syntheses of flavonoid and isoflavonoid synthesis of functionalized
TRANSCRIPT
Content:Organocatalysts have recently received considerable
attention 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 canbe used as organophotoredox catalysts asenvironmentally benign substitutes for conventionaltransition-metal-based photoredox catalysts (e).
Keywords organocatalyst, aerobic oxidation, polymer-photoredox catalystE-mail: [email protected]. +81-88-656-7407Fax: +81-88-656-7407HP: http://www.chem.tokushima-u.ac.jp/a3/
N
N
N
NR1
R1
R2
O
O
R3
R4O
R1O2
Zn, H+
OO
R1
NR1 R3
R2
NR1 R3
R2
O
SR1 R2
O
SR1 R2
HN
R1 R2
NR1 R2
O
R2
R1 R3
R4R2
R1 R3
R4
H H
O2NH2NH2
O2NH2NH2
SR1 R2
SR1 R2
O
O2NH2NH2
O2NH2NH2
O2vitamin C
FlR+
Figure 1. Aerobic oxidation reactions using cationic flavin catalysts
a
a
a
a
b
c
N
N
N
NR1
R1
R2
O
O
R3
R2
R1 R3
R4
R2
R1 R3
R4
H H
h
O2NH2NH2
SR1 R2
SR1 R2
OO2
NH2NH2
Fl
Figure 2. Molecular transformations using neutral flavin catalysts
R1 O
H+
R2NR2
O
R1 O
H
ONR22
R1 H
O+ R2SH
R1 H
R2S SR2
O2, h
R OH
O2, h
R O
H
d
e
e
e
c
Content:Recent research and development of industrial or
functional 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 spectro-scopy) is a powerful technique to measure the molecular-weight 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 (catalytichydrogenation, acidic/basic hydrolysis, etc.) ofmethacrylate copolymers (Fig. 2).
Keywords polymer synthesis, NMR,chromatography, copolymers
E-mail: [email protected]. +81-88-656-7402Fax: +81-88-656-7404HP: http://poly.chem.tokushima-u.ac.jp/
Fig. 1 Molecular weight dependence of chemical
composition in an ethylene-propylene copolymer.
Fig. 2 Principal component score plots showing
chemical composition and monomer sequence
distribution in methacrylate copolymers.
Fig. 3 Monomer sequence distributions in methacrylate copolymers prepared by polymer reactions.
<Background>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 micro-spectroscopy, high pressure studies using a diamondanvil cell (DAC), etc.
<Present research activities>Infrared studies of various materials under highpressure, using DAC and the infrared synchrotronradiation at SPring-8.Materials of main interest are the so-called ‘stronglycorrelated electron systems’, where strong electron-electron interaction results in interesting phenomenasuch as metal-insulator transition, heavy quasiparticleformation, superconductivity, etc.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:HP : http://www.chem.tokushima-u.ac.jp/B2/
Infrared Synchrotron Radiation102~103 times brighter than conventional IR source.Can be focused to a 10 m diameter spot withoutan aperture (in the molecular vibration range).IR microscopy can be easily performed with a veryhigh spatial resolution.
Comparison between SPring-8 and conventional IR source.
A high pressure IR study of YbS using SPring-8.
Keywords Electromagnetic wave, photochemical reactions, reaction intermediate E-mail: [email protected]. +81-88-656-7401
Fax: +81-88-655-7025
Syntheses of flavonoid and isoflavonoid
Synthesis of functionalized polycarbon
DNA cleavage by photoirradiation
Design of an active oxygen liberating molecules
One-way photoisomerization and preparation of anti-tumor reagent
Content:We wish to develop chemical transformations of organic
molecules 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 and
they 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.
Content:Phosphorus is an essential element for plant growth
and has no substitute in food production. Furthermore, itis used in various advanced materials. Phosphate rockas a raw material of phosphorus is finite and non-renewable. 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.
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 C3-and 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 rare resources, solid catalystsE-mail: [email protected]. +81-88-656-7432Fax: +81-88-656-7432>HP :http://www.chem.tokushima-u.ac.jp/C3/
New P Resource
Product Containing P
Waste Containing P
Resource Circulation Map for Phosphorus
(a) Circulation of phosphorus resource
(b) Various chemicals from LNG and LPG
LNG to Ethylene= Direct Employment of LNG
for Petrochemical Plants
LPG to Various Chemicals= Development of Substituted
Resources for Petroleum
Raw material for ethylene plant from LNG
Production of raw material fo MMA from
LPG
(a) Molecular recognition with affinity (b) ChromatogramFig. 1 Separation improvement by affinity interaction
Fig. 2 Partition selectivity of ionic species toward nonionic surfactant micelle
Content: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 thepseudo-homogeneous aqueous solution withoutmechanical 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.
Based on equilibria and kinetics in aqueous solution,development of affinity reagents, analysis of affinityinteractions, and investigation of selectivity expressionfactors are studied.
Keywords 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
We have demonstrated that a color of the perovskite-type 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 oxynitrides, eco-friendly pigment/phosphors,E-mail: [email protected]. +81-88-656-7423Fax: +81-88-655-7025
Figs. 1 Color tuning in LaTiO2N via control of anion and cation stoichiometries
Figs. 2 Redshift of emission for Ba3Si6O12N2:Eu-type phosphors by substitution of Ba by Sr.
Keywords Electrochemistry, biosensor, continuous glucose monitoring system, biocompatible material, eco-friendly water purificationE-mail: [email protected]. 088-656-7410Fax: 088-655-7025
Content:Diabetes is a leading cause of morbidity and mortality and a major
health 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 useful information to predict the upcoming situation such as hyperglycemia and hypoglycaemia. 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.
Minimally invasive type glucose sensor
Enzyme (GOx)immobilized region
ei
Enzymimmob
Sensing region (enzyme immobilized film) is located at a tip of a fine tapered needle
Only the most tip of a fine needle (less than 1.0 mm in length) must be inserted in the skin.
H2O2
O2
GOxH2O2
O2
glucose gluconolactone
Elec
trode
Elec
trode
Electrode
“Inserting”
Sensor placement
Dermis
Subcutaneous tissue Subcutaneous tissue glucose measurement
Minimally invasive type sensorMMMMMMMMMMMMMiiiiiiiiiiiiinnnnnnniiiiiiiiiiiiimmmmmmmaaaaaaallllllllllllllllllllllllllyyyyyyy iiiiiiiiiiiiinnnnnnnvvvvvvvaaaaaaasssssssiiiiiiiiiiiiivvvvvvveeeeeee ttttttttttttyyyyyyypppppppeeeeeee ssssssseeeeeeennnnnnnsssssssooooooorrrrrrr
Dermis glucosemeasurement
“Sticking”
Conventional sensor Minimally invasive type sensor
GOx: glucose oxidase
Content: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 and140 . 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 data. Keywords 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/
0
5000
10000
15000
20000
0 50 100 150 200 250Temperature /
IR in
tegr
ated
inte
nsity
/ cm
g-1
200150
100
50
200
30
0
5000
10000
15000
20000
0 50 100 150 200 250Temperature /
IR in
tegr
ated
inte
nsity
/ cm
g-1
200150
100
50
200
30
Fig. 2 Temperature dependence of IR integrated intensity of adsorbed H2O at 10 Torr on NaY zeolite, : 1st, : 2nd.
Fig. 3 special IR cell.
Fig. 1 Volumetric apparatus for measurement of adsorption & desorption velocity of water on adsorbents..
Content: A. Colloidal crystallization under external fields: Colloidal
crystals are hoping materials for optical circuits and optical computer in the future. We have successfully fabricated bulky grains (~ 6.1 mm3) of a close-packed polystyrene colloidal crystal ((a)) by centrifugation. We have also succeeded in controlling nucleation of the crystals using an optical trapping method (b).
B. In situ observation of molecular steps on protein crystal surfaces and novel crystallization techniques without any precipitants: Fundamental studies and developments of novel techniques of protein crystallization are important for obtaining high quality crystals, which are prerequisites of genomic drug discovery. We are now studying kinetic bahaviors of molecular steps on the surface of a glucose isomerase crystal ((a)). We have also succeeded in fabricating high quality lysozyme crystals without using any precipitants ((b)) for the first time.
C. Precise growth mechanisms of protein crystals under microgravity: Microgravity is known to be a good environment for obtaining high quality protein crystals. Now we are preparing for near future space experiments using parabolic flight opportunities ((a) and (b)).
Keywords Crystal Growth, Protein, Colloid, MicrogravityE-mail: [email protected]. +81-88-656-7415Fax: +81-88-655-7025HP :
Content:main research interest is “synthesis of stereoregular
polymers, which exhibit thermoresponsibility in aqueoussolutions”. The stereospecificity of the radical polymerizationsof amide containing monomers, such as Nisopropylacrylamide (NIPAAm) and N n propylacrylamide(NNPAAm), has been successfully controlled by utilizingcomplex formation of monomers through hydrogen bondings.
Keywords radical polymerization, stereoregularity, LCSTE-mail: [email protected]
Isotactic
Syndiotactic
Heterotactic
EDBC-2 lab HPE-mail
Content:Adsorption phenomena is applied many separation
technologies, 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.
Keywords gas adsorptioncarbon materialsadsorption mechanism
E-mail: [email protected]. +81-88-656-7426Fax: +81-88-656-7426HP : http://www.chem.tokushima-u.ac.jp/C2/
Non porous graphite Highly ordered mesoporous carbon
Content:
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.
Keywords Advanced Materials, CrystallographyE-mail: [email protected]. +81-88-656-7424Fax:+81-88-655-7025
Fig.1. Diagram for dilatometry of Zr2(WO4)(PO4)2.
Fig. 2. Electric conductivities of La1-
xCaxCoO3(x = 0.00, 0.05, 0.10, 0.15)
200
400
500
300
Fig. 3. Variation of in-situ XRD patterns for Zr2(WO4)(PO4)2 at the given temperatures.
C-Disubstituted Nitronates as a Synthetic Equivalent ofFunctionalized Nitrile Oxides
Application to Biologically Active Substance
I 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 five-membered 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 substance
I have accomplished the following matters so far:1) Development of high-rate acceleration and regio-
and 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).
Keywords biologically active substance, stereoselective,regioselective, catalytic reaction
E-mail: [email protected]. +81-88-656-7400Fax: +81-88-655-7025HP :
OHN
NH
N
O
OH O
Lopinavir
NH
O NH
O
HO
CO2
NMe3
Dysibetaine
N N
OHHO
O
NH2H2N
DMP-450
CFG N O
C N O
C N O
HO
HOFG
XO
FunctionalizedNitrile Oxide
NO O
FGXO
R2
Bicyclic IsoxazolidineC-DisubstitutedNitronate
NO
R2
OX
OHON
HO R2
OX
ON
FG R2
R1 R1R1
R1NO O
FGXO R1
R2
ActivationRegio-, Stereo-
selective
Regioselective Fragmentation
Introduction of Various Substituents to 3-position of 2-Isooxazoline
Content:We recently reported an electrochemical flow cell in
which 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 m thickness (see Fig.3). Although manyresearchers have investigated for quantitativeelectrolysis, the simplicity and flexibility of arrangementof electrodes as well as high efficiency of electrolysis isthe greatest feature of the track-etched microporousmembrane electrodes.
1 m
Pt layer
1 m
spacercover
Pre-reactor
Detector Counter
4 mm
Reference (Ag/AgCl)
PFA tubePTFE tube
inlet outlet
10 mm
2 mm
Immobilized enzyme reactor
WE CE
Fig.1 SEM images of track-etched microporous mem-brane electrode. Surface of the electrode (left), and.cross sectional view (right).
Fig.2 Structure of the proposed flow cell
Fig.3 Amperometric enzyme biosensor
< > Content:Biomass-derived poly-saccharides have attracted
attentions as the novel renewable sources. Recently wesucceeded in the production of 5-hydroxymethyl-2-furaldehyde (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 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/Fig. 2. Time course of the reactant and product of
the decomoposition of cellobiose determined by using 13C in situ NMR monitoring.
Fig. 1. 5-HMF yield in the cellobiose decomposition in DMSO/water mixture solvent.
Content:Although organic synthetic chemistry has greatly
contributed 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, polymer-supported 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 metal-free 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.
Keywords 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/
N
N
N
NR2
R1
R3
O
OR435
1087
N(5)-Ethylation
N(5)-Cationization
Anion Exchange
Purification
N
N
N
NR2
R1
R3
O
OR4
Et
NaNO2 (toxic)
NaClO4 (explosive)
O2 (air)
cation exchange resin
recrystalization washing
A
ClO4A = A =
Previous method Our method
safe, easy, inexpensiveinert atmosphereinert atmosphere
hazardous reagents
SO3
crosslinked polystyrene
SO3H
OH
O
OOH
N
N
NH
N O
O
= Riboflavin
R1
R2
R4
R3
H HR1 R4
R2 R3
NH2NH2
O2
H2O1/2 N2
� Reusable more than 10 times� High catalytic acitivity in reduction of olefins
nontoxic byproducts
1
Fig. 1.
2
Reduction of olefins catalyzed by polymer-supported flavin (1)
Fig. 2. Facile preparation of flavinium organocatalysts (2)
Fig. 1 CHP that combines two reactors and a distillationcolumn with energy savings
Fig. 2. Heat-integrated reactive distillation system
Content: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 Process/Chemical engineeringE-mail: [email protected]. +81-88-656-7425Fax: +81-88-656-7425
qS
c n=312.78 kW
PA10 kmol/hr
PS=101 kPa
PR=161 kPa
40.23MA 25.22%
DMC 74.78%
kmol/hr 10.04MA 99.50%
DMC 0.50%
kmol/hr
30.18MA 0.50%
DMC 99.50%
kmol/hr5.01PA 0.10%
DMC 0.40%DPC 99.50%
kmol/hr
RRS=2.68
DMC5.06 kmol/hr
1
NR =80
NS=25
4
2
74
77
11
qR
c n = 561.23 kW
Q2 ,2 5
e x =296 kW
QR
r b =778.58 kW
RRR=0.53
1
Content:Graft copolymers are prepared by monomer and
polymerizable group end-functinaliced polymer, namelymacromonomer. Polymerization of carboxyl end-fuctionalized 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.
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 tert-butylzincate.
Keywords high-functional materials, biodegradablepolymerE-mail: [email protected]: +81-88-656-7404Fax: +81-88-656-7404HP : http://poly.chem.tokushima-u.ac.jp/
Syntheses of Nanosheets of Layered Metal Hydroxides
II. Control of Interlayer ions in Layered Metal Hydroxides
Content:The layered metal hydroxide is a layered compound
consisted 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 by
delamination 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 that
contains 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).
Keywords layered compound, metal hydroxide, nanosheet, ion exchangeE-mail: kurashina.masashi @tokushima-u.ac.jp
Tel. +81-88-656-7418Fax: +81-88-655-7025
ered Metal Hyd
Layered hydroxide
Delamination
Nanosheet
0 105
0 1050m
5nm 3.4 nm
m Abs
orba
nce
Wavelength / nm200 250 300
1st cycle
3rd cycle5th cycle
0
0.05
0.1
0.15
Fig. 1 AFM image of cobalthydroxide nanosheets
Fig. 2 UV absorption spectra of restacking of nickel hydroxide nanosheets
Am-Bm-
H2OBm-Bm-Bm-
H2OH2OH OOOOOO BBBBBBBBBBBBBBBBBBBBBBBBBBBBBBmm--Bm--H2OAm-
Am-Am-
H2OH2OH OOOO AAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAAmm--AAmmmm--
Bm- Bm-
+ +Am- Am-
Fig. 3 Growing tests of Japanesemustard spinach using a Mg/Fe-typelayered double hydroxide
Adsorption of polyoxomolybdateand borateControl of elution of phosphate
Content:Imidazo[1,5-a]pyridine derivatives have been drawn
considerable attention because of their potentialapplication as pharmaceutical agents and functionalmaterials. Therefore, various molecules featuringimidazo[1,5-a]pyridine skelton have been synthesizedand characterized.Recently, we have synthesized the novel dimeric
imidazo[1,5-a]pyridine. These compounds have beenexamined to apply as the ligand in catalytic systems andfunctional materials such as sensing molecules and highefficient light emitting molecules. For example, thepalladium-catalyzed Mizoroki–Heck reaction of arylbromides and chlorides with alkenes using ourimidazo[1,5-a]pyridine-PdCl2 system afforded the desiredproducts in good-to-high yields with the low palladiumloadings and short reaction times. On the other hand, thesubstituted dimeric imidazo[1,5-a]pyridines exhibitedrelatively strong emissions.
Keywords Heterocycle, Functionalized moleculeE-mail: [email protected]. +81-88-656-7405Fax: +81-88-655-7025
Imidazo[1,5-a]pyridine Dimeric structure
<Application as Ligands to Mizoroki–Heck Reaction>
<Fluorescence in solution and in the solid state>