Dual-Surface Functionalization of Metal-Organic Frameworks for Enhancing the Catalytic Activity of Candida antarctica Lipase B in Polar Organic Media

Article abstract of DOI:10.1021/acscatal.6b03222

One of the most attractive characteristics of metal organic frameworks (MOFs) is their diversity in use as functional materials, because their diversity means that the appropriate MOFs for the required applications can be readily generated from numerous elemental compounds. In addition, post-synthetic modifications of MOFs further expand their diversity. We describe a combined approach involving a typical post-synthetic modification and our previously reported surface modification to introduce multicompounds on MOFs. This method has been used to alter the local environments of a target biocatalyst and has enhanced the activity of the biocatalyst in polar organic media. It has been known that lipases are more active in nonpolar organic solvents than in polar ones. Hence, it can be hypothesized that surrounding lipase molecules with nonpolar compounds possibly increases the activity of lipases in polar organic solvents such as acetonitrile. A series of fatty acids (C12-C22) were conjugated with the amino groups of 2-amino-1,4-benzene dicarboxylate (NH₂-BDC) in UiO-66-NH₂ (ZrMOF) and then Candida antarctica lipase B (CAL-B) was covalently bonded to the pendent carboxylate groups on the surface of ZrMOF. The introduction of fatty acids around the covalently conjugated CAL-B molecules on ZrMOF improved the activity in acetonitrile by a factor of up to 13.

Full text of DOI:10.1021/acscatal.6b03222

Letter
pubs.acs.org/acscatalysis
Dual-Surface Functionalization of Metal-Organic Frameworks for
Enhancing the Catalytic Activity of Candida antarctica Lipase B in
Polar Organic Media
Suhyun Jung and Seongsoon Park*
Department of Chemistry, Center for NanoBio Applied Technology, Sungshin Women’s University, Seoul 01133, Korea
S
* Supporting Information
ABSTRACT: One of the most attractive characteristics of
metal organic frameworks (MOFs) is their diversity in use as
functional materials, because their diversity means that the
appropriate MOFs for the required applications can be readily
generated from numerous elemental compounds. In addition,
post-synthetic modifications of MOFs further expand their
diversity. We describe a combined approach involving a typical
post-synthetic modification and our previously reported
surface modification to introduce multicompounds on
MOFs. This method has been used to alter the local
environments of a target biocatalyst and has enhanced the
activity of the biocatalyst in polar organic media. It has been
known that lipases are more active in nonpolar organic
solvents than in polar ones. Hence, it can be hypothesized that surrounding lipase molecules with nonpolar compounds possibly
increases the activity of lipases in polar organic solvents such as acetonitrile. A series of fatty acids (C12−C22) were conjugated
with the amino groups of 2-amino-1,4-benzene dicarboxylate (NH2−BDC) in UiO-66-NH2 (ZrMOF) and then Candida
antarctica lipase B (CAL-B) was covalently bonded to the pendent carboxylate groups on the surface of ZrMOF. The
introduction of fatty acids around the covalently conjugated CAL-B molecules on ZrMOF improved the activity in acetonitrile by
a factor of up to 13.
KEYWORDS: bioconjugation, immobilization, lipase, metal organic frameworks, multifunctionalization, post-synthetic modification,
surface modification
andida antarctica lipase B (CAL-B) is one of the most
widely used biocatalysts in organic synthesis, because it is
separated CAL-B molecules. For instance, Fernandez-Lafuente
and co-workers reported the effect of the introduction of basic
molecules on the lipase activity in aqueous media.8 They used
basic compounds as a blocking compound after the covalently
immobilization of lipases using divinylsulfone on agarose. The
introduction of the basic compounds presumably changes the
local pH around lipase molecules and affects the activity of
lipase. Herein, we explored the hypothesis by dual-surface
functionalization of metal-organic frameworks (MOFs).
MOFs have garnered much more attention in the last few
decades.9 One attractive characteristic of MOFs is their large
void volume. In addition, another fascinating characteristic of
MOFs is their diversity. MOFs can be prepared from numerous
elemental compounds, organic linker compounds and metal
ions. The diversity of MOFs makes them employed for various
applications. For instance, they have been used in catalysis, gas
storage, and separation systems.10 Recently, post-synthetic
modification has been shown to introduce additional organic
C
suitable as a catalyst in synthetic applications.1,2 For example,
CAL-B possesses high enantioselectivity for chiral secondary
alcohols and high thermostability.3 In addition, CAL-B exhibits
high tolerance in various organic media.4 The activity of CAL-
B, however, varies according to the polarity of the organic
media, which is similar to most other lipases.5 For example,
CAL-B exhibits its highest activity in nonpolar organic solvents,
such as hexane and toluene, but exhibits lower activity in polar
solvents, such as acetonitrile.6 Although most lipases are less
active in polar solvents, a polar solvent is often required,
because of substrate solubility issues. Therefore, enhancing the
activity of CAL-B in polar solvents improves the utilization of
CAL-B in organic synthesis. The underlying reason why
hydrolases, including CAL-B, exhibit lower activity in polar
solvents has not been completely elucidated.7 However, it can
be hypothesized that the activity of CAL-B in polar media is
possibly improved by surrounding the CAL-B molecules with
nonpolar organic compounds. Covalent immobilization of
CAL-B on supporting materials can separate all of the CAL-B
molecules, and the introduction of nonpolar molecules onto the
supporting materials can alter the local environments of the
Received: November 13, 2016
Revised: December 5, 2016
Published: December 12, 2016
© XXXX American Chemical Society
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DOI: 10.1021/acscatal.6b03222
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Letter
groups into MOFs, which has expanded their diversity.11 Post-
synthetic modification uses an intact functional group, such as
the amino group of 2-amino-1,4-benzene dicarboxylic acid
(NH2−BDC), in the organic linker compound to react with a
compound after synthesis of an MOF. Besides, our research
group has proposed another approach for the modification of
the surface of MOFs and described the conjugation of
biomolecules onto MOFs.12 While conventional post-synthetic
modifications have focused on using a particular functional
group as a reactive site to introduce the second functional
group in the linker compound, we focused on the surface
modification of MOFs without using such specific organic
linkers. The linker organic compounds or metal ions on the
surface of an MOF do not bind to each other and therefore
remain intact pendent groups. The unreacted functional groups
of organic linker compounds on the surface of MOFs can be
activated and used to introduce other compounds onto MOFs.
We have demonstrated that biomolecules can be conjugated to
various structural MOFs and are also functionally active. In
response to the findings of our previous study, we hypothesized
that the combination of typical post-synthetic modification and
our approach would allow multifunctionalization of the surface
of MOFs (Figure 1a). Such multifunctionalization may allow
control over the environment of a particular molecule that is
surrounded by other compounds (Figure 1b).
surface pendent carboxylate group on the ZrMOF also serves as
a reaction center to bind biomolecules, as we have previously
shown.12 Furthermore, ZrMOF is stable in water, which is an
important property, with respect to the conjugation of
biomolecules onto MOFs, because the modification process
occurs in an aqueous system, because of the solubility issues
with the biomolecules.
ZrMOF was synthesized from ZrCl4 and NH2−BDC with an
equivalent molar amount of water, according to previously
described methods in the literature.15 The average diameter of
the particles was ∼200 nm (Figure 2a). The sized particles are
suitable to reduce the mass-transfer limitations, compared to
micrometer-sized beads.16 Six fatty acids (C12, C14, C16, C18,
C20, and C22, described in Table 1) were then conjugated to
the intact ZrMOF amino group through amide-bond formation.
The fatty acids were first activated by N,N′-diisopropyl
carbodiimide (DIC), which is one of the peptide coupling
reagents, and then were reacted with ZrMOF. Scanning
electron microscopy (SEM) analyses exhibited that the
morphology of the fatty-acid-conjugated ZrMOF was not
altered (Figure 2a). In addition, powder X-ray diffraction
(PXRD) patterns and infrared (IR) analyses demonstrated that
the crystallinity and characteristic peaks of ZrMOF were
conserved after fatty-acid conjugation (see Figure 2c, as well as
Figure S1a in the Supporting Information). Fatty-acid
conjugation was confirmed by electrospray ionization−mass
spectrometry (ESI-MS) and nuclear magnetic resonance
(NMR) analyses of the samples released from the ZrMOF
digestion by hydrofluoric acid (HF). ESI-MS analyses clearly
supported the fatty-acid conjugation by showing the pseudo-
molecular ions (M-H−) of the fatty-acid-conjugated NH2−
BDC (Figure S2 in the Supporting Information). However, the
NMR spectra showed a mixture of the characteristic peaks of
fatty-acid-conjugated NH2−BDC and unreacted NH2−BDC
(see Figure 3). This indicates that not all of the free amino
groups of ZrMOF were conjugated to fatty acids. Presumably,
the fatty acids are too large to enter the ZrMOF, so the amino
groups on the surface are the only ones that are modified.
The pendent carboxylate groups on the surface of the fatty-
acid-conjugated ZrMOFs were then activated by DIC in
dichloromethane (DCM). After the DCI-activated fatty-acid-
conjugated ZrMOFs were sequentially washed with DCM,
acetone, and water, the ZrMOFs were reacted with CAL-B in
an aqueous buffer. To compare the effects of the fatty acids on
the activity of CAL-B, CAL-B-conjugated ZrMOF without
conjugated fatty acids was also prepared using the same
procedure. In addition, ZrMOF without activation by DCI was
also treated with CAL-B to determine whether CAL-B is
physically absorbed by the fatty-acid-conjugated ZrMOF. The
process for the CAL-B conjugation also did not alter the
morphology, XRD patterns, or IR spectra of ZrMOF (see
Figures 2b and 2c, as well as Figure S1b in the Supporting
Information). The amount of the conjugated CAL-B on
ZrMOFs was almost the same for all cases, and was measured
as 3.3 mg of CAL-B per 1 g of fatty-acid-ZrMOF.
We explored our hypothesis using UiO-66-NH2 (ZrMOF),
which is composed of Zr(IV) and 2-amino-1,4-benzene
dicarboxylate (NH2−BDC). The NH2−BDC amino group
remains intact during the synthesis of ZrMOF and can be
modified through post-synthetic modification. In addition, the
After the conjugation of CAL-B on the MOFs, the hydrolysis
activity of the CAL-B-conjugated MOFs was measured whether
the activity of the conjugated CAL-B on ZrMOFs still remains.
The reaction was conducted by mixing ( )-1-phenylethyl
acetate and the CAL-B-conjugated MOFs in BES buffer (5
mM, pH 7.2). ZrMOF without the conjugation of CAL-B does
not show any hydrolysis activity, while the conjugated CAL-B
on ZrMOFs was still functionally active (see Figure S3 in the
Figure 1. (a) 2-Amino-1,4-benzene dicarboxylic acid (NH2−BDC).
NH2−BDC possesses two functional groups. The amino and pendent
carboxyl groups can be used for the decoration of both fatty acids and
biomolecules. (b) Systemic diagram for the dual-surface modification
of MOFs. Immobilization of CAL-B can improve its activity, but its
activity decreases in polar media. Providing a nonpolar local
environment for CAL-B can increase its activity in polar organic
media. CAL-B represents Candida antarctica lipase B.
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Figure 2. Scanning electron microscopy (SEM) images of the unmodified and modified ZrMOFs: (a) ZrMOF (UiO-66-NH2) and fatty-acid-
conjugated ZrMOFs and (b) CAL-B-conjugated ZrMOFs (the scale bars in the SEM images represent 100 nm). Powder X-ray diffraction (PXRD)
analyses of the unmodified and modified ZrMOFs: (c) fatty-acid-conjugated ZrMOFs (left) and CAL-B-conjugated Zr-MOFs (right). (PXRD
patterns are conserved in all cases.)
a
Table 1. Conversion of the Transesterification, As Catalyzed by CAL-B-Fatty-Acid-Conjugated ZrMOFs
b
Reaction Conversion (%)
number of carbons of
fatty acid
hexane
MTBE
THF
t-BuOH
acetonitrile
entry
enzyme
(ENT = 0.009)
(ENT = 0.124) (ENT = 0.207)
(ENT = 0.389)
(ENT = 0.460)
c
c
c
c
c
1
2
ZrMOF
n.d.
n.d.
n.d.
n.d.
n.d.
c
CAL-B + palmitate-ZrMOF (without
DCI activation)
C16
n.d.
n.d.
d
3
4
5
6
7
8
9
CAL-B-ZrMOF
19 1.2
21
29
29
35
24
25
30
5.4
6.8
8.9
8.8
7.0
4.1
7.5
4.7
6.0
6.9
9.9
8.8
6.0
7.1
1.3 0.3
9.0 2.6
12.4 2.2
17 1.1
laurate-CAL-B-ZrMOF
myristate-CAL-B-ZrMOF
palmitate-CAL-B-ZrMOF
stearate-CAL-B-ZrMOF
arachidate-CAL-B-ZrMOF
behenate-CAL-B-ZrMOF
C12
C14
C16
C18
C20
C22
18 1.1
14 5.1
27 3.7
36 4.3
41 5.2
46 3.5
10.9 0.5
10.6 1.4
11.8 0.1
a
b
The maximum conversion is ∼50%, because CAL-B possesses high enantioselectivity for ( )-1-phenylethyl alcohol (E > 200).13 ETN represents
Reichardt’s normalized polarity scale.14 MTBE = tert-butylmethyl ether, THF = tetrahydrofuran, and t-BuOH = tert-butyl alcohol. n.d. = not
detected. The errors are represented by standard deviations for at least three measurements; entries without errors are single measurements.
c
d
Supporting Information). It is noteworthy that the reactions
catalyzed by the fatty-acid-conjugated ones exhibited higher
conversion, by a factor of ∼2.7, compared to the reaction by the
solely CAL-B conjugated one.
detectable activity was observed. These results indicate that
ZrMOF does not have any catalytic activity in the reaction and
that CAL-B does not physically bind to ZrMOF without DCI
activation. In contrast, CAL-B-conjugated ZrMOF exhibited an
∼20% conversion in hexane and MTBE. Although we did not
expect that surrounding CAL-B with fatty acids would enhance
its activity in nonpolar media, fatty-acid-conjugated ZrMOF
exhibited higher reaction conversions in both hexane and
MTBE. One possible explanation is that the conjugated fatty
acids on ZrMOF orient in the direction of CAL-B binding.
Because of the hydrophobicity of the surface of CAL-B,17
hydrophobic interaction would be established between the fatty
acids and the surface of CAL-B during the conjugation of CAL-
B. In contrast, the substrate entrance of CAL-B lacks the
To evaluate the effect of fatty-acid conjugation on the activity
of CAL-B-conjugated ZrMOFs in organic media, we first
measured the reaction conversions of the transesterification of
( )-1-phenylethyl alcohol in nonpolar organic solvents,
including hexane and t-butylmethyl ether (MTBE) (see Table
1). The reaction was performed with ( )-1-phenylethyl alcohol
(1 mmol) and vinyl acetate (1 mmol) at 25 °C for 24 h. For
comparison, the activities of ZrMOF and palmitate-conjugated
ZrMOF treated with CAL-B without DCI activation were also
measured (entries 1 and 2 in Table 1). In both cases, no
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it is noteworthy that the conversion in acetonitrile by CAL-B-
palmitate-ZrMOF was comparable to that in hexane by CAL-B-
ZrMOF. These results demonstrated that the introduction of
hydrophobic molecules near CAL-B can alter the local
environment and improve the activity of CAL-B.
In conclusion, we have successfully demonstrated dual
functionalization of the surface of MOFs and used this strategy
to alter the local environment of a biomolecule that was
conjugated to an MOF. This approach resulted in enhancing
the activity of CAL-B. Because of the number of combinations
of organic linker compounds and metal ions, the possible
combinations of MOFs are almost unlimited, but the organic
linker compounds must be stable during the preparation
process. The conjugation of thermally unstable biomolecules
onto MOFs is able to expand the bioapplications for MOFs,
including enzyme immobilization.19 Moreover, the multi-
functionalization of the surface of MOFs possibly provides
various functionalities on the surface of MOFs and thus can be
employed for a cascade catalytic system by combining a
catalytic MOF and biocatalyst.
Figure 3. 1H NMR spectra of the digested fatty-acid-conjugated
ZrMOFs. Black circles indicate unmodified NH2−BDC and red
squares represent fatty-acid-conjugated NH2−BDC released from the
digested ZrMOFs.
interaction, because no amino acids are present in the substrate
entrance. Hence, the interaction presumably drives the
substrate entrances to be arranged outward from the center
of ZrMOFs, although the orientation is not finely controlled.
Such orientation of CAL-B molecules may decrease the mass-
transfer limitation of substrates and thus increases the reaction
conversion, compared to the randomly orientated CAL-B.18
Besides, the hydrophobic substrates are presumably absorbed
to a greater degree on the hydrophobic surface of the fatty-acid
conjugated ZrMOFs, in comparison with the naked ZrMOF.
This may provide better contact between CAL-B and the
substrates, and improve the reaction rates. The specific effects
of fatty-acid conjugation were different in each solvent. In
hexane, the longer fatty acids increased the conversion up to 2.4
fold (entry 9 in Table 1). In MTBE, the palmitate-CAL-B-
ZrMOF provided the highest conversion (entry 6 in Table 1).
In addition, we examined these reactions in two medium polar
solvents (tetrahydrofuran (THF) and tert-butyl alcohol (t-
BuOH)) and a polar solvent (acetonitrile). As expected, the
fatty-acid conjugation provided an increased conversion in all
three solvents. However, the improvements of the conversion
in THF and t-BuOH are similar to those in hexane or MTBE
(i.e., up to 2.1-fold). On the other hand, a dramatic effect of
fatty-acid conjugation was obtained in the reaction with
acetonitrile. The highest conversion was obtained from the
CAL-B-palmitate-ZrMOF-catalyzed reaction in acetonitrile and
was higher, by a factor of 13, than that obtained using CAL-B-
ZrMOF as the catalyst. The reason is not clear at the current
stage why the highest conversion was obtained in the CAL-B-
palmitate-ZrMOF-catalyzed reaction over the reactions by the
other fatty-acid conjugated ones. However, a certain balance
between stabilization by hydrophobicity and mass-transfer
limitations may account for the result. The hydrophobicity of
fatty acids should be stronger, according to the increasing alkyl
chain length, and may help more stabilization of CAL-B in
polar media. In contrast, the fatty acids with longer chain
lengths probably shield the CAL-B molecule more tightly,
because of lesser flexibility in polar media. Such shielding effect
by fatty acids that are too much longer presumably increases
the mass-transfer limitations, and, as a consequence, the
reaction rate decreases. Therefore, the maximum activity of
CAL-B was obtained with the middle length fatty-acid
conjugated one (i.e., CAL-B-palmitate-ZrMOF). In addition,
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.6b03222.
■
S
Experimental details and Figures S1−S3 (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: spark@sungshin.ac.kr.
ORCID
Seongsoon Park: 0000-0002-9231-7683
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
■
This research was supported by the Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education (No. 2010-
0022069) and the Ministry of Science, ICT, and Future
Planning (No. 2014R1A2A2A01004836).
DEDICATION
■
This paper is dedicated to Prof. Romas Kazlauskas for the
occasion of his 60th birthday.
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DOI: 10.1021/acscatal.6b03222
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