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Nanoscience and Nanotechnology as Manufacturing Core

Lecture 6
Nanoscience in Chemistry:
Effects in nano/micro-particles

R3 Institute for Newly-

Emerging Science Design,
Osaka University
Hitoshi Watarai
渡會 仁
[email protected]
 Lecture 6
Nanoscience in Chemistry:
Effects in nano/micro-particles

1. Weak working force on a molecule and a particle

2. Laser photophoresis
3. Magnetophoresis
4. Electromagnetophoresis
5. External force and chemical reactions
6. Magneto-optical effect in chemical systems

Exercise 2
1. Weak working force on a molecule and a particle
Total chemical potential

 ext
   RT ln c
0

Interaction Interaction with

with external solvent
field
Generalized working force

 d d  RT dc
ext 0
F     
 dx dx  c dx
Prof. J. C. Giddings Force from Force from Diffusion
(1930-1996)
external field solvent, L/L
interface
x is migration axis or separation axis, nm－cm
 Separation force working on molecule and particle
μ*＝ μ（internal potential）＋ μext（external potential）

 d ext d 0  RT dc
Working force F     
 dx dx  c dx
Gradient of Solvent Diffusion by
external field effect at L/L concentration
interface gradient
Shape of separation potential
continuous discontinuous combination
μ* electrophoresis μ* solvent extraction μ* electro-deposition

X（separation axis） X（separation axis） X（separation axis）

 Force and work
1N
1m

Work（Ｊ） ＝ force（Ｎ） × distance（m）

Intensive property Extensive property
Pressure, P Volume, V
Electric potential, E Charge, q
Surface potential, γ Surface area, A
Chemical potential, μ Mole, n

Work in Chemistry = Gibbs free energy or

sum of chemical potentials
 Force in Chemistry?
●Migration force of molecule and particle
●Force of chemical bond
(force to break the bond)
Usually, chemical bonding force is represented by
the formation enthalpy (J/mol), not by force (N).
 Force required to migrate a particle
Viscous force Fs is induced against migration force Fp

Fs Fp

Stokes law, Fs = 6πηｒｖ ≒ 17 fN (10-15 N)

Example; water, 25oC η = 892×10－6 Nsm-2

radius, r = 1μm, ｖ = 1μm/s
More sensitive than AFM (1nN – 0.1nN)
Fs = 0.2 ｆN in air
 Force required to migrate an ion
Viscous force Fs is induced against migration force Fp

Fs Fp

Fs = Fp = qE = 6πηｒｖ ≒ 85 aN (10-18 N)

Example; water, 25oC η = 892×10－6 Nsm-2

radius, r = 0.5 nm, ｖ = 10 μm/s
(electrophoretic velocity of +1 ion under 530V/m)
Chemical bond is hardly broken by this force.
Application of weak working force

External field (U) Minute working force (F)

Gravity  dU  Sedimentation force F ∝ r
F   
Magnetic field  dx  Magnetic force F ∝ r3
Electric field Electrostatic force F ∝ r0
Dielectric field Dielectric force F ∝ r3
Electromagnetic Electromagnetic force F ∝ r3
field
Laser light Scattering force F ∝ r2
Flow
F r n
Viscous force F ∝ r

Electrostatic force can work on a single ion.

Other forces are effective for larger particles. This may be a reason
why many macromolecules are found in biological system.
2. Laser photophoresis

Laser-photophoresis
Photo-thermal laser-photophoresis
Force of laser beam
Acceleration and trapping of a Gradient of photo-intensity
particles by radiation pressure generates the gradient force,
P. N. Lebedew (1899) Optical tweezers
A. Ashkin, Phys. Rev. Lett. (1970). F = α▽E/2
Intensity distribution of laser
Gaussian beam

Scattering force
working to the direction
of light, Photophoresis

The tail of comet is the flowed dust and ice particles

by the photophoretic force of the sun.
The tail of comet is the flowed dust and ice particles by the radiation force of the sun.

SUN

01/06 07:32
Comet Machholz, photo by Kihoku-tenkyuu kan
 Observation of laser photophoresis

FR FP
Laser digital video recorder
v CCD
laser beam dielectric
filter
2 Pnr 2
FP  Q back illumination micro cell
c 2

n, refractive index of medium optical objective microscope

P , laser power
fiber lens lens 50´
r, radius of particle
Q, migration efficiency
c, velocity of light
ω, waist of laser beam lamp cw Nd:YAG laser
dielectric
mirror shutter
Laser photophoresis of polystyrene particle (μg)

r = 7.5 m

Nd:YAG
Laser

532 nm
140 mW

250 m
Photophoretic velocity

Force by laser beam

P : Laser power
2 n : refractive index of medium
2Pnr
Fp  Q r : radius of particle
c 2
c : velocity of light
 : radius of laser beam
Q : photophore tic efficiency
Viscous force

 : viscosity of medium
Fr  6 rv
v : photophore tic velocity

Velocity
Pnr Experiment proved that migration
v Q velocity was proportional to power and
3c 2
radius of particle.
Langmuir (1996)
 Migration efficiency by Ray Optics
Momentum change by the
reflection and refraction of
beam in the particle and at
the interface are integrated
to estimate Q (Q = 0~1).
Advantage
Easy to calculate
Difficult to consider the absorption
No consideration on size and
wavelength n1,n2; refractive index
R,T; reflection and transmittance
 2
Q  0 S  q ,n1 ,n2 d
coefficient of Fresnel

S    2 sin cos 
T 2 cos2  2   R cos 2 
q , n1 , n2   1  R cos 2 
1  R 2  2 R cos 2
 Mie scattering theory
Laser scattering intensity and direction were simulated, and the
efficiency is calculated from the momentum change.

   Csca scattering coefficient, Cabs

Q  Csca 1   F ( ) I ( ) cosd   Cabs
 0  absorption coefficient, F(a) solid angle
＊Calculation fraction at scattering angle  ,I () solid
refractive indexes of particle and medium, angle scattering intensity at angle 
extinction coefficient, laser wavelength,
particle radius

532 nm

r = 1 m r = 2 m
Photophoretic efficiency of polystyrene particles
Hirai, Monjushiro, Watarai, Langmuir (2000)

Photophoretic efficiency, Q
0.15

Ray Optics
Q = 0.129
0.1

Obsd.
0.05

Photophoretic velocity of
Mie
polystyrene particles in theory
water, 1064 nm, 120 mW 0 0.5 1 1.5 2 2.5
radius / m
Laser photophoretic velocity of red blood cell
Analytica Chimica Acta 777(2013)86

normalized velocity
30 red blood cell
90°
white blood cell n
Velocity /m s-1

1 y=Σan x
a0=2.58826544e-16 45°
20 a1=6.39931717e+00
a2=1.86481417e+01 0°
0 20 40 5.52042917e-01
60 80
orientation angle / degree
|r|=9.98018118e-01
10
Velocity was increased n by
the change y=Σan x
of orientation
a0=0.00000000e+00
0 0.5 1 angle of reda1=1.97739971e+00
blood cell.
Laser Power / W 2.51488053e-01
Variation of |r|=9.12039757e-01
size < 10%
●Separation of red blood cell and white blood cell by laser
photophoresis 100
blood platelet
80 white blood cell
red blood cell
60

X / m
Flow
rate V 40
Laser Separation is better
RBC in low flow rate.
20

0
0 0.002 0.004 0.006 0.008 0.01
WBC
1/V / m -1s
532 nm

X axis
100 m

Laser power 532nm,1.0 W

Beam waist 92.4 m
Capillary 100m
●Periodic expansion-contraction induced by laser irradiation
Novel mode of laser-photophoresis Co(Ⅲ)-par complex
O

N
514.5 nm, N
N
O
Co Z+
50mW O N
N
N

Absorption max at 514nm

CH3
+
CH3(CH2)13 N CH2 Cl-
CH3

Water-in-oil (w/o) microemulsion Co(par)2 A

droplet, which includes Co(par)2 in 2- q.
complex, in aqueous solution benzylpyridine
w/o emulsion
~100 nm
M . Tanaka , H . Monjushiro , H . Watarai , Langmuir, 20, 10791-10797 (2004)
 Mechanism of expansion-contraction laser photophoresis
(A) Initial stage of phase separation
Co(III)-PAR/2-benzylpyridine droplet
Frame rate, 1/800 s
Laser
Laser

(B) Sudden break of expanding emulsion

6

Laser

radius / m
4

2
period
0
Laser 0 1 2 3 4
t/s

The period is proportional to

the complex concentration.
514 nm

Phase separation of microemulsion is induced by the photo-thermal

conversion. By the thermal osmosis, water transferred into the microemulsion.
When the liquid membrane thickness decreased to about 100 nm, the droplet
was broken and shrank.
 Summary
★Laser scattering force can separate particles with size.
★A bubble in liquid can be migrated toward the laser by
the thermophoresis due to the surface tension difference
between front and back of the bubble.
★Particles will be separated due to the absorption
spectra.
★Photothermal conversion induces micro-phase
separation in microemulsion droplet and periodic
expansion-contraction photophoretic migration.
Development of magnet Permanent magnet Magnetic coil
Nd-Fe-B 0.5T

Magnetic circuit
made from Nd-Fe-B

8.5 mm f : 64 turns
Pulse width: 0.8 ms
Inductance :
1 kHz / 27.87 H
ca 2cm x 4cm x 5cm
Pole piece gap Pulsed ～15T
0.6mm 2.7T
0.4mm 3.5T
Cryogen-free superconducting
magnet
10T, 10cm bore diameter
Bulk superconducting magnet
5T（magnetized in 10T）
Condenser bank 50 – 450 V, 4,000 F, 10,000 F
Novel application of magnetic field to Analytical Chemistry

Molecular force dynamics Single bond analysis

pN force analysis Single cell analysis

Magnetic field Magnetic mass

Magnetization,
Magnetophoretic analysis,
Velocity analysis
force Composition analysis
Susceptibility
Electromagnetic
field Magneto-optical effect Structure analysis
Electromagneto- MCD, MOLD Magneto-optical
phoretic force spectrometry

Separation, Sorting Nano-particle, Protein

Magnetic chromatography DNA, Cell separation
 3. Magnetophoresis
-Application of magnetic force-
Q: What is the origin of magnetic force?

Iron Permanent magnet

plate
N S

Gravity force

Q: Is the magnet consuming energy?

 Magnetization and Magnetic force
Magnetic force (N), F = m(dB/dz), Magnetic moment, m = cpV(B/0)
cp; magnetic susceptibility, V; volume (m3), B; magnetic flux density (T),
0; Magnetic permeability of vacuum (4πx10-7N A-2)

Paramagnetic Mn2+,Co2+, Diamagnetic Zn2+, Al3+,

Fe3+, Dy3+, U4+, radical Zr4+,H2O, hydrocarbon, SiO2,
etc. cell etc.

cp > 0 cp < 0
Depends on electron spin Depend on electron orbital
Spinning never stops. Rotation of electron induces
Smallest permanent magnet opposite magnetic field.
 Magnetophoresis of a single particle in liquid
cm > 0 > cp
Magnetic force + Magnetic buoyancy = viscous force
N
cp dB cm dB
Fp  VB Fm   VB FD  6rv
0 dx 0 dx
cm
S
cp Magnetophoretic velocity
x
2 ( c p  c m ) 2 dB
vm  r B
Magnetophoretic velocity and radius 9 0 dx
cp : magnetic susceptibility of particle
Determination（10-18mol Mn2+） cm : magnetic susceptibility of medium
Interfacial concentration
（10-10mol/cm2 Dy3+）  :viscosity
Photo-induced spin transition 0 :magnetic permeability of vacuum
Magnetic trap separation B ：magnetic flux density
Magnetophoresis of polystyrene particle

Pole-
pieces Magnetophoretic
0.4 mm velocity
gap

2 ( c p  c m ) 2 dB
v  r B
9 0 dx

S
6 m Polystyrene particles (cp = 8.20  106) are dispersed in 0.5 M MnCl2
solution (cm = 8.23  105).
Silica capillary; inside100 m x 100 m , outside 200 m x 200 m
Question; Which direction does it move？

Piece of plastic tape

Approaching a magnet

Ｎ Ｓ

1M MnCl2 aqueous solution

Magnetic field gradient is determined from the
velocity of polystyrene particle.

3m polystyrene, 0.6M MnCl2

 1mm
Magnetophoresis of a red blood cell
magnet
Solvent：0.1M MnCl2(II) aqueous
100μm
solution
0.1 M MnCl2 c = 1.054 x10-5
0.6 M MnCl2 c = 1.036 x10-4 x
0

50 50

v / m s-1
v / m s-1

0 0

-50 -50

-500 0 500 1000 -2000 -1000 0 1000 2000

x / m 2
B(dB/dx) / T m -1

Migration velocity of red blood cell Migration velocity correlates with B(dB/dx)
Magnetic trap separation is possible. Magnetic susceptibility χ= -5.8 x 10-6

Journal of chromatography. A (2002), 961(1), 3-8.

Measurement of Magnetophoresis in 10 T

Cryogen-free 10T superconducting magnet

 B(dB/dx) was determined from the velocity
Fitted by Lorentz function
dB 9 0
B  v dB h
dx 2 ( c p  c m )r 2 m
B 
dx 1  ( x  x0 )2 / w 2
5 Peak position x0 : 97.8 m
Magnetic field 10 T
B(dB/dx) / 104 T2 m-1

4 Max of B(dB/dx) h : 4.71  104 T2 m1

Half width w : 150 m
3

2
100 time stronger than permanent
1 magnet

0
-1000 -500 0
x / m
●Magnetophoretic velocimetry; Determination by the measurement
of magnetophoretic velocity
Determination of Mn(II) in a single droplet
10-18mol level Mn(II) was detected.
Anal. Chem. (2001), 73(21), 5214-5219. Velocity of Mn(II)-extracted droplet
60
300μm 10T superconducting magnet [TTA]init
0.1 M

vmr -2 / m-1s-1
0.075 M
40 0.05 M
0.025 M

20

Droplet extracted Mn(II) 0

2-fluorotoluene -1000 -500 0

x / m

●Mn(II) in a single droplet was determined from the observed velocity.

●Magnetic susceptibility was used for the determination of amount.
Migration of a single organic droplet in water
100
B(dB/dx)x=0 = 4.0  104 T2 m-1
80

-1
vx / m s
60

40

20

0
-100 0 100
0.2 s interval x /m
Droplet:: 2-fluorotoluene (χp = -8.19  10-6)
Fitted by Lorentzian function
Aqueous phase:
v max
pH 6.8, I = 0.3 M, MES buffer 0.01 M vx 
1  ( x  x 0 )2 / w 2
(χm = -9.01  10-6)
X0 = 30 μm, W = 180 μm
Preparation of Dy(III) solution with dispersed 2-fluorotoluene
Aqueous phase Organic droplet
Dy(III) (5.0  104 M) Lauric acid (1.0  102 M)
: S = 5/2, L = 5, J = 15/2 : C11H23COOH
(eff = 10.5 B. M.) 2-fluorotoluene
pH6.8 (0.01 M MES), Ionic Formation constant [Dy(III)C5H11COO]2+
strength 0.3 M (0.1 M Na2SO4) log b = 2.94
T. Gushuchina, G.Kotenko, Koord. Khim. 12, 325, (1986).

3 mL 10 L

10 sec sonication Dy(III) is not extracted

into 2-fluorotoluene.

Sample
 Magnetic susceptibility of droplets depended on the size.
500 0
60

400 -2

-1
Dy3+ + lauric acid 40

vx r / m s
v x 2 ( c p  c m ) dB
-1


vx / m s

300

-1

cp / 10-6
B -4
r 2 9 0 dx

200 20 -6

-2
100 -8
0
0 -10
0 2 4 6 0 2 4 6
r / m r /m
Dy(III) + lauric acid Fitted by cp = a/r + b
No Dy(III), no lauric acid
Only lauric acid
a = 4.5  106 m
Only Dy(III) b = 8.19  106
When Dy(III) and lauric acid are present, the velocity became
larger and vx/r2 depended inversely on the size of droplet.
Definition of interfacial magnetic susceptibility
Organic droplet in water Volume magnetic
ci susceptibility of
interface

c V
f
Magnetophoresis

Volume magnetic Interface

susceptibility of
organic solvent

S
Observed magnetic susceptibility; c p  c  ciV
f
V
The contribution of interfacial magnetic susceptibility
depends on the specific interfacial area, S/V.
 ●Determination of interfacial concentration of Dy(III)
0

-2 Dy(III) present.
cp / 10-6

-4

-6

No Dy(III)
-8

3 M
-10
0 0.5 1 1.5 c p  cDyCint  c 2FT
V

r / m
-1 -1 r
Dy(III) 5.0  10-4 M, c Dy
M
：Molar magnetic susceptibility of Dy(III)
Lauric acid 1.0  10-2 M c 2FT
V
：Volume magnetic susceptibility of 2-fluorotoluene
Interfacial concentration of paramagnetic Dy(III)
Cint = 2.6  10-10 mol cm-2
This is a new absolute determination method.
M. Suwa and H. Watarai, J. Chromatogr. A, 1013, 3 (2003)
H. Watarai and J. Chen, Anal. Chem. 2017, 89, 10141−10146.

Magnetophoresis in capillary cell

Outside 0.43mm x 0.43mm, Inside
0.20mm x 0.20mm, 5 cm long

Glass
Glassslide
slide
Spacer(0.5mmφ Pt)

B Magnet
1cmx1cmx0.12cm,
0.45 T
0.5 mm gap

Sample vial
 Observation of magnetophoretic velocity
Real time video 20150516

HDEHP

Di(2- ethylhexyl)- phosphoric acid

Wako silica gel ODS-Q3 (ca 45 um)

0.2 mm
10 mg
0.10 M HDEHP in ethanol 25 uL
0.10 M TbCl3 aq. solution 25 uL
5 % Triton X-100 30 uL
H2O 2.95 mL

Magnet Moving upward Magnet

1cmx1cmx0.12cm, 0.45 T
0.5 mm gap
Normalized magnetophoretic velocity of silica particle
8
Tb3+/HDEHP
7 ◆ 1.0 (3)
Velocity/m s-1/(pixel area)
600 m below magnet center ● 0.5 (2)
6 ● 0.3 (2)
■ 0.26 (2)
5 ■ 0.2 (2)
▲ 0.16 (2)
4 ▲ 0.1 (2)

0
500 600 700 800 900 1000 1100
Distance below magnet center / m
0.1M HDEHP in EtOH + 0.1M TbCl3
B(dB/dx) = 160 T2/m at 600 μm
B(dB/dx) = 90 T2/m at 700 μm
 Magnetophoretic mole-ratio plots for
Co(II) and Tb(III)-HDEHP complexes
1.4

Normalized velocity
1.2

1
0.1M HDEHP 0.8 HDEHP
+ 0.1M CoCl2 0.6
Co(HDEHP)2 Di(2- ethylhexyl)-
700 m from 0.4
phosphoric acid
magnet center 0.2

0
0 0.2 0.4 0.6 0.8 1 1.2
1/2
[Co(II)]/[HDEHP]
1.2
Normalized velocity

0.1M HDEHP 0.8

+ 0.1M TbCl3 0.6

600 m from 0.4 Tb(HDEHP)3

magnet center 0.2

0
0 0.2 1/3 0.4 0.6 0.8 1 1.2
[Tb(III)]/[HDEHP]
Wako silica gel ODS-Q3 (ca 45 um) 10 mg, 0.10 M HDEHP in EtOH 50 uL,
0.10 M metal solution 0 − 50 uL, 5 % Triton X-100 30 uL, total 3 mL with water
Summary of the composition of the complexes, the magnetic susceptibility
and the maximum amount of the metal ion in a single particle

Metal p1) Composition Maximum Magnetic Molar magnetic Mole of

ion of complex observed susceptibility susceptibility of metal ion in
velocity of of a particle metal ion χM a particle
particle2) χp /m3mol-1 nMLq/N /
/m s-1 pmol3)
Co(II) 4.8 Co(DEHP)2 255 8.4 x 10-6 1.2 x 10-7 3.3

Tb(III) 9.8 Tb(DEHP)3 340 1.9 x 10-5 5.1 x 10-7 1.8

Dy(III) 10.6 Dy(DEHP)3 367 2.3 x 10-5 5.9 x 10-7 1.9

1) Paramagnetic moment in the units of Bohr magneton, 2) at 0.6 mm from the

magnet center, 3) Calculated from the value of the volume magnetic
susceptibility and the molar magnetic susceptibility, assuming Vp = 4.77 x 10-14
m3. 5.0  mol of HDEHP and 10 mg of the silica ODS particles are included.

H. Watarai and J. Chen, Anal. Chem. 2017, 89, 10141−10146.

 Comparison between electrophoresis and magnetophoresis
Electrophoresis Magnetophoresis

Particle size No dependency ∝ r3

dependency Long distance force Short distant force

Migration distance Electric field gradient Magnetic field

(10-100 cm) gradient of B(dB/dx)
(100 m-10 mm)
Property measured Zeta potential of Magnetic susceptiblity
particle of particle
Obtainable Surface electric Composition of
information density, ion charge surface and bulk phase,
Porosity
Wide variety in magnetic susceptibility：graphite(－4.00 x 10−4), silica(－1.56 x 10-5),
water(－9.05 x 10−6), polystyrene(－8.21 x 10-6 ), ethanol(－7.26 x 10-6),
methanol(－6.64 x 10-6), acetone (－5.77 x 10-6 )
 Exercise 2
An air bubble rising in water will change the velocity around the edge of
magnets. How do you expect about the velocity of the bubble,
accelerated or decelerated?

x ① Completely out of the

magnetic field (B=0).
B(dB/dx)= -3000 T2/m ②At the lower edge of
④ the magnets.
Ｎ Ｓ ③ Ｎ Ｓ ③At the center of the
② magnets ((dB/dx)=0).
B(dB/dx)= 3000 T2/m ④At the upper edge of
the magnets.
Air bubble
χp = 0
10 μm in radius ① Water
χm = - 9.0 x 10-6

If possible, try to calculate the velocities at the positions of ①~④ and

describe the expected behavior of a bubble at each position.
(Send me your answer by the 1st of February.)
Hint for Exercise 2

If you want to calculate the rising velocities of a bubble at the four positions along the x axis,
you will use the following equations.
① far from the magnets (B=0)
② at the lower edge of the magnets
③ at the center of magnets (dB/dx=0)
④ at the upper edge of the magnets

The velocity of a bubble is,

χd = 0 (volume magnetic susceptibility of air bubble)

χa = -9 x 10-6 (volume magnetic susceptibility of
water)
ρd = 0 (density of a bubble)
ρa = 1x103 kg/m3 (density of water)
μ0 =1.256 x 10-6 TmA-1 (T=kgA-1s-2)
Fm magnetic force η = 892 x 10-6 Nsm-2 (viscosity of water) (N=kgm/s2)
Fb buoyancy r = 10 μm (radius of a bubble)
Vd = (4/3)πr3 (volume of a bubble)
Ff friction B(dB/dx) = 3000 T2m-1 (magnetic strength at the lower
edge of magnets)
g = 9.81 ms-2 (acceleration of gravity)
v ms-1 (velocity of a bubble)
 4. Electromagnetophoresis

Application of electromagnetic (Lorentz) force

●pN dynamic force measurement of a single cell
●Adsorption-desorption chromatographic separation
Application of electromagnetic (Lorentz) force, FEMF
Fleming’s left hand rule

F B
I

3 𝜎𝑝 − 𝜎𝑓 𝑖
𝐹EMP = 𝐹EMW + 𝐹EMB = 𝐵𝑉
2 2𝜎𝑓 + 𝜎𝑝 𝑆
Electromagnetic weight, FEMW, is the Lorentz force directly working on a particle, and the
electromagnetic buoyancy, FEMB, is the Lorentz force on the medium that works on the
particle as an equal magnitude and opposite directional force. V (m3) is the volume of a
particle, σp is the electric conductivity (S m–1) of the particle, σf is the electric conductivity
(S m–1) of the medium, i is the current (A), and S(m2) is the inner sectional area of cell.
 ●Electromagnetic velocity of a particle
Anal. Sci. (2000), 16(1), 5-9.
8
Velocity / μm s-1

6 (c)

4
Migration velocity
(b) A. Kolin, Science (1953)
2
4 𝜎𝑝 − 𝜎𝑓 𝑖𝐵𝑟 2
(a) 𝑣=
0 9 2𝜎𝑓 + 𝜎𝑝 𝑆𝜂
0 100 200 300
i / A
Electromagnetophoresis of polystyrene particle using
0.1T permanent magnet (Fe-B-Nd)
1.0 M, KCl；sectional are 100μm×100μm capillary
Particle diameter, (a) 3μm, (b) 15μm, (c) 22μm
Migration velocity ～ (current) x (radius)2
●Electromagnetophoretic adsorption-desorption chromatography
Repetition of desorption-adsorption by electromagnetic buoyancy under flow
i ti 8

Number of events
10μm
iD 6
imax
0 W=100 m t 20μm
4

1 2 3
2
applied current＞desorption current：iD
20 m：d = 39.8 ± 9.5 m 0
0 20 40 60 80 100
10 m：d = 79.3 ± 21.1 m tR / s
In a 1 mm capillary,
saw-typed current with 2s period
separation is attained.
Flow
Flow
Desorption current
Flow rate 60 L h1
20 m：920 A
imax ： 2000 A
10 m：1070 A

Y. Iiguni and H. Watarai, J. Chromatogr. A, 1073, 93 (2005).

Retention time is controlled by the max current and flow rate
Conditions polystyrene particles 4
imax : 1500 A

Counts
B : 10 T, ti : 2 s
vf : 60 l h-1
0
imax : 1000 A

Counts
4

0
8
Counts imax : 500 A
4
20 m
Desorption current iD 10 m
0
0 10 20 30 40 50
20 m : 920 A (939 pN) tR / s
10 m : 1070 A (137 pN)
Dashed line : Theoretical retention time
5. External force and chemical reactions
1) Shift of the equilibrium by the stretching force
2) Dynamic force analysis of bond dissociation
Effect of stretching force on a chemical bond
Shift of equilibrium Dissociation of bond
F F
A B A B A B
x0
x0 + Δx
x0 x0 + Δx

Δx
FΔx
Fx ΔG‡(F) ─ ΔG‡(0) = ─ FΔx
G( F )  G(0)  
n
Gauche-Trans tautomerization of cysteamine Dissociation dynamics
Superparamagnetic particle
Magnetite, Fe3O4, including polymer beads
- High magnetization and dispersity (1 m diameter)
- Various surface modification (-COOH, -NH2)

Magnetization, M

Magnetic field, H

(MagSense Life Sciences, Inc.)

ms = 6.54 ×10-14 Nm/T

(MagSense Life Sciences, Inc.)

SERS observation of stretched cysteamine by magnetic force
Force was controlled by the distance
between glass substrate and magnet
(z direction)

2 mm

(MagSense Life Sciences, Inc.) B = 1.5 T, dB/dz = 1050 T/m at 0 mm

COOH modified, diameter 1 m, Ex wavelength: 514.5 nm, 2 mW
ms = 6.54 ×10-14 Nm/T Exposure time: 50 s
Pole piece gap: 2 mm Objective lens: 18x NA 0.42
●Measurement of SERS spectra of cysteamine stretched by magnetic
particle T. Goto, H. Watarai, Langmujr, 2010, 26(7), 4848-4853.

COOH modified magnetic beads

diameter1 m,
B = 1.5 T, dB/dz = 1050 T/m at 0 mm
514.5 nm, 2 mW

●Stretched by 100pN, Trans

form of cysteamine increased Surface enhanced Raman scattering
from 37% to 52%. (SERS) spectra
 Shift of the equilibrium by the
Ag nanoparticle substrate stretching force

4.04Å
3.2Å

F=100pN

Application of Fx
stretching force G( F )  G(0 pN )  
(100pN) n

Longer structure of Trans form is

Trans form 37% to 52% stabilized under the stretching force.
●Electromagnetophoretic force; Breaking dynamics of bonding
Y.Iiguni, H.Watarai, Bull.Chem.Soc.Jpn,79, 47(2006).

Electromagnetophoretic buoyancy
Lorentz force in electrolyte solution

i p   f
FA  FEMP  2BV ( )
S 2 f   p

1) Increasing force method

B：10 T i：0 → 1000 A,
r = 3 pN/s
2) Constant force method
B：10 T, 10, 20, 30 pN
Con A (p：0.072 S cm-1)
1 M KCl (f：0.112 S cm-1)

Mannose chain on a yeast cell and

lectin linked to the wall of capillary
can bind specifically.
 Electromagnetophoresis measurement system under 10T
PTFE tubing
Amp.
source
Monitor
PC

CCD

Microscope
Ag/AgCl electrodes capillary

Observation
Tube

Capillary B (10 T)

Light source
Intersectional Electrode Syringe pump
無冷媒型超伝導磁石(～ 10 T)
Dissociation force dynamics Pulling force
Yeast - Con A
Yeast cell surface Yeast cell surface

Mannose
cleavage
ConA ConA

10 Con A
0 y=ax+b
Averaged 41 pN koff(0)= 4.9  10-3 s-1 a=0.193
8 b=-5.48
Advantages;
ln(1/t ln(N(0)/N(t)))

-2 r=9.88
6
Counts

-4
1)No
a*x+b contact to particle
a=1.92740113e-01
4 2)High sensitivity
b=-5.50377406e+00
1.16914685e-01
-6 3)Observable
|r|=9.83924660e-01in closed and
2
x = 0.25 nm flowa*x+bsystems
a=1.92860133e-01
0
0 10 20 30 40 50 60
-8
0 10 20 4)Treatment is simple and
b=-5.47541365e+00
1.05811672e-01
FA / pN tD / s easy|r|=9.88272051e-01
 1 N 0   rx 
r = 3 pN/s ln  ln   lnkoff 0   t
 t N t    kBTNb 
6. Magneto-optical effect in chemical systems
1) Faraday rotation
2) Magnetic orientational linear dichroism
1) Faraday rotation
Linear polarized light rotates in the material magnetized to the same
direction of light.

Rotation angle F = VLB

V: Verdet constant, L: Optical cell length,
B: Magnetic flux density

■Widely used in the field of solid magnetic material science

magnetic domain observation, magnetic memory, polarity modulation
■Less studied about chemical systems

Paramagnetic :Left rotation (V < 0) magnetic moment of solute

J. Am. Chem. Soc. 2009, 131, 6328-6329
Diamagnetic :Right rotation (V > 0)
magnetic susceptibility, π-electron property
Anal.Sci., 25, 1-3 (2009)
Application of Faraday rotation
 F  VlB
θF ;Faraday rotation, V; Verdet constant, l; Optical pass length,
B; Magnetic flux density

Magnetism (Paramagnetic, Left rotation, V

< 0; Diamagnetic, Right rotation,V > 0)

Faraday rotation spectra Chirality（Natural rotatory doesn‘t depend

Faraday imaging on magnetic field, so discriminated with
magnetic rotatory)

-electron property (-electrons can

induce high Faraday transition probability)

Faraday imaging will be possible to detect magnetism, chirality and

electron property (sp2/sp3 ratio) for biological tissue and soft
material.
Measurement of Faraday rotation

Optical cell

10 mm

3.5 mm
5 mm

Polarizer & Analyzer

Set with 45º angle (Right rotation is positive.)

Pulsed Magnetic Field

The value of Bl was determined by the
Faraday rotation of toluene.
Vtoluene (410 nm )
2
= 21.8 rad T-1 m-1

Bl / T cm
Solenoidal Coil 5.3 mm 1
10 mm Bl
1 mm 0
40 mm
3 mm Magnetic 0 0.2 0.4 0.6 0.8
field ： 2－7 T time / ms
50 mm
Miyamoto, K., Isai, K., Suwa, M., Watarai, H. J. Am. Chem. Soc., 131, 6328-6329 (2009)
 Verdet constants of lanthanide solution depended on the concentrations.
410 nm 640 nm
Yb3+ 3+ 4 Yb3+ 3+
Lu Eu
10 La3+ Lu3+
Tm3+ Yb3+ Sm3+
Gd3+ Lu3+ Gd3+
3+
Sm3+ 3+
3La 3+ 3+
Tm3+
8 Eu La
Sm
-1

-1
Eu3+
V / rad T m

V / rad T m
Er3+
-1

Tm3+

-1
6 3+
Nd3+ 2Gd3+ Nd3+
Er3+ Nd Ho3+
4 Er3+ Ce3+
Ho3+ Ho3+
Pr3+ 1Pr3+ Dy3+
2 Dy3+ Dy3+ Pr3+
Ce3+ Ce3+ Tb3+
Tb3+
Tb3+
0 0.1 0.2 0.3 0.4 0.5 0.6 0 0.1 0.2 0.3 0.4 0.5 0.6
Concentration / M Concentration / M

# Verdet constants at 410 nm are larger than those at 640 nm.

12
# Intercept was agreement with the Verdet constant of water.
Va ( 410 nm ) = 8.87 rad T-1 m-1 , Va ( 640 nm ) = 3.32 rad T-1 m-1
10 4
# From the slopes, molar Verdet constant, viC (λ), were determined.
-1

8
V / rad T m

-1
-1

V / rad T m

3
V (λ) : Verdet constant of solution
V    Va    viC   Ci
-1

6
Va (λ) : Verdet constant of water
4 2 concentration of Ln3+(mol/L) pH < 2
Ci : Molar

2
 Regularity in the Effective Transition Probability, K, for
Faraday Effect of Lanthanide(III) Ion Solutions
J. Am. Chem. Soc., 131(18), 6328-6329 (2009).

 jn
 
2 J

M
g
 F  VlB  AK ClB K  Im n, M J  X j j  Y n, M J
2 J  1  jn  0
2 2 J
M J  J

100

cm1/2 / 10-4 m3/2 mol-1/2

80 Ho (10)
410 nm 6 80
640 nm Dy (9)
60
4 60
2

2
Er (11)
K/D

K/D
40 Nd (3) cm(Pm) = 3.7
40
20 2 Pr (2)
Tb (8) K = 15.6 D2
20 Pm (4) cm(Pm) calc = 3
0 0 Ce (1)
0
0 5 10 0 2 4 6 8
Number of 4f-Electrons cm 1/2
/ 10 m-4 3/2
mol -1/2

g the Landé splitting factor, J the total angular momentum, jn the a1=1.17087418e+01
a1=4.95972616e+00 transition wavelength,
0 the wavelength of light source, C the concentration
|r|=9.97824984e-01 |r|=9.97210831e-01
of Ln(III) ion, A the constant of 8.09
 10 [s A m T M ] at 298 K .
59 2 -2 -3 -1 -1 a1=1.04193213e+01
|r|=9.82379473e-01
7.979

The effective transition probability, K, containsa0=-3.54238095e+01

the magnetic quantum number, MJ ( = -J, -
a0=-4.51048897e+02
operators,  anda1=7.34159965e+01
J+1, …, J-1, J) and the electric dipole momenta1=2.61697240e+01
|r|=9.82290374e-01X
Y, perpendicular to the
|r|=9.32665176e-01
magnetic field.
Faraday rotation imaging of electron
property and electron property
VC  VC  VC  0.0148 cm  VC
1－Methylnaphthalene 1－ Methylnaphthalene
σ property 27 ％ πproperty 73 ％

glass glass

1 mm

Dodecane Dodecane
σ property 100 ％ πproperty 0 ％

420 nm, 0.62 T, Accumulation 30 times

Discrimination of aliphatic and aromatic compound
Decane Magnetic field：－2.1 T
Accumulation：30 times
1-Methylnaphthalene

Optical image [I / I0] Image

Decane 1-methyl- Decane 1-methyl-

naphthalene I / I0 = 0.552 naphthalene
F = 0.231 rad I / I0 = 0.506
⇒ 0.010 rad F = 0.258 rad
⇒ 0.035 rad

Glass
I / I0 = 0.570
F = 0.222 rad
500 m

squared capillary （500 500 m） at the  I 

bottom of glass rod（f8  10 mm)  F  f  Cos cos f
1

 I 0 

High and low electron property liquids can be discriminated.

Simultaneous measurement of Faraday rotation angle and
natural rotatory angle
Magnetic field and light are same direction
I cos 2 (f     F )
     cos θ  tan (φ  α) sin  2

cos 2 (f   ) B
F F
 I0 P

Magnetic field and light are reversed direction

I cos 2 (f     F )
     cos   tan(f   ) sin  2
B
cos 2 (f   )
F F
 I 0  AP

Faraday rotation angle Natural rotatory angle

I I 0 P  I I 0 AP
1
 F  Cos  1
 I I 0 P  I I 0 AP  
 ,   f  Tan
1

2sin F
2 

Faraday rotation imaging [Evaluation of magnetic susceptibility]

and natural rotatory imaging [Determination of Chirality] are possible.
 Faraday rotation imaging Natural rotatory imaging
1
 F  Cos 1   I I 0 P  I I 0 AP  I I 0 P  I I 0 AP
  f  Tan
1
2  2 sin  F
(A) R S (B) R S
0.230 rad 0.233 rad 0.027 rad 0.016 rad
⇒0.010 rad ⇒0.013 rad

Glass
0.220 rad

R- and S-Limonen showed same positive Rotation direction was reversed.

value (diamagnetic).

R-(+)-Limonen Optical isomers were discriminated.

α=-7.67 mrad
S-()-Limonen Suwa et al., Anal. Chem. 2013, 85, 5176−5183.
α= 7.58 mrad
2) Magnetic orientational linear dichroism
of magnetic nanoparticles

◆Magnetic nanoparticles；magnetite (Fe3O4), maghemite (γ-Fe2O3)

◆Size, surface；2 nm – 20 nm, COOH, NH2 and dextran modified.
◆Magnetic moment; magnetite (10nm), μ = 2.5 x 10-19 JT-1,
maghemite (6.4nm), μ = 7.4 x 10-20 JT-1.
◆Spectroscopic properties；UV-Vis abs. in 300-700nm
Raman shift at 660-670 cm-1 (magnetite), 700, 350, 500 cm-1
(maghemite)
◆Application ；(1)Immunoassay,(2)Separation,(3)Medical use(MRI
contrast agent, drug delivery, hyperthermia, vaccine adjuvant)
Magnetic orientational linear dichroism (MOLD) spectrometry
MOLD= A(horizontal) – A(vertical) Anal. Sci., 35, 951 (2019); Langmuir 36, 12414 (2020).

Rack & pinion V Sample cell

stage
Polarized
light
50 mm H Transversal magnetic field
(Voigt configuration)
Permanent
S magnet(NdFeB 200
N or Ferrite)

Magnetic flux density / mT

180
Light 1 mm, 10mm 160
Beam Quartz cell 140
S 120
N 100
80
50 mm
60
40
20
0
Sample chamber 0 10 20 30 40 50

Jasco J-820E Spectropolarimeter Distance from the closest position / mm

(300-700 nm), LD mode NdFeB permanent magnet
Effect of magnetic field on MOLD spectra of MNPs solution
0.08
MNPs 0.00165 wt% (EMG707, 10nm
0.07 Magnetic field Fe3O4) in water, 10 mm cell
0.06
0.05
MOLD

0.04
35.6 mT MOLD intensity was
0.03
0.02 0 mT increased with magnetic
0.01
0
field.
300 350 400 450 500
Wavwlength / nm
0.7
0.6
No change in the
Absorbance

0.5
0.4
0.3 absorption spectra
0.2
0.1
0
300 350 400 450 500
Wavelength / nm

Magnetic field
dependence can be
fitted by Langevin
equation.

Watarai, Sana, Langmuir 2020 36 (41), 12414-12422

 Langevin analysis of MOLD intensity
Magnetization (M) of N particles with the magnetic moment ( ) under the
Boltzmann thermal distribution,
Slope = 0.00555

Orientation to
magnetic field
Random
orientation
(i) Calculation of the slope of the plots
MOLD vs. B in the range of B = 0 – 2 mT.
(ii) Fitting the MOLD using x and MOLDsat .
x = 3*(slope)*B/(MOLDsat) MNPs 0.00165 wt% EMG707 in water,
MOLD = MOLDsat L(x) 10 mm cell

Magnetic moment parameter, μ/kBT = 203 T-1

(about five 10nm Fe3O4 nanoparticles)
LD spectra of MNPs in a UV curable resin, where the orientation is fixed.
Glass slide
0.08
0.06 90˚, 270˚
0.04
0.02
Ｎ Ｓ Ｎ Ｓ

LD
0
-0.02
-0.04
-0.06 0˚, 180˚, 360˚
37 mT, 5μL EMG707+20μLUV -0.08
curable resin, 365nm irradiation 300 400 500 600 700
Wavelength/nm
0.08
0.06
0.04
LD (396 nm)

0.02
0
-0.02
-0.04
cos2θ
-0.06
-0.08 Malus’ law
0 90 180 270 360
Set in a rotation mount Rotation angle of plate/degree
LD measurement
The magnetic moment and the optical transition moment are
paralleled.
 Effect of CTAB on the MOLD spectra of MNPs
0.12 CH3(CH2)15-N+(CH3)3 Br-
0.1 CTAB

0.08
MOLD

0.06 MNPs (EMG707)

0.00165wt%
0.04
[CTAB] = 0 – 6.84 x 10-5 M
0.02 35.6 mT
0
300 400 500 600 700
Wavelength / nm

 MOLD once increased and then decreased suggesting

agglomeration.
 Max. wavelength shifted to the longer wavelength.
 Addition of cationic surfactant showed characteristic
concentration suggesting the association of MNPs.

-4.70

CH3(CH2)15-N+(CH3)3

-4.94

CH3(CH2)17-N+(CH3)3

EMG707 0.00165%, 1 cm cell, 35.6 mT The electrostatic interaction was suggested.

Effect of metal ions on the MOLD spectra

Max. MOLD values can

detect the critical
association concentration
(cac) proceeding to
agglomeration.

EMG707 0.00165% in water,

1 cm cell, 35.6 mT

Watarai, Sana, Langmuir 2020 36 (41), 12414-12422

Summary of the effect of cationic surfactants and the metal ions on MOLD
spectra of COOH-modified MNPs in water (EMG707, 0.00165 wt%, 1 cm cell)
Cation Log Log Percent Magnetic Apparent Stability
([cation]/M) ([cation]/ increase moment association constants
of critical M) of local at local parameter at number at of acetate
association max. conc. max. /% local max. local max. complexes,
conc. /T-1 a) log β1b)
CTA+ -4.70 (0.09)c) -4.61 59 616 2.93 ---
OTA+ -4.94 (0.06) -4.88 43 288 1.39 ---
Na(I) -2.50 ND ND ND ND - 0.18
Co(II) -3.39 (0.39) -3.00 10 345 1.98 1.46
Cu(II) -3.08 (0.33) -2.75 14 264 1.28 1.83
Al(III) -5.10 (0.14) -4.96 61 301 1.45 1.51
Fe(III) -4.88 (0.09) -4.79 38 287 1.39 3.38
Tb(III) -5.00 (0.29) -4.71 49 1288 6.22 1.91
Dy(III) -5.00 (0.25) -4.75 57 1293 6.25 1.85
a) The averaged magnetic moment parameter of MNP monomer was 207 ± 5 T-1.
b) Martell, A. E.; Smith, R. M. Critical stability constants, Plenum Press, 1974-1989.
c) The numbers in parentheses show the difference between the logarithmic values of the
local maximum concentration and the critical association concentration.
The stability of COOH-modified MNPs depends on the charge
of co-existing positive ion（Zagreb rule）.
J. Lyklema, J. Colloid Interface Sci. 2013, 392, 102–104.

Na+ Cu2+
Co2+
Tb3+
Dy3+
Al3+
Fe3+

CTA+ and OTA+ might strongly adsorb to the surface of COOH-MNPs.

Repulsive force was reduced by the adsorption of the cationic ion.

 (a) (b) (c)

(d) (e)

Summary of the TEM and DLS measurements

Samples TEM measurementa DLS measurement
Diameters (nm), 25˚C
(a) No cation b Loose aggregates of 50 -120 nm 133±3
(b) [CTAB]=2.48 x 10-5 M Small agglomerates 119±1
(c) [CTAB]=1.23 x 10-4 M Large agglomerates 150±4
(d) [Dy3+]=1.64 x 10-5 M Linked agglomerates 190±2
(e) [Dy3+]=1.77 x 10-4 M Large connected agglomerates 348±31
a) Diameter of MNPs was 10.8 ± 3.3 nm. b) One mL of 0.00164 % MNPs in water.
 Submission of your Exercises
Please send me your answer of Exercises 1 and 2 by the date
of the 1st of February.

Thank you for joining my lecture.

Hitoshi Watarai
[email protected]

ありがとう.
Cảm ơn.
Terima kasih.
Thank you.
R3 Institute for Newly-Emerging Science Design (INSD),
Osaka University