Synthesis of 7‐acetyloxy‐3,7‐dimethy1‐7,8‐dihydro‐6H‐isochromene‐6,8‐dione and its analogues

7‐Alkanoyloxy‐3,7‐dimefhyl‐7,8‐dihydro‐6H‐isochromene‐6,8‐diones 12‐15 were synthesized in 69‐16% yields from the reaction of 2,4‐dihydroxy‐3‐methyl‐6‐(2‐oxopropyl)benzaldehyde 11 with p‐toluenesulfonic acid in various carboxylic acids such as acetic acid, propionic acid, butyric acid and heptanoic acid followed by oxidation with lead tetraacetate. On the other hand, (±)‐daldinin A 5 (oleate) was not obtained using oleic acid as a medium. In the cases of heptanoic acid and oleic acid, esters 16 and 17 were produced in 23 and 9% yields, respectively. 6,8‐Dihydroxy‐3,7‐dimethyl‐2‐benzopyrylium p‐toluenesulfonate 31 is considered as the intermediate for the production of 12‐15. Overall yields of isochromenes 12‐15 were 26‐6% starting from 2‐methylresorcinol for seven steps.     

Crystal structure of methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate.

A photochemical cycloaddition reaction of methyl 2-pyrone-5-carboxylate with methacrylonitrile mainly gave a [4 + 2] cycloadduct, assigned as methyl endo-8-cyano-exo-8-methyl-3-oxo-2-oxabicyclo[2.2.2]oct-5-ene-6-carboxylate, whose structure was determined by an X-ray diffraction study. The formation of the cycloadduct was reasonably explained by considering a biradical intermediate having a less steric hindrance between the methoxycarbonyl group and the cyano group.     

Cepaic acid, a novel yellow xanthylium pigment from the dried outer scales of the yellow onion Allium cepa

Cepaic acid was isolated as a novel xanthylium yellow pigment from the dried outer scales of the yellow onion Allium cepa Linne. Its structure was elucidated on the basis of ESI-MS and 2D NMR spectroscopy as a 9-carboxy-1,3,6,8-tetrahydroxyxanthylium, which suggests that cepaic acid and other yellow pigments in the dried outer skin of onion were formed by the nucleophilic reaction of phloroglucinol derived from quercetin, a flavonol in onion scales, by autoxidation to glyoxylic acid. To our knowledge, this is the first report of such a pigment in yellow onion.     

Preparation of poly(1,4-phenylene)s by electro-oxidative polymerization

The effect of substituents on the electropolymerization of benzene derivatives and the redox properrties of the corresponding polymers were determined using Brown's substituent constants (σ⁺). Electron-donating groups lower the oxidation potential by which increase in the current efficiency was observed. However, stabilization of the produced cation radicals by the electron-donating groups resulted in a decrease in the polymerization efficiency. The appropriate values of σ⁺ for the efficient polymerization ranged near ?1.5.     

Borel summability of divergent solutions for singular first-order partial differential equations with variable coefficients. Part I

This article part I and the forthcoming part II are concerned with the study of the Borel summability of divergent power series solutions for singular first-order linear partial differential equations of nilpotent type. Under one restriction on equations, we can divide them into two classes. In this part I, we deal with the one class and obtain the conditions under which divergent solutions are Borel summable. (The other class will be studied in part II.) In order to assure the Borel summability of divergent solutions, global analytic continuation properties for coefficients are required despite of the fact that the domain of the Borel sum is local.     

Carbazole Dendrimers as Solution‐Processable Thermally Activated Delayed‐Fluorescence Materials

Recently, thermally activated delayed fluorescence (TADF) materials have received increasing attention as effective emitters for organic light‐emitting diodes (OLEDs). However, most of them are usually employed as dopants in a host material. In this report, carbazole dendrimers with a triphenyl‐s‐triazine core are reported, which are the first solution‐processable, non‐doped, high‐molecular‐weight TADF materials. The dendrimers were obtained by a new and facile synthetic route using the tert‐butyldimethylsilyl moiety as a protecting group. All dendrimers showed TADF in toluene. Measurements of the temperature‐dependent luminescence lifetime revealed that spin‐coated neat films also showed TADF with moderate quantum yields. OLED devices incorporating these dendrimers as spin‐coated emitting layers gave external quantum efficiencies of up to a 3.4 %, which suggests that this device is harvesting triplet excitons. This result indicates that carbazole dendrimers with attached acceptors are potential TADF materials owing to their polarized electronic structure (with HOMO–LUMO separation).     

A far-red emitting probe for unambiguous detection of mobile zinc in acidic vesicles and deep tissue

Imaging mobile zinc in acidic environments remains challenging because most small-molecule optical probes display pH-dependent fluorescence. Here we report a reaction-based sensor that detects mobile zinc unambiguously at low pH. The sensor responds reversibly and with a large dynamic range to exogenously applied Zn²⁺ in lysosomes of HeLa cells, endogenous Zn²⁺ in insulin granules of MIN6 cells, and zinc-rich mossy fiber boutons in hippocampal tissue from mice. This long-wavelength probe is compatible with the green-fluorescent protein, enabling multicolor imaging, and facilitates visualization of mossy fiber boutons at depths of >100 μm, as demonstrated by studies in live tissue employing two-photon microscopy.     

On the exponential Diophantine equation $$(3pm^2-1)^x+(p(p-3)m^2+1)^y=(pm)^z$$

Let m be a positive integer, and let p be a prime with \(p \equiv 1~(\mathrm{mod}~4).\) Then we show that the exponential Diophantine equation \((3pm^2-1)^x+(p(p-3)m^2+1)^y=(pm)^z\) has only the positive integer solution \((x, y, z)=(1, 1, 2)\) under some conditions. As a corollary, we derive that the exponential Diophantine equation \((15m^2-1)^x+(10m^2+1)^y=(5m)^z\) has only the positive integer solution \((x, y, z)=(1, 1, 2).\) The proof is based on elementary methods and Baker’s method.     

Measurement of energy release rate and energy flux of rapidly bifurcating crack in Homalite 100 and Araldite B by high-speed holographic microscopy

High-speed holographic microscopy is applied to take three successive photographs of fast propagating cracks in Homalite 100 or in Araldite B at the moment of bifurcation. Crack speed at bifurcation is about 540 m/s on Homalite 100, and about 450 m/s on Araldite B. From the photographs, crack speeds immediately before and after bifurcation are obtained, and it is found that discontinuous change of crack speed does not exist at the moment of bifurcation in the case of Homalite 100, but exists in the case of Araldite B. From the photographs, crack opening displacement (COD) is also measured along the cracks as a function of distance r from the crack tips. The measurement results show that the CODs are proportional to √r before bifurcation. After bifurcation, the CODs of mother cracks are proportional to √r, though the CODs of branch cracks are not always proportional to √r. The energy release rate is obtained from the measured CODs, and it is found that energy release rate is continuous at bifurcation point in both cases of Homalite 100 and Araldite B. Energy flux that shows the energy flow toward a crack tip is also obtained.