 9,10‐bis(N‐p‐anisyl‐N‐methylamino)anthracene undergo a substantial structural change to a butterfly‐like structure through a two‐electron oxidation process. The structural changes observed for the oxidized states are ascribed to significant differences in the frontier molecular orbitals of the above‐mentioned three kinds of 9,10‐diaminoanthracenes due to different extents of mixing between the amine‐localized and anthrylene‐localized orbitals.     

Circumventing air bubbles in microfluidic systems and quantitative continuous-flow PCR applications

Polymerase chain reaction (PCR) is an essential part of research based on genomics or cell analysis. The development of a microfluidic device that would be suitable for high-temperature-based reactions therefore becomes an important contribution towards the integration of micro-total analysis systems (μTAS). However, problems associated with the generation of air bubbles in the microchannels before the introduction of the assay liquid, which we call the “initial start-up” in this study, made the flow irregular and unstable. In this report, we have tried to address these problems by adapting a novel liquid-flow method for high-temperature-based reactions. A PDMS-based microfluidic device was fabricated by soft-lithography techniques and placed on a cartridge heater. The generation of the air bubbles was prevented by introducing the fluorinated oil, an inert and highly viscous liquid, as the cap just before the introduction of the sample solutions into the microchannels. The technique was applied for continuous-flow PCR, which could perform PCR on-chip in a microfluidic system. For the evaluation of practical accuracy, plasmid DNA that serves as a reference molecule for the quantification of genetically modified (GM) maize was used as the template DNA for continuous-flow PCR. After PCR, the products were collected in a vial and analyzed by gel electrophoresis to confirm the accuracy of the results. Additionally, quantitative continuous-flow PCR was performed using TaqMan technology on our PCR device. A laser detection system was also used for the quantitative PCR method. We observed a linear relationship between the threshold cycle (Ct) and the initial DNA concentration. These results showed that it would be possible to quantify the initial copies of the template DNA on our microfluidic device. Accurate quantitative DNA analysis in microfluidic systems is required for the integration of PCR with μTAS, thus we anticipate that our device would have promising potential for applications in a wide range of research.     

High-spin radical cations of a dendritic oligoarylamine

A new dendritic oligoarylamine, N,N,N',N',N",N"-hexakis[4-(di-4-anisylamino)phenyl]- 1,3,5-benzenetriamine (BTA) 2, which contains a 1,3,5-benzenetriamine molecular unit as an potential precursor of a high-spin molecule and three oligoarylamine moieties as spin-carrying units surrounding the core BTA, has been prepared by the sequential palladium-catalyzed amination reactions. The redox property has been investigated by cyclic voltammetry, and the highly charged states up to the hexacation are accessible to 2. The polycationic high-spin species have been generated by stepwise chemical oxidation, and the electronic structures have been examined in detail by the continuous wave (CW) and pulsed ESR spectroscopy in comparison with the previously studied 1. The pulsed ESR technique enabled us to determine the definite spin multiplicity of the generated polycationic species of 2. It was confirmed that the dominant oxidized species observed by the two- and three-electron oxidations were assigned to the spin triplet 2(2+) and the spin quartet 2(3+), respectively. Moreover, these high-spin polycationic species turned out to be far more stable as compared to 1, and the isolation of 2(3+) as the SbCl(6)(-) salt has been accomplished. The temperature dependence of the magnetic susceptibility for the 2(3+)(SbCl(6)(-))(3) salt revealed that the intramolecular ferromagnetic interaction exists in 2(3+), and moreover, the trication 2(3+) was found to be deformed in the solid state.     

Redox-switching of intramolecular magnetic interaction through π-conjugation mode change of 1,2-bis(4-dianisylamino)-1,2-bis(3-N-oxylamino)-substituted tetraarylethylene

To develop the redox-switching system of intramolecular magnetic interaction, 1,2-bis[3-(N-tert-butyl-N-oxylamino)phenyl]-1,2-bis[4-{N,N-bis(4-methoxyphenyl)amino}phenyl]ethylene, tetraarylethylene with two nitroxide radical groups at the meta-position, was synthesized, and characterized by the electrochemical method and ESR spectroscopy. Cyclic voltammetry showed the tetraarylethylene core has the lower oxidation potential than the substituted nitroxide radical moiety. ESR spectroscopy in frozen solution revealed that the neutral form shows the fine-structured spectrum characteristic of the spin triplet species, while the dicationic form shows the anisotropic hyperfine-structured spectrum characteristic of the randomly-oriented nitroxide radical, indicating the drastic change of intramolecular magnetic interaction.