Modification of polycondensation of isophthalic and terephthalic acids and bisphenols with tosyl chloride/dimethylformamide/pyridine by the presence of additives

In copolycondensation with 2,2‐bis(4‐hydroxyphenyl)propane (BPP) and bisphenols (BPs) containing various alkylidene linkages, the associative interactions between BP moieties in the resulting oligomers most likely affected the reaction. To modify the interactions to favorably control the reaction, several additives were examined in a two‐stage polycondensation of an equimolar mixture of isophthalic acid and terephthalic acid, first with BPP (50 mol %) and next with additional BPP. Of additives used, diphenylmethane of an equivalent to BPP in the preformed oligomers was most effective. The results are discussed in terms of the distributions of resulting oligomers prepared at 70% extent of reaction. Better results were obtained when the distributions showed profiles similar to the theoretical one calculated on the basis that the reactivity of the oligomers is the same independent of their chain lengths. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 970–975, 2003     

Shape‐Memory Platinum(II) Complexes: Intelligent Vapor‐History Sensor with ON–OFF Switching Function

A novel platinum(II)–diimine complex, [Pt(CN)₂(H₂dcphen)] ( 1 ; H₂dcphen=4,7‐dicarboxy‐1,10‐ phenanthroline), was synthesized and its vapochromic shape‐memory behavior was evaluated. The as‐synthesized amorphous purple solid, [Pt(CN)₂(H₂dcphen)]?2 H₂O ( 1 P ), exhibited vapochromic behavior in the presence of alcoholic vapors through transformation to a red, crystalline, porous, vapor‐adsorbed form, 1 R?vapor . The obtained 1 R?vapor complex released the adsorbed vapors upon heating without collapse of the porous structure. The vaporfree, porous 1 R?open could detect water or n‐hexane vapor, although these vapors could not induce 1 P ‐to‐ 1 R?vapor transformation, and 1 R?open could easily be converted to the initial 1 P by manual grinding. These results indicate that 1 is a new shape‐memory material that functions through formation and collapse of the porous framework with an emission change upon vapor‐adsorption and grinding; this enables it to exhibit vapor history and ON–OFF switching sensing functions.     

Synthesis of cyclo‐olefin copolymer latexes and their carbon nanotube composite nanoparticles

An efficient and environmentally benign synthetic method for the production of the stabilized cyclo‐olefin copolymer latexes and their carbon nanotube composite nanoparticles has been developed using an emulsion ring opening metathesis copolymerization catalyzed by the 2nd generation Grubbs catalyst in aqueous solution. Homopolymerizations of norbornene (NB) and dicyclopentadiene (DCPD) in aqueous solution yield unstable polymer latexes in combination with a large amount of their flocculation fractions. Copolymerizations of NB or DCPD with a selected liquid cyclo‐olefin comonomer dramatically improve not only the colloidal stability of the copolymer latexes but also the thermal stability of the copolymer nanoparticles. The liquid cyclo‐olefin comonomer plays a double role as a liquefied agent for the solid NB and DCPD monomers before the emulsification treatment, and a reactive comonomer itself to control entirely the copolymerization system. The as‐prepared cyclo‐olefin copolymer latexes exhibit an exceptionally high compatibility with a well‐dispersed carbon nanotube (CNT) in aqueous solution due to strong π–π interactions between the graphitic surfaces of the CNT with the C‐C double bonds located on the cyclo‐olefin copolymer main chains. Accordingly, a binary blending of these two well‐dispersed colloidal systems in aqueous solution led to the fabrication, for the first time, of the highly electrical conductive cyclo‐olefin copolymer/CNT composite nanoparticles. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4584–4591     

Finite‐field method with unbiased polarizable continuum model for evaluation of the second hyperpolarizability of an open‐shell singlet molecule in solvents

The static second hyperpolarizability γ of the complexes composed of open‐shell singlet 1,3‐dipole molecule involving a boron atom and a water molecule in aqueous phase are investigated by the finite‐field (FF) method combined with a standard polarized continuum model (PCM) and with a newly proposed unbiased PCM (UBPCM). On the basis of the comparison with the results calculated by the FF method using the full quantum and the quantum‐mechanical/molecular‐mechanical and molecular‐dynamics (QM/MM‐MD) treatments, the present FF‐UBPCM method is demonstrated to remedy the artificial overestimation of the γ caused by standard FF‐PCM calculations and to well reproduce the FF‐QM/MM‐MD and FF‐full‐QM results with much lower costs. © 2013 Wiley Periodicals, Inc.     

Selective Ablation of β‐Galactosidase‐Expressing Cells with a Rationally Designed Activatable Photosensitizer

We have developed an activatable photosensitizer capable of specifically inducing the death of β‐galactosidase‐expressing cells in response to photoirradiation. By using a selenium‐substituted rhodol scaffold bearing β‐galactoside as a targeting substituent, we designed and synthesized HMDESeR‐βGal, which has a non‐phototoxic spirocyclic structure owing to the presence of the galactoside moiety. However, β‐galactosidase efficiently converted HMDESeR‐βGal into phototoxic HMDESeR, which exists predominantly in the open xanthene form. This structural change resulted in drastic recovery of visible‐wavelength absorption and the ability to generate singlet oxygen (¹O₂). When HMDESeR‐βGal was applied to larval Drosophila melanogaster wing disks, which express β‐galactosidase only in the posterior region, photoirradiation induced cell death in the β‐galactosidase‐expressing region with high specificity.     

Antiviral activities of glycyrrhizin and its modified compounds against human immunodeficiency virus type 1 (HIV-1) and herpes simplex virus type 1 (HSV-1) in vitro.

Chemically modified compounds of glycyrrhizin have been synthesized and evaluated for their inhibitory effect on the replication of human immunodeficiency virus type 1 (HIV-1) and herpes simplex virus type 1 (HSV-1). Among them, the 11-deoxo compound having a heteroannular diene structure at the C and D rings proved as active against HIV-1 as glycyrrhizin in MT-4 and MOLT-4 cells. It completely inhibited HIV-1-induced cytopathogenicity in both cell lines at a concentration of 0.16 mM. The compound was also effective against HSV-1 with a 50% inhibitory concentration of 0.5 mM [corrected].     

Origin of the color of π‐conjugated columnar polymers: Poly(p‐n‐octylthiophenyl)acetylene prepared using a [Rh(norbornadiene)Cl]2 catalyst

Highly stereospecific polymerization of a novel sulfur containing aromatic acetylenes, that is, (p‐n‐octylthiophenyl)acetylene (pOctSPA), was successfully performed using the Rh complex, [Rh(norbornadiene)Cl]₂‐TEA, catalyst in the presence of various solvents under mild conditions. The resulting polymers were characterized in detail by ¹H NMR, ESR, laser Raman, diffuse reflective UV‐Vis (DRUV‐Vis), and wide angle X‐ray diffraction methods. The data showed that the resulting polymers bear cis‐transoid form, which can induce the cis‐to‐trans isomerization when the cis polymers are subjected to pressure at room temperature under vacuum, breaking rotationally the cis C?C bonds in the main‐chain giving two kinds of π‐radicals, the so‐called cis radical and trans radical as the origin of a polymer magnet like a novel spin glass material. Further, the resulting cis poly(acetylene)s were found to have a helical main‐chain, which is packed in pseudohexagonal crystal called π‐conjugated columnar or nano π‐conjugated columnar as a novel color controllable material. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2836–2850, 2005     

Design and synthesis of highly sensitive fluorogenic substrates for glutathione S-transferase and application for activity imaging in living cells

Here we report the development of fluorogenic substrates for glutathione S-transferase (GST), a multigene-family enzyme mainly involved in detoxification of endogenous and exogenous compounds, including drug metabolism. GST is often overexpressed in a variety of malignancies and is involved in the development of resistance to various anticancer drugs. Despite the medical significance of this enzyme, no practical fluorogenic substrates for fluorescence imaging of GST activity or for high-throughput screening of GST inhibitors are yet available. So, we set out to develop new fluorogenic substrates for GST. In preliminary studies, we found that 3,4-dinitrobenzanilide (NNBA) is a specific substrate for GST and established the mechanisms of its glutathionylation and denitration. Using these results as a basis for off/on control of fluorescence, we designed and synthesized new fluorogenic substrates, DNAFs, and a cell membrane-permeable variant, DNAT-Me. These fluorogenic substrates provide a dramatic fluorescence increase upon GST-catalyzed glutathionylation and have excellent kinetic parameters for the present purpose. We were able to detect nuclear localization of GSH/GST activity in HuCCT1 cell lines with the use of DNAT-Me. These results indicate that the newly developed fluorogenic substrates should be useful not only for high-throughput GST-inhibitor screening but also for studies on the mechanisms of drug resistance in cancer cells.     

Systemically Injectable Enzyme‐Loaded Polyion Complex Vesicles as In Vivo Nanoreactors Functioning in Tumors

The design and construction of nanoreactors are important for biomedical applications of enzymes, but lipid‐ and polymeric‐vesicle‐based nanoreactors have some practical limitations. We have succeeded in preparing enzyme‐loaded polyion complex vesicles (PICsomes) through a facile protein‐loading method. The preservation of enzyme activity was confirmed even after cross‐linking of the PICsomes. The cross‐linked β‐galactosidase‐loaded PICsomes (β‐gal@PICsomes) selectively accumulated in the tumor tissue of mice. Moreover, a model prodrug, HMDER‐βGal, was successfully converted into a highly fluorescent product, HMDER, at the tumor site, even 4 days after administration of the β‐gal@PICsomes. Intravital confocal microscopy showed continuous production of HMDER and its distribution throughout the tumor tissues. Thus, enzyme‐loaded PICsomes are useful for prodrug activation at the tumor site and could be a versatile platform for enzyme delivery in enzyme prodrug therapy.     

Colloidal crystallization of colloidal silica modified with ferrocenyl group-contained polymers in organic solvents

Surface modification of colloidal silica with ferrocenyl-grafted polymer and colloidal crystallization of the particles in organic solvent were studied. Poly(methyl methacrylate-co-vinylferrocene)-grafted silica never formed colloidal crystals in polar solvent, such as acetone, acetonitrile, ethanol and N,N-dimethylformamide (DMF), while poly(methyl methacrylate-co-ferrocenyl acrylate)-grafted silica gave colloidal crystallization in DMF. The particles prepared by grafting of poly(N,N-dimethylacrylamide-co-vinylferrocene), with vinylferrocene (Vfc) mole fraction of 1/13 and 1/23, were observed to give the crystallization in ethanol and DMF over particle volume fraction of 0.058. Further, silica modified with copolymer of Vfc and N-vinyl-2-pyrrolidone, N-vinylcarbazole or N-isopropylacrylamide formed colloidal crystals in ethanol and DMF. Especially, poly(N-isopropylacrylamide-co-Vfc)-grafted silica, which was composed of the highest mole fraction of vinylferrocene, 1/3, afforded colloidal crystallization in ethanol over particle volume fraction of 0.053. Relatively high polar vinylferrocene copolymer grafting of silica resulted in colloidal polymerization in organic solvents.