Design of novel polymer-supported chiral catalyst for asymmetric transfer hydrogenation in water

New polymer-supported chiral sulfonamides containing sulfonated pendant group have been synthesized. Chiral catalyst prepared from the new polymer-support is more effective for asymmetric transfer hydrogenation of aromatic ketones in water compared to that prepared from conventional polystyrene-support. Polymer-supported catalysts containing quaternary ammonium salt as a pendant increased not only the reactivity but also the enantioselectivity in asymmetric transfer hydrogenation in water. Moreover, this type of polymer can be reused without loss of the catalytic activity.     

Reaction of fullerene with benzocyclobutene homologs

Fullerene was easily converted to its derivatives by the treatment with benzocyclobutene homologs for 20 h at 140 °C. The spectroscopic analyses clearly indicate mono-[4+2]-cycloadduct structures of its derivatives. Isolated yields of mono- and di-adducts were from 4.4 to 15.6% and from 8.1 to 5.3%, respectively.     

Variation of the Alexander-Conway polynomial under Dehn surgery

Let ε₁ and ε₂ belong to {±1}. When the ε₁-surgery along a knot K₁ in S³ produces the same homology sphere as the ε₂-surgery along a knot K₂ in S³, then the Casson surgery formula implies that ε₁Δ_K1″(1)=ε₂Δ_K2″(1), where Δ(t) denotes the symmetric Alexander polynomial. For any pair (Λ₁(t),Λ₂(t)) of possible knot Alexander polynomials such that ε₁Λ₁″(1)=ε₂Λ₂″(1), we exhibit a pair (K₁,K₂) of knots in S³ such that Δ_K1(t)=Λ₁(t), Δ_K2(t)=Λ₂(t) and the ε₁-surgery along K₁ produces the same homology sphere as the ε₂-surgery along K₂.     

Evaluation of the Secondary Pore Structure of Hydrothermally- and Acid-treated Faujasite Type Zeolites

With regard to H-Y type zeolites dealuminated by hydrothermal and acid treatments, their physical properties were characterized by measurements of 29Si- and 27Al-MAS-NMR, IR, and X-ray diffraction. The secondary pores were quantitatively analyzed by the t-plot method for nitrogen adsorption isotherm at liquid nitrogen temperature and were then compared with the results of samples dealuminated by SiCl4 treatment.The plateau region of the nitrogen adsorption isotherm diminished as hydrothermal and acid treatments proceeded, with the result that the shape of the t-plot changed to that of three straight sections. This t-plot shape suggested that the secondary pores with relatively consistent sizes could develop with the progress of the treatment. On the other hand, SiCl4 treatment was found to produce less secondary pores than hydrothermal and acid treatments. The surface area of micropores calculated from the t-plots gave a considerably higher value than values obtained from the BET equation and from that calculated geometrically. This is attributable to the micropore filling effect.     

Determination of psilocybin in hallucinogenic mushrooms by reversed-phase liquid chromatography with fluorescence detection

The determination of psilocybin was carried out by reversed-phase liquid chromatography (HPLC) with fluorescence (FL) detection. Psilocybin was labeled with 5-dimethylaminonaphthalene-1-[N-(2-aminoethyl)]sulfonamide (DNS-ED) at 60 °C for 4 h in the presence of 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC) as the activation reagent. The resulting derivative was separated on a Mightysil RP-18 GP column (150 mm × 4.6 mm, i.d. 3 μm) with the mixture of 50 mM ammonium acetate (AcONH₄) and CH₃CN, and detected at 539 nm (excitation at 321 nm). The structure of the derivative was identified by HPLC-ESI-MS. A good linear relation of the calibration curve of psilocybin was observed under the proposed conditions for labeling, separation and detection. The quantification limit was 4.4 ng in 1 mg dried mushroom. The proposed procedure was successfully used for the determination of psilocybin in real samples. The contents of psilocybin in six magic mushrooms by the proposed HPLC-FL method were less than 20.0 ng in 1 mg dried samples.     

Suppressing proton decay in the minimal SO(10) model

We show that in a class of minimal supersymmetric SO(10) models which have been found to be quite successful in predicting neutrino mixings, all proton decay modes can be suppressed by a particular choice of Yukawa textures. The required texture not only fits all lepton and quark masses as well as Cabibbo-Kobayashi-Maskawa parameters, but it also predicts neutrino mixing parameter U(e3) and Dirac CP phase sin(/delta(MNS)/ to be 0.07-0.09 and 0.3-0.7, respectively.     

Highly regio- and stereoselective hydrostannylation of alkynols with a new Lewis acidic hydrostannane

[reaction: see text] Bu2Sn(OTf)H (1a), easily prepared from Bu2SnH2 and TfOH, was found to be very valuable for highly regio- and stereoselective hydrostannylation of various propargyl alcohols leading to (Z)-gamma-stannylated allyl alcohols. The stannylation with 1a is applicable to the synthesis of hydroxy-substituted (Z)-vinylstannanes from terminal alkynes bearing a hydroxy group at the homoallylic or bishomoallylic position. The coordination of the hydroxy group to the Lewis acidic tin center plays an important role for the observed regio- and stereochemistry.     

Spontaneous reactions of electron‐accepting substituted quinodimethane with substituted styrenes: Inductive and steric effects on the formation of a zwitterionic intermediate

Spontaneous reactions of an electron‐accepting substituted quinodimethane, 1‐(2,2‐dimethyl‐1,3‐dioxane‐4,6‐dione‐5‐ylidene)‐4‐(dicyanomethylene)‐2,5‐cyclohexadiene, with p‐substituted, α‐substituted, and β‐substituted styrenes were investigated. When p‐substituted styrenes were used as comonomers, no spontaneous reactions took place for styrenes with an electron‐accepting p substituent such as COOMe and CN groups, and both terpolymers and cycloadducts were formed for the other p‐substituted styrenes. When α‐substituted and β‐substituted styrenes were used as comonomers, no reactions occurred for α‐ and β‐substituted styrenes with a bulky phenyl group, and spontaneous reactions took place for those with a smaller methyl group. The reaction products were an alternating copolymer for α‐substituted styrene and both terpolymers and 5‐ethylidene‐2,5‐dimethyl‐1,3‐dioxane‐4,6‐dione for β‐substituted styrenes. The position of the methyl group in the styrenes significantly affected the product formation. This behavior in the spontaneous reactions was discussed on the basis of the ability of formation of the zwitterionic tetramethylene intermediate and its conformation, determined by polar and steric effects of the substituents in the substituted styrenes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5195–5206, 2005     

New Phase-Shifting Method Using Two Images

We propose a continuous two-step method (CTSM) to obtain an image from two interference images for the measurement time reduction of optical coherence tomography. Image processing is performed for each pixel in CTSM. The calculated signal intensity has an average and standard deviation after processing since the heterodyne beat signal contains the noise in the measurements. We assume that the heterodyne beat signal contains the random noise in simulations and calculate the influence of the normalized standard deviation (NSD = standard deviation/average) on the random noise intensity for both CTSM and the conventional three-step method (TSM). We found that the NSD of the CTSM is only 1.4 times greater than that of the TSM despite processing only two images.