Aggregation Induced Resonance Raman

Optical Activity (AIRROA)

CHEM 502

Mutasem Alshalalfeh

Jan 22th, 2020

1
 Outline
Background
Raman and Raman Optical Activity (ROA)
Enhancement of ROA signal

Aggregation Induced Resonance ROA (AIRROA)

ROA of carrot root extract
Types of aggerates and their optical properties
Resonance ROA of model aggregates
Requirements for AIRROA

Summary

2
 Raman and Raman Optical Activity

ROA measures a difference in Raman scattered intensity between

right and left circular polarized light in the interaction with a chiral

molecule or assembly.

S. Haraguchi, et al., Angew. Chem. Int. Ed., 54 (2015): 11555-11558. 3

 Four Forms of ROA

➢ Incident Circular SCP

Polarization (ICP)

➢ Scattered Circular
Polarization (SCP)

➢ In-phase Dual Circular

Polarization (DCPI)

➢ Out-of-phase Dual Circular

Polarization (DCPII)

L. D. Barron, Biomed. Spectrosc. Imaging, 4 (2015): 223-253. 4

 Raman and ROA Spectroscopy
Raman Intensity
I  µ2ind
Raman
µind =  * E
(): the electric dipole-electric dipole polarizability tensor
(E):the electric field strength of the external radiation.

ROA

ROA Intensity
Electric dipole-electric dipole polarizability tensor ()
Magnetic dipole–electric dipole polarizability tensor (G´)
Electric quadrupole–electric dipole polarizability tensor (A)

L. A. Nafie, Theor. Chem. Acc., 119 (2008): 39-55. 5

 Advantages and Limitations of ROA

Advantages
Determination of absolute configuration directly in solution

High sensitivity to geometry changes in solution

Limitations
Very low sensitivity under regular conditions

high concentration sample

long acquisition time

T. Wu, et al., Phys. Chem. Chem. Phys., 18 (2016): 23803-23811. 6

 The main paper

Aggregation-Induced Resonance Raman Optical Activity (AIRROA)

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 7
 What Are Carotenoids?

Carotenoids are plant pigments responsible for bright red, yellow

and orange hues in many fruits and vegetables.

The carotenoid family

▪ Xanthophylls
Lutein and Astaxanthin

▪ Carotenes
α-carotene, -carotene

The difference between the two groups is chemical: xanthophylls

contain oxygen while carotenes are only hydrocarbons.
Jessie, S. (2015, Oct 15). Retrieved from https://www.livescience.com/52487-carotenoids.html. 8
 Carotenoid Microcrystals

95% achiral β-carotene (βC)) – 95%

-Carotene

5% secondary components such as • The sample was tested

using ultra performance
liquid chromatography
(UPLC).
-Carotene (C)

Astaxanthin (AXT)

T. Oleszkiewicz, et al., Planta, 248 (2018): 1455–1471. 9

 Electronic CD and ROA Spectra of
Carotenoid Microcrystal

Raman

ROA
Q1 Why such strong ROA?
Q2 Why ROA bands are monosign?
▪ Electronic Circular Dichroism
(ECD): measures the difference in
The authors proposed that the absorbance
observation between
is due to left and right
Aggregation Induced Resonance Raman
circular Optical Activity
polarized (AIRROA).
light in the
interaction with a chiral molecule.

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 10
 Supramolecular Assembly
(Aggregation)
Aggregation: formation of clusters from monomers through
non-covalent interactions.

Hydrophobic effect: maximizes hydrogen bonding

interactions among water molecules and minimizes the
area of contact between water and nonpolar molecules.

S. T. Agbozo, et al., J. Photochem. Photobiol A, 362 (2018): 31-39. 11

 Aggregation Types

H-aggregates
Dimension up to 160 nm
Hydrogen-bonds

J-aggregates
Dimension up to 7 µm
van der Waals interactions

The high concentration of aggregation can be achieved

in aqueous solution
G. Zajac, et al., Phys. Chem. Chem. Phys., 20 (2018): 18038-18046. 12
 H-Aggregates

For example, dye molecules aggregate in a parallel way (plane‐to-

plane stacking) to form a sandwich‐type arrangement.

Blue-shift of the absorption band

with respect to the monomer band. monomer

H-aggregate

700

G. Zajac, et al., Phys. Chem. Chem. Phys., 20 (2018): 18038-18046. 13

 J- Aggregates

Dye molecules aggregate in a head‐to‐tail arrangement

(end‐to-end stacking).

Red-shift of the absorption band with

respect to the monomer band

J-aggregate

700

G. Zajac, et al., Phys. Chem. Chem. Phys., 20 (2018): 18038-18046. 14

 Cause of Blue- and Red-shift
Exciton Coupling Theory

ΔEdimer = ΔEmonomer + ΔW ± |J|

transition energy for the dimer (ΔEdimer) and for the monomer (ΔEmonomer),
energy difference of van der Waals interaction between the excited and ground
states of the dimer (ΔW), exciton coupling strength (J)

Y. Zhang, et al., Nature, 531 (2016): 623-627. 15

 Dipole Coupling Modes in a Dimer

In-line in- phase

α-term θ-term
parallel out -of-phase

orthogonal

parallel in -phase

In-line out- of- phase

Y. Zhang, et al., Nature, 531 (2016): 623-627. 16

 Coupling Modes for Blue- and Red-shift

ΔEdimer = ΔEmonomer + ΔW ± |J|

α=0
α = 180° J>0
E
J>0
E

α=0 E α = 180°
J<0 E J<0

M. Kasha, et al., Pure. Appl. Chem., 11 (1965): 371-392. 17

 Electronic CD and ROA Spectra of
Carotenoid Microcrystal
Laser Excitation Wavelength = 532 nm

Resonance Condition at 532 nm

532 nm
Raman

ROA

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 18
 Resonance ROA (RROA)

If the incident laser light is in resonance with only one electronic state, we
can explain RROA results using the so-called single electronic state theory.
For all bands in the RROA spectrum, the ratio of the RROA to RRaman
intensity is equal to ̶ ½ (ΔεECD / εUV-Vis) at resonance wavelength.

532 nm
Raman

ROA

L. A. Nafie, Chem. Phys., 205 (1996): 309-322. 19

S. Qiu, et al., Phys. Chem. Chem. Phys., 12 (2010): 3005-3013.
 βC-Model (Achiral)

Red-shift of the UV/Vis band upon aggregation

→ J-type aggregates

532 nm

NO ECD or ROA signals can

be observed!

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 20
 αC-Model (Chiral)

NO ECD signal was observed.

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476 . 21
 βC/αC (Soldier/Sergeant)-Model

Soldiers = achiral (80%)

Sergeants = chiral (20%)

Red-shift J-aggregation

Strong ECD

Resonance at 532 nm
532 nm

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 22
 ROA of the βC/αC-Model

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 23
 βC/AXT and AXT models

532 nm
532 nm

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 24
 ROA of the βC/AXT and AXT models

Negative RROA bands

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 25
 βC-d/AXT model

(βC-d)

mirror image
ECD of βC-d/AXT βC/AXT

→ opposite chirality and twisting

direction of the aggregates
(drastic changes)

Red-shift → J-aggregates

M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471 –8476. 26
 ROA spectra of βC-d/AXT model

The hydrogen out-of-plane (HOOP)

mode is recognized as a sensitive
marker of distortion of the polyene chain.

HOOP band

Substantial deuterium-induced change

in the molecular structure of C-d
M. Dudek, et al., Angew. Chem. Int. Ed., 131 (2019): 8471–8476.
T. Fujisawa, et al., J. Am. Chem. Soc., 129 (2017): 10456–10460. 27
 Conclusion

▪ An extremely strong ROA spectrum was observed for

carotenoid microcrystals, extracted from cells of carrot roots
and consisting of 95% of achiral β-carotene.

▪ Several experimental models were used to prove that a small

number of chiral sergeants (a-carotene or astaxanthin) imprint
their chirality to the aggregates consist mostly of achiral building
blocks (β-carotene).

▪ The intense ROA spectrum above is due to a new phenomenon

called aggregation induced resonance ROA (AIRROA).

▪ AIRROA requires both aggregation and resonance.

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 Safety minute

Solid-state lasers like Nd:YAG laser produce a green 532 nm beam

Laser Radiation Hazards Laser Safety

• Damage in the eye tissues • Avoid Exposure of eyes & skin.

• Damage in the skin tissues • Use eye protection.

• Work in Controlled Areas
• Watches & rings which could reflect
the beams should not be worn.

Nd:YAG (neodymium-doped yttrium aluminum garnet)

29
 Acknowledgement

• Dr. Yunjie Xu

• Dr. Wolfgang Jäger

• Members of the Xu and Jäger groups

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 Compute ROA Spectra

ᾰ >>>> Ǵ and Ᾰ

➢ So, ROA is a very weak effect, being approximately

3-5 orders of magnitude less than the normal Raman

scattering.

➢ So, circular intensity difference (CID)

Δ = IROA / IRAMAN = (IR – IL) / (IR + IL) ≈ 5x10-4 Fmoc-glycyl-glycine-OH (FGGO)

Y. Huang, et al. Light: Sci. Appl, 3 (2014): e199. 31

o HOOP
▪ HOO.P modes →sensitive marker for the distortion of the polyene chain.

The supramolecular chiral arrangement is a necessary prerequisite to record the

RROA spectrum, but additionally, resonance conditions are required.

Fujisawa, R. L. Leverenz, M. Nagamine, C. A. Kerfeld, M. Unno, J. Am.

Chem. Soc. 2017, 10456–10460. 32
33
 Compute ROA spectra

Raman Intensity:
➢ Electric dipole-electric dipole polarizability tensor

ROA Intensity
➢ Magnetic dipole–electric dipole ROA tensor

➢ Electric quadrupole–electric dipole ROA tensor

L. A. Nafie, Theor. Chem. Account, 119 (2008), 39-55. 34

a.u = arbitrary units
Molar ellipticity ([θ]) The degree of ellipticity (θ) is defined as
the tangent of the ratio of the minor to major elliptical axis,
Combination bands are observed when more than two or more
fundamental vibrations are excited simultaneously
overtone of a molecule when the molecule makes a transition
from the ground state (v=0) to the second excited state (v=2),