研究題目 肩書 氏名first Name, Family Name

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OONR1R1SR2O2NH2NH2R2O2NH2NH2HNR1OR1aR2R1R1NR1N4 RN 3RR2FlRNR2aONR3SR2OO2 Zn, HcR4OR1bOO2ᶁᶐᵿᶁᶉᴾNH2NH2H HR1R1R3R2SO2vitamin CR2O2N 3R2NHR2NH2R1SaaR2R1R1OOR3R1R4R2Figure 1. Aerobic oxidation reactions using cationic flavin catalystsOR1HR 2SR1 R2SHORONR22O1HhQReHO2, hQHONR2 R2SR2R1O eR2NR1R1NdFlNONOR2R1H HR2HROcO2NH2NH2SO2, hQR3O2SR1 R2 NH2NH2R1eOHR1R3R2R4Content:Organocatalysts have recently received considerableattention as a third group of catalyst in organic synthesisin addition to the conventional biocatalysts and metalcatalysts. To meet the social demand to effectively andsafely produce pharmaceuticals and functional materialson a large scale, it is highly desirable to design anddevelop organocatalysts with superior characteristics,including enhanced catalytic activities, handling ease,and stereochemical controllability.We have developed environmentally friendly aerobicmolecular transformations using cationic flavin moleculesas organocatalysts (Figure 1). Typically, oxygenation ofamines and sulfides (a) and Baeyer-Villiger oxidation ofketones (b) can be carried out with molecular oxygen,and olefins can be readily hydrogenated upon treatmentwith hydrazine hydrate and air (c) using flavin catalysis.We also developed molecular transformation usingreadily available and safe neutral flavin molecules asorganocatalysts (Figure 2). Typically, oxygenation ofsulfides can be performed using neutral flavin catalystsbearing tripeptide (d), and neutral flavin molecules lly benign substitutes for conventionaltransition-metal-based photoredox catalysts (e).R3R4Figure 2. Molecular transformations using neutral flavin catalystsKeywords䠖organocatalyst, aerobic oxidation, polymerphotoredox catalystE-mail: [email protected] 81-88-656-7407Fax: 81-88-656-7407HP: http://www.chem.tokushima-u.ac.jp/a3/

㻌Fig. 1 Molecular weightdependence of chemicalcomposition in an ethylenepropylene copolymer.Fig. 2 Principal componentscore plots showingchemical composition andmonomer sequencedistribution in methacrylatecopolymers.Content:Recent research and development of industrial orfunctional polymers increasingly require precise analysisand control of their molecular parameters (molecularweight, comonomer sequence, stereoregularity, etc.) .The aims of my study are to develop useful methodsof polymer characterization by modern NMR (nuclearmagnetic resonance) and chromatographic techniques,and to synthesize new polymer materials on the basis ofthe characterization.For example, DOSY (diffusion-ordered NMR spectroscopy) is a powerful technique to measure the molecularweight dependence of chemical composition incopolymers (Fig. 1).Multivariate analysis of the NMR spectra ofcopolymers is another example of my approaches toprecise and quantitative characterization of syntheticpolymers (Fig. 2). The use of this multivariate approachrevealed he mechanism of polymer reactions .)ofmethacrylate copolymers (Fig. 2).Keywords䠖 polymer synthesis, NMR,chromatography, copolymersFig. 3 Monomer sequence distributions in methacrylatecopolymers prepared by polymer reactions.E-mail: [email protected] 81-88-656-7402Fax: 81-88-656-7404HP: http://poly.chem.tokushima-u.ac.jp/㢦 䠄 ྍ䠅

Infrared Synchrotron Radiation9 102 103 times brighter than conventional IR source.9 Can be focused to a 10 Pm diameter spot withoutan aperture (in the molecular vibration range).ÆIR microscopy can be easily performed with a veryhigh spatial resolution.ἅὅἑἁἚɧᑣᴾComparison between SPring-8 and conventional IR source. Background 9 Infrared synchrotron radiation is much brighter thanthe conventional, black body radiation-based infraredsources. This brightness is utilized to perform infraredstudies with high spatial resolution, such as microspectroscopy, high pressure studies using a diamondanvil cell (DAC), etc. Present research activities 9 Infrared studies of various materials under highpressure, using DAC and the infrared synchrotronradiation at SPring-8.9 Materials of main interest are the so-called ‘stronglycorrelated electron systems’, where strong electronelectron interaction results in interesting phenomenasuch as metal-insulator transition, heavy quasiparticleformation, superconductivity, etc.9 Development of super-spatial resolution IR microscopyusing SPring-8 and near-field optics.Keywords: Infrared spectroscopy, synchrotron radiation,high pressure, diamond anvil cell.E-mail: [email protected] 088-656-9444Fax:A high pressure IR study of YbS using SPring-8.HP : http://www.chem.tokushima-u.ac.jp/B2/

One-way photoisomerization andpreparation of anti-tumor reagentContent:㻌 We wish to develop chemical transformations of organicmolecules upon irradiation of electromagnetic waves.Various electromagnetic waves can be used, e.g.,ultraviolet, visible, infrared, and microwave. Based on thesource of electromagnetic waves, it is so far known thatunique molecular transformation and acceleration of thereactions have already been realized.LEDs are key technology of Tokushima Prefecture andthey are using as light sources in variety of fields. Bycontrast, LED light is a green and highly-efficient energysource. Thus, the ongoing research aims to produceuseful compounds and functional materials by LEDirradiation. This research would enable the traditionallydifficult chemical transformations and synthesis offunctionalized materials to make easier just by exposingmolecules to electromagnetic waves. Light (photons) isrecognized to be “a reagent with no volume”. Also in linewith the product study, by examining the reactionintermediates produced during the chemical reactionsupon irradiation of light and microwave, useful andcompetent chemical transformation processes will becreated rationally.Synthesis of functionalized polycarbonKeywords䠖Electromagnetic wave, photochemicalreactions, reaction intermediateSyntheses of flavonoid and isoflavonoidDNA cleavage by photoirradiationᶁᶐᵿᶁᶉᴾDesign of an active oxygen liberating moleculesE-mail: [email protected] 81-88-656-7401Fax: 81-88-655-7025

WasteContaining PNew PResourceProductContaining PᶁᶐᵿᶁᶉᴾResource CirculationMap forPhosphorus(a) Circulation of phosphorus resourceLNG to Ethylene Direct Employment of LNGfor Petrochemical PlantsRaw material forethylene plant from LNGLPG to Various Chemicals Development of SubstitutedResources for PetroleumProduction of rawmaterial fo MMA fromLPG(b) Various chemicals from LNG and LPGContent:㻌 Phosphorus is an essential element for plant growthand has no substitute in food production. Furthermore, itis used in various advanced materials. Phosphate rockas a raw material of phosphorus is finite and nonrenewable. Therefore, the development of new rawmaterials for the rock is an urgent issue in Japan. In ourgroup, search of new resource for the rock together withthe development of the easy and economical recoverymethod of phosphorus from the resource is in progress.㻌 As another topics, to prepare for the drying up ofpetroleum, the conversions of main products in liquefiednatural gas (LNG) and liquefied petroleum gas (LPG) tovarious chemicals on solid catalysts are studied. Basedon our earlier studies on the oxidative coupling ofmethane (LNG) on solid catalysts, the oxidation of C3and C4-hydrocarbons (main components in LPG) are inprogress. Recently, we have found out that oxidativedehydrogenation of isobutane (from LPG) onmesoporous silicas favorably produces isobutene, whichis a raw material for methyl methacrylate (MMA); one ofthe most possible monomers obtained from petroleum.Keywords䠖rare resources, solid catalystsE-mail: [email protected] 81-88-656-7432Fax: 81-88-656-7432 HP :http://www.chem.tokushima-u.ac.jp/C3/

(a) Molecular recognition with affinity (b) ChromatogramFig. 1 Separation improvement by affinity interactionFig. 2 Partition selectivity of ionic species towardnonionic surfactant micelleContent:㻌 Nano-sized molecular assemblies of surfactant micelles,vesicles, microemulsions, and polymer gels possesshydrophobic environment. Specific surface area of themolecular assemblies is greatly larger than that of bulkwater-organic solvent interface. Extraction-separationwith the characteristic hydrophobic environment of themolecular assemblies works in pseudo-homogeneousaqueous solution. Liquid-liquid extraction is done in cal shaking of the two phases, with fastextraction kinetics, as well as with the selectivity towardsionic substances.Functional Molecular Assemblyincluding micelles, microemulsions, and hydrophobicmatrices are to be developed.㻌 Based on equilibria and kinetics in aqueous solution,development of affinity reagents, analysis of affinityinteractions, and investigation of selectivity expressionfactors are studied.Keywords䠖Surfactant micelle, microemulsion,hydrophobic partition, aquatic solvent,analytical separationE-mail: [email protected] 81-88-656-7409Fax: 81-88-656-7409HP : http://www.chem.tokushima-u.ac.jp/B1/index.html

ᶁ ᶐ ᵿ ᶁᶉᶁᶐᵿᶁᶉᴾFigs. 1 Color tuning in LaTiO2N via control of anion andcation stoichiometries㻌 We have demonstrated that a color of the perovskitetype LaTiO2N oxynitride could be tuned from orangethrough yellow and green to pale gray or white by properadjustment of the O/N ratio. (Moriga et al., phys. stat. sol.(a), 203, 2818 (2006)), whereas increasing Ti/La ratiodeteriorates the reflectivity after the absorption edge(Moriga et al., J. Ceram. Soc. Jpn., 115, 637 (2007) ).We are now trying to make a redder or bluer oxynitridepowders by partial substitution of the constituent cations,and by controlling of the cation and/or anionstoichiometries as well.Oxynitride phosphors are recently spotlighted as yellowor red phosphors for white LEDs because oxynitrideshave no toxicity, blue light are available for excitationsource and oxynitrides possess low thermal quenchingbehavior, compared with oxide phosphors. We havefound that Ba3Si6O12N2:Eu-type phosphors showedconsiderable redshift in emission wavelengths from520nm for the Sr-free oxynitride up to 550nm for 50%substituted oxynitride by Sr, with increasing Sr content(Sarda, Moriga et al., J. Nano Res., 36, 1 (2016)).Keywords䠖oxynitrides, eco-friendly pigment/phosphors,E-mail: [email protected] 81-88-656-7423Fax: 81-88-655-7025Figs. 2 Redshift of emission for Ba3Si6O12N2:Eu-typephosphors by substitution of Ba by Sr.

Minimally invasive type glucose sensorSensing region (enzyme immobilized film)is located at a tip of a fine tapered trodegluconolactoneEnzym e (GOx)EnzymeimmobilizedregionimmobiGOx: glucose oxidaseOnly the most tip of a fine needle (less than 1.0 mmin length) must be inserted in the skin.MinimallyMinimally iinvasivenvasive ttypeype ssensorensorDermisSubcutaneous tissueDermis glucosemeasurementSubcutaneous tissueglucose measurement㻌 Diabetes is a leading cause of morbidity and mortality and a majorhealth problem around the world. It is well known that keeping goodcontrol of the blood glucose degree can prevent the onset andprogression of serious diabetes complications. Therefore, it isimportant to accurately recognize the blood glucose degree andprovide appropriate treatments. Daily self-monitoring of bloodglucose (SMBG) is the essential procedure for blood glucose levelrecognition. However, it may require stressful action even aftermidnight and the observed value is a point without direction.Recently, implantable glucose sensors for continuous glucosemonitoring system (CGMS) for diabetes patients have beendeveloped and is now available on the market. They can provide usefulinformation to predict the upcoming situation such as hyperglycemia andhypoglycaemia. However, they require the device to be inserted about1 cm in length inside the skin. Therefore, the development of lowerinvasive CGMS is expected for the improvement of diabetic patients“quality of life (QOL)”. We have recently developed a low invasivetype glucose sensor, which has a sensing region at the tip of a finepointed electrode. A clear sensor response correlative with the trendof blood glucose was obtained using a devise inserted in skin nomore than 1 mm in length.Keywords㸸Electrochemistry, biosensor, continuous glucosemonitoring system, biocompatible material, eco-friendly waterpurificationE-mail: [email protected] placementConventional sensorContent:Minimally invasive type sensorTel. 088-656-7410Fax: 088-655-7025“Inserting”“Sticking”

ᶁᶐᵿᶁᶉᴾIR integrated intensity / cm䞉g-1Fig. 1 Volumetric apparatus for measurement of adsorption& desorption velocity of water on adsorbents.2000050䉝30䉝15000Content:The utilization of waste heat for the regeneration ofdesiccant material in a desiccant dehumidifier system isone of the best alternatives because regeneration cost iseliminated. However, it is only suitable for equipmentwhich can exhaust waste heat at temperature 60 Υ and140 Υ . Usually, these types of equipment are onlyavailable in factories or supermarkets.We develop estimation method of water adsorbents(desiccant materials) and propose two kinds ofestimation methods for water adsorption.(1) Estimation of adsorption and desorption velocity ofwater on adsorbents by volumetric apparatus (Fig .1).(2) Estimation of temperature behavior of adsorbed wateron adsorbents by IR spectroscopy.In particular, temperature dependence (Fig. 2) ofadsorbed water on desiccant can be gotten easily byusing special IR cell (Fig. 3). The profile wascorresponding to the equilibrium adsorption 0250Temperature / 䉝Fig. 2 Temperature dependence of IRintegrated intensity of adsorbed H2O at10 Torr on NaY zeolite, 䕿: 1st, 䖃: 2nd.Fig. 3 special IR cell.Keywords䠖water adsorbent, adsorption velocity,IR spectroscopyE-mail: [email protected] 81-88-656-7429Fax: 81-88-656-7429HP : http://www.chem.tokushima-u.ac.jp/C3/

Content:ᶁᶐᵿᶁᶉᴾA. Colloidal crystallization under external fields: Colloidalcrystals are hoping materials for optical circuits and opticalcomputer in the future. We have successfully fabricatedbulky grains ( 6.1 mm3) of a close-packed polystyrenecolloidal crystal ((a)) by centrifugation. We have alsosucceeded in controlling nucleation of the crystals usingan optical trapping method (b).B. In situ observation of molecular steps on protein crystalsurfaces and novel crystallization techniques without anyprecipitants: Fundamental studies and developments ofnovel techniques of protein crystallization are importantfor obtaining high quality crystals, which are prerequisitesof genomic drug discovery. We are now studying kineticbahaviors of molecular steps on the surface of a glucoseisomerase crystal ((a)). We have also succeeded infabricating high quality lysozyme crystals without usingany precipitants ((b)) for the first time.C. Precise growth mechanisms of protein crystals undermicrogravity: Microgravity is known to be a goodenvironment for obtaining high quality protein crystals.Now we are preparing for near future space experimentsusing parabolic flight opportunities ((a) and (b)).Keywords䠖Crystal Growth, Protein, Colloid, MicrogravityE-mail: [email protected] 81-88-656-7415Fax: 81-88-655-7025HP : 㼦㼡㼗㼕㻟㻛㻌

㻾㼑㼜㼞㼑㼟㼑㼚㼠㼍㼠㼕㼢㼑 㼟㼠㼑㼞㼑㼛㼞㼑㼓㼡㼘㼍㼞 ᵿᶁᶉHeterotactic㻼㼔㼍㼟㼑 㼠㼞㼍㼚㼟㼕㼠㼕㼛㼚 㼎㼑㼔㼍㼢㼕㼛㼞 㼛㼒 㼍㼝㼡㼑㼛㼡㼟 㼜㼛㼘㼥㼙㼑㼞㼟㻚Content:㻻㼡㼞 main research interest is “synthesis of stereoregularpolymers, which exhibit thermoresponsibility in aqueoussolutions”. The stereospecificity of the radical Ͳisopropylacrylamide (NIPAAm) and NͲnͲpropylacrylamide(NNPAAm), has been successfully controlled by utilizingcomplex formation of monomers through hydrogen bondings.㻵㼚 㼍㼐㼐㼕㼠㼕㼛㼚㻘 㼠㼔㼑 㼑㼒㼒㼑㼏㼠 㼛㼒 㼟㼠㼑㼞㼑㼛㼞㼑㼓㼡㼘㼍㼞㼕㼠㼥 㼠㼍㼏㼠㼕㼏 㼍㼚㼐 㼔㼑㼠㼑㼞㼛㼠㼍㼏㼠㼕㼏㻕 㼛㼚 㼠㼔㼑 㻸㻯㻿㼀 㻔㼘㼛㼣㼑㼞 㼏㼞㼕㼠㼕㼏㼍㼘㼟㼛㼘㼡㼠㼕㼛㼚 㼜㼔㼍㼟㼑 㼠㼞㼍㼚㼟㼕㼠㼕㼛㼚 㼔㼍㼟 㻵㼠 㼔㼍㼟 㼎㼑㼑㼚 㼞㼑㼢㼑㼍㼘㼑㼐 㼠㼔㼍㼠 㼐㼕㼍㼐 㼠㼍㼏㼠㼕㼏㼕㼠㼥 㼜㼘㼍㼥㼟㼍㼚 㼕㼙㼜㼛㼞㼠㼍㼚㼠 㼞㼛㼘㼑 㼠㼛 㼐㼑㼠㼑㼞㼙㼕㼚㼑 㼠㼔㼑 㼜㼔㼍㼟㼑 㼠㼡㼞㼑 㼕㼚 㼠㼔㼑 㼔㼑㼍㼠㼕㼚㼓 㼜㼞㼛㼏㼑㼟㼟㻘 㼣㼔㼑㼞㼑㼍㼟 㼝㼡㼑㼚㼏㼑㼟 㼘㼛㼚㼓㼑㼞 㼠㼔㼍㼚 㼠㼞㼕㼍㼐 㼐㼛 㼕㼚 㼠㼔㼑 㼏㼛㼛㼘㼕㼚㼓 㼜㼞㼛㼏㼑㼟㼟㻚㻭 㼒㼕㼚㼍㼘 㼓㼛㼍㼘 㼛㼒 㼛㼡㼞 㼞㼑㼟㼑㼍㼞㼏㼔 㼕㼟 㼐㼑㼢㼑㼘㼛㼜㼙㼑㼚㼠 㼛㼒 㼚㼛㼢㼑㼘㼒㼡㼚㼏㼠㼕㼛㼚㼍㼘 㼜㼛㼘㼥㼙㼑㼞㼕㼏 㼙㼍㼠㼑㼞㼕㼍㼘 㼎㼥 㼏㼛㼚㼠㼞㼛㼘㼘㼕㼚㼓 㼠㼔㼑 㼛㼒 㼟㼥㼚㼠㼔㼑㼠㼕㼏 㼜㼛㼘㼥㼙㼑㼞㼟㻚Keywords䠖radical polymerization, stereoregularity, LCSTE-mail: [email protected]㼀㼑㼘㻚 㻜㻤㻤㻙㻢㻡㻢㻙㻣㻠㻜㻟㻲㼍㼤㻦 㻜㻤㻤㻙㻢㻡㻢㻙㻣㻠㻜㻠㻴㻼 㻦

ἅὅἑἁἚɧᑣ䖃NonͲporous graphite䖃Highly ordered mesoporous carbonContent:Adsorption phenomena is applied many separationtechnologies, e.g. gas separation, environmentalpurification. When you use those technologies, you needto choose a suitable adsorbent from many types ofadsorbents. If you could choose right one from those,you can save energy, time and cost. Therefore, it is veryimportant to choose an optimized adsorbent.However, sometimes there are no suitable or optimizedadsorbents for the process, so we might need to developan optimized adsorbent. When you develop a newmaterial, you must understand what kind properties youwant for the process according to the adsorptionphenomena. I can help you to develop the materialusing my adsorption knowledge.E-mailC-2 lab HP EDBKeywords䠖 gas adsorptioncarbon materialsadsorption mechanismE-mail: [email protected] 81-88-656-7426Fax: 81-88-656-7426HP : http://www.chem.tokushima-u.ac.jp/C2/

Fig.1.㻌 Diagram for dilatometry of ὅᵿἑἁᶁᶁᶉᶉ ἚɧἅὅἑἁἚɧᑣᴾἅἑἁFig. 2. Electricconductivities of La1xCaxCoO3(x 0.00, 0.05, 0.10, 0.15)500Υ400ΥContent:㻌The research work is developments of advancedinorganic materials such as negative thermal expansionmaterials (Fig. 1) or thermoelectric materials (Fig.2)made of oxides which is low in price, harmless andstable from physical and chemical viewpoint. X-raydiffraction (XRD) techniques are also used in materialscharacterization in our lab (Fig. 3). Crystal structure ofmaterials has a close connection with its properties.Negative thermal expansion oxide have a range ofpotential engineering, photonic, electronic, and structuralapplications. If a negative thermal expansion material ismixed with a "normal" material which expands on heating,it could be possible to make a zero expansion compositematerial.Today, some alloys are in practical use asthermoelectric materials. However, Perovskite-typematerials are more stable in high temperature region. Inour lab., it was found that some cation-doping oxides hadhigher values than non-doped materials in thermoelectricproperties.Crystal structures of materials above mentioned areinvestigated by XRD and Rietvelt analysis.300Υ200ΥFig. 3. Variation of in-situ XRD patterns forZr2(WO4)(PO4)2 at the given temperatures.㻌Keywords䠖Advanced Materials, CrystallographyE-mail: [email protected] 81-88-656-7424Fax: 81-88-655-7025

C-Disubstituted Nitronates as a㻌 Synthetic Equivalent ofFunctionalized Nitrile OxidesFG C N OR1O N OFGHOO N OR2ActivationRegio-, StereoselectiveC-DisubstitutedNitronateC N OFGHOC N OXOFunctionalizedNitrile OxideFG R1XOXOR2Bicyclic IsoxazolidineᶁᶐᵿᶁᶉᴾRegioselective FragmentationN OR2FGOHO NN OR2R2HOOXR1R1R1OXIntroduction of Various Substituents to 3-position of 2-IsooxazolineI research on the development of the selective andeffective synthetic method of the heterocycle compoundthat the application to biologically active substance(medicine, agricultural chemicals, etc.) is expected.Mainly, about the synthetic method of the hetero fivemembered rings compounds containing nitrogen, oxygenusing 1,3-dipolar cycloaddition reactions :1) Activation of 1,3-DC reaction by catalyst2) Development of regio- and stereoselective reaction3) Synthesis of biologically active substanceI have accomplished the following matters so far:1) Development of high-rate acceleration and regioand stereocontrol of nitrile oxide cycloadditions byLewis acid.2) Development of C-disubstituted nitronates as asynthetic equivalent of functionalized nitrile oxides.3) Formal synthesis of dysibetaine and synthesis ofcore structure of lopinavir (HIV-prtease inhibitor).Application to Biologically Active Me3NH2DMP-450DysibetaineKeywords䠖biologically active substance, stereoselective,regioselective, catalytic reactionE-mail: [email protected] 81-88-656-7400Fax: 81-88-655-7025HP :

1 Pm1 PmPt layerFig.1㻌 SEM images of track-etched microporous membrane electrode. Surface of the electrode (left), and.cross sectional view ECEFig.2㻌 Structure of the proposed flow cellDetectorReference (Ag/AgCl)CounterContent:㻌 We recently reported an electrochemical flow cell inwhich the track-etched microporous membraneelectrodes had been mounted. The electrode wasprepared by sputter deposition of platinum or gold on thetrack-etched microporous membrane filters. The coatingswere produced on the smooth flat surface and entranceof the cylindrical pores. Sample solution flows throughthe membrane filter while performing electrolysis. In thiscase, the sample solution flows through the cylindricalpores of the electrodes (Fig.1). The electrode enablesefficient electrolysis in a flow condition. This propertywould be attributed to the limitation of growth of thediffusion layer at the entrances of pores. Variousanalytical systems can be built merely by piling up thetrack-etched microporous membrane electrodes whichhave a 10 Pm thickness (see Fig.3). Although trolysis, the simplicity and flexibility of arrangementof electrodes as well as high efficiency of electrolysis isthe greatest feature of the track-etched microporousmembrane electrodes.Pre-reactor4 mmI2 㼖㼜㻌10 mmPTFE tubePFA cerImmobilized enzyme reactorFig.3㻌 Amperometric enzyme 㻛㼕㼚㼐㼑㼤㻚㼔㼠㼙㼘㻌

ᅗ ᶁᶐᵿᶁᶉᴾFig. 1. 5-HMF yield in the cellobiose decompositionin DMSO/water mixture solvent.Fig. 2. Time course of the reactant and product ofthe decomoposition of cellobiose determined byusing 13C in situ NMR monitoring.Content:㻌 Biomass-derived poly-saccharides have attractedattentions as the novel renewable sources. Recently wesucceeded in the production of 5-hydroxymethyl-2furaldehyde (5-HMF) from cellobiose, the modeldisaccharide for cellulose (H. Kimura et al., J. Phys.Chem. A, 117, 10987 (2013); Fig. 1). 5-HMF is a centerof focus today as a biomass-derived valuable that can beconverted into biofuels, fine chemicals, and polymers.In the decomposition reaction steps of saccharides, avariety of isomers, tautomers, and precursors aregenerated as intermediate products. Solution NMRspectroscopy is a powerful method to monitor all of thosespecies involved in the reactions. By using 13C NMR,each of the individual species can be distinguished fromeach other. The positions of the glucose units in theoligomers can be specified. The in situ NMR methodallows us to determine the time course of the productand reactant species. As shown in Fig. 2, reliable dataare obtained with a single setup of the in-situ experiment.The best conditions for the target species can bedetermined on the basis of the reaction kinetics.Keywords䠖saccharides, in situ NMR, 5-HMFE-mail: [email protected] 81-88-656-7669Fax: 81-88-655-7025HP : http://www.chem.tokushima-u.ac.jp/B2/

OHOOHONNONHNO1 RiboflavinᶁᶐᵿᶁᶉᴾR4High catalytic acitivity in reduction of olefins R1Reusable more than 10 timesR2nontoxic byproductsNH2NH21/R3R2 O21H HR2R4H 2OR3N2Fig. 1. Reduction of olefins catalyzed by polymer-supported flavin (1)R3NR2Previous methodR15NO3NNOur methodR4safe, easy, inexpensiveN(5)-EthylationN(5)-CationizationNaNO2 (toxic)O2 (air)cation exchange resinAnion ExchangeNaClO4 (explosive)R3NR2crosslinked alization ClO4107Oinert atmospherehazardous reagentsA8NContent:㻌 Although organic synthetic chemistry has greatlycontributed to the development of human society byoffering synthetic methods of various useful substancessuch as pharmaceuticals and plastics, its technologicallevel has to be further evolved for realizing a sustainable,recycling-based society.We have been developing new organic syntheticmethods utilizing polymers. For example, polymersupported flavin (1) as an effective and reusable catalystfor reduction of olefins has been developed (Fig. 1). Thismethod is so clean and practical because of using metalfree organocatalyst and producing nontoxic wastes,whereas similar reactions generally require expensivemetal catalysts. On one hand, a safe, easy, andinexpensive method for preparing flavinium catalysts (2)without using any hazardous reagents as well as inertconditions that were previously required has beendeveloped (Fig. 2), in which ion-exchange resins wereutilized for extracting flavinium ions. This method willboost practical applications of 2 that are known to beeffective organocatalysts for useful oxidation reactions.R4O2Fig. 2. Facile preparation of flavinium organocatalysts (2) SO3Keywords䠖Polymer-supported catalyst, Environmentallybenign synthesis, OrganocatalystE-mail: [email protected] 81-88-656-9704Fax: 81-88-656-7407HP : http://www.chem.tokushima-u.ac.jp/A3/

Fig. 1 CHP that combines two reactors and a distillationcolumn with energy savingsqcRn 561.23 kWPR 161 kP a1RRR 0.53qcS n 312.78 kW2PA10 kmol/hr1PS 101 kP a4RRS 2.6810.04 kmol/hrMA 99.50%DMC 0.50%40.23 kmol/hrMA 25.22%DMC 74.78%11DMC5.06 kmol/hr74NS 2577NR 80exQ2 ,2 5 296 kW5.01 kmol/hr Qr b 778.58kWRPA 0.10%DMC 0.40%DP C 99.50%30.18 kmol/hrMA 0.50%DMC 99.50%Fig. 2. Heat-integrated reactive distillation systemContent:The increase the overall performance of sustainablechemical processes it is necessary to considertheoretical and experimental evaluations.Fig 1. shows a chemical heat pump (CHP) system inwhich waste heat is reused from external and internalsources. Thus, waste heat can be supplied steadily tothe process. In addition, the distillation column is dividedin two sections. The high-pressure column supplied heatto the low-pressure column, thus energy savings arepossible.Fig. 2 shows a heat-integrated reactive distillation system(HIRDS). By using reactive distillation, reaction andseparation can take place simultaneously in one device.By using heat integration, the use of external energysources can be reduced, thus the process attains energysavings. In comparison with the conventional reactivedistillation system, the HIRDS can attain energy savingsaround 25% and economic savings around 12%.Keywords䠖Process/Chemical engineeringE-mail: [email protected] 81-88-656-7425Fax: 81-88-656-7425

ᶁᶐᵿᶁᶁᶉᶁᶐᵿᶁᶉᴾContent:㻌 Graft copolymers are prepared by monomer andpolymerizable group end-functinaliced polymer, namelymacromonomer. Polymerization of carboxyl endfuctionalized vinyl monomers used as macromonomersgave graft copolymers having carboxyl group at the sidechain easily. The carboxyl functionalized graftcopolymers are used for high-functional materials suchas resist material, cross-linking agent, or thermosettingcoating. Especially, carboxyl end-fuctionalized aliphaticpolyesters-type vinyl monomers (Vinyl-Polyester-COOH)are important in the field. New synthesis method withoutusing halide or acid anhydride are required from theperspective of green chemistry.㻌 So, carboxyl end-functionalized aliphatic polyesterswere prepared by ring-opening polymerization of cyclicesters and tranesterification between methacrylates andthe aliphatic polyesters obtained in the presence of tertbutylzincate.Keywords 䠖 high-functional materials,polymerE-mail: [email protected]: 81-88-656-7404Fax: 81-88-656-7404HP : http://poly.chem.tokushima-u.ac.jp/biodegradable

Absorbance㻵㻚㻌Syntheses of Nanosheets of Layeredered Metal HydHydroxides㻌㻌㻌Delamination㻌Layered hydroxideNanosheet㻌5th cycle0.15㻌3rd cycle㻌0.11st cycleᶁᶐᵿᶁᶉᴾ 0.05㻌05 ȝm10㻌052002503003.4 nm㻌 nmWavelength / nm㻌 00Fig. 2 UV absorption5 ȝm10spectra of restacking of㻌Fig. 1 AFM image of cobaltnickel hydroxide㻌 hydroxide nanosheetsnanosheets㻌II. Control of Interlayer ions in Layered Metal Hydroxidesm-m-mAmH2mO AH2O A H2OBm Bm-Bm-m-Bm-- H2O BmmH2O B H2O䞉 Adsorption of polyoxomolybdateand borate䞉 Control of elution of phosphateFig. 3 Growing tests of Japanesemustard spinach using a Mg/Fe-typelayered double hydroxideContent:㻌 The layered metal hydroxide is a layered compoundconsisted of repeating stacking of nano-meter-sizedmetal hydroxides. This compound is mainly synthesizedby addition of base into the metal solution.Inorganic nanosheets have been prepared bydelamination of layered materials. Nanosheet has anultimate two-dimensional anisotropy and manifestsunique physical properties arising from size effects. Wehave synthesized nickel and cobalt hydroxidesnanosheets (Fig. 1) and assembled these nanosheetsby stacking on the glass slide to make new lamellastructure(Fig. 2).Layered double hydroxide is a layered compound thatcontains divalent and trivalent metal ions. It consist ofhydroxide layer and interlayer anion, and the interlayeranion is captured and able to exchange. We use thisproperty for adsorption and controlled-release of anions.Adsorption of polyoxomolybdate and borate control ofelution of phosphate have been investigated and try toapply it to fertilizer(Fig. 3).Am Am-Am-Keywords䠖layered compound, metal hydroxide,nanosheet, ion exchangeE-mail: [email protected] 81-88-656-7418Fax: 81-88-655-7025

Imidazo[1,5-a]pyridineDimeric structureᶁᶐᵿᶁᶉᴾ ᑣἅὅἑἁἚ