Improved preparation of an olefin metathesis catalyst bearing quaternary ammonium tag (FixCat) and its use in ethenolysis and macrocyclization reactions after immobilization on metal-organic framework (MOF)

Article abstract of DOI:10.24820/ARK.5550190.P011.373

An optimized synthesis of a key intermediate Ru4 in substantially improved yield of 50% and in scale up to 1 gram was described. Such obtained Ru4 was quantitatively converted into useful quaternary ammonium tagged catalyst Ru1 (FixCat) and immobilized in a metal-organic framework (MOF). Next, two challenging applications, not studied previously with hybrid Ru1@MOF catalyst were attempted. In the case of the RCM reaction yielding a macrocyclic musk lactone, heterogeneous Ru1@MOF exhibited under high-dilution conditions high resistance towards unwanted C-C double bond migration, thus offering superior selectivity as compared to analogous homogeneous catalysts. In ethenolysis of ethyl oleate, Ru1@MOF exhibited only slightly better selectivity as compared to well-known general-purpose Hoveyda-Grubbs SIMes and SIPr catalysts, while it was not able to challenge the benchmark Bertrand-Hoveyda-Grubbs catalyst in this transformation.

Full text of DOI:10.24820/ARK.5550190.P011.373

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Improved preparation of an olefin metathesis catalyst bearing quaternary
ammonium tag (FixCat) and its use in ethenolysis and macrocyclization reactions
after immobilization on metal-organic framework (MOF)
a
a,
a,
Mariusz Milewski, Anna Kajetanowicz, * and Karol Grela *
a
Biological and Chemical Research Centre, Faculty of Chemistry, University of Warsaw, Żwirki i Wigury Street
1
01, 02-089 Warsaw, Poland
Email: karol.grela@gmail.com, a.kajetanowicz@uw.edu.pl
Dedicated to Professor Zbigniew Czarnocki
Received mm-dd-yyyy
Dates to be inserted by editorial office
Abstract
Accepted Manuscript mm-dd-yyyy
Published on line mm-dd-yyyy
An optimized synthesis of a key intermediate Ru4 in substantially improved yield of 50% and in scale up to 1
gram was described. Such obtained Ru4 was quantitatively converted into useful quaternary ammonium
tagged catalyst Ru1 (FixCat) and immobilized in a metal-organic framework (MOF). Next, two challenging
applications, not studied previously with hybrid Ru1@MOF catalyst were attempted. In the case of the RCM
reaction yielding a macrocyclic musk lactone, heterogeneous Ru1@MOF exhibited under high-dilution
conditions high resistance towards unwanted C-C double bond migration, thus offering superior selectivity as
compared to analogous homogeneous catalysts. In ethenolysis of ethyl oleate, Ru1@MOF exhibited only
slightly better selectivity as compared to well-known general-purpose Hoveyda-Grubbs SIMes and SIPr
catalysts, while it was not able to challenge the benchmark Bertrand-Hoveyda-Grubbs catalyst in this
transformation.
Keywords: olefin metathesis, ruthenium, metal-organic framework (MOF), immobilization, ethenolysis,
macrocyclization
DOI: https://doi.org/10.24820/ark.5550190.p011.373
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Introduction
Olefin metathesis is a modern catalytic transformation that allows for effective formation of C–C double
1
,2
bonds. Therefore, this Nobel-prize winning methodology has emerged as one of the most powerful chemical
transformations available to synthetic organic chemists.3 The success of this transformation is mostly due to
the discovery of ruthenium, tungsten and molybdenum catalysts. From this successful family, Ru-carbene
catalysts are of particular interest, as they combine good catalytic activity with excellent compatibility with a
wide number of functional groups, including polar ones. Good air and moisture stability of Ru-catalysts led
eventually to development of water soluble catalysts for aqueous metathesis.6 One of the possible ways to
make a ruthenium carbene water soluble (or at least more polar) is the application of specially designed tags.9
Among the proposed catalyst architectures, complexes containing “-onium” groups (e.g. quaternary
ammonium groups) installed in the backbone of so-called N-heterocyclic carbene (NHC) ligand (Figure 1)
gained some popularity and are nowadays commercially available.1
-5
-8
0,11
“
Instant” immobilization of a ruthenium complex on various supports to form stable heterogeneous
1
2
catalysts is another interesting possibility associated with the presence of a polar ammonium tag. In this
context polar (but water insoluble) catalyst FixCat (Ru1) developed by Skowerski et al. was supported on
materials such as SBA-15 or 13X molecular sieves Recently, we have developed hybrid metalo-organic
systems, where FixCat was immobilized on selected metal-organic frameworks (MOF).1
1
3
1
4
15
6,17
Such hybrid
FixCat@MOF catalysts exhibit several desirable features, such as (i) relatively straightforward preparation
consisting of simply mixing of a tagged catalyst and a solid MOF, (ii) high degree of tunability and modularity,
(iii) compatibility with environmentally friendly solvents such as ethyl acetate, (iv) simple and effective
removal of the ruthenium contamination by filtration. One of the most effective metal-organic supports used
1
5
by us in this context was aluminum MOF—(Al)MIL-101-NH Cl.
3
Figure 1. Selected ruthenium-based complexes bearing quaternary ammonium tags
Results and Discussion
Optimized alternative synthesis of Ru1
To continue our research on MOF immobilized Ru catalysts, we needed an independent access to larger
1
3
quantities of Ru1. To do so, we attempted to reproduce its synthesis published by Skowerski et al. This
procedure consists of a multi-step one-pot reaction between in situ generated free carbene 1 with ruthenium
precursor Ru2 in a presence of styrene derivative 2 (Scheme 1). While in our hands the original recipe worked,
some inconveniences were noted during its scale up. Firstly, the obtained yields were always below 40%,
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which we considered to be unsatisfactory. Secondly, the precursor used originally by Skowerski—
triphenylphospine complex Ru2—is no longer commercially available. While this material can be obtained in
and 1,1-diphenyl-2-propyn-1-ol,1
8,19
we noted some problems during
the known reaction of RuCl
2
(PPh
3
)
3
purification of the product to the sufficient grade. In addition, we observed partial degradation of Ru2 within
several weeks after its synthesis. To overcome this, we decided to replace triphenylphospine (PPh ) ligands in
Ru2 with tricyclohexylphospine (PCy ) ones, which are known to give a more stable ruthenium indenylidene
3
3
complex (Ru2'). To our surprise, however, such complex was completely inactive as the precursor in the above
multi-component reaction leading to Ru4. Interestingly, despite many attempts we were unable to force this
reaction to work, as we were not able to isolate or observe any form of ruthenium complex containing tagged
NHC ligand 1. Unfortunately, the reasons of this failure are not clear to us. Facing the risk of a possible dead-
end, we decided to switch to a substrate belonging to another class of complexes that can be used as
ruthenium precursors—to Grubbs benzylidene I-generation catalyst (Ru3). In this case, gratifyingly, even the
first exploratory trial gave the expected product Ru4 with yield similar to the one reported previously by
1
3
Skowerski. Further optimization experiments showed that replacing 1-isopropoxy-2-(prop-2-en-1-yl)benzene
with 1-isopropoxy-2-vinylbenzene 3 and manipulation the stoichiometry of the reaction gave the desired
intermediate Ru4 in improved yield of 50% (Scheme 1). Worthy of note, the above procedure can be scaled up
2
2
0
to 1 gram, producing Ru4 in fully reproducible yield. Next, the previously described alkylation of Ru4 with
methyl chloride in a pressurized reactor give us desired catalyst Ru1 in quantitative yield (Scheme 1).
Scheme 1. Comparison of selected synthetic pathways leading to FixCat intermediate Ru4.
Immobilization of Ru1 on MOF and two exemplary applications of the obtained hybrid catalyst
1
6
Using a previously described procedure, tagged complex Ru1 was absorbed in solid (Al)MIL-101-NH Cl from
3
a dichloromethane (DCM) solution (Scheme 2). The resulted material contained 2.5 wt.% of Ru1 inside MOF,
which equals 1 catalyst molecule per four cages of MOF.16
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Scheme 2. Preparation of Ru4@MOF hybrid material.
Previously, the (Al)MIL-101-NH
3
Cl–ruthenium hybrid system has been used only in a few simple model
1
6
21
metathesis transformations and in reactive distillation. In the present research, we selected two
transformations that are considered very challenging in the context olefin metathesis. To the best of our
knowledge, none of them has been tested with Ru@MOF catalytic systems.
Scheme 3. Formation of 15-membered macrocyclic lactone 5 from hex-5-en-1-yl dec-9-enoate (4)
Macrocyclisation by RCM
First, the ring-closing metathesis (RCM) cyclisation of hex-5-en-1-yl dec-9-enoate (4) leading to macrocyclic
2
2
lactone 5—a valuable musk fragrance —was tried (Scheme 3). Dienes like hex-5-en-1-yl dec-9-enoate (4) are
known to undergo spontaneous C-C double bond migration (“isomerization”) during the metathesis reaction
2
3
course. This undesirable parasitic process was for the first time noted by Fürstner, and later confirmed by
2
4,25
numerous reports.
We decided to check if Ru1@MOF material, where the catalyst molecules are
1
6
distributed between separate voids present inside a MOF framework, thus mimicking catalysis in confined
2
6
spaces, can increase the selectivity of the RCM reaction towards cyclic not-isomerized product 5. To do so, in
an exploratory experiments Ru1 immobilized in (Al)MIL-101-NH Cl was reacted with 4 dissolved in EtOAc
Scheme 3). To compare the results obtained with heterogeneous catalyst, we used two non-immobilized
3
(
catalysts: Ru1 and the standard non-tagged complex Ru5. The reactions were carried in boiling ethyl acetate—
a green solvent compatible with ruthenium olefin metathesis catalysts.27
Table 1. RCM reaction of 4 catalyzed under homogeneous and heterogeneous conditions a
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Entry Catalyst
Conversion (%)b Yield (%)c
Selectivity (%)d
1
2
3
Ru5
99
99
99
17
30
51
17
30
51
Ru1
Ru1@MOF
a
b
Conditions: Catalyst 2.5 mol%; EtOAc (C = 5 mM); 5 h, 80 °C. Conversion was determined using internal
c
standard, Conversion = 100 – [100 × (final moles of 4/initial moles of 4)]. GC yield of 5 was determined using
calibration curve. Selectivity of the process is described as a ratio between expected RCM product to the sum
c
of RCM product plus isomerization and oligomerization side-products. Selectivity = (yield of 5) / (conversion of
4
) × 100
Standard general-purpose catalyst Ru5 very quickly consumed the substrate, but among expected
products (E- and Z-isomers of oxacyclopentadecen-2-one, 5) a large proportion of “isomerized” cyclic products
' resulted from C-C double bond migration28 as well as oligomers exhibiting a broad molecular mass
5
distribution was observed. Because a mixture of 5 and 5' (isomerized products) was not possible to be
separated, GC was used to analyze the reaction mixture and to calculate the yield of 5 using a calibration
curve. Comparing with Ru5, better selectivity, but still far from satisfying, was observed in the reaction
catalyzed by Ru1 (for these two cases selectivity of the process is described as a ratio of expected RCM
product 5 to the sum of RCM product 5 plus both isomerization and oligomerization byproducts). Importantly,
immobilized Ru1@MOF gave no C-C double bond migration, as no isomerized products 5' were observed in
the reaction mixture by GC, and only the oligomers accompanied the expected product (5). The observed
perfect selectivity of the RCM process can be connected with the increased stability of immobilized
Ru1@MOF, where catalysts molecules are separated in individual voids of the metal-organic framework. We
speculate that such encapsulation of Ru1 shall (at least partially) block the bimolecular decomposition
pathway, thus limit formation of isomerization-active species.29
The second limitation in macrocyclization of unbiased dienes is related to thermodynamic equilibrium
between a cyclic product and the oligomers. It is well known that RCM macrocyclization typically requires
high-dilution conditions (C ≤ 5 mM) to avoid competitive cross-metathesis oligomerization process.2
4,25,30
As
the high-dilution conditions are not cost-effective at larger scale, various approaches have been tried to
conduct such macrocyclizations in more concentrated solutions. For example, Jee and Hong were able to
partially suppress such parasitic oligomerization by placing a ruthenium catalyst inside a carefully designed
3
1
mesocellular siliceous foam (MCF). In light of this observation, we decided to check if encapsulation of Ru1 in
MOF can offer any advantages in this context as well. Quantitative conversions observed in RCM of 4 (Scheme
3
) encouraged us to decrease the catalyst loading to 0.5 mol% only. In addition, we have extended the
32
reaction time to aid the oligomers, which are the kinetic product of the reaction, to possibly be transformed
into desired macrocycle 5 (Table 2). While the RCM reaction with Ru1@MOF was selective in terms of C-C
bond migration (only 5 was observed after the reaction by GC analysis). Unfortunately, MOF encapsulation did
not restrict the oligomerization process. Results (Table 2) show visibly the enhanced formation of oligomers
when the concentration of the reaction mixture was increased from the standard 5 to 20 mM. Further
concentration of the reaction mixture quickly led to even more intensive formation of oligomers, thus limiting
the yield of the desired macrocyclic product. In that sense, immobilized Ru1 resemble homogeneous
metathesis catalysts, where the similar disadvantageous influence of concentration was observed.21
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Table 2. RCM reaction of 4 catalyzed by Ru1@MOF at increasing concentration a
Concentration
Entry
Conversion (%)b Yield (%)c
Oligomerization (%)d
(mM)
1
2
3
4
5
25
65
90
97
19
31
26
10
24
52
72
20
40
80
89
a
b
Conditions: Catalyst 0.5 mol%; EtOAc (C
m
= 5–80 mM); 24 h, 80 °C. Conversion was determined using
c
internal standard, Conversion = 100 – [100 × (final moles of 4 / initial moles of 4)] GC yield of 5 was
determined using calibration curve. Oligomerization = 100 − [100 × (yield of 5) / (conversion of 4)]
c
Ethenolysis
The second challenging transformation used by us to test FixCat@MOF was the ethenolysis reaction.
Ethenolysis is a sub-type of olefin metathesis process in which an internal olefin is “split” using ethylene as the
cross-metathesis partner (Scheme 4). The most promising applications of ethenolysis are directed at using
3
3,34
renewable feed stocks.
For example, ethyl oleate 6, derived from natural seed oils, can be converted to 1-
3
5
decene (7) and alkyl 9-decenoate (8). The utility of ethenolysis in renewable materials valorization is driven
by the low cost of ethylene as a reagent, however high selectivity of this process must be ensured in order to
make it cost-effective. In the case of oleic acid esters ethenolysis selectivity is defined as the ratio of desired
terminal alkene products 7 and 8 (α-olefins) versus “homodimers” 9 and 10 that are the unwanted products of
parasitic self-cross metathesis process (Scheme 5).
Figure 2. Ethenolysis of ethyl oleate (6) leading to mixture of desired (7 & 8) and undesired products (9 & 10)
As it can be seen in Table 2, heterogeneous Ru1@MOF provided selectivity similar to that obtained with
its closest untagged analogue—SIPr Hoveyda-Grubbs catalyst (Ru5). The other homogeneous catalysts tested,
a SIMes bearing Ru6 provided even lower selectivity (43 vs. 75%). Prolonged reaction time led to practically no
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erosion of observed selectivity (73 vs. 75%). Interestingly, Bertrand-Hoveyda-Grubbs catalyst Ru7—the state-
3
6
of-the-art catalyst in ethenolysis, —gave visibly better selectivity (Table 2, entry 5). These results show that
unfortunately, in case of the ethenolysis reaction, the encapsulation in MOF exhibits no, or only little
“
protecting” effect, and the studied heterogeneous catalyst Ru1@MOF cannot rival the best Bertrand-type
3
6,37
catalysts.
Table 2. Ethenolysis conducted under homo- and heterogeneous conditionsa
Entry Catalyst
Conversion (%)b Selectivity (%)c Yield (%)d
1
Ru1@MOF
73
72
80
71
84
75
73
72
43
83
54
53
58
30
70
2
Ru1@MOF (5 h)
3e
4e
5e
Ru5
Ru6
Ru7
a
Conditions: Catalyst loading 500 ppm; ethylene purity 99.9% (3.0 grade); 3 h, 50 °C 10 bar. Reaction
conversion and selectivity determined by GC using n-tetradecane as the internal standard with calibration
b
curves for ethyl oleate, tetradecane, and all the metathesis products. Conversion = 100 – 100 × (final moles of
c
6
+
/ initial moles of 6). Selectivity = 100 × (moles of 7 + moles of 8) / [(moles of 7 + moles of 8) + 2 × (moles of 9
d
e
moles of 10)]. Yield = Conversion × selectivity. Taken from Ref. 38
Conclusions
An optimized synthesis of valuable intermediate Ru4 in substantially improved yield of 50% was tested up to
scale of 1 gram. The newly developed procedure uses easily available substrates: 2-(isopropoxy)styrene and
Grubbs' 1-generation catalyst. Such obtained intermediate Ru4 was then quantitatively converted into useful
quaternary ammonium tagged catalyst Ru1 (FixCat).
To prove the merits of the tagged catalyst, complex Ru1 was immobilized in a metal-organic framework
(MOF) according to previously described procedure. Next, two challenging applications, not studied previously
with hybrid Ru1@MOF catalyst, were attempted. In the case of the RCM reaction yielding a macrocyclic musk
lactone, heterogeneous Ru1@MOF exhibited much better resistance towards unwanted C-C double bond
migration, thus offering perfect selectivity as compared to analogous homogeneous catalysts. Unfortunately,
this macrocyclization still required high-dilution conditions (5 mM) to avoid extensive formation of oligomers.
Ethenolysis of ethyl oleate was selected as the second target-ground to test the performance of Ru1@MOF. In
this transformation the hybrid catalyst exhibited only slightly better selectivity levels as compared to well-
known general-purpose Hoveyda-Grubbs SIMes and SIPr catalysts, and was not able to challenge the current
ethenolysis benchmark—the Bertrand-Hoveyda-Grubbs catalyst.
Experimental Section
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General. Reactions were carried using standard Schlenk technique using argon 6.0 grade as an inert gas unless
otherwise stated. All glassware was dried overnight in oven (130 °C) prior to use. GC analyses were performed
by means of PerkinElmer Clarus 580 chromatograph with FID detector and GL Sciences InertCap 5MS/Sil
Capillary Column (Inner Diameter 0.25 mm, Length 30 m, df 0.50 µm). Calibration curves were made for ethyl
oleate, tetradecane and all the metathesis products described in paper. Reaction mixtures were analyzed
using the following method: initial temperature 145 ° C — 0.1 min. — 9 °/min to 180 ° — 0.1 min — 20 °/min
to 305 ° — 2 min.). The flash column chromatography was performed using Merck silica gel 60 (230–400
mesh) typically using an n-hexane/ethyl acetate eluent system.
Unless otherwise noted, all common laboratory reagents were purchased from Avantor Performance
Materials Poland S.A. and used as received. Ethyl acetate and n-hexane were distilled before used as eluent in
column chromatography. Technical oleic acid (purity 90%), 9-decenoic acid and hex-5-en-1-ol were purchased
from Sigma-Aldrich. Ethylene gas 3.0 grade (99.9%) was purchased from Linde (3.0 grade; O
150 ppm, C <1800 ppm). Tetradecane (purity 99%) and SnatchCat scavenger were purchased form Sigma-
Aldrich, ethanol (purity 96%) was purchased from Linegal Chemicals. Dry DCM was obtained from MB SPS-800
2
< 30 ppm, N
2
<
H
n m
3
8
solvent purification system. Ethyl Oleate was prepared according to a published procedure. Hex-5-en-1-yl
3
9
dec-9-enoate was prepared according to a published procedure. The structure of synthesized substrates was
1
13
confirmed using H and C NMR spectroscopy.
Synthesis of NHC precursor 1’
1
3
Tetraamine (Synthesized according to the procedure described in the literature ) (28.8 g, 56.8 mmol) was
dissolved in triethyl orthoformate (96.6 mL, 568 mmol) and HCl (4 M in 1,4-dioxane, 28.4 mL, 114 mmol) and
methanol (35 mL) were added. The resulted mixture was stirred at 95 °C for 2 h. Solvents were removed and
water (650 mL) was added followed by addition of NH
was filtered off and rejected; saturated solution of NH
filtrate and product was extracted with dichloromethane (3 × 70 mL). The solvents were evaporated and the
3
(28% in water, 11.4 mL, 170 mmol). Insoluble material
4
BF in water (12.3 g, 114 mmol) was added to the
4
formed yellow solid was crystallized from the MeOH/Et
crystalline powder (23 g, 67%).
2
O at -6 °C, which allowed to obtain a colorless
Synthesis of Ru4
1
3
Complex Ru4 was synthesized based on the procedure available in the literature with the following changes:
Potassium t-amylate (25% in toluene, 1.35 mL, 2.41 mmol) was added to the suspension of NHC precursor 1’
(1.53 g, 2.53 mmol) in degassed toluene (50 mL). Reaction mixture was stirred for 10 minutes at room
temperature. Next, Grubbs I generation catalyst Ru3 (2.00 g, 2.41 mmol) was added and resulted mixture
immersed into oil bath preheated to 80 °C and stirred for 30 minutes. Then 1-isopropoxy-2-vinylbenzene (1.17
g, 7.23 mmol) and CuCl (0.50 g, 5.3 mmol) were added and stirring was continued for 15 minutes at 80 °C.
After cooling down to room temperature the solvent was evaporated and the residue was dissolved in EtOAc
and filtered through cotton wool. After evaporation of EtOAc the crude product was purified using column
chromatography (eluent: from 5 to 20% of EtOAc in n-hexane). Product (1.01 g, 50%) was isolated as a green
1
13
13
powder. H and C NMR spectra of the obtained material correspond to those reported in literature. The
brown band before main product was also collected and crystallized from cold n-pentane leading to obtain
Hoveyda first generation catalyst (210 mg, 14% based on starting material).
Macrocyclization
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4
0
Synthesis of hex-5-en-1-yl dec-9-enoate (4) was performed using literature procedure. In a 100 mL Schlenk
vessel equipped with magnetic stirrer hex-5-en-1-yl dec-9-enoate (101 mg, 0,4 mmol) and tetradecane (80 mg,
0
,4 mmol, 10 μL) were dissolved in anhydrous and deaerated EtOAc (80 mL). The resulting 5 mM solution was
stirred for 10 minutes and used as mother solution for following reactions. More concentrated solutions were
prepared in the same way.
Using the protective atmosphere of an inert gas in a 20 mL Schlenk vessel equipped with a magnetic
stirrer, 8 mL of previously prepared 5 mM solution of ester hex-5-en-1-yl dec-9-enoate was added. The
solution was then placed in an oil bath preheated to the 80 °C, conditioning the mixture for about 1 minute.
Then the MOF supported catalyst (35.5 mg of carrier containing 2.5 % weight of FixCat catalyst (0.887 mg,
1
μmol) was weighed and immediately added to the solution. The vessel was equipped with a reflux
condenser and heated at a set temperature by stirring (400 rpm) for next 5 h. The progress of reaction was
monitored by thin layer chromatography (5% EtOAc in n-hexane, visualization was made using anisadehyde
solution). After that time the reaction mixture was cooled to room temperature. The supported catalyst was
filtered using a syringe filter and the filtrate was concentrated on a rotary evaporator. The resulting oil was
transferred entirely to a GC vial and then diluted with dichloromethane up to 1.5 mL. The post-reaction
mixture prepared in this way was subjected to GC and TLC analysis. Reactions at a higher concentration or
lower concentration of the catalyst were carried out in a similar manner.
For reference reactions with catalysts without support the appropriate solutions in DCM were prepared (5
mg of ruthenium complex in 1 mL of dry DCM). To stop catalyst, the SnatchCat metal scavenger was used after
mixture was cooled down do rt. After stirring for 30 minutes mixture was filtered through syringe filter and
then concentrated under reduced pressure. The resulting oil was subjected to GC and TLC analysis as was
mentioned earlier.
Ethenolysis
3
8
Reactions were performed as was described in literature, with minor changes as indicated. Each reaction
was repeated, and the average result of both reactions was calculated. Reactions were performed using Armar
and Roth autoclaves. Catalysts' stock solution was made in air using DCM. A solution of a catalyst (500 ppm) in
DCM (100 μL) was added to a mixture of ethyl oleate (4.66g, 15.0 mmol) and tetradecane (0.61 g, 3.05 mmol)
placed in a glass vessel containing a magnetic stir bar. The vessel was immediately installed into an autoclave
which was then flushed three times with ethylene (10 bar). The mixture was stirred for 3 or 5 h at 50 °C. After
that time a sample of the reaction mixture was collected (1 mL) and immediately quenched with ethyl vinyl
ether (4 mL, used as 2 M solution in DCM). Next an aliquot (0.2 mL) was taken from this mixture and diluted
with DCM (0.8 mL). Such obtained solution was analyzed by GC. Conversion was calculated using the internal
standard and calibration curves.
Acknowledgements
Authors are grateful to the “Catalysis for the Twenty-First Century Chemical Industry” project carried out
within the TEAM-TECH programme of the Foundation for Polish Science co-financed by the European Union
from the European Regional Development under the Operational Programme Smart Growth. The study was
carried out at the Biological and Chemical Research Centre, University of Warsaw, established within the
project co-financed by European Union from the European Regional Development Fund under the Operational
Programme Innovative Economy, 2007–2013.
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