Dielectrically controlled resolution (DCR) of 3-aminopiperidine via diastereomeric salt formation with N-tosyl-(S)-phenylalanine

A useful key intermediate for the dipeptidyl peptidase-4 (DPP-4) inhibitor, 3-aminopiperidine 1, was successfully resolved with an enantiomerically pure resolving agent, N-tosyl-(S)-phenylalanine 2, to give both stereoisomers (R)-1 and (S)-1 as a less-soluble diastereomeric salt with (S)-2, via a dielectrically controlled resolution (DCR) phenomenon.     

Synthesis of end‐functionalized polyethers by phosphazene base‐catalyzed ring‐opening polymerization of 1,2‐butylene oxide and glycidyl ether

For the living ring‐opening polymerization (ROP) of epoxy monomers, the catalytic activity of organic superbases, tert‐butylimino‐tris(dimethylamino)phosphorane, 1‐tert‐butyl‐2,2,4,4,4‐pentakis(dimethylamino)‐2Λ⁵,4Λ⁵‐catenadi(phosphazene), 2,8,9‐triisobutyl‐2,5,8,9‐tetraaza‐1‐phosphabicyclo[3.3.3]undecane, and 1‐tert‐butyl‐4,4,4‐tris(dimethylamino)‐2,2‐bis[tris(dimethylamino)phosphoranylidenamino]‐2Λ⁵,4Λ⁵‐catenadi(phosphazene) (t‐Bu‐P₄), was confirmed. Among these superbases, only t‐Bu‐P₄ showed catalytic activity for the ROP of 1,2‐butylene oxide (BO) to afford poly(1,2‐butylene oxide) (PBO) with predicted molecular weight and narrow molecular weight distribution. The results of the kinetic, post‐polymerization experiments, and MALDI‐TOF MS measurement revealed that the t‐Bu‐P₄‐catalyzed ROP of BO proceeded in a living manner in which the alcohol acted as the initiator. This alcohol/t‐Bu‐P₄ system was applicable to the glycidol derivatives, such as benzyl glycidyl ether (BnGE) and t‐butyl glycidyl ether, to afford well‐defined protected polyglycidols. The α‐functionalized polyethers could be obtained using different functionalized initiators, such as 4‐vinylbenzyl alcohol, 5‐hexen‐1‐ol, and 6‐azide‐1‐hexanol. In addition, the well‐defined cyclic‐PBO and PBnGE were successfully synthesized using the combination of t‐Bu‐P₄‐catalyzed ROP and click cyclization. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

A variant of Shelah's characterization of Strong Chang's Conjecture

Shelah considered a certain version of Strong Chang's Conjecture which we denote , and proved that it is equivalent to several statements, including the assertion that Namba forcing is semiproper. We introduce an apparently weaker version, denoted , and prove an analogous characterization of it. In particular, is equivalent to the assertion that the the Friedman‐Krueger poset is semiproper. This strengthens and sharpens results by Cox and sheds some light on problems posed by Usuba, Torres‐Perez and Wu.     

Decomposition of Insoluble and Hard-to-Degrade Animal Proteins by Enzyme E77 and Its Potential Applications

Insoluble and hard-to-degrade animal proteins are group of troublesome proteins, such as collagen, elastin, keratin, and prion proteins that are largely generated by the meat industry and ultimately converted to industrial wastes. We analyzed the ability of the abnormal prion protein-degrading enzyme E77 to degrade insoluble and hard-to-degrade animal proteins including keratin, collagen, and elastin. The results indicate that E77 has a much higher keratinolytic activity than proteinase K and subtilisin. Maximal E77 keratinolytic activity was observed at pH 12.0 and 65 °C. E77 was also adsorbed by keratin in a pH-independent manner. E77 showed lower collagenolytic and elastinolytic specificities than proteinase K and subtilisin. Moreover, E77 treatment did not damage collagens in ovine small intestines but did almost completely remove the muscles. We consider that E77 has the potential ability for application in the processing of animal feedstuffs and sausages.     

Synthesis of chiral 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine and their application to enantioselective borane reduction of prochiral ketones as chiral catalysts

Chiral diamines, 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine, were prepared from N-(tert-butoxycarbonyl)pyrrolidine or (S)-proline as a starting material, respectively. These chiral diamines were efficient for the catalytic enantioselective borane reduction of acetophenone. Using (S)-2-(anilinodiphenylmethyl)pyrrolidine, chiral secondary alcohols were obtained from prochiral ketones with good to excellent enantiomeric excesses (up to 98% ee).     

Bleaching effect of a 405-nm diode laser irradiation used with titanium dioxide and 3.5% hydrogen peroxide

A 405-nm diode laser has recently been developed for soft tissue problems in dentistry. A new in-office bleaching agent consisting of a titanium dioxide photocatalyst and 3.5% hydrogen peroxide has proven to react well with light irradiated at a wavelength of around 400 nm. In this study, we evaluated the bleaching efficacy of a newly developed 405-nm diode laser on bovine teeth treated with a bleaching agent composed of titanium dioxide and 3.5% hydrogen peroxide. Sixteen bovine incisors were randomly divided into two groups: Group A, irradiated by the 405-nm diode laser at 200 mW; Group B, irradiated by the 405-nm diode laser at 400 mW. The bleaching agent with titanium dioxide and 3.5% hydrogen peroxide was applied to bovine enamel and irradiated for 1 min. The specimens were then washed and dried, and the same procedure was repeated nine more times. After irradiation, we assessed the effects of bleaching on the enamel by measuring the color of the specimens with a spectrophotometer and examining the enamel surfaces with a scanning electron microscope. L* rose to a high score, reaching a significantly higher post-treatment level in comparison to pretreatment. In a comparison of the color difference (ΔE) between Group A and Group B, the specimens in Group B showed significantly higher values after 10 min of irradiation for the post-treatment. No remarkable differences in the enamel surface morphology were found between the unbleached and bleached enamel. The use of a 405-nm diode laser in combination with a bleaching agent of titanium dioxide and 3.5% hydrogen peroxide may be an effective method for bleaching teeth without the risk of tooth damage.     

Inhibition of Thiol-Mediated Uptake with Irreversible Covalent Inhibitors

Thiol-mediated uptake is emerging as method of choice to penetrate cells. This study focuses on irreversible covalent inhibitors of thiol-mediated uptake. High-content high-throughput screening of the so far largest collection of hypervalent iodine reagents affords inhibitors that are more than 250 times more active than Ellman’s reagent and rival the best dynamic covalent inhibitors. Comparison with other irreversible reagents reveals that inhibition within one series follows reactivity, whereas inhibition across series deviates from reactivity. These trends support that molecular recognition, besides dynamic covalent exchange, contributes significantly to thiol-mediated uptake. The most powerful inhibitors besides the best hypervalent iodine reagents were Fukuyama’s nosyl protecting group and super-cinnamaldehydes that have been introduced as irreversible activators of the pain receptor TRPA1. Considering that several viruses use different forms of thiol-mediated uptake to enter cells, the identification of new irreversible inhibitors of thiol-mediated uptake is of general interest for the discovery of new antivirals.     

Anion–π and Cation–π Interactions on the Same Surface

Herein, we address the question whether anion–π and cation–π interactions can take place simultaneously on the same aromatic surface. Covalently positioned carboxylate–guanidinium pairs on the surface of 4‐amino‐1,8‐naphthalimides are used as an example to explore push–pull chromophores as privileged platforms for such “ion pair–π” interactions. In antiparallel orientation with respect to the push–pull dipole, a bathochromic effect is observed. A red shift of 41 nm found in the least polar solvent is in good agreement with the 70 nm expected from theoretical calculations of ground and excited states. Decreasing shifts with solvent polarity, protonation, aggregation, and parallel carboxylate–guanidinium pairs imply that the intramolecular Stark effect from antiparallel ion pair–π interactions exceeds solvatochromic effects by far. Theoretical studies indicate that carboxylate–guanidinium pairs can also interact with the surfaces of π‐acidic naphthalenediimides and π‐basic pyrenes.