Intramolecular iron(II)-catalyzed aminobromination of allyl N-tosyloxycarbamates

Allyl N-tosyloxycarbamates are found to be catalytically transformed into β-brominated oxazolidinones with FeBr(2)/n-Bu(4)NBr in t-BuOH.     

A temperature-cancellation method of pressure-sensitive paint on porous anodic alumina using 1-Pyrenesulfonic acid

A temperature-cancellation method of pressure-sensitive paint is introduced. It uses an intermediate wavelength of two luminescent peaks, which are opposite in the temperature dependency. 1-Pyrenesulfonic acid is used as a luminophore to describe this method, which is applied onto a porous anodic alumina using the dipping deposition. The concentration of the luminophore solution is varied from 0.001 to 0.09 mM. It controlled the luminescent peak ratio, temperature cancelled wavelength, and pressure sensitivity. The cancellation wavelength is ranged from 429±13 to 493±23 nm. An optical band-pass filter with the temperature cancellation can be also provided by controlling the concentration.     

Distributional response to biases in deterministic superdiffusion

We report on a novel response to biases in deterministic superdiffusion. For its reduced map, we show using infinite ergodic theory that the time-averaged velocity (TAV) is intrinsically random and its distribution obeys the generalized arcsine distribution. A distributional limit theorem indicates that the TAV response to a bias appears in the distribution, which is an example of what we term a distributional response induced by a bias. Although this response in single trajectories is intrinsically random, the ensemble-averaged TAV response is linear.     

Ammonia IRMS-TPD measurements on Brønsted acidity of proton-formed SAPO-34

By utilizing the advantages of a combined method of IRMS-TPD of ammonia and DFT calculations, the solid acidity of HSAPO-34 was studied. The number, strength and structure of the Br?nsted OH were measured experimentally. The quantitative measurements and DFT calculations supported the identification of Br?nsted OH to account for the generation model of the Br?nsted OH primarily located in the edge of the Si domain (island). The acid strength of SAPO-34 was slightly weaker than that of chabazite, a zeolite with the same structure. Thus, some important insights were obtained to understand the acid site generation of SAPO-34.     

Preparation of 2-Methoxy-3,4-methylenedioxybenzaldehyde (Croweacin Aldehyde) from Pyrogallol

2-Methoxy-3,4-methylenedioxybenzaldehyde (croweacin aldehyde) of high purity was prepared in 55% overall yield from pyrogallol.     

Release of small molecules from aggregates consisting of an amphiphilic oligonucleotide functionalized by a photochromic azobenzene unit

Stimuli-responsive nanocarriers offer favorable properties for the target-specific delivery of drugs. Herein, we employed photoirradiation as an external stimulus for the construction of a molecular system that encapsulated small molecules, which were released upon photoirradiation. These nanocarriers consisted of DNA amphiphiles (ODAz 1), in which an oligodeoxynucleotide and an alkyl chain were employed as the hydrophilic and hydrophobic parts, respectively, and these two parts were linked by a photochromic azobenzene unit. In aqueous solutions, ODAz 1 formed nanosized aggregates that encapsulated hydrophobic molecules in their hydrophobic core. Photoirradiation induced isomerization of the azobenzene unit led to changes in aggregate size and the immediate release of the molecules. The aggregate smoothly penetrated the cell membrane, and the photochemical release and delivery of small molecules into living cells were achieved. Thus, ODAz 1 aggregates represent promising photosensitive nanocarriers that may be applicable to drug delivery and targeting.     

Multistable attractors in a network of phase oscillators with three-body interactions

Three-body interactions have been found in physics, biology, and sociology. To investigate their effect on dynamical systems, as a first step, we study numerically and theoretically a system of phase oscillators with a three-body interaction. As a result, an infinite number of multistable synchronized states appear above a critical coupling strength, while a stable incoherent state always exists for any coupling strength. Owing to the infinite multistability, the degree of synchrony in an asymptotic state can vary continuously within some range depending on the initial phase pattern.     

Phosphorylation of 5'-deoxy-5-fluorouridine with inorganic phosphorylating agents

The phosphorylation of 5'-deoxy-5-fluorouridine (doxifluridine, 5'-DFUR) has been achieved using inorganic cyclo-triphosphate (P(3m), Na(3)P(3)O(9)) and monoimido-cyclo-triphosphate (MCTP, Na(3)P(3)O(8)NH) in aqueous solution. In the reaction of 5'-DFUR with P(3m), 2'-monophospho-5'-DFUR and 3'-monophospho-5'-DFUR were synthesized with a total yield of more than 95%. In the reaction of 5'-DFUR with MCTP, 2'-diphosphoramidophosphono-5'-DFUR and 3'-diphosphoramidophosphono-5'-DFUR were synthesized with a total yield of more than 40%. The phosphorylated products with P(3m) and MCTP were stable in neutral and alkaline solutions.     

A novel method for analyzing energy relaxation in condensed phases using nonequilibrium molecular dynamics simulations: application to the energy relaxation of intermolecular motions in liquid water

We present a novel method to investigate energy relaxation processes in condensed phases using nonequilibrium molecular dynamics simulations. This method can reveal details of the time evolution of energy relaxation like two-color third-order IR spectroscopy. Nonetheless, the computational cost of this method is significantly lower than that of third-order response functions. We apply this method to the energy relaxation of intermolecular motions in liquid water. We show that the intermolecular energy relaxation in water is characterized by four energy transfer processes. The structural changes of the liquid associated with the energy relaxation are also analyzed by the nonequilibrium molecular dynamics technique.