Curcumin: A Naturally Occurring Long-Wavelength

Photosensitizer for Diaryliodonium Salts

JAMES V. CRIVELLO, UMUT BULUT
Department of Chemistry and Chemical Biology, Rensselaer Polytechnic Institute, 110 8th Street, Troy, New York 12180

Received 6 May 2005; accepted 21 July 2005

DOI: 10.1002/pola.21017
Published online in Wiley InterScience (www.interscience.wiley.com).

ABSTRACT: Curcumin, a naturally occurring, intensely yellow dye extracted from the
spice turmeric, is an efcient photosensitizer for diaryliodonium salt photoinitiators
at wavelengths ranging from 340 to 535 nm. With curcumin as a photosensitizer, it is
possible to carry out the cationic photopolymerization of a wide variety of epoxide,
oxetane, and vinyl monomers with long-wavelength UV and visible light. An example
of the photopolymerization of an epoxide monomer with ambient solar irradiation is
provided. Several other curcumin analogues were synthesized, and their use as photo-
sensitizers is examined. With such photosensitizers, the range of spectral sensitivity
can be extended well into the visible region of the electromagnetic spectrum. V C 2005

Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 52175231, 2005
Keywords: cationic polymerization; curcumin; diaryliodonium salts; epoxides; oxe-
tanes; photopolymerization; photosensitization; ring-opening polymerization; vinyl
ethers

INTRODUCTION ces. Most onium salts are intrinsically photoactive

The use of aromatic onium salts such as diarylio-
donium and triarylsulfonium salts as photoacid
generators in photolithography and as photoini-
tiators for cationic photopolymerizations in coat-
ing, printing ink, and adhesive applications is
well documented.1 The ability to conduct both
types of these applications with light with a wide
range of wavelengths is an especially challenging
undertaking. This is particularly the case in the
eld of imaging science, in which a wide variety
of light sources with different emission wave-
lengths are employed. The next generation of
microlithographic photoresists will require the
use of very short UV wavelength radiation (198
and 157 nm) to produce an even smaller and
higher density packing of discrete electronic devi-
Correspondence to: J. V. Crivello,
edu)
Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 43, 52175231 (2005)
V
C 2005 Wiley Periodicals, Inc.
in the short and middle wavelength regions of
the UV spectrum, and so photosensitizers are not
required. Present microelectronic photoimaging
employs onium salts for deep UV (I-line, 365 nm)
photolithography, and because most onium salts
do not absorb at this wavelength, photosensi-
tizers are commonly employed. Furthermore,
many current and future imaging processes are
being designed with light sources such as lasers
and light-emitting diodes (LEDs) that deliver
narrow-band or monochromatic radiation in the
long-wavelength UV and visible regions, in which
onium salts are either poorly responsive or com-
pletely inactive. Examples of such imaging proc-
esses include stereolithography, rapid prepress
prototyping, electronic transmission and printing
of images, circuit board imaging, patterning of
TV screens and liquid-crystalline displays, and
photopolymer printing plates. There are also sev-
(E-mail: crivej@rpi. eral applications such as photocurable dental
llings and restoratives that make use of long-
wavelength ultravioletvisible (UVvis) radiation
5217
5218 CRIVELLO AND BULUT
Scheme 1
(430490 nm) to avoid skin damage. One effec-
tive method for spectrally broadening the sensi-
tivity of onium salt photoinitiators at long wave-
lengths is through the use of electron-transfer
photosensitization.2 Polynuclear aromatic hydro-
carbons such as anthracene,3 pyrene, and pery-
lene4,5 have the requisite long-wavelength absorp-
tion characteristics and also undergo efcient
photoinduced electron-transfer photosensitization
with onium salt photoinitiators. In Scheme 1 is
shown the general mechanism by which such pho-
tosensitization occurs with diaryliodonium salts as
an example. Analogous mechanisms can be writ-
ten for the photosensitization of triarylsulfonium
and dialkylphenacylsulfonium salts. Electron-
transfer photosensitization is, in essence, a photo-
induced redox process that involves rst the
absorption of light by the photosensitizer, PS, to
give the corresponding excited species, [PS]* (eq 1).
An excited state complex (exciplex) is often
formed as an intermediate between the onium
salt and the excited photosensitizer (eq 2). Subse-
quently, the onium salt is reduced by a formal
one-electron transfer between the two reaction
partners (eq 3), and this yields a diaryliodine
free radical and the photosensitizer cation radical.
The rapid decomposition of the resulting unstable
diaryliodine free radical (eq 4) prevents back elec-
tron transfer and renders the overall process
essentially irreversible. Cationic polymerization
(eq 5) takes place by a number of possible path-
ways, either by the direct interaction of the
monomer with the photosensitizer cation radical
or by rst radical dimerization and then polymer-
ization by the resulting dication. During electron-
transfer photosensitization, both the onium salt
and the photosensitizer are irreversibly consumed.
Because of their lower reduction potentials, diaryl-
iodonium salts are more easily photosensitized by
an electron-transfer process than triarylsulfonium
salts.2
Although polynuclear aromatic hydrocarbons
are the most efcient known examples of elec-
tron-transfer photosensitizers for onium salts,
they have several serious drawbacks that limit
their use. For example, they are generally expen-
sive, toxic, and poorly soluble in most reactive
monomers and polymer systems. In previous
work from this laboratory,6,7 we have shown that
it is possible to prepare derivatives of these com-
pounds that address these latter two issues.
However, such derivatives remain prohibitively
expensive for general-purpose uses. As a result,
there is a continuing unsatised need for long-
wavelength-active photosensitizers that will cir-
cumvent the aforementioned complications. This
article describes the discovery and application of
a naturally occurring dye photosensitizer that is
highly effective, inexpensive, and soluble in a
wide variety of reactive monomers and polymers.
EXPERIMENTAL
Materials
Curcumin (6570%) and all organic starting
materials, reagents, and monomers employed in
this investigation were reagent-quality and were
used as purchased from Aldrich Chemical Co.

Table 1. Structure, Physical Characteristics, and Spectra of Curcuminoids
Notation Structure (Ar) Yield (%) mp (8C)
I 56 182
II 53 138140
III 59 212220
IV 41 163166
V 21 185190
(Milwaukee, WI), unless otherwise noted. Curcu-
min was puried before use by recrystallization
from isopropyl alcohol. The difunctional oxetane
monomer, bis{[1ethyl(3-oxetanyl)]}methyl ether
(DOX), was supplied as a gift from Toagosei
Chemical Industries, Ltd. (Nagoya, Japan). 3,4-
Epoxycyclohexylmethyl 30 ,40 -epoxycyclohexane
carboxylate (ERL-4221E) was obtained from
Union Carbide Corp. (Bound Brook, NJ). Epoxi-
dized soybean oil (ESO) and epoxidized linseed
oil (ELO) were kindly supplied as samples by
Viking Chemical Co. (Minneapolis, MN). The
photoinitiators (4-n-decyloxyphenyl)phenyliodonium
hexauoroantimonate (IOC-10SbF6),8 (4-n-decyl-
oxyphenyl)diphenylsulfonium hexauoroanti-
monate (SOC-10SbF6),9 and S-n-dodecyl-S-methyl-
S-phenacylsulfonium hexauoroantimonate (DPS-
C1-C12SbF6)10 were prepared as described in
earlier publications from this laboratory. Ele-
mental analyses were conducted by Atlantic Mi-
croanalysis (Norcross, GA). All melting points
were recorded on a Thomas Hoover capillary
melting point apparatus and are uncorrected.
1
H NMR spectra were recorded on a Varian XL
500-MHz spectrometer at room temperature in
dimethyl sulfoxide-d6. UV spectra were recorded
on a PerkinElmer Lambda 2 spectrometer.
Fluorescence Quenching Studies
Curcumin uorescence quenching studies were
conducted on a PerkinElmer LS-3B uorescence
CURCUMIN 5219
Lit. mp (8C) UV kmax (nm) Reference
183 427 11
140142 384 36
209211 421 36
166168 398 11
164165 34
184185 427 34
189190 454 (weak) 39
spectrometer. An excitation wavelength of 304 nm
was used, and the uorescence emission band at
501 nm was monitored. The curcumin concen-
tration was 1
103 M in tetrahydrofuran.
Synthesis of Curcumin and Other Curcuminoids
A modication of the method of Babu and Raja-
sekharan11 was used for the synthesis of curcu-
min and the other curcumin analogues reported
in Table 1. The synthesis of curcumin described
next is typical of the procedures used for all the
curcuminoids prepared during the course of
this work. Into a clean vial were placed 1.53 g
(0.01 mol) of vanillin, 0.51 mL of acetylacetone,
1 g of boric acid, and 1 mL of dimethylformamide.
The mixture was heated for 5 min in a water bath
at 8090 8C. Then, a mixture of 0.1 mL of 1,2,3,4-
tetrahydroquinoline, 0.3 mL of glacial acetic acid,
and 1 mL of dimethylformamide was added, and
heating was continued at 8090 8C for 4 h. After
cooling, 50 mL of 20% aqueous acetic acid was
added with vigorous stirring. The yellow-orange
precipitate of curcumin was isolated by ltration,
washed with water, and dried. The product was
further puried by recrystallization from iso-
propyl alcohol.
Fourier Transform Real-Time Infrared Spectroscopy
(FT-RTIR) Photopolymerization Studies
The photopolymerizations of the monomers and
oligomers were monitored with FT-RTIR. Previ-
5220 CRIVELLO AND BULUT
ously,12 we described the apparatus and techni-
ques employed in this laboratory for kinetic
analyses using this analytical technique. The
FT-RTIR experiments described in this investi-
gation were performed at room temperature
with broadband UV light emitted by a medium
Hg arc source and ltered through a liquid optic
light pipe. The transmitted light radiation con-
sisted entirely of wavelengths greater than
300 nm. In a given system under study, the
intensity of the UV light was adjusted so that
the photopolymerization could be completed
within a period of approximately 150250 s.
Three kinetic runs were obtained for the photo-
polymerization of each monomer, and the results
were averaged to obtain the nal conversion
time curve.
Monitoring the Photopolymerization of
Monomers and Oligomers by Optical
Pyrometry (OP)
The apparatus and method employed for moni-
toring the photopolymerizations reported in this
investigation by OP were described in an earlier
communication from this laboratory.13 Samples
for analysis were prepared as follows. Homoge-
neous solutions of the desired monomer with the
designated photoinitiator were prepared (all con-
centrations are given as molar percentages with
respect to the monomer unless otherwise noted).
A 10-lm corona-treated oriented polypropylene
lm was rst laid down, and a thin polyester
ber mesh to serve as a spacer was placed on
top of the plastic lm. The liquid sample was
placed on this assembly, and an identical layer
of polypropylene lm was placed over the top.
The resulting sample sandwich was mounted in
a 2.0 cm
2.0 cm plastic slide holder and irra-
diated with UV light, from a UVEX model SCU-
110 mercury lamp, directed via a 95-cm liquid
light pipe onto the sample. The end of the wand
was placed at a predetermined distance and
directed at an incident angle of 458 onto the
sample window. All optical pyrometer experi-
ments made in this investigation were con-
ducted at the ambient temperature (2528 8C).
In every case, the samples were allowed to equi-
librate and establish a at baseline for 20 s
before the start of the UV irradiation. Tempera-
ture data were collected at a rate of 1 measure-
ment per second and directly recorded and
downloaded to an IBM 350-P137 personal com-
puter for analysis. Several kinetic runs were
performed for each polymerizable system, and
the results reported in this article were the
average of at least three kinetic runs.
The aforementioned OP apparatus was modi-
ed in two ways during the course of this inves-
tigation. For example, a Schott BG-12 optical l-
ter with a midpoint wavelength of 407 nm and a
transmission bandwidth of approximately 355
460 nm was placed at the end of the light pipe
to provide a narrow-wavelength irradiation beam.
The OP apparatus was modied to accommo-
date a circular array composed of 22 individual
InGaN LED devices as a light source. The LED
array was supplied by the Naval Warfare Sys-
tems Command (Panama City, FL) and was
positioned directly beneath the sample stage.
The array was energized with a common 6-V
battery. The peak emission wavelength of the
array was 470 nm. The preparation of the sam-
ples and the collection of the data with this
apparatus were the same as those employed in
the UVvis OP studies.
Solar-Irradiation-Induced Polymerization
Glass cloth was impregnated with a solution of
ELO containing 1.0 mol % (4-n-decyloxyphenyl)-
phenyliodonium hexauoroantimonate (IOC-10
SbF6) and 0.1 mol % curcumin. Four layers of
the impregnated cloth were stacked on top of
one another on a polyethylene lm, and the
resulting laminate was exposed to direct solar
irradiation for 10 min at Troy, New York (lati-
tude 428 north) on April 6, 2005, at 15:00 h. The
ambient temperature during the irradiation was
25 8C. After 5 min of continuous irradiation, the
composite was tack-free to the touch. Irradiation
was continued for an additional 5 min to ensure
completion of the photopolymerization. After
this time, the orange-colored composite was fully
hardened. It was removed from the polyethylene
backing and was trimmed.
RESULTS AND DISCUSSION
Curcumin as an Electron-Transfer
Dye Photosensitizer
Curcumin [(E,E)-1,7-bis(4-hydroxy-3-methoxy-
phenyl)-1,6-heptadiene-3,5-dione (I)] is a natu-
rally occurring, intensely yellow dye that is

isolated from rhizomes of the plant Curcuma
longa:
C. longa, a member of the ginger family (zingi-
beraceae) of plants, is widely grown in India and
Southeast Asia and used as the spice turmeric to
give curry and other dishes their characteristic
yellow color and avor. Curcumin can be
obtained by solvent extraction from commercial
turmeric, in which it is present at a concentra-
tion of 1.52.0 wt %.14 Although curcumin
obtained in this way is often quite impure, we
have found that the dye may be readily puried
by recrystallization from isopropyl alcohol. Given
in Figure 1 is the UV spectrum of curcumin
measured in acidic and basic media.15 The data
show that curcumin possesses broad UV absorp-
tion from 300 to 500 nm that is strongly solvent-
and pH-dependent because of the presence of the
phenolic groups.16,17 Of particular importance for
the photosensitization of onium salts in neutral
or acidic media is the strong UV absorption band
at 427 nm (e 55000). Curcumin exists almost
entirely in the enol form, as shown in the pre-
vious structure, and this provides the highly con-
jugated chromophore responsible for the long-
wavelength absorption of this compound. Also
signicant is the presence of the two electron-
rich aromatic groups at both ends of the conju-
gated chain. These groups are expected to lower
the oxidation potential of the molecule by facili-
tating the removal of an electron during the elec-
tron-transfer photosensitization process.
Curcumin is readily available and compara-
tively inexpensive ($40/kg). As a result of its
long and well-established history of human
usage as a foodstuff and in a multitude of tradi-
tional medical applications, curcumin is a sub-
stance with well-known benign and benecial
effects on human physiology.18 The dye is essen-
tially nontoxic and widely applied to the skin as
a sunblock to prevent sunburn, leucoderma, and
other skin ailments.12,19,20,21 In recent years,
curcumin has been shown to possess a broad
range of pharmacological activity, and its anti-
cancer, antitumor,23 antioxidant,22 and anti-
inammatory24 properties have been touted.
CURCUMIN 5221
Curcumin displays a blue solvent-dependent
uorescence emission (446549 nm) when irradi-
ated with UV light (excitation at 355 nm).25 The
photophysics of photoexcited curcumin were well
studied by Khopde et al.26 The lifetime of the
excited singlet state of the dye, which is usually
involved in electron-transfer processes, is short
(50350 ps). The quantum yield for the forma-
tion of the excited triplet is quite low (F  0.12).
In the presence of an onium salt, the uores-
cence of curcumin is markedly quenched be-
cause of electron transfer. In Figure 2 is shown
a typical SternVolmer plot for the uorescence
(501 nm) quenching of curcumin as a function of
the concentration of the diaryliodonium salt,
IOC-10 SbF6. The linear correlation shown in
the plot is strong conrming evidence for the
electron-transfer photosensitization mechanism
depicted in Scheme 1. During the photolysis,
there is a rapid and marked change in the color
of the solution, which is indicative of the forma-
tion of the curcumin radical cation and the fur-
ther reaction of this species with the solvent or
monomer to form various secondary products.
The photodegradation of curcumin and its ana-
logues has been studied, and it has been
observed27 that these compounds undergo a slow
photoinduced reaction in the presence of oxygen
to give a number of products, including avones.
The nature of the products of the photolysis of
curcumin in the presence of onium salts has not
been determined.
Figure 1. UVvis spectra of curcumin. The solid
line was obtained from 3.09
105 M curcumin in a
basic aqueous solution (NaOH 0.5 M). The dashed
line was obtained from 3.04
105 M curcumin in
glacial acetic acid.
5222 CRIVELLO AND BULUT

Figure 2. SternVolmer plot of the quenching of curcumin (1
103 M) by IOC-10

SbF6 in THF (excitation wavelength 304 nm). I0 uorescence intensity of curcu-
min, I uorescence intensity in the presence of IOC-10 SbF6.

Photosensitized Cationic Polymerization typical cationic vinyl and ring-opening polymer-

Besides its broad long-wavelength UV absorp-
tion and low toxicity, there are two additional
properties of curcumin that make it an ideal
photosensitizer for onium salts. First, curcumin
is a slightly acidic dye that does not possesses
basic or other groups that can retard, inhibit, or
otherwise interfere in cationic photopolymeriza-
tions. Second, curcumin is highly soluble in a
wide range of polar and nonpolar monomers and
polymers. In this article, we focus on the use of
curcumin as a dye photosensitizer for several
izations.
Figure 3 depicts an OP study of the photopo-
lymerization of cyclohexene oxide (CHO) carried
out in the presence and absence of curcumin
with 1.0 mol % IOC-10 SbF6 with broad-band
UV light with wavelengths greater than 300 nm.
As may be noted in this gure, the photopolyme-
rization in the presence of the dye takes place
very rapidly and substantially without an in-
duction period in comparison with the photo-
polymerization without the dye. The optimum

Figure 3. OP study of the photopolymerization of CHO with 1.0 mol % IOC-10

SbF6 in the absence of a photosensitizer and in the presence of 0.1 or 0.25 mol % cur-
cumin as a photosensitizer (light intensity 387 mJ/cm2 min).
 CURCUMIN 5223

Figure 4. Photopolymerization of CHO with 1.0 mol % IOC-10 SbF6 in the absence
of a photosensitizer and in the presence of 0.1 mol % curcumin as a photosensitizer
(light intensity 1510 mJ/cm2 min, 407-nm lter).

curcumin concentration for this particular pho-
topolymerization was found to be 0.10.25 mol %.
At higher concentrations, the efciency of pho-
tosensitization declines markedly because of
screening effects. Figure 4 depicts an OP study
conducted with an optical lter that permits
the passage of only a relatively narrow band
(midpoint 407 nm) of irradiation with wave-
lengths from 355 to 460 nm. In the absence of
curcumin, photopolymerization proceeds only
after a very long induction period and then
rather slowly. In contrast, when curcumin is
present, immediate polymerization of CHO
takes place rapidly and exothermically when
irradiation is commenced. A parallel study using
FT-RTIR is shown in Figure 5. Here, the IR
band at 782 cm1 corresponding to the epoxy
group was monitored. Again, the conversion of
the monomer takes place much more rapidly
in the presence of the dye than in its absence.
In Figure 6 is shown the curcumin-photosen-
sitized polymerization of CHO carried out with
the triarylsulfonium salt, (4-n-decyloxyphenyl)-
diphenylsulfonium hexauoroantimonate (SOC-
10 SbF6). Similar results were obtained for
the dialkylphenacylsulfonium salt, S-n-dodecyl-S-
methyl-S-phenacylsulfonium hexauoroantimonate
(DPS-C1C12 SbF6). Although there is clearly an

Figure 5. FT-RTIR study of the photopolymerization of CHO with 1.0 mol % IOC-
10 SbF6 in the absence of a photosensitizer and in the presence of 0.1 mol % curcu-
min as a photosensitizer (407-nm lter).
5224 CRIVELLO AND BULUT

Figure 6. Photopolymerization of CHO with 1.0 mol % SOC-10 SbF6 in the absence
of a photosensitizer and in the presence of 0.1 mol % curcumin as a photosensitizer
(light intensity 1510 mJ/cm2 min, 407-nm lter).

enhancement of the photopolymerization in the
presence of curcumin, the effect is considerably
less pronounced than in the case of diaryliodo-
nium salts. It has already been pointed out that
the photosensitization of triarylsulfonium or di-
alkylphenacylsulfonium salts by an electron-
transfer process is more problematic than the
corresponding diaryliodonium salts because these
salts are more difcult to reduce.2 This is in-
creasingly the case as one attempts to achieve
photosensitization with longer wavelength light
where the available excitation energy is lower.
Thus, curcumin appears to be less efcient as
a photosensitizer for the former photoinitiators
than for the latter ones, and for this reason, we
have focused our attention in this investigation
on the use of curcumin and its analogues as pho-
tosensitizers for diaryliodonium salt induced cat-
ionic photopolymerizations.
Figures 79 show the use of curcumin as a
dye photosensitizer for the photopolymerizations
of the difunctional epoxide monomer ERL-
4221E, the difunctional oxetane monomer DOX,
and 2-chloroethyl vinyl ether, respectively. These
studies denitively demonstrate that curcumin
can be applied as a photosensitizer for both
vinyl and ring-opening cationic photopolymeriza-
tions. ERL-4221E, which is the major epoxide
monomer used in numerous coating and adhe-
sive applications, undergoes facile photosensi-

Figure 7. Cationic photopolymerization of ERL-4221E carried out in the presence

and absence of curcumin as a photosensitizer (light intensity 1482 mJ/cm2 min,
407-nm lter 1.0 mol % IOC-10 SbF6).
 CURCUMIN 5225

Figure 8. OP study of the photopolymerization of DOX carried out in the presence

and absence of curcumin as a photosensitizer (1.0 mol % IOC-10 SbF6, light intensity
1500 mJ/cm2 min, 407-nm lter).

tized polymerization in the presence of curcu-
min (Fig. 7). The photopolymerization of DOX
(Fig. 8) is particularly interesting. No polymer-
ization was observed even after 5 min of irradia-
tion in the absence of curcumin, whereas when
this dye is present, polymerization takes place
rapidly and exothermically. The vinyl ether
monomer, 2-chloroethyl vinyl ether, was selected
for study because it is highly reactive and mod-
erately polar and readily dissolves both curcu-
min and the diaryliodonium salt photoinitiator.
As Figure 9 shows, the photopolymerization of 2-
chloroethyl vinyl ether is readily initiated in the
presence of curcumin, whereas in its absence
polymerization takes place only after a pro-
longed induction period.
Photosensitized Cationic Polymerization with an
LED Light Source
As previously mentioned in the introduction, the
ability to carry out cationic photopolymeriza-
tions with long-wavelength, narrow-band-emit-
ting light sources is critically important for
many current and future applications. Figure 10
depicts the photopolymerization of CHO carried
out with an array of 22 InGaN LEDs with a nar-
row-band emission centered at 470 nm. The

Figure 9. OP study of the photopolymerization of 2-chloroethyl vinyl ether carried

out in the presence and absence of curcumin as a photosensitizer (1.0 mol % IOC-10
SbF6, light intensity 1500 mJ/cm2 min, 407-nm lter).
5226 CRIVELLO AND BULUT

Figure 10. LED-induced photopolymerization of CHO carried out in the presence

and absence of curcumin (1.0 mol % IOC-10 SbF6 as a photoinitiator).

light ux generated from this battery-powered
light source is very low. As can be seen in this
gure, the polymerization proceeds satisfactorily
in the presence of curcumin with the tempera-
ture of the sample reaching a maximum of
83 8C. In contrast, no polymerization is observed
in the absence of the dye even after prolonged
irradiation times.
Solar-Induced Photopolymerization
An area of special interest in this laboratory
over many years is the application of photoiniti-
ated cationic polymerization to monomers and
polymers derived from natural sources such as
epoxidized vegetable oils and epoxidized natural
rubber.28 Curcumin is readily soluble in these
substrates. An OP study of the curcumin-photo-
sensitized polymerization of ESO is shown in
Figure 11. The reactivity of this system is quite
good, and the product is a exible crosslinked
polymer. As may be noted in Figure 1, although
the chief absorption band of curcumin lies at
427 nm, there is appreciable absorption well
into the short-wavelength visible region of the
spectrum. For this reason, curcumin can be used
as a photosensitizer for the solar-radiation-
induced polymerizations of the aforementioned

Figure 11. OP study of the photopolymerization of ESO in the presence and

absence of curcumin (1.0 mol % IOC-10 SbF6, light intensity 1500 mJ/cm2 min,
407-nm lter).

Figure 12. Four-layer ELO/glass ber composite (A) before exposure to solar irradi-
ation and (B) after 10 min of irradiation.
naturally derived substrates as well as entirely
synthetic monomers and polymers.
A demonstration of this concept is given in
Figure 12. A four-layer glass cloth laminate was
prepared by the infusion of the laminate with a
solution of ELO, containing a diaryliodonium
salt photoinitiator (IOC-10) and curcumin.
The laminate was then subjected to direct solar
irradiation. The irradiation conditions are de-
scribed in detail in the Experimental section of
this article. At the start of the irradiation
[Fig. 12(A)], the intense yellow color of the com-
posite is apparent. As the irradiation continues,
the yellow color is discharged, and the composite
rapidly takes on a pronounced orange coloration
[Fig. 12(B)]. Coincident with the color change is
the exothermic crosslinking polymerization of
ELO, which can be noted rst by a loss of sur-
face tack and then by stiffening of the compo-
site. This aforementioned process took place
over the course of 5 min of continuous solar
irradiation. Exposure was continued for an
additional 5 min to ensure completion of the
crosslinking polymerization. After termination
of the irradiation, the hard, rigidied com-
posite was removed from the polyethylene back-
ing and trimmed. ELO contains on average
seven to nine epoxy groups per molecule, so net-
work formation occurs as a result of both
intramolecular and intermolecular epoxide ring-
opening polymerization. This work suggests that
this technology can be applied to the construc-
tion of building and roong panels, boats, and
water delivery and sewerage systems using bio-
renewable monomers together with a naturally
occurring photosensitizer.
CURCUMIN 5227
Analogues of Curcumin
At this point in this investigation, we set three
additional objectives for this investigation: (1) to
understand the structural and electronic fea-
tures that make curcumin an active photosensi-
tizer, (2) to test whether other curcumin ana-
logues are similarly active as photosensitizers,
and (3) to attempt to further extend the range of
spectral sensitivity of onium salts into the visi-
ble region through the use of curcumin ana-
logues. There are three features of the structure
of curcumin that are important for its function
as a long-wavelength UVvis photosensitizer.
The rst feature is the extended conjugation
due to the presence of both the aromatic and
enol groups that provides the basic long-wave-
length absorption. A second prominent feature
is the presence of the methoxy and hydroxy
groups, respectively, in the 3- and 4-positions of
the terminal phenyl groups, which results in a
further bathochromic shift of the maximum
(kmax) absorption of this compound. Lastly, it is
important to note that curcumin is a conju-
gated phenolic compound. In concert with this
observation, it has been reported that curcumin
and its analogues possess antioxidant proper-
ties as a result of the presence of this latter
structural feature29 and that this may be
linked to its reported antitumorigenic30,31 and
related biological activities such as the inhibi-
tion of low density lipid (LDL) oxidation.32,33
These observations indicate that curcumin has a
low oxidation potential in the ground state and
suggest that the oxidation potential may be fur-
ther lowered on photoexcitation. As noted in the
mechanism depicted in Scheme 1, the ability of
5228 CRIVELLO AND BULUT
Scheme 2
a compound to undergo photoinduced one-elec-
tron oxidation is essential for its activity as a
photosensitizer.
To further examine the effects of structure on
the activity of curcumin, it was decided to con-
duct the synthesis of a number of well-dened
curcumin-related compounds and to examine their
activity as photosensitizers. The syntheses of
curcumin and several related compounds have
been undertaken by a number of research
groups.3437 The synthetic method developed
by Babu and Rajasekharan11,38 and shown in
Scheme 2 for curcumin is especially attractive
because it is simple and straightforward and
Figure 13. Comparative OP study of the photosensitized polymerization of CHO
with 1.0 mol % IOC-10 SbF6 as a photoinitiator and 0.1 mol % II, III, and IV as pho-
tosensitizers (light intensity 1530 mJ/cm2 min, 407-nm lter).
affords these naturally occurring and synthetic
analogues of curcumin (curcuminoids) in good
yields. This method involves the precomplexa-
tion of acetylacetone with boric acid, which
serves to block the Knoevenagel condensation at
the central methylene group and to direct the
reaction with aromatic aldehydes (shown, 4-
hydroxy-3-methoxy-benzaldehyde) to the termi-
nal methyl groups. The syntheses of curcumin
and several model curcumin analogues were car-
ried out in this laboratory, and the structures of
these compounds, together with their physical
and spectroscopic characteristics, are given in
Table 1.
Compound II in Table 1 is a curcumin ana-
logue that bears no substituents on the aromatic
rings, whereas compounds III [bisdemethoxycur-
cumin; 1,7-bis(4-hydroxyphenyl)-1,6-heptadiene-
3,5-dione] and IV [1,7-bis(4-methoxyphenyl)-1,
6-heptadiene-3,5-dione] possess hydroxy and
methoxy substituents, respectively, in the 4-posi-
tions of the terminal phenyl groups. The strong
auxochromic effects of the methoxy and particu-
larly the hydroxy groups on the UV absorption
maxima can be seen in both of the latter com-
pounds and in curcumin. In Figure 13, the OP
studies of the photosensitized polymerization of
CHO using compounds II, III, and IV as photo-
sensitizers are directly compared. In all cases,
the 407-nm bandpass optical lter was used.
Compound II displays very poor photosensitiza-
tion behavior and, compared with the control
polymerization (no photosensitizer), appears to

Figure 14. Comparative OP study of the photosensitized polymerization of CHO
with 1.0 mol % IOC-10 SbF6 as a photoinitiator and 0.1 mol % curcumin (I) and III
(light intensity 1530 mJ/cm2 min, 407-nm lter).
exhibit a retarding effect on the photopolymeri-
zation. This may be due to the poor UV absorp-
tion characteristics of II at the irradiating wave-
lengths. Figure 13 also clearly shows that III is
a more efcient photosensitizer than IV. A fur-
ther photosensitization study is depicted in
Figure 14, in which curcumin (I) is compared
with III. The superiority of curcumin as a pho-
tosensitizer is apparent in this gure. The
results of these studies can be rationalized
by consideration of the mechanism depicted in
Scheme 3.
The photoexcitation of curcumin in the pres-
ence of a diaryliodonium salt photoinitiator
results in the initial formation of the curcumin
cation radical. This species can undergo fur-
ther reaction by the loss of a proton and the
formation of a highly resonance stabilized sym-
metrical phenolate radical. A very similar me-
chanism was proposed by Bisby and Parker31
to explain the antioxidant behavior of hydroxy-
cinnamates. On the basis of this mechanism,
curcumin and III bearing 4-hydroxy groups
would be predicted to have the greatest activity
as photosensitizers, whereas compounds IV
and II would be predicted to exhibit reduced
and poor photosensitizing behavior. The addi-
tional presence of the two methoxy groups in
curcumin facilitates its photoinduced oxidation
CURCUMIN 5229
and also aids in stabilizing the resulting phe-
noxy radical, thereby making it a better photo-
sensitizer than III. Thus, it appears that
curcumin is optimally designed to act as a pho-
tosensitizer for onium salt induced cationic
photopolymerizations.
The curcumin analogues prepared thus far by
us and other researchers have either very simi-
lar or shorter UVvis wavelength absorption
characteristics than curcumin. Accordingly, we
undertook the preparation of derivative V by
the condensation of acetylacetone with cinna-
maldehyde. The addition of two double bonds
further extends the conjugation, and this is
reected by the generation of a weak band in
the UVvis spectrum at 454 nm.40 As can be
seen in the OP study given in Figure 15, V is an
active photosensitizer for the diaryliodonium
salt induced cationic ring-opening polymeriza-
tion of CHO. It is anticipated that the introduc-
tion of additional stabilizing hydroxy or methoxy
groups into the structure of V would further
enhance its activity.
The facile synthesis of curcumin and its ana-
logues raises the possibility of preparing a wide
variety of dye photosensitizers for onium salts
and tailoring their absorption characteristics as
desired. Current efforts are ongoing in this labo-
ratory to explore these aspects further.
5230 CRIVELLO AND BULUT

Scheme 3

CONCLUSIONS vinyl, epoxide, and oxetane monomers were car-

Curcumin is a naturally occurring dye obtained
from the common spice turmeric. Curcumin is
an efcient electron-transfer photosensitizer for
diaryliodonium salt cationic photoinitiators.
With curcumin, the photopolymerizations of
ried out with long-wavelength UV and visible
light in the range of 340535 nm. Besides its
long-wavelength photosensitizing activity, curcu-
min has several other advantages that are
important for its use in applications of photoini-
tiated cationic polymerization. It is inexpensive,

Figure 15. Photopolymerization of CHO in the presence and absence of V as a pho-

tosensitizer (1.0 mol % IOC-10 SbF6, light intensity 1530 mJ/cm2 min, 407-nm l-
ter).

nontoxic, and highly soluble in many useful
monomers, including those of natural origin.
Furthermore, curcumin displays no inhibiting or
retarding effects in the cationic polymerizations.
Analogues of curcumin incorporating the same
extended conjugated 1,3-diketone chromophore
can be readily prepared and also display excel-
lent photosensitizing activity. Further studies
using these curcumin analogues as photosensi-
tizers are in progress.
REFERENCES AND NOTES
1. Crivello, J. V. In Ring-Opening Polymerization;
Brunelle, D. J., Ed.; Hanser: Munich, 1993; p 157.
2. Crivello, J. V. In UV Curing Science and Technol-
ogy; Pappas, S. P., Ed.; T echnology Marketing:
Stamford, CT, 1978; p 24.
3. Crivello, J. V.; Jang, M. J Photochem Photobiol
2003, 159, 173.
4. Crivello, J. V.; Lam, J. H. W. J Polym Sci Part A:
Polym Chem 1976, 16, 2441.
5. Crivello, J. V.; Lam, J. H. W. J Polym Sci Part A:
Polym Chem 1979, 17, 1059.
6. Crivello, J. V.; Jiang, F. Chem Mater 2002, 14, 4858.
7. Crivello, J. V.; Jang, M. J Macromol Sci Pure
Appl Chem 2005, 42, 1.
8. Crivello, J. V.; Lee, J. L. J Polym Sci Part A:
Polym Chem 1989, 27, 3951.
9. Akhtar, S. R.; Crivello, J. V.; Lee, J. L. J Org
Chem 1990, 55, 4222.
10. Crivello, J. V.; Kong, S. Macromolecules 2000, 33, 833.
11. Babu, K. V. D.; Rajasekharan, K. N. Org Prepr
Proc Intern Briefs 1994, 26, 674.
12. Crivello, J. V.; Acosta Ortiz, R. J Polym Sci Part
A: Polym Chem 2001, 39, 2385.
13. Falk, B.; Vallinas, S. M.; Crivello, J. V. J Polym
Sci Part A: Polym Chem 2003, 41, 579.
14. Anderson, A.; Mitchell, M. S.; Mohan, R. S.
J Chem Educ 2000, 77, 359.
15. Spectrochim Acta Part A 2004, 60, 1091.
16. Mishra, B.; Priyadarsini, K. I.; Bhide, M. K.;
Kadam, R. M.; Mohan, H. Free Radical Res 2004,
38, 355.
17. Zsila, F.; Bikadi, Z.; Simonyi, M. Tetrahedron:
Assymmetry 2003, 14, 2433.
18. The Merck Index, 13th ed.; ONiel, M. J.; Smith,
A.; Heckelman, P. E., Eds.; Merck: Whitehouse
Station, NJ, 2001; p 2707.
19. Chopra, R. N.; Chopra, I. C.; Honada, K. L.;
Kapur, L. D. Indigenous Drugs of India, 2nd ed.;
Dhur: Calcutta, 1958.
CURCUMIN 5231
20. Nadkarni, K. M. In India Materia Medica; Nad-
karni, K. M., Ed.; Popular Prakashan: Mumbai,
1976; pp 414416.
21. Krishnamoorthy, A. The Wealth of India: A
Dictionary of Indian Raw Materials and Indus-
trial Products; CSIr: New Delhi, 1950; Vol. 2,
p 402.
22. Rao, C. V.; Rivenson, A.; Simi, B.; Reddy, B. S.
Cancer Res 1995, 55, 259.
23. Sharma, O. P. Biochem Pharmacol 1976, 25, 1811.
24. Ammon, H. P.; Wahl, M. A. Planta Med 1991,
57, 1.
25. Chignell, C. F.; Bilski, P.; Reszka, K. J.; Motten,
A. G.; Sik, R. H.; Dahl, T. A. Photochem Photobiol
1994, 59, 295.
26. Khopde, S. M.; Priyadarsini, K. I.; Palit, D. K.;
Mukherjee, T. Photochem Photobiol 2000, 72,
625.
27. Sundaryono, A.; Nourmamode, A.; Gardrat, C.;
Grelier, S.; Bravic, G.; Chasseau, D.; Castellan, A.
Photochem Photobiol 2003, 2, 914.
28. (a) Crivello, J. V.; Narayan, R. Chem Mater 1992,
4, 692; (b) Crivello, J. V.; Narayan, R. Proceedings
of the Radtech 92 Conference, Boston, MA, April
26, 1992; p 526.
29. Leu, T. H.; Maa, M. C. Curr Med Chem Anti-Can-
cer Agents 2002, 2, 357.
30. Jovanovic, S. V.; et al. J Am Chem Soc 2001, 123,
3064.
31. Bisby, R. H.; Parker, A. W. Central Laser Facility
Annual Report 1999/2000; Division of Biological
Sciences, University of Salford: Salford, United
Kingdom, 2000; p 111.
32. Ramirez-Tortosa, M. C.; Mesa, M. D.; Aguilera,
M. C.; Quiles, J. L.; Baro, L.; Ramirez-Tortosa,
C. L.; Martinez-Victoria, E.; Gil, A. Atherosclerosis
1999, No. 2, 371.
33. Naidu, K. A.; Thippeswamy, N. B. Mol Cell Bio-
chem 2002, 229, 19.
34. Pabon, H. Y. Y. Recl Trav Chim 1964, 83, 399.
35. Roughlev, P. J.; Whiting, D. A. J Chem Soc Perkin
Trans 1 1973, 2379.
36. Nurna, A. N.; Reksohadiprodjo, M. S.; Timmer-
man, H.; Jenie, U. A.; van der Goot, H. Eur
J Med Chem 1997, 32, 321.
37. Pedersen, U.; Rasmussen, P. B.; Lawesson, S.-O.
Liebigs Ann Chem 1985, 1556.
38. Dinkova-Kostova, A. T.; Talalay, P. Carcinogenesis
1999, 20, 911.
39. Pavolini, T.; Gambarin, F.; Grinzat, A. M. Ann
Chim Roma 1950, 40, 280.
40. Arrieta, A.; Beyer, L.; Kleinpeter, E.; Lehmann,
J.; Dargatz, M. J Prakt Chem 1992, 334,
696.