A Bioinspired Synthesis of (±)‐Rubrobramide, (±)‐Flavipucine,and (±)‐Isoflavipucine

A biomimetic synthesis of naturally occurring lactams rubrobramide, flavipucine, and isoflavipucine is described. The key step is a regioselective Darzens reaction between isobutyl glyoxal and an α‐bromo‐β‐ketoamide. The construction of the core tricyclic ring system of rubrobramide was achieved by a cascade reaction in a single step from an α,β‐epoxy‐γ‐lactam. Furthermore, the absolute configuration of naturally occurring (+)‐rubrobramide was determined by vibrational circular dichroism. (±)‐Flavipucine and (±)‐isoflavipucine were synthesized from an epoxyimide, which was prepared by reaction of isobutyl glyoxal with a protected α‐bromo‐β‐ketoamide. Deprotection of the epoxyimide and formation of the pyridone ring gave (±)‐flavipucine, which was converted into (±)‐isoflavipucine by thermal isomerization.     

Synthesis of dicarboxylate oligosaccharide multilayer terminal functionality upon poly(lysine) dendrimer scaffolding

A reactive three‐layered dendrimer containing carboxyl groups was synthesized by the coupling of dicarboxylic acid and a highly reactive, two‐layered glycopeptide dendrimer. Lactose, maltose, or maltotriose was reacted with the poly(lysine) dendrimer in its third and fourth generations by reductive amination and afforded two‐layered glycolysine dendrimers. The reaction was conducted in a borate buffer (pH 9.0). ¹H NMR, ¹³C NMR, and matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry analyses were applied for the determination of the structures of the products. When an excess amount of the oligosaccharide and a long reaction time were used, the degree of substitution increased to 1.5–2.0 against an amino group. For the preparation of highly reactive, multilayered dendrimers for an antigen carrier, C6 hydroxy groups of the oligosaccharides were selectively esterified by adipic acid and suberic acid to give 6‐O‐adipoyl oligosaccharide–poly(lysine) dendrimers and 6‐O‐suberoyl oligosaccharide–poly(lysine) dendrimers. The reactivity of these multilayered dendrimers was examined by a model reaction with phenylalanine ethyl ester. The dendrimer showed high reactivity, providing phenylalanine ethyl ester–dicarboxylate oligosaccharide–poly(lysine) dendrimers with a considerably high proportion of phenylalanine residues. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3622–3633, 2002     

Synthesis of 5,10,15-triazaporphyrins--effect of benzo-annulation on the electronic structures

Novel triazaporphyrins were synthesized using 1,9-dibromodipyrromethene as a key starting material. These triazaporphyrins exhibit comparatively intense Soret and Q bands in the UV/vis region due to their hybrid properties between porphyrins and phthalocyanines.     

Direct meso-alkynylation of porphyrins doubly assisted by pyridyl coordination

Direct meso-alkynylation of β,β'-dipyridylporphyrin with various alkynyllithium reagents has been achieved, in which the β,β'-dipyridyl groups play an important role in facilitating the nucleophilic addition of the reagents through double coordination. This method enabled the synthesis of a meso-ethynylene-bridged diporphyrin.     

Optical second-harmonic generation in a thin-film waveguide without control of film thickness

An optical second-harmonic wave can be generated in a three-layered optical waveguide of arbitrary film thickness under phase-matching condition. Phase-matching is achieved by utilizing mode dispersion in an optical waveguide with a two-dimensional configuration. A numerical analysis of the matching condition is given and the results of the observation of the optical second-harmonic wave of a guided Nd : YAG laser in a Ti-indiffused LiNbO₃ nonlinear film are described.     

Periphery-Fused Chiral A2B-Type Subporphyrin

Despite significant interest, the chiroptical properties of subporphyrins have rarely been investigated because chiral subporphyrins are elusive. Here, inherently chiral subporphyrins are elaborated by forming a fused pyran ring at the periphery of an A₂B-type meso-aryl-substituted subporphyrin. Their circular dichroism (CD) properties are largely affected by the peripheral substituents and the dihedral angles between the meso-aryl substituents and the subporphyrin core: the β-perbromo subporphyrin with an orthogonal arrangement of the meso-phenyl substituents to the subporphyrin core exhibits weak CD signals corresponding to the Q bands, whereas the unsubstituted species with smaller dihedral angles shows relatively intense CD signals. A detailed structure–property relationship of these chiral subporphyrins was elucidated by time-dependent (TD) DFT calculations. This study reveals that the CD properties of chiral subporphyrins can be controlled by peripheral substitution and meso-aryl substituents.     

Detection of mismatched DNA on partially negatively charged diamond surfaces by optical and potentiometric methods

The effects of surface charge density on DNA hybridization have been investigated on a mixture of hydrogen-, oxygen-, and amine-terminated diamond surfaces. A difference in the hybridization efficiencies of complementary and mismatched DNA was clearly observed by fluorescence and potentiometric observations at a particular coverage of oxygen. In the fluorescence observation, singly mismatched DNA was detected with high contrast after appropriate hybridization on the surface with 10-20% oxygen coverage. The amount of oxygen in the form of C-O(-) (deprotonated C-OH) producing the surface negative-charge density was estimated by X-ray photoelectron spectroscopy. Electrolyte solution gate field-effect transistors (SGFETs) were used for potentiometric observations. The signal difference (change in gate potential) on the SGFET, which was as large as approximately 20 mV, was caused by the difference in the hybridization efficiencies of complementary target DNA (cDNA) and singly mismatched (1MM) target DNA with a common probe DNA immobilized on the same SGFET. The reversible change in gate potential caused by the hybridization and denaturation cycles and discriminating between the complementary and 1MM DNA targets was very stable throughout the cyclical detections. Moreover, the ratio of signals caused by hybridization of the cDNA and 1MM DNA targets with the probe DNA immobilized on the SGFET was determined to be 3:1 when hybridization had occurred (after 15 min on SGFET), as determined by real-time measurements. From the viewpoint of hybridization kinetics, the rate constant for hybridization of singly mismatched DNA was a factor of approximately 3 smaller than that of cDNA on this functionalized (oxidized and aminated) diamond surface.     

AtTrxh3, a Thioredoxin,Is Identified as an Abscisic AcidBinding Protein in Arabidopsis thaliana

Abscisic acid (ABA, 1) is a plant hormone that regulates various plant physiological processes such as seed developing and stress responses. The ABA signaling system has been elucidated; binding of ABA with PYL proteins triggers ABA signaling. We have previously reported a new method to isolate a protein targeted with a bioactive small molecule using a biotin linker with alkyne and amino groups, a protein cross-linker, and a bioactive small molecule with an azido group (azido probe). This method was used to identify the unknown ABA binding protein of Arabidopsis thaliana. As a result, AtTrxh3, a thioredoxin, was isolated as an ABA binding protein. Our developed method can be applied to the identification of binding proteins of bioactive compounds.