Kyoto Institute of Technology

Poly(ethylene terephthalate) (PET) is used extensively worldwide in plastic products, and its accumulation in the environment has become a global concern. Because the ability to enzymatically degrade PET has been thought to be limited to a few fungal species, biodegradation is not yet a viable remediation or recycling strategy. By screening natural microbial communities exposed to PET in the environment, we isolated a novel bacterium, Ideonella sakaiensis 201-F6, that is able to use PET as its major energy and carbon source. When grown on PET, this strain produces two enzymes capable of hydrolyzing PET and the reaction intermediate, mono(2-hydroxyethyl) terephthalic acid. Both enzymes are required to enzymatically convert PET efficiently into its two environmentally benign monomers, terephthalic acid and ethylene glycol.

autophagic responses. Here, we critically discuss current methods of assessing autophagy and the information they can, or cannot, provide. Our ultimate goal is to encourage intellectual and technical innovation in the field.

A new kind of localized mode is proposed to occur in a pure anharmonic lattice. Its localization properties are similar to those of a localized mode for a force-constant defect in a harmonic lattice. These modes, which are thermally generated like vacancies but with much smaller activation energies, may appear at cryogenic temperatures in strongly anharmonic solids such as quantum crystals as well as in conventional solids.

Continuous porous silica rods consisting of a mesoporous (pore size, 14 or 25 nm) silica skeleton of ∼1 μm size and through-pores of ∼1.7 μm were prepared and derivatized to C(18) phase by on-column reaction with octadecyldimethyl-(N,N-diethylamino)silane. The C(18) silica rods gave plate heights of 10-20 μm for aromatic hydrocarbons in 80% methanol and 20-40 μm for insulin in acetonitrile-water mixtures in the presence of trifluoroacetic acid. The performance of the silica rods was much better at a high flow rate than that of conventional columns packed with 5 μm C(18) silica particles having 12 and 30 nm pores, especially for high molecular weight species.

A π-conjugated nanosheet comprising planar nickel bis(dithiolene) complexes was synthesized by a bottom-up method. A liquid-liquid interfacial reaction using benzenehexathiol in the organic phase and nickel(II) acetate in the aqueous phase produced a semiconducting bulk material with a thickness of several micrometers. Powder X-ray diffraction analysis revealed that the crystalline portion of the bulk material comprised a staggered stack of nanosheets. A single-layer nanosheet was successfully realized using a gas-liquid interfacial reaction. Atomic force microscopy and scanning tunneling microscopy confirmed that the π-conjugated nanosheet was single-layered. Modulation of the oxidation state of the nanosheet was possible using chemical redox reactions.

ADVERTISEMENT RETURN TO ISSUEPREVArticleUltrafast Dynamics of Photochromic SystemsNaoto Tamai and Hiroshi MiyasakaView Author Information Department of Chemistry, Faculty of Science, Kwansei Gakuin University, Uegahara, Nishinomiya, Hyogo 660-8581, Japan, Department of Polymer Science and Engineering, Kyoto Institute of Technology, and CREST, Japan Science and Technology Corporation, Matsugasaki, Sakyo, Kyoto 606-8585, Japan Cite this: Chem. Rev. 2000, 100, 5, 1875–1890Publication Date (Web):March 7, 2000Publication History Received6 July 1999Published online7 March 2000Published inissue 1 May 2000https://pubs.acs.org/doi/10.1021/cr9800816https://doi.org/10.1021/cr9800816research-articleACS PublicationsCopyright © 2000 American Chemical SocietyRequest reuse permissionsArticle Views9442Altmetric-Citations757LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Absorption,Fluorescence,Isomerization,Lasers,Light absorption Get e-Alerts

Wurtzite InN films were grown on a thick GaN layer by metalorganic vapor phase epitaxy. Growth of a (0001)-oriented single crystalline layer was confirmed by Raman scattering, x-ray diffraction, and reflection high energy electron diffraction. We observed at room temperature strong photoluminescence (PL) at 0.76 eV as well as a clear absorption edge at 0.7–1.0 eV. In contrast, no PL was observed, even by high power excitation, at ∼1.9 eV, which had been reported as the band gap in absorption experiments on polycrystalline films. Careful inspection strongly suggests that a wurtzite InN single crystal has a true bandgap of 0.7–1.0 eV, and the discrepancy could be attributed to the difference in crystallinity.

A Coulomb crystal was successfully formed as a result of the growth of spherical and monodisperse carbon particles suspended in a methane plasma. The crystal structure was confirmed to be hexagonal from top- and side-view photographs. The particle growth was monitored by Mie-scattering ellipsometry and correlated with the formation process of the Coulomb crystal. The liquid-to-solid phase transition occurred when particle diameter grew to 1.3 µm, and when the Wigner-Seitz radius was about 90 µm.

In the last decade, we have seen very rapid and significant developments in Raman scattering experiments on GaN and related nitride compounds: the Γ-point phonon frequencies have been identified for both cubic and hexagonal structures of binary compounds of GaN, AlN, and InN. The phonon spectra of their ternary alloys, InGaN and AlGaN, were also intensively studied. On the basis of these studies, characterizations of strain, compositional fluctuation, defects, impurities, etc, are now being intensively conducted. Besides such pure lattice properties, coupled modes between a lattice vibration (LO phonon) and a collective excitation of free carriers (plasmon) in GaN have been thoroughly studied, and the results are now widely applied to characterize carrier-transport properties. Low-dimensional structures of nitrides such as quantum dots and superlattices will soon enter the most active field of Raman scattering characterization. This article briefly reviews the present status of Raman scattering experiments on GaN and related nitride compounds and presents some future prospects.

Rubisco is a large enzyme with a molecular mass of approximately 550 kD. The maximum rate of CO2 fixation (i.e. ribulose-1,5-bisphosphate [RuBP] carboxylation) at CO2 saturation is only 15 to 30 mol CO2 mol−1 Rubisco protein s−1 at 25°C. Affinity to CO2 is also low, and the K m, K c, at 25°C

Most petroleum-derived plastics, as exemplified by poly(ethylene terephthalate) (PET), are chemically inactive and highly resistant to microbial attack. The accumulation of plastic waste results in environmental pollution and threatens ecosystems, referred to as the “microplastic issue”. Recently, PET hydrolytic enzymes (PHEs) have been identified and we reported PET degradation by a microbial consortium and its bacterial resident, Ideonella sakaiensis. Bioremediation may thus provide an alternative solution to recycling plastic waste. The mechanism of PET degradation into benign monomers by PET hydrolase and mono(2-hydroxyethyl) terephthalic acid (MHET) hydrolase from I. sakaiensis has been elucidated; nevertheless, biodegradation may require additional development for commercialization owing to the low catalytic activity of these enzymes. Here, we introduce PET degrading microorganisms and the enzymes involved, along with the evolution of PHEs to address the issues that hamper microbial and enzymatic PET degradation. Potential applications of PET degradation are also discussed.

ADVERTISEMENT RETURN TO ISSUEPREVReviewNEXTEnzymatic Polymer Synthesis: An Opportunity for Green Polymer ChemistryShiro Kobayashi*†‡ and Akira Makino‡View Author Information R & D Center for Bio-based Materials, Kyoto Institute of Technology, Kyoto 606-8585, Japan and Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto 615-8510, Japan* To whom correspondence should be addressed. Fax/Tel: (+81)-75-724-7688. E-mail: [email protected]†Kyoto Institute of Technology and Emeritus Professor of Kyoto University.‡Kyoto University.Cite this: Chem. Rev. 2009, 109, 11, 5288–5353Publication Date (Web):October 13, 2009Publication History Received24 April 2009Published online13 October 2009Published inissue 11 November 2009https://pubs.acs.org/doi/10.1021/cr900165zhttps://doi.org/10.1021/cr900165zreview-articleACS PublicationsCopyright © 2009 American Chemical SocietyRequest reuse permissionsArticle Views16652Altmetric-Citations534LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail Other access optionsGet e-Alertsclose SUBJECTS:Monomers,Peptides and proteins,Polymerization,Polymers,Ring-opening polymerization Get e-Alerts

Enzymatic hydrolysis of polyethylene terephthalate (PET) has been the subject of extensive previous research that can be grouped into two categories, viz. enzymatic surface modification of polyester fibers and management of PET waste by enzymatic hydrolysis. Different enzymes with rather specific properties are required for these two processes. Enzymatic surface modification is possible with several hydrolases, such as lipases, carboxylesterases, cutinases, and proteases. These enzymes should be designated as PET surface-modifying enzymes and should not degrade the building blocks of PET but should hydrolyze the surface polymer chain so that the intensity of PET is not weakened. Conversely, management of PET waste requires substantial degradation of the building blocks of PET; therefore, only a limited number of cutinases have been recognized as PET hydrolases since the first PET hydrolase was discovered by Müller et al. (Macromol Rapid Commun 26:1400-1405, 2005). Here, we introduce current knowledge on enzymatic degradation of PET with a focus on the key class of enzymes, PET hydrolases, pertaining to the definition of enzymatic requirements for PET hydrolysis, structural analyses of PET hydrolases, and the reaction mechanisms. This review gives a deep insight into the structural basis and dynamics of PET hydrolases based on the recent progress in X-ray crystallography. Based on the knowledge accumulated to date, we discuss the potential for PET hydrolysis applications, such as in designing waste stream management.

Polymer gels have two types of concentration fluctuations; liquidlike and solidlike fluctuations. The former are time-dependent (thermal) fluctuations and the latter are time-independent spatial inhomogeneity. The static structure factor, obtained by small-angle X-ray (SAXS) or neutron scattering (SANS), consists of both contributions. Several methods which allow to decompose the static structure factor into the individual contributions are reviewed. In practice, however, the decomposition is not as easy as that predicted by the theory due to the lack of information about dynamic fluctuations. The dynamic light scattering technique (DLS), on the other hand, provides the complimentary information of the dynamic fluctuations. It will be shown that DLS becomes a powerful tool to distinguish the two contributions if it is coupled with ensemble averaging. In this article, recent developments of the structure investigation of polymer gels, particularly those of environmental sensitive polymer gels, are reviewed from both experimental and theoretical points of view. The advantage to use the environmental sensitive gels is that the structure of a gel can be examined as a function of its environmental parameters, e.g., temperature, concentration, and pH. Furthermore, the characteristic features of these environmental sensitive gels, such as a volume phase transition and phase separation, are extensively discussed in terms of the thermal fluctuations and the spatial inhomogeneity.

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 μm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 μm).

The present article comprehensively reviews the macromolecular synthesis using enzymes as catalysts. Among the six main classes of enzymes, the three classes, oxidoreductases, transferases, and hydrolases, have been employed as catalysts for the in vitro macromolecular synthesis and modification reactions. Appropriate design of reaction including monomer and enzyme catalyst produces macromolecules with precisely controlled structure, similarly as in vivo enzymatic reactions. The reaction controls the product structure with respect to substrate selectivity, chemo-selectivity, regio-selectivity, stereoselectivity, and choro-selectivity. Oxidoreductases catalyze various oxidation polymerizations of aromatic compounds as well as vinyl polymerizations. Transferases are effective catalysts for producing polysaccharide having a variety of structure and polyesters. Hydrolases catalyzing the bond-cleaving of macromolecules in vivo, catalyze the reverse reaction for bond forming in vitro to give various polysaccharides and functionalized polyesters. The enzymatic polymerizations allowed the first in vitro synthesis of natural polysaccharides having complicated structures like cellulose, amylose, xylan, chitin, hyaluronan, and chondroitin. These polymerizations are "green" with several respects; nontoxicity of enzyme, high catalyst efficiency, selective reactions under mild conditions using green solvents and renewable starting materials, and producing minimal byproducts. Thus, the enzymatic polymerization is desirable for the environment and contributes to "green polymer chemistry" for maintaining sustainable society.

A spectroscopic method, which enables characterization of a single isolated quantum dot and a quantum wave function interferometry, is applied to an exciton discrete excited state in an InGaAs quantum dot. Long coherence of zero-dimensional excitonic states made possible the observation of coherent population flopping in a 0D excitonic two-level system in a time-domain interferometric measurement. Corresponding energy splitting is also manifested in an energy-domain measurement.

A variety of octadecylsilylated silica gel phases are prepared under various conditions, and their chromatographic properties are studied in order to carry out chromatographic characterization of commercial C18 packing materials. The test scheme, utilizing several sets of solutes, provides information about hydrophobicity, steric selectivity, and the extent of hydrogen bonding and electrostatic interactions. The results permit the estimation of how the commercial packing materials were prepared.

The subject of this paper, sun leaves are thicker and show higher photosynthetic rates than the shade leaves, is approached in two ways. The first seeks to answer the question: why are sun leaves thicker than shade leaves? To do this, CO2 diffusion within a leaf is examined first. Because affinity of Rubisco for CO2 is low, the carboxylation of ribulose 1,5-bisphosphate is competitively inhibited by O2, and the oxygenation of ribulose 1,5-bisphosphate leads to energy-consuming photorespiration, it is essential for C3 plants to maintain the CO2 concentration in the chloroplast as high as possible. Since the internal conductance for CO2 diffusion from the intercellular space to the chloroplast stroma is finite and relatively small, C3 leaves should have sufficient mesophyll surfaces occupied by chloroplasts to secure the area for CO2 dissolution and transport. This explains why sun leaves are thicker. The second approach is mechanistic or 'how-oriented'. Mechanisms are discussed as to how sun leaves become thicker than shade leaves, in particular, the long-distance signal transduction from mature leaves to leaf primordia inducing the periclinal division of the palisade tissue cells. To increase the mesophyll surface area, the leaf can either be thicker or have smaller cells. Issues of cell size are discussed to understand plasticity in leaf thickness.

Sol-gel processes for fabricating oxides or metalloxane polymers with controlled porous structures have been reviewed. Gel materials having controlled macropores are synthesized by polymerization-induced phase separation and concurrent sol-gel transition in a variety of chemical compositions. Several variations of tailoring mesopore structures within the macroporous materials are introduced, which enable one to design hierarchically porous metal oxide and metalloxane polymer materials. Applications of monolithic silica gels having hierarchical macro/mesoporous structure to the separation media of high-performance liquid chromatography, HPLC, are described.