Practical Synthesis of 2-Iodosobenzoic Acid (IBA) without Contamination by Hazardous 2-Iodoxybenzoic Acid (IBX) under Mild Conditions

We report a convenient and practical method for the preparation of nonexplosive cyclic hypervalent iodine(III) oxidants as efficient organocatalysts and reagents for various reactions using Oxone^® in aqueous solution under mild conditions at room temperature. The thus obtained 2-iodosobenzoic acids (IBAs) could be used as precursors of other cyclic organoiodine(III) derivatives by the solvolytic derivatization of the hydroxy group under mild conditions of 80 °C or lower temperature. These sequential procedures are highly reliable to selectively afford cyclic hypervalent iodine compounds in excellent yields without contamination by hazardous pentavalent iodine(III) compound.     

Interrogation of fiber-Bragg-grating temperature and strain sensors with a temperature-stabilized VCSEL

The interrogation of fiber-Bragg-grating (FBG) sensors using a vertical-cavity surface-emitting laser (VCSEL) is discussed. A long-wavelength (1.54 μm) VCSEL was used as a wavelength-tunable source by variation in the current. Temperature stabilization was performed with a thermoelectric device. Characteristics of temperature and strain sensing were investigated. FBGs with different reflectivities were compared. For temperature sensing, the root-mean-square error in the measurement was reduced to 1/3 that without temperature stabilization. The dependence of the measurement error on the reflectivities of the FBGs was investigated. The measurement error was larger for FBGs with lower reflectivities in both temperature and strain sensing. Improvement on the sensing with low-reflectivity FBGs is discussed.     

Detection of high-energy gamma rays from winter thunderclouds

A report is made on a comprehensive observation of a burstlike gamma-ray emission from thunderclouds on the Sea of Japan, during strong thunderstorms on 6 January 2007. The detected emission, lasting for approximately 40 sec, preceded cloud-to-ground lightning discharges. The burst spectrum, extending to 10 MeV, can be interpreted as consisting of bremsstrahlung photons originating from relativistic electrons. This ground-based observation provides the first clear evidence that strong electric fields in thunderclouds can continuously accelerate electrons beyond 10 MeV prior to lightning discharges.     

Palladium‐Catalyzed Direct Thiolation of Aryl CH Bonds with Disulfides

A catalytic variant of the direct thiolation of arenes, bearing directing groups, with disulfides or thiols has been developed under palladium and copper co‐catalysis. Both sulfenyl moieties of the disulfide could be incorporated into the thiolated products, therefore, the reactions reached completion with only half an equivalent of disulfide, with respect to the starting arene. Experimental evidence suggested that the reaction proceeds through a Pd^II/Pd^IV mechanism.     

Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton‐Coupled Electron Transfer

We report a catalytic, light‐driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible‐light irradiation in the presence of an Ir^III‐based photoredox catalyst, a Brønsted base catalyst, and a hydrogen‐atom transfer (HAT) co‐catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O?H bonds through a proton‐coupled electron‐transfer mechanism. This method exhibits a broad substrate scope and high functional‐group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.     

High-Affinity Ratiometric Fluorescence Probe Based on 6-Amino-2,2′-Bipyridine Scaffold for Endogenous Zn2+ and Its Application to Living Cells

Zinc is an essential trace element involved in many biological activities; however, its functions are not fully understood. To elucidate the role of endogenous labile Zn²⁺, we developed a novel ratiometric fluorescence probe, 5-(4-methoxyphenyl)-4-(methylsulfanyl)-[2,2′-bipyridin]-6-amine (6 (rBpyZ)) based on the 6-amino-2,2′-bipyridine scaffold, which acts as both the chelating agent for Zn²⁺ and the fluorescent moiety. The methoxy group acted as an electron donor, enabling the intramolecular charge transfer state of 6 (rBpyZ), and a ratiometric fluorescence response consisting of a decrease at the emission wavelength of 438 nm and a corresponding increase at the emission wavelength of 465 nm was observed. The ratiometric probe 6 (rBpyZ) exhibited a nanomolar-level dissociation constant (K_d = 0.77 nM), a large Stokes shift (139 nm), and an excellent detection limit (0.10 nM) under physiological conditions. Moreover, fluorescence imaging using A549 human lung adenocarcinoma cells revealed that 6 (rBpyZ) had good cell membrane permeability and could clearly visualize endogenous labile Zn²⁺. These results suggest that the ratiometric fluorescence probe 6 (rBpyZ) has considerable potential as a valuable tool for understanding the role of Zn²⁺ in living systems.     

Spontaneous racemization and epimerization behavior in solution of chiral nitroxides

[reaction: see text] Enantiomerically enriched samples of chiral cyclic nitroxides with a 4-hydroxyphenyl group on the stereogenic center bearing the NO radical group undergo unprecedented spontaneous racemization and/or epimerization in aprotic solvents, which can be well accounted for by the multistep equilibrations involving planar quinoid intermediates.     

Comonomer-unit compositions, physical properties and biodegradability of bacterial copolyhydroxyalkanoates

The comonomer-unit compositions and their distribution of as-produced bacterial copolyesters, including poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxy-butyrate-co-3-hydroxypropionate), poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) and poly(3-hydroxybutyrate-co-4-hydroxybutyrate) are described in this paper. Each copolyester sample can be comonomer-unit compositionally fractionated into several fractions, indicating that the original copolymers are mixtures of copolymers with different comonomer-unit compositions. The effects of comonomer-unit compositional distribution on thermal properties, crystallization, biodegradability and solid-state phase behavior are investigated using comonomer compositionally fractionated copolymers.     

Amphidinolide Y, a novel 17-membered macrolide from dinoflagellate Amphidinium sp.: plausible biogenetic precursor of amphidinolide X

A novel cytotoxic 17-membered macrolide, amphidinolide Y (1), has been isolated from a marine dinoflagellate Amphidinium sp., and it was elucidated to exist as a 9:1 equilibrium mixture of 6-keto- and 6(9)-hemiacetal forms (1a and 1b, respectively) on the basis of 2D NMR data and chemical means. The feeding experiments with (13)C-labeled acetates suggested that amphidinolide Y (1) may be a biogenetic precursor of 16-membered macrodiolide, amphidinolide X (2).     

Primal-dual algorithms and infinite-dimensional Jordan algebras of finite rank

We consider primal-dual algorithms for certain types of infinite-dimensional optimization problems. Our approach is based on the generalization of the technique of finite-dimensional Euclidean Jordan algebras to the case of infinite-dimensional JB-algebras of finite rank. This generalization enables us to develop polynomial-time primal-dual algorithms for ``infinite-dimensional second-order cone programs.' We consider as an example a long-step primal-dual algorithm based on the Nesterov-Todd direction. It is shown that this algorithm can be generalized along with complexity estimates to the infinite-dimensional situation under consideration. An application is given to an important problem of control theory: multi-criteria analytic design of the linear regulator. The calculation of the Nesterov-Todd direction requires in this case solving one matrix differential Riccati equation plus solving a finite-dimensional system of linear algebraic equations on each iteration. The number of equations and unknown variables of this algebraic system is m+1, where m is a number of quadratic performance criteria. Key words.polynomial-time primal-dual interior-point methods – JB-algebras – infinite-dimensional problems – optimal control problemsThis author was supported in part by DMS98-03191 and DMS01-02698.This author was supported in part by the Grant-in-Aid for Scientific Research (C) 11680463 of the Ministry of Education, Culture, Sports, Science and Technology of Japan.Mathematics Subject Classification (1991):90C51, 90C48, 34H05, 49N05