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Abstract：Weprovidefmrtherinsightintothephotochemicalcontrolofviscoelasticitythr⑪ughtheuseof
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‐azobemzenedicarboxylate(3,3'一Azo2Na)wasaddedtoasolutionofcetyltrimethylammoniumbromide
（CmB)/sodiumsalicylate(NaSal),whichisknownf0rinducingthefbrmationofwormlikemicelles・This
solutionmaintainedawormIikemiceⅡarstmcture,althoughareductioninzero-shearviscositywasobserved，
Whenthismixedaqlueoussolutioｎ０ｆＣｍＢ/NaSaI/3,3'一Azo2Na(16.7,Ｍeach)wasirradiatedbyultraviolet
light，ｔｈｅ3,3'一Azo2NaexhibitedmoIecularか”s-cjSph0toisomerization・Wemeasuredthedynamic
viScoelasticityofthesampleintheph0tostationarystateandfbundthatthezero-shearviscosityincreased
approximatelysevenfbldcomparedtothepreirradiationstate・Thisphenomenonistheopposite0fthesystem
whereinviscosityreducedbyirradiation,asreportedbyus・Wediscussthemechanism0fthisviscositychange．
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１１NTRODUCTlON
Surfactantmoleculesfbrmvanousmolecularassemblies
suchasmiceuesandvesiclesinwatemlfthecouapseand
refbrmationofsuchassembliescouldbecontronedbyex-
temalstimuli,thiscontroltechnologywouldbeusefUlfbra
widerangeofapplications､Forexample,itwouldallowthe
sustainedreleaseofmedjcineorperfUmewithinamolecularassemblyorthecontrolledreleaseofdrugsinadrug
ecule､However,thesesystemswerecharacterizedbyareductionintheviscosityuponthecreationofthecdsfOrm
byultravioletirradiation
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aqueoussolutionviscosity,wefbcusedonSodium3β'一azo-
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molecule､Weexpectedthat3,3'一Azo2NawouldfUnctionas
anorganicsalttofbrmwormlikemicelleswhenaddedto
theCn4Baqueoussolution,andalsoasaphotoresponsive
moleculeexhibitingtm?zs-cjsphotoisomerizationbyirradiationwithultraviolet/Visiblelight,Inthisstudy,wefbund
thattheaqueoussolutionvｉｓｃｏｓｉｔｙｏｆｔｈｅＣＴＡＢ/Ｎａ‐
Sal/3,3'一Azo2Nasystemwasincreasedbyirradiationwith
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-trimethylammoniumbromide,AZTMA).Wealsofbundit
possibletocontroltheviscosityofamixedaqueoussolutionofCmB(acationicsurfactant)andsodiumcinnamate
thatworkedsimultaneouslyasanorganicsaltinducingthe
wormlikemiceUefbrmationandasaphotoresponsivemol‐
fromtheopticalcontrolsystemofaqueoussolutionviscos‐
thisphenomenonｃａｎbeappliedtopreventblurredprint‐
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Wavelength／nｍ
０ ２ ４ ６ ８ １ ０ １ ２ １ ４ １ ６
Concentrationｏｆ3,3'一Azo2Na／mM
Fig､２Relationshipbetweenconcentrationof3,３，
Fig.３ＴｈｅｃｈａｎｇｅｓｉｎＵＶ/ＶｉｓｓｐｅｃｔｒａｆｂｒＣＴＡＢ
（16.7,Ｍ)/NaSal（16.7,Ｍ)/3,3,-Ａｚｏ２Ｎａ
（
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‐Azo2Naandzeroshearviscosity（no）fbr
CTAB(16.7,Ｍ)/NaSal(16.7,Ｍ)/3,3'一Azo2Na
u
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CTAB/Sodiumsalicylate/3,3'一Azo2Namixedaqueoussolu‐
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tionreachedthephotostationaIystate,wemeasuredthe
dynamicviscoelasticityibutthefrequencydependenｃｅｏｆ
ｂｏｔｈＧ'ａｎｄＧ"exhibitedalmostnochangecomparedwith
thatobtamedbefbreultravioletirradiationlncalculating
thezero-shearviscosity,wefOundthatthevaluewas
slightlyincreasedfrom2.ｌｔｏ３．３Ｐａ・sbyultravioletirradi‐
ation
Next,weexaminedanultraviolet-irradiatedsamplewith
adifferentcomposition,CTAＢ(16.7,Ｍ):NaSal(１６．７
，M):3,3'一Azo2Na(16.7,M)＝l:l:l,andcheckedthepho‐
“
Themonitoringresultsof3,3'一Azo2Naphotoisomerization
througｈｔｈｅＵＷＶisabsorptionspectrummeasuremenｔｓｒｅ‐
vealedthatultravioletirra〔nationsigniiicantlyreducedthe
peakat320.5nmthatisattributedtothet7mzsfbrmofthe
azogroupandincreasedthepeakat431nmthatisattIib-
皿すいＯ﹃９．８異合○ヨゴ︵■︶
solution､First,weexaminedthesampleofCTAB(16.7
,Ｍ)/NaSal(16.7,Ｍ)/3,3'一Azo2Na(8.35,Ｍ)solutions・
0.10
８０
６
０
０
００
viscosityoftheCTykB/NaSal/3,3'一Azo2Namixedaqueous
︵●︶Ｅ匡召図、①Ｕ匡呂﹄ＯＢ、
Weexaminedtheeffectsofultravioletirradiationonthe
２０８
０６
０４
０
1
４
mixedsolutions．
0.02
0.2
０
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０
５ ０ １ ０ ０ １ ５ ０ ２ ０ ０
l
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/
ｍ
i
n
、
Fig.４Relationshipbetweenirradiationtimeand
absorbancefbrtransandc耐ｆｂｒｍｓｆｂｒＣＴＡＢ
（16.7,Ｍ)/NaSal（16.7,Ｍ)／3,3'一Ａｚｏ２Ｎａ
（
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5
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)
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s
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．
vealedthatultravioletirradiationincreasedtheviscosityby
approximatelysevenfbld;zero-shearviscositybefbreirradi‐
a
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i
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n
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‐
toisomerizationofthe3,3'一Ａｚｏ２Ｎａmoleculesintheworm‐
likemicellesolutionthoughUWVisabsorptionspectrum
ticitymeasurementsbefbreandafterultravioletirradiation，
weobservedanenlargementoftheplateauinthestorage
modulusG'causedbyirradiation,suggestingachangein
measurements・
thewormlikemiceUestructure・
Ｔｈｅｒｅsultsofdynamicviscoelasticitymeasurementsof
thesamplesthatreachedthephotostationarystatere-
A
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２０５
』.Ｍｈ応"柳"、,ＫＳｂ”j,ＨＳｂ"iα"ｄＭＡ６ｅ
arereplacedwithNaSal・Itisconsideredthat,asaresult，
the3,3'一Azo-2Nacontainedinthewormlikemicenesde‐
creasedandtheviscoelasticityincreased,Therefbre，the
increaseinviscositybyultravioletirradiation,whichisa
碗●、巳へ。亘
phenomenonthatisoppositetothecurrentlyknownpho‐
tochemicalcontrolofviscosity,wasobserved,Becausethis
increaseinviscositywouldbeusefUlfbrvariousapplica‐
tions,includingphotocurableinkstopreventblurring,we
arepresentlyexammlngwaystoimprovethee髄ciencyof
p
h
o
t
o
i
s
o
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e
r
i
z
a
t
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n
．
０
．
１
０
．
０
１
０ ． ０ １ ０ ． １ １ ０
４ＣＯＮＣＬＵＳｌＯＮ
trast,thepresentstudyyieldedsomeinterestingresults
thatdifferedfromthoseofourearlierreports:ultraviolet
irradiationincreasedtheviscosityofthissystemWeexam‐
Ｗｅｓｕｃｃｅｅｄｅｄｉｎｔｈｅｐｈｏｔochemicalcontrolofthevisco‐
elasticityinCmAB/NaSal/3,3'一Azo2Nasystemandfound
thattheaqUeoussolutionviscositywasincreasedbyirradi‐
a
t
i
o
n
w
i
t
h
u
l
t
r
a
v
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h
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e
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e
n
t
f
r
o
m
t
h
e
p
h
o
‐
tochemicalcontrolsystemofaqueoussolutionviscosity
thatwehadreportedpreviously・Weexammedthemecha‐
nismofthjsviscosityincreaseandinferredthatitisasfbl‐
lows:Ｉｎｔｈｅｃａｓｅｏｆｔｈｅｊｍ７ｚｓｆｂＩｍ,ｔｈｅ3,3'一Azo2andthe
salicylateions,whichareanionic，formacomplexwith
CTAB,acationicsurfactant,inanelectrostaticmannerBecauseｔｈｅｃｊｓ-3,3'一Azo2Namoleculehasabentstructure，
thecapacitytofbrmcomplexwithC'IYkBviaelectrostatic
inedthemechanismfbrthisviscositymcreaseasfbuows・
m
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a
c
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i
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c
l
u
s
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o
n
）
Ａ､9.frequency／rad/s
Fig・SRelationshipbetweenAngularfiFequencyand
T1＊fbrCTAB(16.7,Ｍ)/NaSal(16.7,Ｍ)/３，３，
‐Azo2Na(16.7,Ｍ)(l:l:l)befbreandafterUVL
i汀adiation．
b
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)
．
Ｉ
ｎ
ｃ
o
n
‐
InthewolTnlikemicenesconsistingofthreeelements，
thanthatofthet7mzsfOrm,Becauseofthisdecreasemthe
ＣTAB/NaSal/3,3'一Azo2Na,ultravioletirradiationon3,3'一
fbrmationcapacityofthecomplexinducedbyt7wzs-cds
photoisomerizaｔｉｏｎｓｏｍｅ３,3'一Azo2Namoleculesexitfrom
Azo2NamoleculespromotedZm"zs-cjsphotoisomerization
andconfbrmationinmoleculechanges.InthecaseofAZTL
MAandsodiumcinnamate，whichwereusedforoptical
molecularswitchingintheprevlousresearch,thewormlike
micellesconapsedduetolargeconfbrmationchangealong
withphotoisomerization,andtheviscositydecreasedsig‐
niiicantlyHowever,ｍｔｈｅｃａｓｅｏｆ３,3'一Azo2Nausedinthe
presentstudy,ｔｈｅｍｏｌｅｃｕｌｅｓｉｚｅｗａｓｎｏｔａｓｌａｒｇｅａｓｔｈａｔｉｎ
ＡＺＴＭＡ,andtheconfOrmationchangeintheCTykB:Ｎａ‐
Sal:3,3'一Azo2Na＝ｌ:l:１ｓystemalongwithphotoisomeriza‐
tionwasrelativelysmall,Inaddition,bothNaSaland3,3'‐
Azo2Naexistassubstancesthatinducewormlikemicene
fbrmationandthesumofeachconcentrationistwiceas
largeasthatofCTABfbrthecompositionofCTAB(16.7
,Ｍ):NaSal(16.7,M):3,3'一Azo2Na(16.7,M)＝l:l:１.Ｂｅ‐
causethecfs-3,3'一Azo2Namoleculehasabentstructure,it
isconsideredthatbecauseofitsstericexclusion,ｔｈｅcapacitytofbrmacomplexwithCTABviaelectrostaticintelL
actionｉｓｌｏｗｅｒｔｈａｎｔｈａｔｏｆｔｈｅｊ７ｍｚｓｆｂｒｍ､Therefbre,ｉｎ
ｔｈｅｃａｓｅｏｆｔｈｅｍｕ７ｚｓｆＯｒｍ,thesalicylateions,whichare
anionic,ａｎｄthe3,3'一Azo2ionsfbrmacomplexwithCTykB，
acationicsurfactant,manelectrostaticmanner,However，
theformationcapacityofthiscomplexwoulddecrease
thewormlikemiceⅡesandarereplacedwithNaSal・Asa
result,ｔｈｅ3,3'一Azo2Nacontainedinthewormljkemiceues
decreasesandtheviscoelasticityincreasesbyUVughtilTa‐
d
i
a
t
i
o
n
．
References
l
）
S
a
j
i
,
T
l
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o
s
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d
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s
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u
b
i
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a
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n
w
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a
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ionicsurfactantbearingferrocenylmoiety.〃ate髄
姥
C
ﾉ
m
o
j
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,
2
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(
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．
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l
e
c
t
r
o
c
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m
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j
z
a
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o
n
u
s
i
n
g
a
f
e
r
r
o
cene-modifiednonionicsurfactant､CojJoldsS叫び,Ａ
someofthemoleculesexitfromthewormlikemicenesａｎｄ
1
8
3
1
8
5
,
7
5
7
7
6
5
(
2
0
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J
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6
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5
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0
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）
P〃Ｏｍｉ"ぬced〃7c'℃“e伽Sz",/hαα"rSbﾉ”o〃応ＣＯ”
５
）
M
e
d
i
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a
,
』
.
Ｃ
・
;
G
a
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C
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E
c
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e
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n
,
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;
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o
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l
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1
9
9
1
)
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６
）
Ｗ
a
n
9
,
Ｋ
.
;
M
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;
Z
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K
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喝
Ａ
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､
；
Goke1,Ｇ.WOIganometallicamphiphiles:oxidizedfe雁
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(
1
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n
g
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c
l
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6
5
,
6
6
9
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7
2
(
1
9
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)
．
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）
K
a
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,
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､
;
K
o
n
d
o
,
Ｙ
;
Y
b
‐
shino,Ｎ､;Ａbe,MElectrochemicalcontrolofvesicle
formationwithadouble-tailedcationicsurfactant
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0
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2０７

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