“Clicked” Porphyrin-Cucurbituril Conjugate: A New Multifunctional Supramolecular Assembly Based on Triglycosylated Porphyrin and Monopropargyloxycucurbit[7]uril

Article abstract of DOI:10.1002/chem.201804024

The design, synthesis, and characterization of a new multifunctional supramolecular assembly based on a photoactive glycosylated porphyrin and covalently attached monofunctionalized cucurbit[7]uril (CB7) are reported. To obtain the target supramolecular a

Full text of DOI:10.1002/chem.201804024

A Journal of
Accepted Article
Title: "Clicked" Porphyrin-Cucurbituril Conjugate: A Novel
Multifunctional Supramolecular Assembly Based on tri-
Glycosylated Porphyrin and Monopropargyloxycucurbit[7]uril
Authors: Donus Tuncel, Ahmet Koc, and Rehan Khan
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Chemistry - A European Journal
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“
Clicked” Porphyrin-Cucurbituril Conjugate: A Novel Multifunctional Supramolecular
Assembly Based on tri-Glycosylated Porphyrin and Monopropargyloxycucurbit[7]uril
Ahmet Koc, Rehan Khan, Dönüs Tuncel,[a,b]*
[
a]
[a,b]
[
[
a]Department of Chemistry, Bilkent University, 06800 Ankara, Turkey
b]UNAM–National Nanotechnology Research Center, Institute of Materials Science and
Nanotechnology, Bilkent University, Ankara 06800, Turkey
*
Corresponding author:dtuncel@fen.bilkent.edu.tr
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.2018xxxxx.
Abstract
Herein, we report the design, synthesis and characterization of a novel multifunctional
supramolecular assembly based on a photoactive glycosylated porphyrin and covalently
attached mono-functionalized cucurbit[7]uril (CB7). To obtain the target supramolecular
assembly, azido-functionalized tetraphenylporphyrin (TPP) was used as a building block. TPP
was first glycosylated by copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction and
then, a monopropargyloxy-functionalized-CB7 unit was conjugated to glycosylated TPP with
1
a second CuAAC reaction. The host-guest chemistry of the assembly was investigated by H-
NMR experiments in order to find out the availability of the CB7 as a host. The imidazole-
based guest which is known to have high affinity toward CB7 was observed to form inclusion
complex with CB7. It was also demonstrated that this supramolecular assembly can serve as an
efficient photosensitizer for the generation of singlet oxygen.
Keywords: Monopropargylcucurbit[7]uril, supramolecular assembly, tri-glycosylated
porphyrin, photosensitizer, singlet oxygen.
1
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Introduction
Multi-functional supramolecular materials combining various important functions and abilities
[
1]
in one platform can find a wide range of applications in the emerging technologies. In this
regard, porphyrin derivatives are highly appealing as a chromophore and a building block in
the construction of photoactive multifunctional assemblies as they can exhibit photocatalytic,
photodynamic and electroactive properties and allow the attachment of various functionalities
to their large hydrophobic cores in order to bring together multi-functionalities.[2-7]
A number of different functional groups were attached to porphyrin core including
hydrophilic oligoethylene glycols, dendrons, mono or polysaccharides in order to alter the
solubility and photophysical properties and to make use of these compounds for various
applications (e.g., photocatalysis, light harvesting, sensing, photodynamic therapies, etc.). [8-14]
There are also examples in the literature in which cucurbit[n]urils (CBs) are attached to
the porphyrin core through non-covalent interactions,[15, 16] however,those works do not involve
in the conjugation of functionalized CBs directly to porphyrin core in order to be able to utilize
the CBs as receptors. CBs are highly versatile macrocycles possessing a hydrophobic cavity
along with carbonyl decorated hydrophilic portals. Owing to these features they have an ability
of binding to various guests with high affinity and selectively including dyes, drugs and
peptides. Due to their distinctive features, they have been utilized in the construction of
supramolecular assemblies.[17] Although post-surface functionalized CBs with reactive
functional groups are very useful building blocks in the assembly of supramolecular structures,
the examples are still rather limited. One of the reasons might be due to the difficulties
associated with the functionalization of CB derivatives especially monofunctionalization.[18-23]
To date, mainly two approaches have been employed for the synthesis of functionalized CB
derivatives: (1) post-functionalization[19-22] and (2) using the functionalized precursors.[23, 24]
Post functionalization seems to be more practical as it allows the modification of as-prepared
2
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10.1002/chem.201804024
CB homologues in moderate yields. Kim et al. used these functionalized CB derivatives in the
preparation of various nanostructured materials.[20, 17b, 17d] Isaacs and co-workers recently
reported the synthesis and the application of monofunctionalized CB7 derivatives, which was
synthesized from a functional group containing precursor.[23, 24]
Here, we report first time the conjugation of mono-propargyloxy-CB7 unit to a tri-
mannosylated-TPP) core through copper-catalyzed azide–alkyne cycloaddition (CuAAC)
reaction. The rationale behind the design of this assembly as follows: TPP is selected as a core
1
of the assembly because of its singlet oxygen ( O
2
) production ability that could be used as a
photosensitizer for photodynamic therapies against cancer cells or bacteria inactivation as well
as photocatalysis. Multi mannose groups were chosen because of their hydrophilic nature that
may increase the solubility of the resulting assembly and for the multivalent interaction as the
mannose units have ability to interact with mannose receptors on the bacterial surface that
would be useful for the photodynamic antibacterial therapy. CB7 was chosen to be conjugated
to this platform for several reasons. First due to its bulky nature, interactions between the
porphyrin units are expected to be minimized and as a result, singlet oxygen efficiency will be
enhanced. In the photodynamic cancer or antibacterial therapies, in order to increase the
efficiency of the therapy, anticancer drugs or antibiotics, respectively, can be further
encapsulated and carried by CB7 units. This assembly could also be used for photocatalysis and
energy harvesting in which CB units could encapsulate respectively, an analyte and
donor/acceptor molecules for an efficient photocatalytic and energy transfer processes.
However, the current scope of this manuscript will be on the synthesis, full characterization,
host-guest chemistry and singlet oxygen generation ability of the assembly. Other
aforementioned applications will be explored in our future works.
Results and Discussion
3
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The synthetic route of our target assembly is shown in the reaction Scheme 1. First, CB7 was
1
13
synthesized and characterized by H NMR, C NMR spectroscopies and ESI-MS (Figures S1-
S4).[25] Then, monohydroxy-CB7 (CB7-OH
) and mono-propargyloxy-cucurbit[7]uril (CB7-
1
(
O-propargyl)
1
) were prepared as shown in Scheme 1a according to literature procedures.[19-21]
1
13
The formation of CB7-OH
1
and CB7-(O-propargyl) was confirmed by H NMR, C NMR
1
spectroscopies, ESI-MS, FT-IR and thermal characterization was done with TGA (Figures S5-
S13).
Scheme 1. a) Synthesis of mono-fucntionalized CB7: (i) K
2
S
2
O
8
, H O, 85 °C; (ii) NaH,
2
°
propargyl bromide, DMSO, 0 C-25 °C, N
2
(g), 48 h. b) (iii) Synthesis of the assembly:
CuSO
4
4
.5H
2
2
O/Na-L-Ascorbate, THF/H
2
O, 60 °C; 14h (iv) NaOCH
3
, MeOH, 25 °C, 14 h; (v)
CuSO
.5H
O/Na-L-Ascorbate, DMSO/H
2
O, 48h.
4
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After having mono- propargyloxylated CB7 at hand, we set out for the synthesis of the
porphyrin derivatives. First, the synthesis of 5,10,15,20-tetrakis(α-bromo-p-tolyl)porphyrin
(
TPP-Br) was accomplished[26] followed by azidation to afford TPP-N
in 93% yield. TPP-Br
3
1
and TPP-N
3
were characterized by H NMR spectroscopy and ESI-MS (Figures S14-S18).
Before proceeding with Cu-catalyzed azide-alkyne click reaction (CuAAC), the core of TPP-
was metallated with Zn so as to prevent inclusion of Cu that will decrease its catalytic effect.
Metallation was successfully achieved by refluxing TPP-N with Zn(OAc) in MeOH and
N
3
3
2
1
13
characterized by H and C NMR spectroscopies, ESI-MS, FT-IR and TGA (Figures S19-S23).
1
In H NMR spectrum, the upfield shift from 4.88 ppm to 4.75 ppm and the disappearance of
singlet at -2.78 ppm was the proof for the successful metallation. The TGA of the compound
demonstrated two types of decomposition (Figure S23). The first decomposition starts at 233
°
C which is due to the loss of azide groups from the compound. The second decomposition that
starts around 517 °C is probably for the loss of benzene rings attached to the core.
Acetylated propargylated mannose (1-α-propargyloxy mannose) was synthesized using
the literature procedure.[14b] and characterized by H NMR and FT-IR spectroscopies (Figures
S24, S25). The click (CuAAC) reaction between three equivalents of 1-α-propargyloxy mannose
1
and one equivalent Zn-TPP-N
porphyrins. These were successfully separated by column chromatography to afford TPP-Az-
AcMan (tri-clicked analogue) in 50% yield together with 4% of TPP-3Az-1AcMan (mono-
clicked analogue), 16% of TPP-2Az-2AcMan (di-clicked analogue), and 20% of TPP-
3
yielded a mixture of analogues of 1, 2, 3 and 4-mannosyl-clicked
3
4
AcMan (tetra-clicked analogue), successively. TPP-Az-3AcMan was selected for the further
use due to solubility considerations and fully characterized by H-NMR, 13C-NMR, FT-IR
1
1
spectroscopies and ESI-MS (Figures S26-S29). In the H-NMR spectrum (Figure 1C), the
characteristic singlet at 8.55 ppm for the hydrogen of triazole ring and the multiplet around 2.00
ppm for acetylic hydrogens are evident for the attachment of mannosyl units. The peak at 170.1
5
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1
3
ppm coming from carbonyl carbon in C NMR further confirms the presence of acetylated
mannose groups attached to TPP (Figure S27). In the ESI-mass spectrum, the related signals
are readily assigned to corresponding molecular ions as shown in Figure S28. Another
important proof for the formation of TPP-Az-3AcMan was obtained from FT-IR spectrum
-
1
which shows the partial reduction of azide stretching at 2095 cm and the existence of C=O
-
1
stretching peak at 1748 cm as expected (Figure 2a). TPP-Az-3AcMan) dissolves well in
DMSO, DMF and partially in methanol, THF, chloroform, acetone, acetonitrile but not well in
ethanol and water.
Prior to setup the final synthetic step, acetyl groups on mannose of TPP-Az-3AcMan,
were hydrolyzed via Zemplén deacetylation using sodium methoxide solution in methanol. [24]
The product obtained after hydrolysis (TPP-Az-3Man) dissolves well in DMSO partially in
1
methanol but it has a poor solubility in water. TPP-Az-3Man was characterized by H-NMR,
13C-NMR, FT-IR spectroscopies and ESI-MS and (Figures S30-S33). The disappearance of
1
acetylic hydrogen peaks around 2.00 ppm in H NMR spectrum (Figure 1B) and the C=O
-
1
stretching peak at 1748 cm in the FT-IR spectrum along with the emergence of a broad peak
-
1
at 3350 cm for hydroxyl groups confirm the success of the deacetylation reaction (Figure 2b).
The ESI-mass spectrum clearly shows the molecular ions of the product and there was no trace
from acetylated form (Figure S32).
In the final step, TPP-CB7 conjugate (TPP-3Man-CB7) was synthesized by a second
CuAAC reaction between TPP-Az-3Man and excess CB7-(O-propargyl)
mixture (4:1). The product was isolated after purification using sephadex G-25 column
MeOH/water, 1:1, v/v) in 91% yield. The solubility properties of TPP-3Man-CB7 were
investigated and summarized as follows: in DMSO, 10 mg/mL; in H O, 0.2 mg/mL and in
O:DMSO mixture (4:1, v/v), 2 mg/mL. It also dissolves in acidic water (e.g. 0.1M HCl (aq)
1
in DMSO/H
2
O
(
2
H
2
solution). Poor solubility in neat water, probably due to extensive H-bonding between the
6
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mannosyl-OH groups but the presence of even small amount of DMSO weakens the interactions
1
13
and solubilizes the assembly in water. TPP-3Man-CB7 was fully characterized by H and C
NMR, FT-IR spectroscopies and ESI-MS (Figures S35-S38). Figure 2 shows the overlaid FT-
IR spectra of TPP-Az-3AcMan, TPP-Az-3Man and TPP-3Man-CB7 for comparison. FT-IR
spectrum of the TPP-3Man-CB7 (Figure 2c) reveals the absence of azide stretching at 2100
-
1
-1
cm and the presence of strong carbonyl stretch at 1725 cm , which supports the successful
1
synthesis of TPP-3Man-CB7. Figure 1A shows the H-NMR spectrum of TPP-3Man-CB7
recorded in DMSO-d
6
. As can be seen from the spectrum, the peaks for porphyrin and mannosyl
1
protons are relatively sharp but the peaks due to CB protons are quite broad. In the H NMR
spectrum, the singlet at 8.49 ppm for the hydrogen of triazole ring formed during the second
13
click reaction and the peak at 155.6 ppm for carbonyl carbon of CB in C NMR further
confirms the success of the reaction (Fig. S35, S37). In the ESI-MS spectrum, the related signals
are readily assigned to corresponding molecular ions as shown in Figure S35.
7
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1
Figure 1. Overlay of the H NMR (400 MHz, 25 °C) spectra of (A) TPP-3Man-CB7 (B) TPP-
Az-3Man and (C) TPP-Az-3AcMan (Spectra were recorded in DMSO-d ).
6
Figure 2. Overlay of the FT-IR spectra of (a) TPP-Az-3AcMan (b) TPP-Az-3Man (c) TPP-Az-
Man-CB7 in absorption mode.
3
8
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In order to find out whether CB7 will be available as a host in the assembly, 1,1'-(1,4-
phenylenebis(methylene))-bis(3-methyl-1H-imidazol-3-ium) iodide (bisimidazolium), which
1
is known to have high affinity toward CB7 was selected as a guest molecule and H-NMR
1
experiment was carried out. As can be seen from H-NMR spectrum of bisimidazolium guest
recorded in D
f and b/c, respectively) overlap and resonate at 7.5 ppm. However, upon addition of 1 equiv
CB7-OH , the phenyl protons exhibit an upfield shift of around 1 ppm and imidazole protons
labelled as b and c) appear as two distinct peaks (Figure 3B). These changes indicate the
2
O (Figure 3A), chemical shifts for the phenyl and imidazole protons (labelled as
1
(
encapsulation of phenyl moiety of the imidazole guest by CB7-OH
1
as the suggested inclusion
1
complex structure shown on Figure 3B. We have also observed similar changes in the H-NMR
spectrum of the TPP-3Man-CB7 (Figure 3C) when bisimidazolium solution in D
2
O (1 equiv)
was added to the NMR tube containing the DMSO-d solution of TPP-3Man-CB7.
6
Furthermore, the broadened CB7 peaks acquired their well-defined shapes after complexing
with bisimidazolium guest. These observations confirm that CB7 is available as a host for
complexation and there is no conformational restriction for CB7 in the assembly to exhibit its
nature as being a receptor.
9
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1
Figure 3. H NMR (400 MHz, 25 °C) spectra of (A) 1,1'-(1,4-phenylenebis(methylene))bis(3-
methyl-1H-imidazol-3-ium) iodide (bisimidazolium) (in D
bisimidazolium, (in DMSO-d :D O mixture, 1:2, v/v); (C) TPP-3Man-CB7+1 equiv
bisimidazolium (1.2 mM, in DMSO-d :D O mixture, 2:1, v/v); (D) TPP-3Man-CB7 (1.2
2
O); (B) CB7-OH +1 equiv
1
6
2
6
2
mM, DMSO-d ).
6
Photophysical properties of TPP-3Man-CB7, TPP-Az-3AcMan and TPP-Az-3Man
in DMSO were also investigated. Figure 4 shows an overlay of the UV-Vis absorbance and
fluorescence spectra of TPP-Az-3AcMan, TPP-Az-3Man and TPP-3Man-CB7. UV-vis
absorbance spectra show no significant difference in a typical sharp Soret band (λmax= 429 nm)
and Q-bands (λabs = 561 and 600 nm). Similarly, emission spectra also do not show any
significant difference (λem = 608 and 661 nm). The fluorescence quantum yields (Φ
f
) of TPP-
3
Man-CB7 and TPP-Az-3Man in DMSO were found to be 3.5 and 4.1, respectively. The
10
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fluorescence lifetime (τ) is 1.8 ns for both TPP-3Man-CB7 and TPP-Az-3Man (Fig. S34,
S40).
Figure 4. Normalized UV-Vis absorbance and fluorescence spectra of TPP-Az-3AcMan
(
green), TPP-Az-3Man (blue), and TPP-3Man-CB7 (red) in DMSO.
Low fluorescence quantum yields of these compounds would suggest us that the excited
molecules may follow nonradiative relaxation pathways, which could possibly increase their
1O
generation capacity. In order to prove this, a widely known indirect method for the
2
1
determination of produced O
2
was employed. 1,3-diphenylisobenzofuran (DPBF) was used as
1O
photosensitizer upon irradiation was correlated with the amount of O
trapping agent and time-dependent decrease in the absorbance of DPBF in the presence of
2
1
2
generated. For this
experiment, the samples in DMSO were irradiated with 460 nm LED with 10 sec intervals. The
reduction in the absorbance intensity of DPBF was monitored with the increasing irradiation
time (Fig. S41). From the absorbance graphs, –ln[DPBF]/[DPBF] vs. time plots were extracted
0
1
to indirectly calculate O
2
quantum yields of the samples using the equation below:
Φsam = Φ (m /m )(F /F )
MB
sam
MB
MB sam
11
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where the subscripts ‘MB’ and ‘sam’ stand for methylene blue (ΦMB = 0.52 in DMSO) and
acetylated bis-mannose TPP, hydrolyzed bis-mannose TPP and TPP-3Man-CB[7], respectively.
m is the slope of –ln[DPBF]/[DPBF]
0
vs. time plot and F is the absorption correction factor that
is given by F=1-10-OD (OD: optical density at the irradiation wavelength). The O
1
quantum
2
yields of the corresponding samples can be order as:
TPP-Az-3Man ᴝ TPP-3Man-CB7 > TPP-Az-3AcMan; [Φ = 0.77 ᴝ 0.77 > 0.80]
Δ
Figure 5 Linearized plots based on the decrease in the absorbance intensity of DPBF in the
presence of methylene blue, TPP-Az-3AcMan, TPP-Az-3Man and TPP-3Man-CB7 irradiated
at 460 nm with 10 sec intervals.
1
In the literature the O
2
quantum yield of unfunctionalized TPP was reported as 0.60 in
DMF.[27] The synthesized novel materials were seen to have O
1
quantum yields around 80%,
2
1
which are significantly higher than that of TPP. The reason of high O
2
quantum yields could
be explained by reduced π-π interactions between the porphyrin cores resulted from the
presence of bulky functional groups (mannosyl and CB7).
Conclusions
In summary, a multifunctional supramolecular assembly based on a photoactive glycosylated
porphyrin and covalently attached mono-functionalized CB7 was synthesized first time and
fully characterized successfully. With a CuAAC reaction of 1-α-propargyloxy mannose and Zn-
12
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TPP-N3, first tri-mannosyl clicked porphyrin, TPP-Az-3AcMan, was synthesized and isolated
from the other mono, di and tetra mannosyl analogues and subsequently hydrolyzed to obtain
its deacetylated version. Tri-mannosyl clicked porphyrin was selected to be used for the
construction of assembly because it allowed us to obtain well-defined and as result, well-
characterized structure after its second CuAAC reaction with mono-propargyloxy-CB7. The
resulting assembly dissolves in DMSO (10 mg/mL), in H
2
O (0.2 mg/mL), in H O:DMSO
2
mixture (4:1, v/v), 2 mg/mL) and in aqueous acid solution.
1O
generation efficiencies of the synthesized compounds were investigated and they
2
were found to be significantly higher than that of the unfunctionalized TPP. Moreover, the
1
availability of the CB7s as a host in the assembly was confirmed by H-NMR experiments in
which the imidazole-based guest was observed to form inclusion complex with the CB7s of the
assembly.
This photoactive supramolecular assembly has a potential to be used in the multimodal
chemo and photodynamic therapies as its photoactive porphyrin core can act as a
photosensitizer and in order to increase the efficiency of the therapy, anticancer drugs or
antibiotics, respectively, can be further encapsulated and carried by CB7 units. This assembly
could also be used for photocatalysis and energy harvesting in which CB units could
encapsulate respectively, an analyte and donor/acceptor molecules for an efficient
photocatalytic and energy transfer processes.
Experimental Section
Experimental details and procedures, characterization data and spectra provided in the
supporting information part.
Acknowledgements
13
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We thank The Scientific and Technological Research Council of Turkey-TÜBİTAK for funding
KBAG 215Z035).
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Chemistry - A European Journal
10.1002/chem.201804024
Table of Contents
Sugar coated porphyrin-cucurbituril host ready to serve: A novel multifunctional
supramolecular assembly was synthesized by clicking an azide functionalized photoactive
glycosylated porphyrin with mono-propargyloxy functionalized cucurbit[7]uril (CB7). This
supramolecular assembly can serve as a host to bind with guests and an efficient photosensitizer
for the generation of singlet oxygen.
16
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