Preparation of 9-hydroxy grayanotoxin derivatives and their acute toxicity in mice

Novel 9alpha and 9beta-hydroxy grayanotoxin II derivatives were prepared by photo-sensitized oxygenation of iso-grayanotoxin II and oxidation of grayanotoxin II tetraacetate with selenium dioxide respectively. The lethal dosage of 9alpha and 9beta-hydroxy grayanotoxin II were lower than that of grayanotoxin II. In addition, the lethal dosage of 9beta-hydroxy-dihydro grayanotoxin II was higher than that of dihydro grayanotoxin II.     

Preparation and characterization of hyaluronate-hydroxyethyl acrylate blend hydrogel for controlled release device

Hyaluronate-hydroxyethyl acrylate blend hydrogels were investigated as matrices for controlled release devices. Glycidyl methacrylate (GMA) derivatized HA (GMA-HA) was synthesized by coupling of GMA to HA in the presence of a suitable catalyst. These hydrogels were prepared by a free radical copolymerization of GMA-HA and hydroxyethyl acrylate. The water content of these hydrogels at equilibrium swelling in water (Ww) was 0.978+/-0.0073 (n=18); however, these hydrogel was mechanically tough and could be used as disk shape. The hydrogels swelling were found to depend on ionic strength and pH. The dried hydrogels quickly regained their original condition in water, and they swelled to more than 90% of its initial water contents after 30 min. This swelling-deswelling behavior was reproducible. The release of chlorpromazine HCl as a model cationic drug from the gels was suppressed significantly in water. The release increased with increasing the ionic strength and decreasing pH of bulk solutions.     

Synthesis of a capillarisin sulfur-analogue possessing aldose reductase inhibitory activity by selective isopropylation

We describe the synthesis of 2-[(4-hydroxyphenyl)thio]-7-isopropoxy-5,6-dimethoxy-4H-chromen-4-one 2 from 3,4,5-trimethoxyphenol 6 via the key intermediate, 3-iodo-7-isopropoxy-5,6-dimethoxy-4H-chromen-4-one 3. An important feature of this synthetic scheme involves selective alkylation, which can be achieved by two different routes. One route involves the selective isopropylation of a triacetate derivative 4 under basic conditions. The second route employs the selective demethylation of a trimethoxy derivative 5 under acidic conditions followed by isopropylation. The product of these alternative routes, compound 3, is then converted to a capillarisin sulfur analogue 2 in a one-pot reaction via the imidazolyl intermediate 22.     

Side-chain liquid crystalline homo- and copolymethacrylates with a carbonate linkage between the benzylideneaniline mesogen and ethylene chain

Abstract

New liquid crystalline (LC) homo- and copolymethacrylates having a carbonate linkage between a benzylideneaniline mesogen and ethylene chain in the side chain were prepared by free radical polymerization of methacrylate derivatives comprising 4-cyano- and/or 4-methoxybenzylide-neaniline units using AIBN as an initiator. The structures of the polymers were characterized by FTIR, ¹HNMR, and elemental analyses. The LC properties were evaluated by differential scanning calorimetry (DSC), polarizing microscopic observation of textures and X-ray diffraction. These measurements showed that all the homo- and copolymers form nematic phases. The isotropization temperatures on composition exhibited a negative deviation from a linear relationship between them predicted by the Schroeder-Van Laar equation. This phenomenon might be caused mainly by an unusual geometry arising from a smaller bond angle in the carbonate linkage.     

Highly parity linked graphs

A graph G is k-linked if G has at least 2k vertices, and for any 2k vertices x ₁,x ₂, …, x _k ,y ₁,y ₂, …, y _k , G contains k pairwise disjoint paths P ₁, …, P _k such that P _i joins x _i and y _i for i = 1,2, …, k. We say that G is parity-k-linked if G is k-linked and, in addition, the paths P ₁, …, P _k can be chosen such that the parities of their length are prescribed. Thomassen [22] was the first to prove the existence of a function f(k) such that every f(k)-connected graph is parity-k-linked if the deletion of any 4k-3 vertices leaves a nonbipartite graph. In this paper, we will show that the above statement is still valid for 50k-connected graphs. This is the first result that connectivity which is a linear function of k guarantees the Erdős-Pósa type result for parity-k-linked graphs. Research partly supported by the Japan Society for the Promotion of Science for Young Scientists, by Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research and by Inoue Research Award for Young Scientists.     

Highly emissive organic solids containing 2,5-diboryl-1,4-phenylene unit

We disclosed a series of pi-conjugated systems containing 2,5-bis(dimesitylboryl)-1,4-phenylene as the core unit and electron-donating amino groups at the terminal positions. The extension of the ppi-pi* conjugation in the diborylphenylene moiety along the short axis of the pi-conjugated framework as well as the incorporation of two bulky dimesitylboryl groups at the para-positions makes this moiety act as a unique bulky pi-electron-accepting unit. As a consequence, these systems behave like donor-acceptor-donor quadrupolar pi-electron systems and show a large solvatochromism in the fluorescence spectra. Moreover, these organoboron pi systems exhibit intense fluorescence even in the solid state with the quantum yields of 0.73-0.90.     

Utilization of the pleiotropy of a peptidic aptamer to fabricate heterogeneous nanodot-containing multilayer nanostructures

Peptide aptamers (=binders) against inorganic materials often show a capacity for mineralization of their target atoms; thus they are able to function both as binding molecules and as mediators for mineralization. Although the mechanisms underlying these two properties of peptide aptamers are not yet fully understood, they have been used separately to fabricate various nanostructures. Here, we present a novel method of nanofabrication, in which binding and mineralization by a peptide aptamer are alternately utilized to assemble multilayered nanostructures comprised of metal loaded cage proteins ornamented with Ti-binding peptides.     

From an S(T) = 3 single-molecule magnet to diamagnetic ground state depending on the molecular packing of Mn(III)salen-type dimers decorated by N,N'-dicyano-1,4-naphthoquinonediiminate radicals

Two manganese(III) tetradentate Schiff-base dimers to which N,N'-dicyano-1,4-naphthoquinonediiminate (DCNNQI) radicals are attached have been selectively synthesized by varying the solvents used in the reactions: [Mn2(5-MeOsaltmen)2(DCNNQI)2].MeOH (1) and [Mn2(5-MeOsaltmen)(2)(DCNNQI)(2)] x 2CH2Cl2.2CH3CN (2) [5-MeOsaltmen2- = N,N'-(1,1,2,2-tetramethylethylene)bis(5-methoxysalicylideneiminate)]. These two complexes share the same molecular core, [(DCNNQI.-)-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)], where -(O)2- is a biphenolate bridge in the out-of-plane dimerized [Mn(2)(5-MeOsaltmen)2]2+ moiety. However, their packing arrangements are completely different. Whereas complex 1 is found to be relatively isolated, strong intermolecular dimerization of the DCNNQI moieties (with the nearest contact being approximately 3.0 A) is observed in 2, forming a one-dimensional chain of [-Mn(III)-(O)2-Mn(III)-(DCNNQI.-)2-](infinity). The magnetic susceptibility of 1 can be modeled with an [S = 1/2, 2, 2, 1/2] four-spin system including strong antiferromagnetic Mn(III)/DCNNQI radical coupling (J(Mn/rad)/kB = -23 K) and ferromagnetic Mn(III)/Mn(III) coupling through the biphenolate bridge (J(Mn/Mn)/kB = +2.0 K). These interactions lead to an ST = 3 ground state that possesses significant uniaxial anisotropy (D(S=3)/kB = -2.1 K). Low-temperature ac and dc magnetic data of 1 reveal its single-molecule magnet behavior with quantum tunneling of the magnetization. By contrast, 2 possesses the diamagnetic ground state induced by dominating Mn(III)-Mn(III) antiferromagnetic interactions mediated by the diamagnetic DCNNQI dimers and/or pi-pi contact along the b axis.