A practical one-pot procedure for the synthesis of pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidinones by a tandem aza-Wittig/heterocumulene-mediated annulation strategy

A simple one-pot and efficient method is described for the synthesis of pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidinone derivatives 6 via a tandem aza-Wittig/heterocumulene-mediated annulation process. The iminophosphorane 3 reacted with aryl isocyanates, followed by heterocyclization on addition of secondary amines to give the corresponding guanidine intermediates 5, which were cyclized in the presence of a catalytic amount of potassium carbonate to tricyclic compounds 6. Similarly, iminophosphorane 3 reacts with phenols, thiophenol, or ROH to give 2-aryl(alkyl)oxy(thio)pyrazino[2′,3′:4,5]thieno[3,2-d]pyrimidinone derivatives 7 in good yields. The corresponding carbodiimide 4c and guanidine-type intermediate compounds 5 could be isolated and characterized, thus confirming the suggested reaction pathway. However, two isomeric pyrazinothienopyrimidinones 8 and 9 may be produced in the reaction of iminophosphorane 3 with aromatic isocyanates and subsequent reaction with primary amines in the presence of a catalytic amount of potassium carbonate. The effects of the nucleophiles and isocyanates on the regioselectivity of the cyclization have been investigated.     

Pairings of function spaces

Pairings and copairings of topological spaces induce pairings of function spaces. These induced pairings of function spaces are studied. For this purpose, the C-open topology of function spaces is studied for subcategories C of Top. It is shown that the C-open topology enjoys good properties for homotopy theory. Making use of the C-open topology, theory of induced pairings is established and fundamental results on pairings which deduce various commutativity properties of elements in homotopy set are extended to function spaces.     

1.625-μm high-power strained multiple quantum well lasers for optical time-domain reflectometers

An optical output power exceeding 210 mW has been achieved using 1.625-μm strained multiple quantum well lasers at a forward current of 800 mA under pulsed operation. We introduced tensile-strained barrier layers to increase internal quantum efficiency. High quantum efficiency is attributed to improved of hole injection efficiency and suppressed electron overflow from wells. The 1.625-μm high-power lasers are expected to be applied to optical time-domain reflectometers, which enable regular communication light to be used.     

Ultra Deep Hydrodesulfurization of Gas Oils Over Sulfide and/or Noble Metal Catalysts

Deep hydrodesulfurization (HDS) of sterically hindered sulfur compounds in gas oils will require enhanced hydrogenation activity to hydrogenate the aromatic rings of the sulfur compounds. Although H₂S is known to inhibit the direct HDS route for most of the sulfided catalysts, its promotion to the hydrogenation and subsequent HDS was newly observed for unsupported MoS₂. This promotion suggests that ultra deep HDS over sulfide catalysts can be achieved along with high metal loading, minimal support-metal interactions and optimal dependence on the Ni species. On the other hand, the strong hydrogenation activity of sulfur-tolerant noble metal catalysts suggests that ultra deep HDS as well as deep aromatics saturation can be achieved. This paper discusses recent catalytic approaches for ultra deep HDS using conventional sulfide catalysts and/or noble metal catalysts, such as the newly developed Pd-Pt/Yb-USY zeolite catalyst.     

ELECTROCHEMICAL ISOMERIZATION OF SULFINE

Abstract

Electrochemical isomerization of 1-phenyl-2, 2-dimethylpropane-1-thione S-oxide (phenyl-t-butylsulfine, E and Z form, 1a and 1b) was studied. Anodic isomerization of 1a gave the two isomers of the sulfine only, but cathodic reductive isomerization of 1a gave pivalophenone and 1-cyano-2-phenyl-3, 3-dimethyl-1-butene in addition to the E and Z isomers. This is the first example of an electrochemical reaction of a sulfine.     

Detection of small RNA molecules by a combination of branched rolling circle amplification and bioluminescent pyrophosphate assay

Polyfluorinated compounds (PFCs) are a relatively new and diverse set of compounds analyzed as contaminants in food. Their unique physical-chemical properties dictate the methods used for their analysis. Current analyses of the more volatile PFCs involve gas chromatography–mass spectrometry; liquid chromatography–tandem mass spectrometry is generally used for the less volatile PFCs. Considerations in the analysis of PFCs in foods include contamination from the widespread presence of materials that contain various PFCs, endogenous interfering compounds, and matrix effects. Future opportunities for research on PFCs in food exist, particularly in the areas of biological molecule–PFC interactions and the effects of food processing on these interactions. Future research will be facilitated by the synthesis of a wider variety of analytical standards.     

Colorimetric sensing of polyhydroxy compounds by an inclusion complex of boronic acid-modified amylose

A novel sensing method for polyhydroxy compounds has been established based on the stimuli-responsive inclusion complex of boronic acid-modified amylose with iodine. An aqueous solution containing the boronic acid-modified amylose and iodine was coloured bluish purple due to encapsulation of iodine within the helical cavity of amylose. When polyhydroxy compounds were added, the solution gradually lost its colour with increasing concentration of polyhydroxy compounds. This colour change was attributed to the dissociation of iodine from the amylose cavity in response to the polyhydroxy compounds. According to detailed examinations, it was concluded that the origin of the responsiveness is derived from an electrostatic repulsion between anionic boronate groups and iodine.     

Exponential homeomorphisms in the category of topological spaces with base point

Topologies on base point preserving function spaces are studied making use of the Brown-Booth-Tillotson C-smash product and the topologies on function spaces defined by the classes C of exponentiable spaces. Some conditions on the classes C are obtained for exponential bijections and exponential homeomorphisms in the category of topological spaces with base point. Conditions for exponential homeomorphisms are obtained for CW-complexes whose cellular structure implies precise results.