Sonochemistry

And Spin Trapping and EPR Studies

Ph.D course work

Sonochemistry V 1
 Ultrasonics/Sonochemistry – Applications

- Electronics industry (coating with metals)

- Therapy (surgery with ultrasounds), diagnostics
- Food industry
- Materials (metallurgy)
- Synthesis
- Environmental applications

Sonochemistry 2
 Ultrasonics/Sonochemistry – Basics

Frequency ranges of sound

Sonochemistry 3
 Sound transmission through a medium

Sonochemistry 4
 Ultrasonics/Sonochemistry – Acoustic Cavitation

Sonochemistry 5
 Acoustic cavitation in a homogeneous liquid

Sonochemistry 6
 Acoustic cavitation in solid/liquid system

Sonochemistry 7
 Acoustic cavitation in solid/liquid system
Ultrasonics/

Sonochemistry 8
Introduction to Acoustic Cavitation and Sonochemistry
• Sonochemistry:chemical effects of ultrasound on aqueous and non-aqueous
solutions. The effects are due to Acoustic Cavitation: the nucleation, growth and
violent collapse of gas/vapor filled microbubbles in a liquid.
• The widely accepted Hot Spot Theory proposes that collapse of these
microbubbles is an almost adiabatic process.
Glass Beaker with water
• This results in the creation of very high
temperatures (thousands of Kelvin) and Acoustic
pressures (hundreds of atmospheres) in Cavitation
extremely small and transient regions in Bubbles
the liquid ( Hot Spots).
• The collapse of bubbles is accompanied Hot
by the simultaneous emission of light Spot
(Sonoluminescence).
Ultrasonic
• This presentation describes the detection pressure
of radical species produced as a result of wave
acoustic cavitation in aqueous solutions. Ultrasonic Transducer

Sonochemistry 9
 Figure 1: Apparatus purchased from L3-
Communications - ELAC Nautik GmbH, Germany.

Gas Inlet Tube

Gas Outlet
Experimental Set-up: Clamp with
Rubber Septum
Rubber O-ring Exposure
Vessel
Water Jacket Sample
• To identify free radicals generated by Solution
ultrasound, suitable spin traps were added (1mL)
Cooling
to the sample solution before sonolysis. water out Coupling
The stable spin adducts were identified by Solution
(Water,
EPR immediately after sonolysis. Flat plate 300 mL)
for ultrasound
• Recently, we have employed a more transmission
sophisticated experimental set-up to study Rubber
O-Ring
radical formation after sonolysis at various 354 kHz 1057 kHz
ultrasound frequencies and intensities. Clamp
Temperature control should be employed
for extended sonolysis times or high
ultrasound intensities. Lead connected Cooling
to the Generator Water in

Outer Casing of the

Dual Frequency Transducer

Sonochemistry 10
 Acoustic Cavitation:
i) Characteristics of the Ultrasonic Wave:
Ultrasound travels through a liquid as a longitudinal wave, i.e., the molecules of the
liquid oscillate about their equilibrium positions in the direction of the motion of the
wave. Therefore, the effective pressure in any given region of liquid is determined
by the equation, Pt = Ph + Pa, where Pt = the total pressure in a specific region in the
liquid, Ph = the hydrostatic pressure and Pa = the acoustic pressure in a particular
region and time.

Relatively low pressure regions

Direction of the
ultrasonic wave:

Relatively high pressure regions

Figure 2: Pressure effects in the liquid due to an ultrasonic wave.

Sonochemistry 11
ii) Nucleation, Growth and Collapse of Microbubbles:
• Pockets of gas are trapped on microscopic impurities (e.g., dust particles), inherently
present in any liquid, or in imperfections on the wall of the vessel.
• The gas nuclei expand under the influence of the ultrasonic wave and detach to form free
microbubbles in the liquid. The microbubbles continue to adsorb energy from the wave
and grow isothermally.
• When the microbubbles reach a critical size (approximately 2 to 3 times the resonance
radius), they implode violently. Assuming adiabatic collapse, the temperature of the hot
spot can be estimated using the equation below. This equation demonstrates the
importance of  in determining the collapse temperature (note, the collapse is not
completely adiabatic, so the thermal conductivity will effect T f in a real system).

Rmax 3(-1)
Tf = Ti Figure 3: The Sonochemical Hot Spot*
Rmin Bulk Solution:
Room Temperature
Where, Tf is the temperature of the core, Ti is ambient
temperature, Rmax and Rmin are the maximum and
Core:
minimum bubble radius and  is the ratio of specific
 5000 K
heats (Cp/Cv) of the gas inside the bubble.  = 1.67 for  1000 atm
monoatomic gases and 1.40 for diatomic gases.
Interfacial Zone:
 1900 K

Sonochemistry 12
 Sonochemistry
i) The Three Regions of Chemical Activity:
Sonochemical reactions can occur in three different regions.

Region 1: interior of collapsing gas bubbles (i.e., the core) in which very high temperatures and
pressures exist. Under these conditions the solvent vapor inside the bubble undergoes
pyrolysis reactions.

Region 2: interface between the collapsing bubble and the bulk solvent, where high temperature and
pressure gradients exist. In aqueous solutions, the relative efficiency of non-volatile solutes to
decompose thermally or to scavenge radicals formed in the hot spot depends on their ability
to accumulate at the gas/solution interface of the growing microbubble.

Region 3: bulk solution at ambient temperature. Free radicals formed in the hot regions may diffuse to
the bulk solution and react to yield products similar to those found in aqueous radiation
chemistry. Thus, sonochemistry can partly be understood in terms of a combination of
combustion chemistry and radiation chemistry.

ii) Spin Trapping and EPR Following Sonolysis of Liquids:

It is well known that volatile and/or surface active solutes can thermally decompose in the
core of the hot spot or in the hot interfacial zone. These factors must be considered in
choosing the spin trap for detection of radicals formed during sonolysis. The following slides
illustrate the choice and use of various spin traps in sonochemistry.

Sonochemistry 13
 Spin-Trapping during the Sonolysis of Aqueous Solutions
i) Important Characteristics of the Spin Trap:
Spin traps with greater hydrophobicity and/or volatility thermally decompose more readily in the hot
interfacial zone or in the core of the hot spot. An example of this is shown in the figure below.
Because, in general, alkyl radicals react much faster with aromatic nitroso spin traps than with nitrone spin
traps, DBNBS-d2 could be used to identify the carbon centered radicals produced following decomposition
of a number of spin traps. The figure below shows the methyl radical yield following sonolysis of spin traps
as a function of solute concentration.
The hydrophobicity of the spin traps follows the order NPBN > PBN > POBN > SPBN.
The greater the hydrophobicity of the spin trap, the lower the spin trap concentration
at which radicals can be observed.

Figure 4: CH3 yield as a function of the

• 5

[DBNBS-d2- •CH3]/a.u.
bulk concentration of spin traps
4 Acetate
of varying hydrophobicities.
PBN
3
NPBN = -(4-nitrophenyl) N-tert-butylnitrone
PBN = -phenyl-N-tert-butylnitrone 2
POBN = -(4-pyridyl-1-oxide) N-tert-butylnitrone
SPBN = -(2-sulfophenyl) N-tert-butylnitrone SPBN
1 POBN
NPBN
0
0.1 0.2 0.5 1 2 5 10 20 50 100 200 500 1000

[Solute]/mM

Sonochemistry 14
ii) Probing the Temperatures of the Hot Spot:
(a)
• The semi-classical model of the temperature H2O
dependence of the kinetic isotope effect for •H and •D
atom formation was used to estimate the effective
temperature of the hot cavitation region in which •H and
•
D atoms are formed by ultrasound-induced pyrolysis of
water molecules. (b)
D2O
• For example, the ratio of H/ D could be determined by
• •

spin trapping of •H and •D atoms from a 1:1 molar

mixture of H2O:D2O in the presence of POBN (10 mM).
The ratio of •H/ •D = kH/kD = 1.20  0.06, which
corresponds to a hot spot temperature of between
(c)
2600 K to 4600 K, using: kH/kD = exp{(1.24 kcal H2O + D2O
mol-1)/RT}

Figure 5: EPR Spectra of spin adducts produced

by sonolysis of argon-saturated (a) H 2O;
(b) D2O; (c) 1:1 molar H2O:D2O. (d) is a POBN/ •H
POBN/ •D
computer simulation of (c). The species POBN/ •phenyl
that contribute to the spectrum in (c) are (d) POBN/ •CR
shown in (d).

10 G

Sonochemistry 15
 iii) Identifying the Primary Species during the Sonolysis of Argon Saturated Water
Using the spin trap DMPO, EPR spectra characteristic of the Figure 6: Spectra obtained following sonolysis
of POBN (25 mM) in water (a and b)
•
H/ •OH - DMPO spin adducts were observed following the
and (c) D2O.
sonolysis of water. Assignment was confirmed by using other
•
OH radical scavengers and isotopically labeled water (D 2O (a) Sonolysis
and H2O17). Other nitrone spin traps (PBN, POBN and PYBN) POBN
were also used.
For example, the EPR spectrum (a) obtained by sonolysis of
an aqueous, argon saturated POBN solution (25 mM)
resulted in the formation of the •H-POBN adduct, as 10 G
illustrated by the stick diagram. The life-time of the •OH-
POBN adduct is too short to be detected using the
conventional EPR technique. In order to show that •H-POBN Sonolysis POBN,
(b)
adducts were formed by trapping of •H atoms, we added well 5.2 M Formate
known •H atom (and •OH) scavengers during sonolysis in the
presence of POBN.
In Figure 6(b), the addition of the formate ion (5.2 M) to
solution resulted in an EPR spectrum due to the •CO2--POBN
spin adduct, following the scavenging of •H atoms (and •OH
radicals) by HCO2-. (c) Sonolysis D2O, POBN
Finally, sonolysis of D2O solutions under the same conditions
resulted in the formation of •D-POBN, spectrum (c). The small
amount of •H-POBN in spectrum (c) is due to the
decomposition of POBN.
.

Sonochemistry 16
 iv) Evidence Against Formation of Hydrated Electrons during Sonolysis of Water:
4
It has been proposed that the formation of hydrated MgSO4
electrons occurs following the exposure of aqueous 3 CdSO4

[POBN/ •D]/M
solutions to ultrasound (Margulis M. A. (1995)
Sonochemistry and Cavitation, Gordon and Breach
Publishers, Luxembourg). 2

Cadmium ions (Cd2+) are efficient scavengers of

hydrated electrons, but do not react with •H atoms. 1
Therefore, the effect of Cd2+ on the •D-POBN yield
following sonolysis of D2O solutions (shown in Figure 6)
0 0 0.01 0.1 1
was investigated.
[Salt]/M
D2O was used to avoid any errors due H atom
•
Figure 7: Effect of salt concentration on the yield
formation from the decomposition of POBN during of POBN/D following sonolysis of argon
sonolysis. saturated solutions.
Figure 7 shows that the •D-POBN yield is independent
of the Cd2+ concentration (up to 0.1 M), where 98.8 % of
hydrated electrons would be scavenged by Cd 2+.
The sharp rise and subsequent decrease in the D-POBN yield at concentrations of CdSO 4 > 0.1 M were
also observed with the addition of MgSO 4.
This effect may be due to a number of phenomena which are observed during the sonochemistry of high
salt concentration solutions. However, any observed changes at CdSO 4 concentration > 0.1 M are not
relevant for the discussion of the possibility of the existence of hydrated electrons.

Sonochemistry 17
 v) Detection of Radicals from Aqueous Surfactant Solutions:
Addition of surface active organic solutes to aqueous Organic surfactant molecules can scavenge the
solutions can result in dramatic enhancements in the primary •H atoms and •OH radicals at the
chemical reactivity observed during sonolysis, gas/solution interface. This has at least two
especially through enhanced redox and radical effects. First, it creates relatively long-lived
reactions occurring in the bulk solution. These carbon radicals that can diffuse into the bulk
effects can be attributed to the preferential solution to react with other solute molecules.
accumulation of the surfactants at the gas/solution Secondly, the radical scavenging reaction of •H/
interface of cavitation bubbles: •
OH with the surfactant is in competition with
radical recombination reactions which produce
Figure 8: Collapsing Cavitation Bubble non-reactive species such as H2 and H2O.

The non-volatile surfactants can also thermally

Surfactant decompose at the hot interfacial zone of the hot
spot. This results in the formation of methyl and
other carbon centered radicals that are derived
+ H/ OH
 from the homolysis of C-C bonds.

H2O

Radicals +

OH 
H
H2/H2O

Bulk Solution H2O2 H2O H2

Sonochemistry 18
 3 1
3 3
Preferential accumulation of surfactants at the (a) 1 1 3 Sonolysis,
1
gas/solution interface of cavitation bubbles was 1 1 OGP/DBNBS-d2
shown to occur by spin trapping with DBNBS-d 2. 3 2 2
2 3
Sonolysis of aqueous solutions of a homologous 2
2
series of non-volatile n-alkyl glucopyranosides
1
[methyl (MGP), n-octyl (OGP) and n-decyl (DGP)]*
was conducted in the presence of DBNBS as the
spin trap. CH radicals (formed by abstraction
reactions - e.g., Figure 8) and methyl radicals
(formed by pyrolysis of the non-volatile surfactants
at the gas/solution interface of cavitation bubbles)
were observed. An example of the EPR spectrum (b) Simulation
observed following sonolysis of OGP in the
presence of DBNBS-d2 and argon gas is shown in
Figure 9a, which is typical of the spectra observed
for all of the glucopyranosides. A simulation of the
spectrum in Figure 9a is shown in Figure 9b. The 10 G
simulation shows that the acquired EPR spectrum
can be interpreted in terms of contributions from Figure 9: (a) EPR spectra following sonolysis of
aqueous OGP solutions in the presence of
methyl (CH3), primary (- CH2), secondary (- CH-)
DBNBS-d2. A simulation of (a) is shown in
and tertiary
(b). 1 = CH; 2 = CH2; 3 = CH3

[C-(R1R2R3)] radicals. Each component in the EPR

spectrum was quantified. The results of this are
shown in Figure 10 of the following slide.

Sonochemistry 19
 200 It can be seen from Figure 10 that as the bulk solution
MGP Radiolysis concentration of surfactant is increased up to 1000 M, the
150 Sonolysis yield of carbon centered radicals increases up to a plateau
value. Interestingly, the relative yield of carbon centered
100 radicals was much smaller for the non-surfactant analogue

C
(MGP) compared to the surfactants, OGP and DGP. In
50 
C fact, methyl radicals could be detected at bulk solution
[Spin Adduct]/Arbitrary Units

concentrations as low as 250 M for OGP and DGP, which

0
1000 
CH3 was 500 fold lower than the concentrations of MGP
required (data not shown). This was the first definitive
800 
CH evidence using EPR and spin trapping experiments to
show that solutes with surfactant properties can
600 OGP accumulate more readily at the gas/solution interface of
violently oscillating cavitation bubbles.
400 
CH

200 CH3

CH2
Figure 10: DBNBS-d2 spin adduct yield following sonolysis as a
0
800 function of surfactant concentration. [DBNBS-d 2] = 3

CH mM, sonolysis was conducted under argon gas and
600 radiolysis under N2O.
DGP 
CH
400


200 CH3

CH2
0 0 250 500 750 1000

[Surfactant]/M

Sonochemistry 20
 Recently, we have used DBNBS-d2 to study the An interesting result, considering that the n-alkyl
accumulation and decomposition mechanisms of n- chain of the surfactants is pointing toward the
alkyl chain possessing ionic, zwitterionic and non- interior of the hot spot.
ionic surfactants at the gas/solution interface of
cavitation bubbles. A summary of the groups of Figure 12: EPR spectra following sonolysis of argon
surfactants used is shown below, where x = total saturated, aqueous solutions of DBNBS
(8.2 mM) and (a) SDS (3 mM, ionic); (b)
number of carbon atoms in the n-alkyl chain: C8-Zwitterionic (10 mM); (c) C10-non-ionic
(0.3 mM).
Figure 11:
CH3(CH2)x-1 OSO3
Ionic
(a) SDS
CH3(CH2)x-1 OSO2

Zwitterionic CH3(CH2)x-1 +
N(CH3)2(CH2)3OSO2

Non-ionic CH3(CH2)x-1 (OCH2CH2)8OH

C8-ammonio-
(b) propane sulfonate
Typical EPR spectra observed following sonolysis of
ionic, zwitterionic and non-ionic surfactants are
shown in Figure 12. The spectra of Figure 12
provide information about the mechanism of
decomposition of non-volatile surfactants. For •
CH3
example, the zwitterionic and non-ionic surfactants, (c)
C10-polyoxy ethylene
having more complex head group structures, gave
higher yields of •CH3 radicals compared to the ionic
.surfactants.

Sonochemistry 21
 vi) Free Radical Intermediates in Sonodynamic Therapy:
Sonodynamic therapy is a promising new
modality for cancer treatment based on the
The biological effects of ultrasound are synergistic effect on cell killing by the
summarized in Figure 13: combination of a drug (sonosensitizer) and
ultrasound. Relevant research in sonodynamic
Figure 13: therapy is listed in Table 1 (on the following
slide). However, the mechanism by which cell
killing is enhanced in the presence of
Biological Effects Adsorption of ultrasound
sonosensitizers has not been fully elucidated.
of Ultrasound in tissues resulting in
Our research has focussed on determining the
heating effects
type of radicals formed following sonolysis of
known sonosensitizers.
Microstreaming/shearing
Jeffers et al. (J. Acoust. Soc. Am., 1995, 97, 669-
forces result in changes to
676) showed that N,N-dimethyl formamide (DMF)
membrane permeability and
had a synergistic effect on the killing of HL-60
mechanical damage to cells
Effects human promyelocytic leukemia cells using
related to ultrasound. Using the spin trap DBNBS in
acoustic Free radical damage: OH nitrogen saturated aqueous solutions, the
cavitation and H. However, drug formation of CH3 and CH2N(CH3)CHO were
derived ROO and RO detected*. In air saturated solutions, these carbon
would be more effective centered radicals reacted with oxygen to form the
due to longer diffusion corresponding peroxyl radicals which were spin
distances and selectivity. trapped with 5,5-dimethyl-1-pyrroline-N-oxide
(DMPO)*. Studies of this type* were helpful in
contributing to our understanding of the
mechanism of sonodynamic therapy.

Sonochemistry 22
 Ultrasonics/Sonochemistry – Synthesis

1. Homogeneous sonochemistry

1.1. Aqueous sonochemistry

Sonochemistry 23
Sonochemistry 24
Sonochemistry 25
Sonochemistry 26
Sonochemistry 27
Sonochemistry 28
Sonochemistry 29
Sonochemistry 30
Sonochemistry 31
Sonochemistry 32
Sonochemistry 33