Synthetic studies toward aplysiasecosterol A: Construction of the novel tricyclic core

Aplysiasecosterol A, a 9,11-secosterol compound, has a unique tricyclic γ-diketone skeleton including a hemiacetal. The novel tricyclic core of aplysiasecosterol A is constructed by using intramolecular radical cyclization as a key step.     

Dynamic nuclear polarization studies on deuterated nitroxyl spin probes

Detailed dynamic nuclear polarization and electron spin resonance studies were carried out for 3‐carbamoyl‐2,2,5,5‐tetramethyl‐pyrrolidine‐1‐oxyl, 3‐carboxy‐2,2,5,5‐tetramethyl‐pyrrolidine‐1‐oxyl,3‐methoxycarbonyl‐2,2,5,5‐tetramethy pyrolidine‐1‐oxyl nitroxyl radicals and their corresponding deuterated nitroxyl radicals, used in Overhauser‐enhanced magnetic resonance imaging for the first time. The dynamic nuclear polarization parameters such as dynamic nuclear polarization (DNP) factor, longitudinal relaxivity, saturation parameter, leakage factor and coupling factor were estimated for deuterated nitroxyl radicals. DNP enhancement increases with agent concentration up to 3 mm and decreases above 3 mm . The proton spin–lattice relaxation time and the longitudinal relaxivity parameters were estimated. The leakage factor increases with increasing agent concentration up to 3 mm and reaches plateau in the region 3–5 mm . The coupling parameter shows the interaction between the electron and nuclear spins to be mainly dipolar in origin. DNP spectrum exhibits that the full width at half maximum values are higher for undeuterated nitroxyl radicals compared with deuterated nitroxyl radicals, which leads to the increase in DNP enhancement. The ESR parameters such as, the line width, line shape, signal intensity ratio, rotational correlation time, hyperfine coupling constant and g‐factor were calculated. The narrow line width was observed for deuterated nitroxyl radicals compared with undeuterated nitroxyl radicals, which leads to the higher saturation parameter value and DNP enhancement. The novelty of the work permits clear understanding of the DNP parameters determining the higher DNP enhancement compared with the undeuterated nitroxyl radicals. Copyright © 2017 John Wiley & Sons, Ltd.     

Improvement of efficiency of piezoelectric element attached to beam based on mechanical impedance matching

This paper describes new methods that improve the efficiency of a piezoelectric element attached to a beam based on mechanical impedance matching. Piezoelectric elements are often used to suppress bending vibration. They are also used as sensors or energy-harvesting sources. In such cases, the piezoelectric element is usually bonded onto the host structure by an adhesive bond. The efficiency of the piezoelectric element depends on the bonding location. When the efficiency is insufficient despite a good location, the size or number of piezoelectric elements is increased. However, the efficiency of the piezoelectric element is usually insufficient even if these methods are applied. In order to enhance the efficiency of the piezoelectric elements without using active methods, this paper proposes a mechanical impedance matching method that uses spacers or tuning for the size of the piezoelectric element. Because the attached piezoelectric element and host structure in this region behave as springs in parallel to the bending deformation, the stored strain energy in the piezoelectric element is maximized under the condition that their spring constants match. The proposed methods were theoretically investigated with consideration for the effects of the bonding layer, spacers, and host structure. The optimum conditions for the proposed methods were theoretically formulated, and the effectiveness of the proposed methods and theoretical analysis was verified through simulations and experiments.     

Femtosecond luminescence decay due to exciton energy transfer in single-walled carbon nanotube bundles

We investigated luminescence decay kinetics in single-walled carbon nanotubes in large bundles excited by femtosecond pulses. The time constant of luminescence decay becomes longer with decrease in photon energy: 40 fs at 1.2 eV and 380 fs at 0.6 eV. This behavior is explained by exciton energy transfer from an excited to neighboring tubes.     

One-pot conversion of aromatic bromides and aromatics into aromatic nitriles via aryllithiums and their DMF adduct

Various aromatic bromides and iodides were smoothly converted into the corresponding aromatic nitriles in good to moderate yields by the treatment with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃. The same treatment of typical aromatics and heteroaromatics with n-butyllithium and subsequently DMF, followed by treatment with molecular iodine in aq NH₃ also provided the corresponding aromatic nitriles in good yields. Moreover, the same treatment of aromatic bromides and aromatics with half amount of DIH (1,3-diiodo-5,5-dimethylhydantoin) instead of molecular iodine worked effectively to give the corresponding aromatic nitriles, respectively, in good yields. These reactions are novel and environmentally benign one-pot methods for the preparation of aromatic nitriles from aromatic bromides and aromatics, respectively, through the formation of aryllithiums and their DMF adducts.     

Structure-reactivity relationship of piperidine nitroxide: electrochemical, ESR and computational studies

We have synthesized several nitroxides with different substituents which vary the steric and electronic environment around the N-O moiety and have systematically investigated the role of substituents on the stability of the radicals. Our results demonstrated the reactivity toward ascorbate correlates with the redox potential of the derivatives. Furthermore, ab initio calculations also indicated a correlation between the reduction rate and the computed singly occupied molecular orbital-lowest unoccupied molecular orbital energy gap, but not with solvent accessible surface area of the N-O moiety, supporting the experimental results and suggesting that the electronic factors largely determine the radicals' stability. Hence, it is possible to perform virtual screening of nitroxides to optimize their stability, which can help to rationally design novel nitroxides for their potential use in vivo.     

Differentiation between sulfoaildenafil and its analogs

An analog of aildenafil, which is a potent and highly selective inhibitor of phosphodiesterase 5, was found in a dietary supplement marketed for enhancement of sexual function. The compound was isolated by silica gel column chromatography, and its structure was identified by means of 13C-NMR spectrometry, 1H-NMR spectrometry, high-resolution MS, and X-ray structure determination. The compound was identified to be sulfoaildenafil (other names: thioaildenafil, dimethyl sildenafil thione, and thiomethisosildenafil). Sulfoaildenafil is very similar to the compound thiohomosildenafil. As it is difficult to distinguish between them by LC-photodiode array detector analysis, ultra-performance LC (UPLC)/MS, ion trap LC/MS/MS (LC/IT-MS/MS), and GC/MS were performed. The mass spectra of thiohomosildenafil by UPLC/MS and LC/IT-MS/MS showed mass fragments of m/z 58, 72, and 355, and the mass spectrum by GC/MS showed mass fragments of m/z 56, 72, and 420. Some of these fragments had low intensities, but they were useful for distinguishing between the two compounds. The relationship between aildenafil (other names: dimethylsildenafil and methisosildenafil) and homosildenafil is similar to that between sulfoaildenafil and thiohomosildenafil. Therefore, these compounds were also examined.     

Preparation of novel fluoroalkyl end-capped oligomers/polyaniline and/<Emphasis Type="Italic">N,N′</Emphasis>-diphenyl-1,4-phenylenediamine nanocomposites

Fluoroalkyl end-capped acrylic acid oligomer [R_F-(ACA)_n-R_F]/, 2-(methacryloyloxy)ethanesulfonic acid oligomer [R_F-(MES)_n-R_F]/, 2-acrylamido-2-methylpropanesulfonic acid oligomer [R_F-(AMPS)_n-R_F]/polyaniline [PAn] nanocomposites were prepared by the polymerization of aniline initiated by ammonium persulfate in the presence of the corresponding oligomers, respectively. These fluorinated oligomers were also applied to the preparation of the corresponding fluorinated oligomers/phenyl-capped aniline dimer (An-dimer: N,N′-diphenyl-1,4-phenylenediamine) nanocomposites by the interaction of the fluorinated oligomers with An-dimer. These fluorinated composites thus obtained were found to afford nanometer size-controlled fine particles possessing a good dispersibility and stability in water and traditional organic media such as methanol. UV–vis spectra of R_F-(MES)_n-R_F/PAn nanocomposites and R_F-(AMPS)_n-R_F/PAn nanocomposites showed the similar absorption peaks around 350, 430, and 780 nm to those of the usual Brønsted acid-doped PAn; however, interestingly, R_F-(ACA)_n-R_F/PAn nanocomposites were found to exhibit only an absorption peak around 430 nm based on the polaron transition.

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