2107年7月2日
台湾 国立交通大学理学院

SC102 at SBIII

増原塾

講義２

「光化学、分子光科学、光捕捉化学」
増原 宏
masuhara@masuhara.jp, http://www.masuhara.jp/

臺灣

国立交通大學 理学院応用化学系講座教授

増原の略歴1966年 東北大学理学部化学科卒業（小泉研）
1968年 東北大学大学院理学研究科化学専攻修士課程修了（小泉研）
1971年 大阪大学大学院基礎工学研究科化学系化学博士課程修了（又賀研）
1972年 大阪大学基礎工学部合成化学科助手（又賀研）
1984年 京都工芸繊維大学繊維学部高分子学科教授
1991年 大阪大学工学部応用物理学科教授
2004年 大阪大学生命機能研究科兼任教授

2007年 財団法人濱野生命科学研究財団主席研究員
2008年 奈良先端科学技術大学院大学物質創成科学研究科特任教授
2008年 国立交通大学理学院應用化學系及び分子科学研究所講座教授

小泉正夫先生
１９７３年東北大理化学ご退官

１９７４年ご逝去Hybrid orbital

混成軌道と訳された有機化学
無機分析化学
物理化学？？（１９６７年ごろ、修士時代）

構造、反応、物性、（機能）に関する研究
構造研究は絶対的な真理に繋がる研究

反応もそうであるけれど・・・？

反応の研究室は具体的な対象をもっている、豊な分野

阪大広田鋼蔵、同位体
東北大小泉正夫、光反応
東大田丸謙二、触媒

阪大叉賀昇、電子移動反応
・・・・・・

小泉研究室（1966‐1968）
資源のない敗戦国の日本が生きていくために太陽光を使う＝＝＞光化学（昔）

化学反応の中間体を直接捕らえることにより化学反応を理解する＝＝＞光化学（1966年）フラッシュホトリシス、剛性溶媒法

増原（1966－1968）
分子の電子状態から反応を理解したい

叉賀研究室（1968－1984）
光化学反応の素過程を明らかにすることが出来るレーザーを使って光化学の研究を可能にしてくれたら学位をあげる
将来すべての光源はレーザーに置き換わる、新しい現象が可能になる物理化学とは？？（１９７０年代）
構造、反応、物性、（機能）に関する①新しい研究方法論の開発②新しい化学結合と反応に関する概念の提出

小泉、長倉、田中郁三、坪村、叉賀先生
化学反応の時々刻々の変化を直接見る、動的構造

1960年台～、光、レーザー、ビーム・・・
1970代後半、Pimentel Report,

レーザー、SOR、計算機

Prof. Noboru Mataga & Albert Weller (MPI Goettingen)1981 Osaka University

Porter Medal 1996,
IUPAC Symposium on Photochemistry, Helsinki

桃李不言下自成蹊「成蹊」という名は、司馬遷が「李将軍列伝」（史記）において李廣の人物を述べるため引用した諺「桃李不言下自成蹊」（桃李ものいはざれども、下おのづから蹊を成す）から採ったものです。意味は「桃や李（すもも）は、口に出してものを言うわけではないが、美しい花やおいしい実があるから自然と人がやって来て、そこに小道（蹊）ができる。つまり、桃や李は、人格のある人のたとえで、そういう徳のある人には、その徳を慕って人々が集まってくる。」ということです。

Laser Forming Frontiers in Chemistry

時間分解の化学
1992，R.A.Marcus （Electron Transfer）

1986，D.R.Herschbach，Y.‐T.Lee，J.C.Polanyi （Elementary Reaction Process）
1971，G.Herzberg （Free Radical）

1999, A. H. Zewail（fs Chem.）

1967，M.Eigen，R.G.W.Norrish，G.Porter （Fast Reaction）

10-9 sec
1960
10-6 m 10-9 m

10-14 sec

10-12 sec 10-13 sec
1970

1980
10-10 m

1990

2000

NSOM (< 10-7 m)（STM（Confocal)（TEM, SEM）
） H.Rohrer (Microscope）
1986，E.Ruska, G.Binnig,

時間分解と空間分解の化学
Laser & Microscope have high potential in opening new molecular research !

Stage I; 時間分解分光と光化学過程
Time-resolved Spectroscopy and Photochemical Processes(1965-1991)
増原の光化学入門：東北大小泉研
Quantum chemical and electronic spectroscopic studies on π-radicals,
Koizumi Laboratory at Tohoku University (1965-1968)
レーザーホトリシスによる電子移動過程の研究：阪大又賀研
Laser Photolysis Studies on Electron-Donor-Acceptor Systems,

Mataga Laboratory at Osaka University (1968-1984)
時間分解反射分光による不均一分子固体反応の測定：京都工芸繊維大学増原研
Time-resolved Reflection Spectroscopy on Films and Powders,
Kyoto Institute of Technology (1984-1991)

Stage II; 時間分解分光と光化学からマイクロ化学へ
From Spectroscopy and Photochemistry to Micro Chemistry(1988-1994)
単一微粒子・液滴の操作、分光、化学

Spectroscopy, Photochemistry, and Electrochemistry of Single Trapped
Nicro Particles and Droplests,
ERATO project (1988-1994)

単一マイクロ結晶の超高速分光
Ultrafast Spectroscopy of Single Micro Crystals,
ERATO project (1988-1994)
走査型電気化学顕微鏡による半導体表面の超微細加工
Surface Fabrication in Solution by Scanning Electro Chemical Microscope,
ERATO Project (1988-1994)

Stage III; マイクロ化学からレーザーナノ化学へ

From Micro Chemistry to Laser Nano Chemistry(1991-2007)
ナノ分光とナノ光化学
Nano Spectroscopy and Nano Photochemistry,
Osaka University (1998-2007)

ナノトラッピングと光圧化学
Nano Manipulation and Chemistry of Photon Pressure,
ERATO project and Osaka University (1991-2007)
ナノアブレーションのダイナミクスとメカニズム
Nano Ablation Dynamics and Mechanism,
Kyoto Institute of Technology and Osaka University (1991-2005)

Stage IV; 高輝度レーザー光によるバイオおよび分子系の操作
Manipulation of Bio/Molecular Systems by Intense Laser Beams(2003-present)
レーザー捕捉結晶化
Laser Trapping Crystallization,
Hamano Foundation (2007), NAIST (2008-2011), and NCTU (2008- )レーザー制御結晶成長

Laser-Controlled Crystal Growth,
Osaka University (2006-2007), NAIST (2008-2011), and NCTU (2008- )フェムト秒レーザーブレークダウンによる単一細胞の操作と機能制御
Femtosecond Laser Manipulation and Functionallization of Single Living Cells
Osaka University (2003-2007), NAIST (2008-2011), and NCTU (2008-2015)

1990

1991

1994

1993

1999
1993

Books Edited and Written by Masuhara et al.

2003

2005

2004

2004

2006

1999

2007

2009

Books Edited and Writtenby Masuhara et al.

2003

2009

Porter Medal 2006,
IUPAC Symposium on Photochemistry, Kyoto

Thanks to funding and support
MOE (Ministry of Education) ATU (Aiming-Top-University)
Project (National Chiao Tung University), Taiwan
MOST (Ministry of Science and Technology), Taiwan

JSPS (Japan Society for Promotion of Science), Japan
And

Prof. Yuan-Pern Lee of National Chiao Tung University,
TaiwanIntroduction

Sugiyama, Yuyama, Masuhara,“Laser trapping chemistry: From polymer assembly to amino acidcrystallization”
Acc. Chem. Res., 2012, 45, 1946-1954

Laserdisplacement
meter

Morphologicalanalysis

Imaging analysis
EMCCD
video camera

SampleTrapping laser
Dynamic analysis
Avalanche
photodiodeSpectroscopic analysis
Polychrometer

CCD
Detector

Objectivelens

CW NIR laser(λ=1064 nm)

Excitation
light sourcesFor
fluorescenceForscatteringPrinciple of laser trapping of nanometer-sized particles

Fphot = Fgrad + Fscat + Fabs
Near IR laser beam
Objective

Fphot  Fgrad1= em a  E
2
e p − ema = 3Ve p + 2e m

Gradient force

 r − a drV = 4p  r exp
0
 d 
a

2

(d = l / 2pk )0

Scattering force, Absorption force2p

“Trapping, Assembling, and Nucleation Phenomena”
Extended trapping

Just trapping
Optical potential~1 μm

a few μm ~ several tens μm

Metal or polymer nanoparticles

Polymer chains

Nucleation and Growthzzzz
several tens μm ~ a few mm

Molecular clusters

Laser trapping

Nucleation

GrowthLaser trapping of polymers inside solution reported by us in 1990’s
CH 3[

CH CH2[(]n

CH2 CH )

N

C

1

O

NH
H3 C

CH

[(

( CH2CH ) ] n

60

60

C O

C

NH

NH

( CH 2 ) 17

CH 3

CH2 CH )H3 C( CH2CH ) ] n

(

1

O

C O
NH

C H2

C

)

(

C H 2 CH

X

C O

C

NH

NH
H 3C

(CH 2 )3

CH

CH 3

C

CH3
CH2

n

C

C
C

O

CH3
CH2 C

1~3

H3C

CH3

Poly(N-isopropylacrylamide)

n

C

O

N
H 3C

CH3

CH3

Poly(N, N-dimethylacrylamide)

Poly(N-isopropylmethacrylamide)
CH2

CH2

CH

CH2

50

O
R3

CH

n

C

N

CH3

C

CH3

CH2 C 1000

R2

N

O

R1

C

H 3C

CH2

n

CH

CH
H 3C

H

NH

NH

Swelled micelles

Amphiphilic copolymer withcarbazolylalkyl groups

Pyrene-labeled PNIPAM

H
CH2

CH3

SO3 - Na+PNIPAM / alkanoic acid copolymer

C12H25SO4- Na+ONHcomonomer R1

R2

R3

NIPAM

-H

-CH(CH3)2-H

NIPMAM-CH 3-CH(CH3)2

-H

DMAM

-H

-CH 3

-CH 3

P(VDP-co-comonomer)

100 - X

CH 2

N

CH3

Poly(n-vinylcarbazole)

C

)
O

CH3

C

C
NH

CH3

C

49

O

1

C

O

n

NH
CH 2

CH2
SO3- Na+

Pyrene-labeled poly (2-(acrylamido)-methylpropanesulfonate-coN- cyclododecylmethacrylamide)

(a)

(b)

(c)

(d)

(e)

(f)

(g)

(h)

(i)

(j)

Laser Trapping Assembling inside Solution
Forming a Single Sphere
PEO polymer

Dye-doped Polystyrene NPs(Particle size:100 nm)

Back-scattered light from the focus

Fluorescence intensity(Molecular weight:100-900 kDa)

Amino acid(glycine)

6

(105)

4

Fluorescence from the focus

2

0

0

20

40

60

80

100

Back-scattered light from the focus

Time (s)Singer W. et al., Phys. Rev. E
2007, 75, 011916

Hosokawa C. et al., Phys. Rev. E
2007, 70, 0614140

Tsuboi Y. et al., J. Phys. Chem. C
2013, 114, 5589

➢ Nanometer-sized objects like polymers, nanoparticles,amino acids are sequentially trapped in the focal
volume, and the local concentration is increased with
irradiation time.
26

Laser Trapping of Amino Acids at Solution Surface
Inducing Crystallization
Focal point

1s

16 s

50 µm

12 s

Glycine in heavy water
Sugiyama, Adachi, Masuhara, Chem. Lett., 2007, 36, 1480

A near infrared CW laser focused at an air/solution interface induced
crystallization of glycine, giving a length of 50 micrometer.

Sugiyama, Adachi, Masuhara, Chem. Lett., 36, 1480, 2007

Laser trapping crystallization of amino acids
Name

Glycine

AlaninePhenylalanine

Structure

Rungsimanon, Yuyama, Sugiyama, Masuhara,
Tohani, Miyata,
J. Phys. Chem. Lett., 2010, 1, 599

Yuyama, Ishiguro, Sugiyama, Masuhara,
Proc. of SPIE, 2012, 8458, 84582D-1

Yuyama, Sugiyama, Masuhara,
J. Phys. Chem. Lett., 2013, 4, 2436
Yuyama, Wu, Sugiyama, Masuhara,
Photochem. Photobio. Sci., 2014, 13, 254

Rungsimanon, Yuyama, Sugiyama, Masuhara,
Cryst. Growth Des., 2010, 10, 4686
Yuyama, Rungsimanon, Sugiyama, Masuhara,
Cryst. Growth Des., 2012, 11, 2427
Sugiyama, Yuyama, Masuhara,
Acc. Chem. Res., 2012, 45, 1946

Name

SerineThreonine

ValineLeucineIsoleucine

Structure<Unpublished>https://www.sigmaaldrich.com/japan.html/

Laser trapping amyloid formation
in solution
Cytochrome cYuyama, Ueda, Nagao, Sugiyama, Hirota, Masuhara
In preparation (2016)

Horse hear cytchrome cmonomer

C-terminal helix

Domain-swapped dimer

Fluorescence characterization of amyloid formation by thioflavin T

SEM observation

TEM observation

TEM observation

100 nm

50 nm

20 nm

Protein crystallization uponswitching trapping laser off
at glass/solution interface

Lysozyme
Yuyama, Chang, Tu, Sugiyama, Masuhara
In preparation, 2016

Preparation procedure of HEWL buffer solution

Side
view
Overh
ead
view

20
mm
Proteinsolution

Concentration(Total Volume)

40 mg HEWL in 1.0 ml D2O
buffer(80 µL)

NaCl

2.7 %

Laser power

0.5, 0.8 and 1.1 W

Laser Polarization

Linear, Right- and Lefthanded
Circular, Depolarized

Irradiation time30, 60, and 90 min

2 mm

4-6 hours for
Spontaneous nucleation
Adding HEWL
buffer solution
into the container(80 mL)

Turning
off laser
60-min laser irradiation ata point of 3 µm above a
glass surface

Comp
uter

Observation

39

Laser trapping of protein at solution surface
gives a single disc-like assembly instead of a crystal
Lysozyme 40mg/ml with 2% NaCl, Transmittance images
Solutionsurface

Transmittance images
1064nm: 1W

50min

30min

60min

30mm
40

Laser trapping inside the solution gave no crystal and assembly, but wefound many crystals were formed upon stopping laser trapping.
26 mm
ChamberY

Optical Setup
Halogenlamp

Objective
lens
60X, N.A.=
0.9

CW: Nd3+:YVO4
laser(l: 1064 nm)
Motorize
d
XY
stage

26 mm

X
(0.0, 0.0)

CW: Diodelaser(l : 532 nm)

Inverted microscope

Glass substrate
Half-wave
plate
Polarizing
beam splitter

CCD
CameraComputer
41

Distribution of crystallization position
depending on laser power
Laser trapping-induced nucleation

Spontaneous nucleation
Aging time

Observation time

Irradiation time

Observation time

4 hrs

20 hr

1 hr

30 min (for 0.8 and 1.1 W)
120 min (for 0.5 W)

4 hr

0 hr

24 hr

0 hr

1.5 hr (or 3 hr)

1hr(Linearly polarization)
Each condition : 10 samples(a) Spontaneous

Unit : mm(d) 1.1 W

10

10

10

5

5

5

0
-10

(c) 0.8 W(b) 0.5 W

-5

0

0
0

5

10 -10

-5

0

5

-10

10

-5

0

-5

-5

-5

-10

-10

-10

Total # of Crystal : 99

Total # of Crystal : 107

Total # of Crystal : 103

5

10

Total # of Crystal : 98

42

The position distribution of HEWL
crystal depending on laser power

50

20

15

30
10
20
5
10

AVG : 2.3 mm
SD : 1.7 mm

20

15

30
10
20
5
10

0

0

40

0

0

(mm)

40

60

25

AVG : 2.3 mm
SD : 1.2 mm

50

20

15

30
10
20
5
10

0

(mm)

0

(mm)

Number of crystal

Number of crystal

50(c) 0.8 W

Number of crystal / mm2

60

25

Number of crystal / mm2

AVG : 4.7 mm
SD : 2.4 mm(b) 0.5 W

40(d) 1.1 W

25

AVG : 2.3 mm
SD : 1.2 mm

20

15

30
10
20
5
10

0

Number of crystal / mm2

40

60

25

Number of crystal

Number of crystal

50(a) 0 W

Number of crystal / mm2

60

0

(mm)

43

We proposed that a large highly concentrated
domain formed around the focus by laser trapping.
Here we extend systematic study toward control
of HEWL nucleation through the domain.

Highly concentrated
domain formation of
HEWL clusters

Laser
trapping

Glass
substrate

Crystal generation insidethe domain formed by laser
trapping

Laser
irradiation

Laser focus

Chamber

Highly concentrated domain

44

Fluorescence study on highly concentrated domain
formation in D2O
5-TRITC(Tetramethylrhodamine-5-isothiocyanate)

0 min

15 min30 minFocal spot

20 μm

HEWL : F-HEWL =16000 : 1

(F-HEWL is 5-TRITC labeled
HEWL)

Temporal change in distribution of fluorescence intensity by laser trapping

10 mm away from a
focus

45

Supramolecular assembling uponswitching trapping laser on and off
at solution surface
azobenzene-based bis-calix[4]arene

Yuyama, Marcelis, Su, Chung, Masuhara
In preparation, 2016

Absorption spectra of trans-cis isomerization ofcompound 14 (bis-isoxazole)

0.8

0.8

0.6
solution
UV for 10 s
UV for 30 s
UV for 1 min
UV for 2 min
UV for 3 min
UV for 4 min
UV for 5 min
UV for 6 min
UV for 7 min

0.4

0.2

0.0
300

400

500

600

Wavelength (nm)(a) 10-5 M in CH2Cl2/MeOH = 1/5 under UV lightfor different times

Absorption

Absorption

0.6

UV for 7 minlight for 2 minlight for 4 minlight for 6 minlight for 8 minlight for 10 min
light for 12 minlight for 14 minlight for 16 min

0.4

0.2

0.0
300

400

500

600

Wavelength (nm)(365 nm) irradiation(b) 10-5 M in CH2Cl2/MeOH = 1/5 under UV light irradiation for 7 mins
and further visible light irradiation for different times48

Absorption spectra of trans-cis isomerization ofcompound 7 (tri-oxazole)trans-azo-Bis-triazole 7 (Gel)(a) 0.40

cis-azo-Bis-triazole 7 (Solution)(b) 0.40

0.35

0.35
0.30

0.25
0.20
Before UV light irradiation
UV light irradiation for 10s
UV light irradiation for 20s
UV light irradiation for 30s
UV light irradiation for 40s
UV light irradiation for 50s
UV light irradiation for 60s

0.15
0.10
0.05
0.00
300

500

400

600

Wavelength (nm)(a) Absorption spectrum of compound 7 in Acetonitrile (1 x 10 -5 M),
using 365 nm irradiation for different times

Absorption

Absorption

0.30

0.25
UV light irradiation for 60s
visible light irradiation for 20s
visible light irradiation for 60s
visible light irradiation for 120s
visible light irradiation for 4 mins
visible light irradiation for 6 mins
visible light irradiation for 10 mins
visible light irradiation for 15 mins

0.20
0.15
0.10
0.05
0.00
300

400

500

600

Wavelength (nm)(b) Absorption spectrum of compound 7 in Acetonitrile (1 x 10 -5 M), after
UV light irradiation for 60 s, and further using tungsten irradiation fordifferent times

Gelation properties for compound 7 and 14 in different organic solvents
Solvent

7 (Bis-triazole)

14 (Bis-isoxazole)

17 (triazole-control)

18 (isoxazole-control)

CH2Cl2CHCl3
1,2-dichloroethane
DMSO
DMF
THF
BenzeneToluenep-Xylenep-Dioxane
Pyridine
Ethyl acetate
AcetoneAcetonitrilen-Hexane
MeOH
EtOH
n-Propanol
Isopropanol
n-Butanol
t-Butanol

a

S
S
P
S
S
S
P
P
P
S
S
S
S
P
I
I
I
P
I
P

I
P
I
G (2.22, 50 mg/mL)
G (3.40, 50 mg/mL)
P
P
P
P
P
PG
I
I
I
I
I
I
I
I
I
I
I

S
S
P
P
P
S
P
P
P
S
P
P
PGf
P
I
I
I
I
I
P
I
-

Cyclohexane
Cyclopentanone
Cyclohexanone

S
S
S
S
S
S
Pb
S
c
G (3.73, 33 mg/mL)dS
S
SS
G (1.79, 14 mg/mL)
Ie
G (0.19, 1.5 mg/mL)
G (0.20, 1.6 mg/mL)
G (0.56, 4.5 mg/mL)
G (0.24, 1.9 mg/mL)
G (0.87, 7.1 mg/mL)
G(0.67, 5.3 mg/mL)
S
S
S

I
S
S
S

aS = solution (溶液); bP = Precipitate (沉澱); cG = gel (凝膠) ; d( ) : wt %; eI = Insoluble.(不溶解); fPG= Partial gel (部分凝膠)

SEM images of compound 7(a)10-3 M in Acetonitrile
1 mm(b)10-3 M in Methanol(c)10-3 M in Ethanol

80 nm
50 nm
80 nm

800 nm
60 nm
1 mm
600 nm(d)10-3 M in Isopropanol(e)10-3 M in t-Butanol(f)10-3 M in p-Xylene

47 nm
50 nm

233.2 nm

83 nm
202.8 nm

66 nm

51

Dipole-dipole interaction

OH
OH
OH
OH
OH
OH

Van der Waals interaction

p−p stacking interaction and photoresponsive functional group
H-bonding52

The X-ray structure of compound 14

Assembly formation by laser trapping
at a solution surface
Switch ontrapping
laser

0 sec

2 sec

4 sec

10 secsea urchin like structure

Switch offtrapping
laser

Size of images; 80×60 μm2

Assembly morphology after switching off trapping laser
Rayleigh scattering image
Transmission
image

100 × 80 μm2(with confocal scanning microscope)

100 × 80 μm2

A large mm-sized domain of liquid-likeclusters where crystallization takes
place
at solution surface
L-Phenylalanine
Yuyama, Sugiyama, Masuhara
J. Phys. Chem. Lett., 2013, 4, 2436-2444
Yuyama, George, Thomas, Sugiyama, Masuhara
Cryst. Growth Des., 2016, 16(2), 953-960

Laser trapping crystallization of L-phenylalanine
L-Phe unsaturated
aqueous solution（supersaturation degree; 0.83）

L-phenylalanine (L-Phe)

Laser power
1.1W
120-160 μm

objective lens
x60, NA=0.90

CW laser（λ=1064nm）
CCD camera

Laser trapping of L-Phe inside solution
Under unsaturated condition

molecular assembly

5 μm

Crystallization of L-phenylalanine
Crystallization behavior (SS=0.83)

Crystallization behavior (SS=0.67)(1) 0 sec

(2) 170 sec

focal
spot
20 μm

(3) 180 sec(4) 195 sec•The formation of the plate-shaped anhydrous crystal from the focal spot
•The 100% crystallization probability (unsaturated and saturated solutions)

10/23

Laser trapping crystallization of L-Phe at solution surface
Under unsaturated condition<CCD image>(2) 543 sec

Focal
spot
20 μm

(3) 568 sec(4) 588 sec

45 μm
80 μm

60 μm

23 μm

Crystal plane area (mm2)(1) 0 sec

<Time evolution of crystal plane area>
2000
1500

21 μm2/sec

1000
500
0
0 10 20 30 40 50 60 70
Irradiation time after crystallization (sec)Crystal plane area (mm2)

Crystal growth control
2000
1.1 W

1.1 W

1500

6.7
6.2
mm2/sec mm2/sec

1000

0.06 W(0 mm2/sec)

1.1 W
6.3
mm2/sec

0.06 W(0 mm2/sec)

500
0
0
100
200
300
Irradiation time after crystallization (sec)Crystal dissolution

Crystal plane area (mm2)

200
150

1.1 W

98 sec138 sec

188 sec

238 sec

0.06 W

Crystallization

100
50
0
0

50
100 150 200
Irradiation time (sec)250

Image size;2 40×30
μm

Crystal size is decreased through crystal dissolution.

Possible mechanism
Irradiation at 1.1 W

formation of a dense domain

nucleation

crystal growth

crystal dissolution
Outward diffusion of a dense domain
Irradiation at 0.06 W

A highly concentrated d0main surrounding the crystal
Original focal position
Movement
distance

Crystallization by laser
irradiation

200 μm/sec

Manipulation of thecrystal

Dissolution of the crystal

Crystal plane area (mm2)50
40

300 μm700 μm

900 μm

30
20
10
0

0
250
500
750
1000
Distance from the original position (mm)Image size; 30×22.5 μm2Lateral manipulation of the crystal at the surface suggeststhat the crystal is surrounded with a dense domain.

Laser trapping coupled with opticalscattering/propagation gives a single crystal
at solution surface
L-Phenyalanine
Yuyama, Sugiyama, Masuhara
J. Phys. Chem. Lett., 2013, 4, 2436-44
Yuyama, George, Thomas, Sugiyama, Masuhara
Cryst. Growth Des., 2016, 16(2), 953-960

Trapping at the crystal edge (1.1 w)
PS beads（1 μm）
Addition of colloidal solution

1s

Re-trapping of crystal

17
s

10 μm

Trapping at the crystal edge is possible.

Trapping at the crystal edge
PS beads（1 μm）
Addition of colloidal solution

Re-trapping of crystal

Trajectories of PS beads
Particle (4)Crystal
Focal spot

Particle (1)<every 0.2 sec>

Particle (2)Particle (3)Laser trapping of L-Phe crystal
Laser offcrystal7s

20 μm
Laser on (0.06W)

0.2 s

1s

diffusion

Trapping 1
Repetitive behavior

0.8 sTrapping 2

Trapping 3

Trapping site shift from the focal point to theedge surface of the growing crystal(1) Crystallization(2) Crystal growth• Crystal nature of L-Phe• Trapping laser
peculiar structure(3) Efficient light scatteringor light propagation(3) Further crystal growth

Laser trapping coupled with optical scattering andpropagation gives a single assemblyat solution surface

Polystyrene nanoparticles

Wang, Yuyama, Kudo, Sugiyama, Masuhara
J. Phys. Chem. C, 2016, 120, 15578-15585
Wang, Yuyama, Kudo, Sugiyama, Masuhara
Langmuir, 2016, in press

Mr. Shun-Fa WANG, Ph. D. student getting the degree this autumn.

Experimental Setup

Detected position

0 mm 4 mm 8 mm

Laser power: 1.4 W

74

Observation Methods of Trapping Dynamics
Transmission imaging

Imaging and spectroscopic analysis
of backscattered light

Halogen
lamp
Cover
glass

SamplebottleSamplebottleStage

Transmitted
light
CameraStage

Backscattered
light

White light from
halogen lamp

Camera orSpectrograph75Transmission Imaging of
Nanoparticle Assembly Formation

2X Speed

Halogen lamp illumination from top side

20 mm
76

Transmission Images of
Nanoparticle Assembly Formation➢ Nanoparticle assembly showed coloration, although polystyrene
nanoparticles have less absorption in visible region.
Coloration on the assembly may be structural color.
77

Backscattering Imaging of
Nanoparticle Assembly Formation
2X Speed

20 mm
Halogen lamp illumination from back side (through objective lens)78

Backscattering Images and Reflection Spectra of
Nanoparticle Assembly Formation
Detected position0 mm

Reflectance (%)

12
8
4
0

90
70
50
30
15

Irradiation time (sec)

110

5
400

500

600

700

Wavelength (nm)➢ Reflectance band appeared at 600 nm.

It implies that an ordered structure like a colloidal
crystal was formed in the assembly.
79

Bragg’s Law for Colloidal Crystal

Bragg’s law:mλ = 2ndsinθ
m: diffraction order
λ: wavelength of diffracted lightn: refractive index of the colloidal crystal
d: inter-particle distanceθ: incident angle of light80Bragg’s Law for Colloidal Crystal

Bragg’s law:mλ = 2ndsinθ
m: diffraction order
λ: wavelength of diffracted lightn: refractive index of the colloidal crystal
d: inter-particle distanceθ: incident angle of light

In colloidal crystal, the wavelength of reflected light is shifted toshorter wavelength with the decrease in particle distance.
81

Backscattering Images and Reflection Spectra of
Nanoparticle Assembly Formation
Detected position0 mm

Reflectance (%)

12
8
4
0

90
70
50
30
15

Irradiation time (sec)

110

5
400

500

600

700

Wavelength (nm)➢ Reflectance band appeared at 600 nm.

It implies that an ordered structure like a colloidal
crystal was formed in the assembly.
82

Analysis of Time Evolution of Reflection Spectra
(A)
660

12

640
9
620

(C)

(A)

6
600
580

0

20

40

60

80

100

120

3

Peak reflectance (%)

Peak wavelength (nm)

(B)
(B)

(C)

Irradiation time (sec)➢ Increase in peak reflectance➢ Blue shift of peakwavelength• Increase in assembly thickness• Decrease in particle distance83Analysis of Time Evolution of Reflection Spectra
700

Wavelength (nm)
650
600
550

500

Normalized reflectance

1.0

80 sec80 sec90 sec100 sec

0.8
0.6
0.4
0.2
0.0

1.8

2.0
2.2
Photon energy (eV)

2.4

➢ Narrowing of band width

100 sec• Increase in homogeneity ofparticle packing structure84

Reflection Spectra at Different Positions
120 sec irradiation
700

Normalized reflectance

1.0

Detected position 0 mm

Wavelength (nm)
650
600
550

4 mm

8 mm

500

Detection position
0 mm
4 mm
8 mm

0.8
0.6
0.4
0.2
0.0

1.8

2.0
2.2
Photon energy (eV)

2.4

➢ In normalized spectra, reflection band at the boundary of theassembly was narrower compared to that of the assembly center.
Homogeneity of the assembly structure becomes better toward theassembly boundary.
85

Reflection Spectra at Different Positions
Detected position
0 mm 4 mm 8 mm

(A)

Peak reflectance (%)

15
center
4 mm
8 mm

12
9

(B)

(B)

(C)

(A)

6

(C)

3
0

0

20

40
60
80
100
Irradiation time (sec)120➢ Peak reflectance decreased along the assembly center to the boundary.

The assembly becomes thicker and it has thickness distribution.
86

Reflection Spectra at Different Positions
Detected position
0 mm 4 mm 8 mm

(A)

Peak wavelength (nm)

680

(B)

660
640

(B)

center
4 mm
8 mm

(C)

(A)
620

(C)

600
580

0

20

40
60
80
100
Irradiation time (sec)120➢ In the assembly boundary, the peak wavelength was located inlong position.

The assembly structure is tighter in the center whilelooser in the boundary.
87

Spectral Change after Turning off Laser

0.9
0.6
0.3
500

600

0
1.2
0.9
0.6
0.3

700

500

Wavelength (nm)600

Wavelength (nm)

700

8
4
0
1.2
0.9
0.6
0.3

500

600

Irradiation time (sec)

1.2

4

8 mm

Irradiation time (sec)08

Irradiation time (sec)

4

4 mm

12

Reflectance (%)

8

12

Reflectance (%)

0 mm

Reflectance (%)

12

700

Wavelength (nm)Peak wavelength (nm)750

Laser off after 120 sec irradiation
700
650
0 mm
4 mm
8 mm

600
550
0.0

0.3

0.6

0.9

1.2

➢ Peak wavelength was shifted to longer
wavelength, accompanying with reflectancedecrease in all positions.

Irradiation time (sec)Assembly structure is under dynamical balance between gradient
force of trapping laser and repulsive force between particles.
88

A nanoparticles assembly expands out of the focus!
Inhomogeneous structure is confirmed.

89Direct confirmation on light propagationin laser trapping assemblingat glass/solution interface

Polystyrene nanoparticles

Wang, Yuyama, Sugiyama, Masuhara
J. Phys. Chem. C, 120, 15578-15585
Kudo, Wang, Yuyama, Masuhara
Nano Lett., 16, 3058-3062 (2016)

Dr. Tetsuhiro KUDO styed with us for several months as a PhD
student of Osaka Prefecture Univeristy studying on Optical
Properties of Matters. After he obtained his degree, he joined me
to start his new career as an experimentalist in NCTU.

Optical setup and sample

Polystyrene
particles(500 nm indiameter)
Nd3+:YVO4 laser

1.4 W
focused in 1 μm2(several 100 MW/cm2)

Transmission images of the colloidal assembly
formed by optical trapping at the interface
Linearly polarized light, 1.4 W

10 μm

Transmission images of the colloidal assembly
formed by optical trapping at the interface
Linearly polarized light, 1.4 W

Movie

Transmission images of the colloidal assembly
formed by optical trapping at the interface
Linearly polarized light, 1.4 W

Sequence images

Transmission images of the colloidal assembly
formed by optical trapping at the interface
Circularly polarized light, 1.4 W

10 μm

Transmission images of the colloidal assembly
formed by optical trapping at the interface
Circularly polarized light, 1.8 W

Movie

Backscattering image of1064 nm trapping laser
Just after thelaser irradiation

Four horns

Six horns

10 μm

(a, b) Laser intensity distribution in focal plane(c, d) Structure of formed assembly(e, f) Back scattering images of 1064 nm trapping laser
Linearly polarized light

Tetragonal

10 μm

Circularly polarized light

Close-packed

Trapping at the interface

Strong laser intensity
The present laser power of 1.4 W is about 100 times higher
than minimum laser power (15 mW)
Laser wavelength vs. particle size
1064 nm laser
500 nm particle

Our proposals on laser trapping dynamics

A large millimeter-sized domain of liquid like-clusters isformed at solution surface for amino acids, proteins, andsupramolecules.
A single crystal and a single assembly are formed atsolution surface for amino acids and polystyrene
nanoparticles, respectively.
Packing and orientation prepared at the focus propagate
to the outside through strong intermolecular interactions..

Optical trapping, scattering, and propagation are coupled,which is named optically evolved assembling.

Mr. Wei-Yi Chiang, Ph. D. student who stayed in KUL and isstaying again for 20 October 2016 - 19 July 2017.

Laser Trapping by Femtosecond pulses
Point Dipole (Rayleigh) Approximation

Laser trapping with Pulsed lasers

Lorentz Force

1
FLorentz = [P  ]E +  t E  Hc

P = c (1) E + c ( 2) EE + c (3) EEE + ...

Ftemporal = 1 (nm3 e 0a / c) t E
2

J.P. Gordon, Phys. Rev. A 1973, 8,14;
LG Wang, LG Zhao, Opt Express 2007,15,16015

NLO effects

Pulsed Lasers
Temporal ForceNLO Effects
Impulsive Peak Powers
Periodical Field; Periodical Optical Forces
Relaxation and diffusion between consecutive
pulses.

2

CW
Constant Field,
Constant Optical Forces,
Suppressed Diffusion,
Steady Trap

Our Experimental Setupzyx

Pulse Compression

White Light
Laser Pulses(800 nm; 120 fs,
80 MHz)Dark Field
Condenser Lens
(NA 1.4‒1.2)
Sampleλ/2Objective Lens

Rayleigh Scattering Imaging

Objective Lens
(60× NA 0.90)

Oil

Dichroic Mirror
750 nm SP filter

Collimation Control

800 nmCCD
LPF SPF
CCD

DM

Optical Trapping and Directional Ejections of Polystyrene NPs
CWLight Scattering Intensity/ a.u.

J. Photochem. Photobiol. A: Chemistry 2012, 234, 83

20 mm

E

250

fs

200

150
20
15
10
5
0

CW
0

20

40
60
80
Trapping Time/ s

100

120

0

100

200

300

400

500

600

700

Occurence

350 mW

fs

E

E

E

We have prepared silica NPs covered with TEOS and PDI.
TEOS

SiNPs
100 nm+PDI

In Toluene
Room temperature,
24 hr stirring

Controlling different concentration ratio of alkysilane and PDI to obtain varied dyecoverage on SiNPs and avoid PDI aggregations on particle surface.
Ejection behavior is observed now for silica NPs covered with TEOS and PDI!

(In preparation for J. Phys. Chem. C)
Femtosecond Laser Trapping, Assembling, and Ejection Dynamics ofHydrophobic Nanoparticles in Aqueous Solution
Wei-Yi Chiang,1,3 Anwar Usman,2,* Teruki Sugiyama,1 Johan Hofkens,3,* Hiroshi
Masuhara1,*

450 nm

150 nm

128 nm

100 nm

450 nmwhen we used the sample modified by low concentration silane solution, which means thecoverage on surface of silice was low, the ejection from ball shape changed to fan shapeagain as what polystyrene beads showed.

Dyes synthesis

Synthesizing unsymmetrical perylene dye (PDI) which
has ethoxysilane groups that can react on the silica surface.

H-NMR measurement
2

1

5

8
10

10

9

9

9

9

10

10
8

7

6 7
3

4
10

3

9

7 3
7
3

2
8

65 4

1

Experimental setupzPulse Compression

White LightyLaser Pulses(800 nm; 120 fs,
80 MHz)x

Sampleλ/2Objective Lens
(60× NA 0.90)
Dichroic Mirror
Collimation Control

polychromator

CCD

750 nm SP filter

Objective
Lens

Sample:100-nm-sized SiNPs
Suspended in waterC = 3.9×1013 particles/mL
Laser power : 300 mW
Spectra exposure time = 0.033 s

Introducing fs pulsed laser into sample chamber which contain particle solution.
Taking advantage of polychromator to measure fluorescence spectra.

9000

5400

3600

1800

0

m
Ti

20

e

40

30

[s
]

50

10
400

450

500

550

600

650

700

750

800

Wavelength [nm]Video and spectra are different measurement!

Fluorescence Intensity [a.u.]

10000

8000

550

6000

4000

590

2000

657
0
0

10

20

30

Time [s]4050Intensith [au]

7200

9000

5400

3600

1800

0

m
Ti

20

e

40

30

[s
]

50

10
400

450

500

550

600

650

700

750

800

Wavelength [nm]Video and spectra are different measurement!
7000

Fluorescence Intensity [a.u.]

6000
5000

550

4000
3000

590

2000
1000

657

0
0

10

20

30

Time [s]4050Intensith [au]

7200

9000

5400

3600

1800

0

m
Ti

20

e

40

30

[s
]

50

10
400

450

500

550

600

650

700

750

800

Wavelength [nm]Video and spectra are different measurement!
6000

Fluorescence Itensity [a.u.]

5000

4000

550
3000

2000

590

1000

657

0
0

10

20

30

Time [s]4050Intensith [au]7200

増原スタイル： 深謀遠慮
研究成果は人生の全積分
情勢分析は必要不可欠
Pimentel Report （1970年代）
レーザー、コンピューター、シンクロトロン
又賀コメント （1968年）「あらゆる光はレーザーに取って代わられる」
物理化学者は方法論で、有機化学者は合成で、理論化学者は数学（計算機ではない）で勝負。
レーザー、光学顕微鏡・・・・・・・光と物質の相互作用
STM, AFM, SEM・・・・・・・・・電子と物質の相互作用
これらの間を乗り換えてはいけない、自分を失くす

Thank you very much for your kind attention !!
All of you are welcome to Hsinchu Taiwan !!