Synthesis of 3,6-Disubstituted-2-nitrotoruenes by Methylation of Aromatic Nitrocompounds with Dimethylsulfonium Methylide

3,6-disubstituted-2-nitrotoluenes were obtained in moderate yield by methylation of 2,5-disubstituted nitrobenzenes with dimethylsulfonium methylide in DMSO-THF mixture.     

Synthesis of high thermal stability polybenzoxazoles via ortho‐imide‐functional benzoxazine monomers

We report our work for preparing cross‐linked polyimide via a series of imide functional benzoxazine resins as precursors. The structures of synthesized monomers have been confirmed by ¹H NMR and FT‐IR. Among this class of benzoxazine monomers, the ortho‐imide functional benzoxazine resins show useful features both in the synthesis of benzoxazine monomers and the properties of the corresponding thermosets. For the cross‐linked polyimides based on ortho‐imide functional benzoxazine, an additional route is adopted to form a more thermally stable cross‐linked polybenzoxazole with the release of carbon dioxide. The ortho‐imide functional benzoxazine resins show the possibility to form high performance and even super high performance thermosets with low cost and easy processability. The thermal properties are evaluated by DSC and TGA. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1330–1338     

Development of a rapid method for the quantitative determination of deoxynivalenol using Quenchbody

Quenchbody (Q-body) is a novel fluorescent biosensor based on the antigen-dependent removal of a quenching effect on a fluorophore attached to antibody domains. In order to develop a method using Q-body for the quantitative determination of deoxynivalenol (DON), a trichothecene mycotoxin produced by some Fusarium species, anti-DON Q-body was synthesized from the sequence information of a monoclonal antibody specific to DON. When the purified anti-DON Q-body was mixed with DON, a dose-dependent increase in the fluorescence intensity was observed and the detection range was between 0.0003 and 3 mg L⁻¹. The coefficients of variation were 7.9% at 0.003 mg L⁻¹, 5.0% at 0.03 mg L⁻¹ and 13.7% at 0.3 mg L⁻¹, respectively. The limit of detection was 0.006 mg L⁻¹ for DON in wheat. The Q-body showed an antigen-dependent fluorescence enhancement even in the presence of wheat extracts. To validate the analytical method using Q-body, a spike-and-recovery experiment was performed using four spiked wheat samples. The recoveries were in the range of 94.9–100.2%. The concentrations of DON in twenty-one naturally contaminated wheat samples were quantitated by the Q-body method, LC-MS/MS and an immunochromatographic assay kit. The LC-MS/MS analysis showed that the levels of DON contamination in the samples were between 0.001 and 2.68 mg kg⁻¹. The concentrations of DON quantitated by LC-MS/MS were more strongly correlated with those using the Q-body method (R² = 0.9760) than the immunochromatographic assay kit (R² = 0.8824). These data indicate that the Q-body system for the determination of DON in wheat samples was successfully developed and Q-body is expected to have a range of applications in the field of food safety.     

Precise measurement of plastic behaviour of mild steel tubular specimens subjected to combined torsion and axial force

In the present paper, as an investigation for obtaining detailed information about the plastic behaviour of real materials, precise measurement of plastic deformation of thin-walled tubular specimens of initially-isotropic mild steel was performed under combined loading of torsion and axial force having trajectories consisting of two straight lines at a constant rate of the effective strain.From the experimental results, it is found that the effect of the third invariant of the strain tensor appeared even for proportional deformation consisting of torsion and axial force. Moreover, it may be seen that the effective stress drops suddenly with increasing effective strain, and coaxiality between the stress deviator and the plastic strain increment tensor is seriously disturbed just after the corner of the strain trajectory. However, these local disturbances are recovered along the second branch of the trajectory.The effect of the third invariant of the strain tensor was eliminated from the experimental results by the introduction of the modified local stress space for isolating the influence of anisotropy due to the deformation history. This permits a systematic evaluation of the influence of anisotropy for various types of combined loading.     

Regioselective CF Bond Activation of Hexafluoropropylene on Palladium(0): Formation of a Cationic η2‐Perfluoroallylpalladium Complex

A chemoselective C(sp²)? F or C(sp³)? F bond activation of hexafluoropropylene (HFP) was achieved by adopting the proper combination of a Lewis acid co‐additive with a ligand which coordinates Pd⁰. The treatment of [(η²‐HFP)Pd(PCy₃)₂] with B(C₆F₅)₃ allowed a chemoselective C(sp³)? F bond cleavage of HFP to give a unique cationic perfluoroallypalladium complex. In this complex, the coordination mode of the perfluoroallyl ligand was considered to be of the unique η²‐fashion.     

Theory for optical assembling of anisotropic nanoparticles by tailored light fields under thermal fluctuations

In order to evaluate the assembling processes of arbitrary-shaped nanoparticles (NPs) by the irradiation of a tailored laser beam under thermal fluctuations, we have developed a “Light-induced-force Nano Metropolis Method (LNMM)” as a new theoretical method based on the stochastic algorithm in the energy region and the general formula of light-induced force. By using LNMM, we have investigated the change of configurations of silver NPs with anisotropic shapes under the irradiation of laser beams with various polarizations and intensity distributions (Gaussian beam and axially-symmetric vector beams) in an aqueous solution at room temperature. As a result, it has been clarified that silver NPs can be selectively arranged into a characteristic spatial configuration reflecting the properties of an irradiated laser beam (wavelength, intensity distribution, and polarization distribution), and that the assembled structures possess broadband spectra and exhibit a strong optical response to the irradiated laser beam through the optimization with the help of fluctuations.     

Dynamics of Excess‐Electron Transfer through Alternating Adenine:Thymine Sequences in DNA

This paper presents the results of an investigation into the sequence‐dependent excess‐electron transfer (EET) dynamics in DNA, which plays an important role in DNA damage/repair. There are many published studies on EET in consecutive adenine:thymine (A:T) sequences ( Tn ), but those in alternating A:T sequences ( ATn ) remain limited. Here, two series of functionalized DNA oligomers, Tn and ATn , were synthesized with a strongly electron‐donating photosensitizer, a trimer of ethylenedioxythiophene ( 3 E ), and an electron acceptor, diphenylacetylene ( DPA ). Laser flash photolysis experiments showed that the EET rate constant of AT3 is two times lower than that of T3 due to the lack of π‐stacking of Ts in AT3 . Thus, it was indicated that excess‐electron hopping is affected by the interaction between LUMOs of nucleotides.