Chemistry Lettershttp://www.csj.jp/journals/chem-lett/

Vol.39 No.12 CMLTAGDecember, 2010 ISSN 0366-7022

Copyright © 2010 The Chemical Society of Japan

Highlight Review

1226 Tailoring Material Properties through DefectEngineering

Harry L. Tuller* and Sean R. Bishopdoi:10.1246/cl.2010.1226

Many advanced materials today derive their function from precise control of point defects. Through manipulation of pointdefects, the electrical, optical, mechanical, and other properties of materials can be systematically modified and optimized. Thisfeature paper illustrates the type of progress that has been made in understanding the often complex equilibria exhibited by manymaterials and shows, by use of examples, how this knowledge can be applied to tailor materials’ properties through defectengineering. Examples which highlight key points of defect engineering include: dark conductivity of radiation detectors,chemomechanics and nanoionics of solid oxide fuel cell materials, sensitivity of high frequency resonators for high-temperaturemass measurements, and emission lifetime and luminescence intensity of phosphor materials.

1232 Recent Progress in Living Cationic Polymer-ization of Vinyl Ethers

Arihiro Kanazawa, Shokyoku Kanaoka, andSadahito Aoshima*doi:10.1246/cl.2010.1232

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1238 Timing-controlled Decompaction of Poly-plexes In Vivo Greatly Enhances TransgeneExpression

0

0.5

1

1.5

2

2.5

3

0C/A

Rel

ativ

e ge

ne e

xpre

ssio

n

P1P2P3

0

at 37 °C

Time/h

10 20 30 40 50

at 4 °C

24 48

Yoichi Tachibana, Tomoko Hashimoto, HisaeNozaki, Akira Murakami, and Tetsuji Yamaokadoi:10.1246/cl.2010.1238

Letter

1240 Prevention of Adsorption of FluorescentAmino Acids to Gels by Using a PeptideContaining Dendritic Amino Acids

Mizuki Kitamatsu,* Kazumasa Akagi, andMasahiko Sisidodoi:10.1246/cl.2010.1240Electronic Supporting Information

1242 Phase Transition and Thermal BehaviorChange of Low Silica X Zeolite at [Al] = 90

Mana Yasui-Hiraiwa, Teruhisa Hongo,* HirokoHayashi, Tetsuo Takaishi, Shinichi Nataka, andAtsushi Yamazakidoi:10.1246/cl.2010.1242Electronic Supporting Information

1245 Sialylglycan-modified Field Effect Transistorfor Detection of Charged Lectin underPhysiological Conditions

SSA concentration

∆Vg

/ mV

Blank 5 µg mL 50 µg mL 500 µg mL HSA(200 µg mL−1)

100

80

60

40

20

-20

0

FET gate oxide

25 Å

BSA Streptavidin

SSA

Biotinylatedsialylglycan

Source Drainp-type Si

SiO2SiO2

A

Vds

Ids

Vg

DraincurrentDrainvoltage

Gate voltage

Reference electrode

Probe molecule (sialylglycan)

n+ n+

Buffer solution

Gate area

Target protein (SSA)

−1−1−1

Takahiro Nakamura, Yoshihiro Sakurai, ShoHideshima, Shigeki Kuroiwa, and TetsuyaOsaka*doi:10.1246/cl.2010.1245Electronic Supporting Information

1248 Synthesis and Metal-like Luster of NovelPolyaniline Analogs Containing AzobenzeneUnit

Minoru Kukino, Junpei Kuwabara, KiyotoMatsuishi, Takashi Fukuda, and TakakiKanbara*doi:10.1246/cl.2010.1248Electronic Supporting Information

Chemistry Letters Vol.39, No.12 (2010)C-136

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1251 Lignin Gasification over Charcoal-supportedPalladium and Nickel Bimetal Catalysts inSupercritical Water The mixture of Pd(NH3)4(NO3)2/C and Ni(NO3)2/C is more active for the lignin gasification than

the individual monometal catalysts. EXAFS and XRD show the formation of small Pd−Ni alloy particles, which are the active sites for the lignin gasification.

Aritomo Yamaguchi, Norihito Hiyoshi, OsamuSato, Mitsumasa Osada, and Masayuki Shirai*doi:10.1246/cl.2010.1251Electronic Supporting Information

1254 Modified OligoDNA Having Two Consecu-tive Silylated-pyrene Moieties in MinorGroove Exhibiting an Excimer FluorescentSignal upon Binding to Fully Complemen-tary DNA Strand

OligoDNA possessing consecutive modified nucleotide residues bearing silylated pyrene molecule at C-2′ position exhibited marked excimer fluorescent signal upon binding to the fully matched complementary DNA strand.

Mika Mogi, Md. Gias Uddin, MayumiIchimura, Tomohisa Moriguchi, and KazuoShinozuka*doi:10.1246/cl.2010.1254

1256 Water-soluble Inclusion Complexes of[60]Fullerene Derivatives Using £-Cyclo-dextrin -CDx

+

-CDx

+

γγ γ

Atsushi Ikeda,* Tomoya Genmoto, NaotakeMaekubo, Jun-ichi Kikuchi, MotofusaAkiyama, Takayuki Mochizuki, Shuhei Kotani,and Toshifumi Konishidoi:10.1246/cl.2010.1256Electronic Supporting Information

1258 One-step Preparation of Gold NanoparticlesUsing 4-Acylamidobenzenethiol as a Reduc-tive Stabilizer

Hiroaki Okamura,* Junichi Kurawaki, TetsuoIwagawa, Toshiyuki Hamada, and MasatakeKawashimadoi:10.1246/cl.2010.1258Electronic Supporting Information

1261 Triazole-linked Benzylated Glucosyl, Galac-tosyl, and Mannosyl Monomers and Dimersas Novel Sugar Scaffold-based PTP1B In-hibitors

Yin-Jie Zhang, Xiao-Peng He, Cui Li, Zhen Li,De-Tai Shi, Li-Xin Gao, Bei-Ying Qiu,Xiao-Xin Shi, Yun Tang,* Jia Li,* andGuo-Rong Chen*doi:10.1246/cl.2010.1261Electronic Supporting Information

Chemistry Letters Vol.39, No.12 (2010) C-137

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1264 Solid-state Thermal and Photochemical E/ZIsomerization of Bidentate-N,S Schiff BaseLigands in Iridium(III) Complexes

N

Ir

N

S

N

Me

Me

Me

CF3

F3C

CF3

F3CE N

Ir

N

S

N

Me

Me

Me

CF3

F3C

CF3

F3C Zhν

∆

The complete thermal and photochemical switching processes have been observed at a C=N double bond in a Schiff base IrIII complex derived from 2-substituted benzothiazoline.

Tatsuya Kawamoto,* Yusuke Takino, KeiichiSakoda, and Takumi Konnodoi:10.1246/cl.2010.1264Electronic Supporting Information

1267 The First Experimental Demonstration ofSide Chain Extension of Geoporphyrins inSediments

N

NN

N

OMeO2C

Mg

CO2Phytyl

Chlorophylls

N

HNN

NHDiagenesis

A high carbon numbergeoporphyrin

Kenta Asahina, Junya Asano, Gen Kumagai,Mitsuru Satou, Kouichi Nomoto, YuichiroKashiyama, Hajime Mita, and Shinya Nomoto*doi:10.1246/cl.2010.1267

1270 The Synthesis and Flame Retardance of aHigh Phosphorus-containing UnsaturatedPolyester Resin

A high phosphorus-containing unsaturated polyester resin (P-UPR) with UL94 V-0 rate was synthesized by a one-step or two-step method with a low amount of 15.0 wt % dimethyl methylphosphonate (DMMP) as a reactive flame retardant.

CH2HO O

O

O

O

O

O

CH

CH3

OH

Polymerization

HOCH2CH2OHP

O

OCH3H3CO

CH3

Catalyst

CC

OO

OCH

CH3

CH2O C

O

CH CH C

O

OCH2CH2O P

O

CH3

O

500

Abs

orba

nce

Wavenumber/cm-1

113°C153°C

196°C240°C285°C

329°C373°C416°C

459°C502°C544°C

586°C627°C668°C

4000350030002500200015001000

Chen Zhang, Shu-Mei Liu,* Jun-Yi Huang, andJian-Qing Zhaodoi:10.1246/cl.2010.1270

1273 Dynamic Response of a Cholesterol-contain-ing Model Membrane to Oxidative Stress

Tsuyoshi Yoda, Mun’delanji C. Vestergaard,Yoko Akazawa-Ogawa, Yasukazu Yoshida,Tsutomu Hamada,* and Masahiro Takagidoi:10.1246/cl.2010.1273

1275 AFM Interaction Study of Poly(ammoniumacrylate) Adsorbed on a Si Surface inAqueous KCl Solution

Force curve of the PAA on the Si substrate in the KCl solution. Short- and long-range interactions were explained, respectively, by steric hindrance of the polymer adsorbed onto the solid surface and DLVO theory.

Toshihiro Isobe,* Yosuke Nakano, YoshikazuKameshima, Kiyoshi Okada, and AkiraNakajimadoi:10.1246/cl.2010.1275

Chemistry Letters Vol.39, No.12 (2010)C-138

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1277 MCM-41 Grafted Quaternary AmmoniumSalts as Recyclable Catalysts for the Sequen-tial Synthesis of Dimethyl Carbonate fromEpoxides, CO2, and Methanol

One kind of novel heterogenous bifunctional catalysts, MCM-41 grafted quaternary ammonium salts with terminal amino groups was prepared for the first time. These catalysts exhibited excellent catalytic performance and good reusability in the sequential synthesis of dimethyl carbonate from epoxides, CO2, and methanol.

Jian Li, Liguo Wang, Shimin Liu, Xueli Li,Feng Shi,* and Youquan Deng*doi:10.1246/cl.2010.1277Electronic Supporting Information

1279 Oxidation of Dihydrazones of Diaryl ¡-Diketones to Diarylacetylenes Using SodiumPeriodate

NaIO4, Water:EtOAcR2R1room temperature

NNH2

NNH2

R2R1

Balaram S. Takale and Vikas N. Telvekar*doi:10.1246/cl.2010.1279Electronic Supporting Information

1281 Synthesis of 13C-Labeled 5,6,11-Trideoxy-tetrodotoxin

BocHNOP

OP

O

NN OH

H

H

HNO

HO

13C N

NN O

13CH

H

HN

HO O

HO

R

6 11

5

R = 4α-OH: 13C-5,6,11-trideoxytetrodotoxinR = 4β-OH: 13C-4-epi -5,6,11-trideoxytetrodotoxin

4Intramolecular

Cyclization

Na13CN

NH

OP

HO

O

13CN

BocHN

NBoc

P

MgCl2

Deprotection

Taiki Umezawa, Tetsuro Shinada,* andYasufumi Ohfune*doi:10.1246/cl.2010.1281Electronic Supporting Information

1283 Beat of Frequency Modes with an ArtificialNegative Frequency in Spectrogram Analysis Artifact caused by negative frequency mode

on spectrogram.

Atsushi Yabushita,* Chih-Hsien Kao, Yu-HsienLee, and Takayoshi Kobayashidoi:10.1246/cl.2010.1283Electronic Supporting Information

1285 Nanoaggregate Formation of AmphiphilicAlternating and Random Copolyimides inWater

1Diameter/ nm

Alternating coPI

Random coPI

N

O

N

O

X N

O

ON

O

O

Y

O

O

O 2CH2O

OO

O

O

O

OO 2

n

Amphiphilic alternating coPI

Amphiphilic random coPI

Amphiphilic copolyimides

4

DAn

9CH

CH

100010010Takashi Hamada and Kazuaki Kudo*doi:10.1246/cl.2010.1285Electronic Supporting Information

Chemistry Letters Vol.39, No.12 (2010) C-139

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1288 Band Gap and Absorption Profile Change byChanging Molecular Weight and Conforma-tion of Water-soluble Narrow-band-gapPolymers

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

00.511.52

Py(10)Py(12)Py(14)Py(20)Py(40)Py(70)

Abs

orba

nce

Photon energy / eV

N

SO3Nan

Band gaps and absorption profiles of water-soluble π-conjugated polymers, which were prepared by the addition−condensation of pyrrole with sodium o-formylbenzenesulfonate, changed with changing their molecular weights and conformations in different solvents. The band gaps were changed from less than 0.19 eV in a solid to 0.59 eV in a solution.

Hiroyuki Aota,* Takeshi Ishikawa, YutaAmiuchi, Hirofumi Yano, Tatsuya Kunimoto,and Akira Matsumotodoi:10.1246/cl.2010.1288Electronic Supporting Information

1291 Clustering of Lipid Rafts in Plasma Mem-branes by Hybrid Liposomes for LeukemiaCells along with Apoptosis

Hybrid liposomes (HL-23) composed of 90 mol % L-α-dimyristoylphosphatidylcholine (DMPC) and 10 mol % polyoxyethylene(23) dodecyl ether (C12(EO)23) could induce the clustering of lipid rafts in the plasma membranes for human leukemia HL-60 cells leading to apoptosis.

Yuji Komizu, Sayuri Nakata, Koichi Goto,Yoko Matsumoto, and Ryuichi Ueoka*doi:10.1246/cl.2010.1291

1294 Self-generated Motion of Droplets Inducedby Korteweg Force

Unidirectional motion of a droplet in aqueous Na2SO4/PEG two-phase system.

(b) t =65s (c) t =115s =165s(d) t(a) t =15s

2 mmTakahiko Ban,* Ai Aoyama, and TakuyaMatsumotodoi:10.1246/cl.2010.1294

1297 Blocking Oxidation of Al Surfaces withOrganic Thiol Monolayers Cured by Elec-tron Beam

Shuhei Nomura, Taro Yamada,* and MakiKawaidoi:10.1246/cl.2010.1297Electronic Supporting Information

1300 Fluoro-substituted Phenyleneethynylenes:Acetylenic n-Type Organic Semiconductors

F F

F3C

F F F F

FF FF

F F

CF3

F

F

F

F

n-type semiconductor, µ = 5.5 x 10−2 −1 −1 cm2 V s

Daisuke Matsuo, Xin Yang, Akiko Hamada,Kyo Morimoto, Takuji Kato, Masayuki Yahiro,Chihaya Adachi,* Akihiro Orita,* and JunzoOtera*doi:10.1246/cl.2010.1300Electronic Supporting Information

Chemistry Letters Vol.39, No.12 (2010)C-140

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1303 Thermal Properties of Alkali (Fluorosulfo-nyl)(trifluoromethylsulfonyl)amides

300

400

500

600

700

0 100 200 300 400

C0C1-C0C0-

C0C2-

C1C1-

C2C2-

[C4F9SO3]-[BF4]-

[ClO4]-

[PF6]-

[CF3SO3]-

C1C2-Tm

/ K

Molecular weight of anion

[NO3]-

This figure is the plots of melting temperature of anhydrous lithium salts against molecular weight of constituent anions. Some perfluorosulfonylamide anions are abbreviated as follows; [(FSO2)2N]−: C0C0−, [(FSO2)(CF3SO2)N]−: C0C1−, [(CF3SO2)2N]−: C1C1−, [(FSO2)(C2-F5SO2)N]−: C0C2−, [(CF3SO2)(C2-F5SO2)N]−: C1C2−, [(C2F5SO2)2N]−: C2C2−.

Keigo Kubota, Toshiyuki Nohira, RikaHagiwara, and Hajime Matsumoto*doi:10.1246/cl.2010.1303

1305 Magnetic Resonance-visible Coating for Endo-vascular Device Visualization: Gadolinium-(III)­Diethylenetriaminepentaacetic Acid-based Insoluble Polymer Coating

qp

ON OO O

/N

NN

O

O O

O

O

OO

O

O

NH

NH

OGd

HO

H

1. MR-visible polymer 2. Analog polymer (no Gd-DTPA) 3. Negative control (without coating)

MR-visible polymer

1 2

Saline

Polymer coated part

Catheter

3

Tomoka Kurita,* Kagayaki Kuroda, and TakeoOhsakadoi:10.1246/cl.2010.1305

1307 Development of a Flux Stabilizer for Solid-state Nuclear Magnetic Resonance with aHybrid Magnet

Solid-state NMR at 28 T.

6000

5000

4000

3000

2000

1000

0FT Power Intensity/arb unit

-20 -10 0 10 20

Shift/kHz

KBr79Br-MAS-NMR

28T

Kenjiro Hashi,* Tadashi Shimizu, TeruakiFujito, Atsushi Goto, Shinobu Ohki, ToshihisaAsano, Shigeki Nimori, Giyuu Kido, and JunKidadoi:10.1246/cl.2010.1307

1309 Fabrication of Novel Reflective­EmissiveDual-mode Display Cell Based on Electro-chemical Reaction

Initial state Reflective mode Emissive mode

by applying DC voltage by applying AC voltageYuichi Watanabe, Kazuki Nakamura, andNorihisa Kobayashi*doi:10.1246/cl.2010.1309

1312 Silicalite Pervaporation Membrane Exhibit-ing a Separation Factor of over 400 forButanol

Butanol solution was able to be concentrated to 80 wt % or more from a 1 wt % butanol solution on silicone-rubber-coated silicalite membranes. The butanol concentration process was simplified greatly by the development of this separation membrane. The energy needed to refine the butanol from 1 wt % butanol solution was equal to 13% of the energy of the butanol.

Hideyuki Negishi,* Keiji Sakaki, and ToruIkegamidoi:10.1246/cl.2010.1312

Chemistry Letters Vol.39, No.12 (2010) C-141

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1315 Robust Hole Transport in a ThienothiopheneDerivative toward Low-cost Electronics

S

SBr BrS B

O

OC6H13

S

SS

SC6H13

C6H13

K2CO3

Pd(PPh3)4

+

GS/V

|I DS

|/A

| I DS|1/

2/A

1/2

BareODTSHMDSOHPMMA

-50

0

0.001

0.002

0.003

0.004

10-12

10-10

10-8

10-6

10-4

transport characteristics of organic thin film transistor

air-stability surface dependence

/cm

2–1

–1V

s

th/V

V

Air exposure/day010-3

10-2

10-1

100

-50

-40

-30

-20

-10

0

V20100-10-20-30-40

µ

50

Shinya Oku, Kazuhiro Takamiya, DaisukeAdachi, Shuhei Ishikawa, Shuichi Nagamatsu,Wataru Takashima,* Shuzi Hayase, and KeiichiKanetodoi:10.1246/cl.2010.1315Electronic Supporting Information

1317 Rapid Adsorption of Rh(III) by Polyamine-functionalized Cellulose Fiber Combinedwith Microwave Irradiation

Fibrousadsorbent

MicrowaveRh(III) + Cell-dien

Polyamine-grafted fibrous cellulose rapidly adsorbed Rh(III), assisted by microwave irradiation.

Ahmed M. Yousif, Masateru Nishioka, YoshitoWakui, and Toshishige M. Suzuki*doi:10.1246/cl.2010.1317Electronic Supporting Information

1319 Catalytic Beckmann Rearrangement ofCyclododecanone Oxime

N OH

NH

OSiCl4

Nitrile-HexaneSatoshi Sato,* Hideaki Hoshino, TsunemiSugimoto, and Kohichi Kashiwagidoi:10.1246/cl.2010.1319

1321 Guest Binding, Cellular Uptake, and Molecu-lar Delivery of Water-soluble CyclophanesHaving a Pyrene Moiety

Osamu Hayashida,* Chika Eguchi, KeiichiroKimura, Yu Oyama, Tomomi Nakashima, andKosei Shiojidoi:10.1246/cl.2010.1321Electronic Supporting Information

1323 Hybrid Inorganic­Organic Crystals Com-posed of Octamolybdate Isomers and Pyr-idinium Surfactant

Takeru Ito,* Keisuke Mikurube, Yukihiro Abe,Takahisa Koroki, Masaki Saito, Jun Iijima,Haruo Naruke, and Tomoji Ozeki*doi:10.1246/cl.2010.1323Electronic Supporting Information

Chemistry Letters Vol.39, No.12 (2010)C-142

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan

1326 Thin TiO2 Films Prepared via High-pressureCrystallization for Dye-sensitized Solar Cells

Crystallized thin TiO2 films were successfully prepared via the high-pressure crystallization (HPC) process. Comparing to conventional heating process, the crystallized temperature for thin TiO2 films was significantly decreased. The IPCE values of the crystallized films were significantly increased by the UV-irradiation after the HPC treatment.

DI water

substrateautoclave

High pressure

Assembled for cells

Jeng-Shin Ma and Chung-Hsin Lu*doi:10.1246/cl.2010.1326

1329 Synthesis and Gelation Behavior of 4¤-Propyl-1,1¤-bi(cyclohexyl)-4-one 4-Alkoxy-benzoylhydrazone

RONHNH2

ORO

OEt

OHO

OEt

O RBr

K2CO3

N2H4 H2O

ORO

O

NH

N

.

R = CnH2n+1 ; n = 4, 5, 6, 7, 8, 12

(3HHB-n)

dc

ba

A series of new alkoxybenzoylhydrazones of 4′-propyl-1,1′-bi(cyclohexyl)-4-one were prepared as novel low molecular weight organogelators (LMOGs). Their gelation behaviors in 10 solvents were tested.

Juan Li, Pei Chen,* Xinbing Chen, ZhongweiAn, and Yan Lidoi:10.1246/cl.2010.1329

1331 Ferromagnetic Gd­Cu, Tb­Cu, and Ho­CuCouplings in Isomorphous [Ln2Cu] Com-plexes

Atsushi Okazawa, Ryo Watanabe, MasaruNezu, Takashi Shimada, Shunsuke Yoshii,Hiroyuki Nojiri,* and Takayuki Ishida*doi:10.1246/cl.2010.1331Electronic Supporting Information

1333 Preparation of Thin CuInSe2 Films UsingCu­In Alloy Nanoparticles

Evolution of H2

e-

In

Cu-In

alloys

Cu

High activities

of metallic

nanoparticles

B

Na+H

H

HH

-

Cu2+

In3+

Cu−In alloy nanoparticles were successfully synthesized via the chemical reduction method. The selenization of the obtained alloy nanoparticles coated on the substrates was demonstrated to be a potential route to prepare monophasic thin CuInSe2 films with large grains.Shih-Hsien Liu, Fu-Shan Chen, and

Chung-Hsin Lu*doi:10.1246/cl.2010.1333

Chemistry Letters Vol.39, No.12 (2010) C-143

http://www.csj.jp/journals/chem-lett/Copyright © 2010 The Chemical Society of Japan