Design of chemical shift-switching 19F magnetic resonance imaging probe for specific detection of human monoamine oxidase A

Monoamine oxidase (MAO) A is a flavoenzyme that catalyzes the oxidation of biologically important monoamines and is thought to be associated with psychiatric disorders. Here, we report a strategy for rationally designing a (19)F magnetic resonance imaging probe for the specific detection of human MAO-A (hMAO-A) activity. Our designed (19)F probe was oxidized expeditiously by hMAO-A to produce 2-fluoro-4-nitrophenol via a spontaneous β-elimination mechanism. Concomitant with the structural change of the probe to the product, the (19)F chemical shift changed by 4.2 ppm, which was enough to visualize the probe and enzymatic product separately. Importantly, our probe achieved excellent discrimination of hMAO-A from its isoform hMAO-B.     

Stereoselective synthesis of benzyl-protected β-galactosides by propionitrile-mediated glycosylation

β-Selective galactosylation was studied using a series of 2-O-benzylated phenyl 1-thio-galactosides and glycosyl acceptors in propionitrile with BSP-TTBP-Tf₂O. The glycosylation enabled us to synthesize useful precursors of N-acetyllactosamine and core 1 O-glycoserine derivatives in a highly convergent manner.     

Adaptive Ion-Gel: Stimuli-Responsive,and Self-Healing Ion Gels

Ion gels are an emerging class of polymer gels in which a three-dimensional polymer network swells with an ionic liquid. Ion gels have drawn considerable attention in various fields such as energy and biotechnology owing to their excellent properties including nonvolatility, nonflammability, high ionic conductivity, and high thermal and electrochemical stability. Since the first report on ion gels (published ∼30 years ago), diverse functional ion gels exhibiting impressive physicochemical properties have been reported. In this review, recent developments in functional ion gels that can modulate their physical properties in response to environmental conditions are outlined. Stimuli-responsive ion gels that can adaptively undergo phase transitions in response to thermal and light stimuli are initially discussed, followed by an evaluation of diverse self-healing ion gels that can spontaneously mend mechanical damage through judiciously designed ion-gel networks.     

Synthesis of biantennary LacNAc-linked O-glycan (core 4) and glycopeptide thioester by benzyl protection strategy: rapid zinc reduction of GlcNTCA to GlcNAc by microwave irradiation

A synthetic method for the core 4 O-glycan-linked Ser and Thr was developed. Highly stereoselective 3-O- and 6-O-glycosylation was achieved by using two distinctively protected N-trichloroacetyllactosaminyl fluorides (3 and 12). Microwave-assisted Zn reduction rapidly and efficiently converted N-trichloroacetylglucosamine (GlcNTCA) to N-acetylglucosamine (GlcNAc). In order to demonstrate the usefulness of the protected core 4 O-glycan a segment (Gly³⁴-Gly⁵⁸) of emmprin (extracellular matrix metalloproteinase inducer), a cancer metastasis-related glycoprotein, was synthesized by the solid-phase method, utilizing the pentasaccharyl Thr (2) to introduce an O-glycan in place of the native N-glycan at Asn⁴⁴.     

Compact composition operators acting between weighted Bergman spaces of the unit ball

In this paper, we study a composition operator ${C_{\varphi}}$ on the weighted Bergman space ${A_{\alpha}^p(B)}$ of the unit ball B in ${{\mathbb{C}}^N}$ . Under a natural condition we estimate the essential norm of ${C_{\varphi}}$ . As a consequence of this estimate, we also give a function-theoretic characterization of ${\varphi}$ that induces a compact composition operator on ${A_{\alpha}^p(B)}$ .     

Self-organization of low-symmetry adjacent-type metallophthalocyanines having branched alkyl chains

Low-symmetry, adjacent-type metallophthalocyanines 1 and 2 with four branched alkyl chains on one side and a chiral bridging segment on the other were synthesized, and their self-organization properties were investigated. The synthesized adjacent-type phthalocyanines were liquid-crystalline and exhibited a phase transition from the crystalline phase to the mesophase below room temperature. X-ray diffraction indicated that the molecules are stacked in one-dimensional columnar aggregates with a hexagonal arrangement. The self-organization behavior of zinc complex 1 and cobalt complex 2 was also investigated with a monolayer experiment at the air-water interface. The adjacent-type phthalocyanines formed a stable monolayer at the air-water interface, and the monolayers could be transferred onto quartz substrates by a Y-type deposition. UV-vis, XRD, and CD measurements for the resulting Langmuir-Blodgett films indicated that 1 and 2 had different molecular orientations.     

(1)H NMR probe for in situ monitoring of dopamine metabolism and its application to inhibitor screening

Dopamine (DA) is a monoamine neurotransmitter that plays important roles in the brain, and whose levels in the brain are associated with several neurological and psychiatric disorders. Therefore, DA metabolism inhibitors have been used as therapeutic agents. Here, we report a (1)H NMR probe for the in situ analysis of DA metabolism, and its application to DA inhibitor screening. We designed doubly (13)C-labeled DA ((13)C(2)-DA) as the probe. The combination of the (13)C(2)-DA and (1)H-{(13)C-(13)C'} NMR technique allowed the selective and thus in situ monitoring of DA metabolism. Using (13)C(2)-DA, we successfully measured the efficacies of different inhibitors in a tissue sample, allowing us to improve the in situ inhibitory efficacy of the known DA metabolism inhibitor, clorgyline.     

Unlocking of interlocked heteropolymer gel by light: photoinduced volume phase transition in an ionic liquid from a metastable state to an equilibrium phase

An azobenzene-containing heteropolymer gel in an ionic liquid exhibits thermally reversible volume phase transition when the azobenzene moiety mainly exists in the cis-state, whereas the transition becomes irreversible when it is in the trans-state and an interlocked collapsed state is stabilized; however, the unlocking of the metastable state occurs by UV light irradiation.