Catalytic Three-Component Machinery: Control of Catalytic Activity by Machine Speed

Article abstract of DOI:10.1002/anie.201709644

Three supramolecular slider-on-deck systems DS1–DS3 were obtained as two-component aggregates from the sliders S1–S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two-footed slider to the deck varies with the donor qua

Full text of DOI:10.1002/anie.201709644

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Accepted Article
Title: Katalytische Drei-Komponenten-Maschinen: Steuerung der
katalytischen Aktivität mittels Maschinengeschwindigkeit
Authors: Michael Schmittel, Indrajit Paul, Abir Goswami, and Nikita
Mittal
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201709644
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10.1002/anie.201709644
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COMMUNICATION
Catalytic Three-Component Machinery: Control of Catalytic
Activity by Machine Speed
Indrajit Paul,[a] Abir Goswami,[a] Nikita Mittal [a] and Michael Schmittel*[a]
Abstract: Three supramolecular slider-on-deck systems DS1-DS3
were created as two-component aggregates from the sliders S1-S3
and deck D with its three zinc porphyrin (ZnPor) binding sites. The
binding of the two-footed slider to the deck varies with the donor
quality of and steric hindrance at the pyridine/pyrimidine (pyr) feet
and was effected by two Npyr → ZnPor interactions. Accordingly, the
sliders move at different speed over the three zinc porphyrins in the
deck: with 32.2, 220 and 440 kHz at room temperature. Addition of
N-methylpyrrolidine as organocatalyst to DS1-DS3 generates
catalytic three-component machinery. Using a conjugate addition as
a probe reaction, we observe a correlation between the operating
speed of the slider-on-deck systems and the yields of the catalytic
reaction. With decreasing thermodynamic binding of the slider, both
the frequency of the sliding motion and yield of the catalytic reaction
increase.
the catalyst into solution may be triggered by the motion of the
slider. (5) The amount of catalyst in solution shall be quantifiable
by a catalytic process. Thereby, significantly dissimilar sliding
speeds of DS1-DS3 should lead to divergent yields in the
catalytic reaction.
The connection of protein conformational dynamics and
enzymatic activity is hotly debated,[1,2] because both precise
spatial arrangement and high dynamics have to work together
synergistically for high turnover rates in enzymes.[3] It is thus an
appealing challenge to systematically use dynamic effects in
artificial catalysts for speed-up.[4,5] Herein we describe how a
dynamic slider-on-deck system is coupled to an organocatalyst
and how the sliding speed (machine speed) in this three-
component aggregate impacts catalysis. The results show
clearly the prevalence of kinetic over thermodynamic factors in
the liberation of catalyst into solution and highlight the
usefulness of dynamic multicomponent machinery.
Scheme 1. Molecular structures and cartoon representations of deck D,
sliders S1-S3 and aggregates DS1-DS3.
Based on our recent work on rotors[32] we decided to implement
meso-protons (r-H) in the ZnPor units of deck D, because a
kinetic analysis by 1H NMR requires diagnostic changes upon
formation of Npyr → ZnPor interactions. The sliders’ feet were
chosen after establishing enough distinct binding affinities for 4-
iodopyridine (1), 4-iodopyrimidine (2) and 4-bromo-2-
methylpyridine (3) toward zinc porphyrin 4, i.e. log K1•4 = 4.31 ±
0.12 (Supporting Information = SI, Figure S72), log K2•4 = 3.35 ±
0.15 (SI, Figure S73) and log K3•4 = 2.72 ± 0.04 (SI, Figure S77).
Although most biological machine archetypes are multiprotein
complexes, very few examples of artificial devices[6-18] that arise
from self-sorting of diverse components[19-21] have been reported,
quite in contrast to the large gamut of known covalently and
topologically constructed machines.[23-31]
For the present study we have chosen the two-component
slider-on-deck systems DS1-DS3 = D(S1-S3) (Scheme 1) due
to the following reasoning: (1) In DS1-DS3 the two-footed slider
S1-S3 should move quickly on the D3h-symmetric deck D with its
three identical zinc porphyrin (ZnPor) binding sites. (2) The
speed should be adjustable by changing the binding foot of S1-
S3. (3) Addition of one equiv of an organocatalyst to DS1-DS3 is
expected to generate the catalytic three-component machinery
catD(S1-S3). (4) The slider’s foot (various pyridine/pyrimidine
derivatives: pyr) and the organocatalyst should have comparable
affinity toward the binding sites of the deck, so that liberation of
In response to above considerations, we synthesized and fully
characterized the symmetric deck D as well as the three two-
footed sliders S1-S3 with their different pyridyl/pyrimidyl binding
sites (Schemes S1-S4 in SI). To prepare the slider-on-deck
systems DS1-DS3, the slider units S1-S3 were simply mixed
with tris(zinc porphyrin) D in CDCl3 in a 1:1 ratio. The aggregates
DS1-DS3 are furnished quantitatively and are fully characterized
again by 1H NMR, 1H-1H COSY, 1H-1H NOESY, 13C NMR, DOSY
and elemental analysis (SI).
[a]
I. Paul (M.Sc.), A. Goswami (M.Sc.), N. Mittal (M.Sc.), Prof. Dr. M.
Schmittel
Center of Micro and Nanochemistry and Engineering, Organische
Chemie I, University of Siegen, Adolf-Reichwein Str. 2, 57068
Siegen, Germany
E-mail: schmittel@chemie.uni-siegen.de
Supporting information and the identification number (ORCID) of
one author is provided under http://dx.doi.org/10.1002/.
As expected, an upfield shift of meso-protons r-H from 10.33
ppm in D to 10.20 ppm in DS1 is observable upon coordinating
the pyridyl terminals of S1 to the ZnPor units (Figure 1). Parallel,
the pyridyl proton signals a1-H and b1-H are shifted upfield to
2.24 and 5.37 ppm in DS1 from 8.61 and 7.40 ppm in S1,
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10.1002/anie.201709644
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COMMUNICATION
respectively. The Npy→ZnPor interaction was further validated
by UV-vis investigations showing that the Q-band of DS1
appears as a broad absorption at λ = 547 nm, in contrast to the
Q-band signature of uncoordinated ZnPor in D (absorption at λ =
542 nm, SI, Figure S75). Finally, a single set of signals in the 1H
DOSY (D = 2.70 × 10−10 m2s−1, r ~19.5 Å) confirms the clean
formation of the sliding system (SI, Figure S54).
Analogous to DS1, 1H NMR signals of meso-protons r-H in DS2
are shifted to 10.22 ppm (Figure 1) while the pyrimidine protons
a2-H, a’2-H and b2-H are equally shifted upfield (SI). The Q-band
absorption showing the Npym→ ZnPor interaction is located at λ =
545 nm (SI, Figure S76). Likewise a single set of signals in the
1H DOSY (D = 2.80 × 10−10 m2s−1, r ~18.5 Å, SI, Figure S55)
suggests the clean formation of the aggregate. Similar
characteristic shifts are given in DS3.
process compared to k25 = 32.2 kHz in DS1 with the stronger Npy
→ ZnPor binding (log K1•4 = 4.31 ± 0.12). Accordingly, the
weakest Nα-Me-py → ZnPor interaction (log K3•4 = 2.72 ± 0.04)
results in the fastest exchange frequency (440 kHz at 25 °C). As
shown by a control experiment, the exchange frequencies in
Figure 2B are not affected by a bimolecular component (SI,
Figure S82).
First insights into the sliding dynamics of the slider-on-deck
systems DS1-DS3 are already obtained from the 1H NMR
spectrum at 25 °C (Figure 1). The rapid motion of the slider
across deck D is indicated by a single sharp 1H NMR signal
representing protons r-H at all three ZnPor units. In a static
situation one would expect two sets of signals at a ratio 2:1. In
order to quantify the sliding dynamics, the slider-on-deck
aggregates DS1-DS3 were measured at various temperatures in
toluene-d8 (VT-1H NMR). While all protons r-H of DS1 appear as
sharp singlet at 10.02 ppm at 25 °C, coalescence starts at –
22 °C (Figure 2A). On further cooling, the signal starts to split
and is completely separated at –75 °C, resulting in two singlets
at 10.03 and 9.85 ppm at a ratio of 1:2. The first signal is
assigned to free ZnPor and the second one to the pyridine-
loaded ZnPor units. The exchange frequency in DS1 is
Mechanistically, one should consider two different alternatives:
(1) complete dissociation of DS1-DS3 and re-association of D
and S1-S3, or (2) sliding based on disconnection/reconnection
of only one foot of the slider. The first possibility demanding the
complete dissociation of S1-S3 and
D is energetically
incommensurate with the thermodynamic data. From a titration
of S1 to D the binding constant in DS1 was determined as log
KD•S1 = 9.61 ± 0.03 (∆G25 = 54.8 kJ mol–1; SI, Figure S75). As
the activation barrier has to comply at least with the
endergonicity of dissociation, a disconnection of DS1  S1 + D
cannot be present since the experimental barrier for sliding in
DS1 (∆G‡ = 47.3 kJ mol–1) is lower. This conclusion is
25
confirmed by the fact that the barrier of a cognate rotor which is
based on a single Npy → ZnPor dissociation amounts to ∆G‡
=
determined as k25 = 32.2 kHz and the free activation energy as
25
1
G‡ = 47.3 kJ mol–1. Alike, the H NMR spectrum of DS2 at
47.6 kJ mol–1.[32]
25
25 °C shows all protons r-H at 10.01 ppm in a single signal set
while coalescence occurs around −35 °C (SI, Figure S60). At
−75 °C the resonance for protons r-H is split into two signals at
10.00 and 9.86 ppm (1:2). The exchange frequency is k25 = 220
This barrier may be compared to the activation energy for the
Npy → ZnPor dissociation in the simple complex 14 (∆G‡
=
25
32.4 kJ mol–1, log K1•4 = 4.31; ∆G25 = 24.6 kJ mol–1).[32] Visibly,
the sliding mechanism (2) that is based on a single Npy → ZnPor
bond cleavage in DS1 has a barrier which is ca. 1.5-fold of that
in the simple system 14. The higher kinetic barrier possibly
arises from intramolecular co-operative effects[ 33 ] and the
angular restrictions for Npy → ZnPor dissociation in DS1. The
same line of arguments can equally be given for DS2 and DS3.
kHz and G‡ = 42.5 kJ mol–1. DS3 behaves analogously (SI,
25
Figure S62) with k25 = 440 kHz and G‡ = 40.7 kJ mol–1. All
25
activation data are given in Figure 2B.
As expected, the weaker Npym → ZnPor interaction (log K2•4
3.35 ± 0.15) in DS2 leads with k25 = 220 kHz to a faster sliding
=
Figure 1. Comparison of partial 1H NMR spectra (CDCl3, 400 MHz, 298 K) of
(a) deck D, (b) DS3 (D : S3 = 1:1), (c) DS2 (D : S2 = 1:1) and (d) DS1 (D :
S1 = 1:1).
After preparing three slider-on-deck systems with different speed,
we decided to interrogate whether distinct exchange frequencies
would also influence the speed of a coupled catalytic reaction.
Formally, in each slider-on-deck assembly DS1-DS3 only two
ZnPor units are occupied at any given time by the two-footed
slider. The third ZnPor unit may therefore be used to bind a
catalytically active nitrogen heterocycle, such as N-
methylpyrrolidine (5). If the amine/slider-on-deck complexes, i.e.
DS15, were static, we would expect no catalytic activity as the
heterocycle 5 is firmly bound and thus not available for catalysis.
For a dynamic system, however, we would expect a dynamic
liberation of the catalyst.
Figure 2. (A) Experimental (left) and simulated (right) VT 1H NMR spectra
(toluene-d8, 600 MHz) of proton signal r-H in DS1. (B) Experimental exchange
frequency k at 25 °C and activation parameters of DS1-DS3.
To probe the concept of dynamic release of the catalyst from e.g.
5DS1, we have chosen the prototypical conjugate addition
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10.1002/anie.201709644
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COMMUNICATION
reaction (1) of thiophenol (6) onto 2-cyclopentenone (7) with N-
methylpyrrolidine (5) as catalyst (10 mol%) (Figure 3).[34]
which the yield of 8 is 14% after 4 h (Figure 4). T14% can directly
be extracted from the data furnished in Figure 3. In the reference
reaction of 5+6+7+4, thus with zinc porphyrin 4 inhibiting the
activity of catalyst 5, formation of product 8 in 14% yield requires
a T14% of 60 °C. When the binding of the catalyst at the ZnPor
unit was reduced due to the increasing machine speed in DS1,
DS2 and DS3 the T14% dropped to 48, 37 and 33 °C, respectively.
If one extrapolates the correlation shown in Figure 4 to infinite
machine speed the lowest possible T14% can be determined as
30.5 °C. This T14% is very close to the temperature of 28 °C at
which the unimpeded system 5+6+7 produces 14% of 8!
Before testing the slider-on-deck systems, we assessed the
yields of model reaction 5 + 6 + 7 for reference purposes in the
temperature range from 25 to 60 °C. After 4 h in each case,
product yields were determined by 1H NMR using
tetrachloroethane (TCE) as internal standard (Figure 3). In
presence of zinc porphyrin 4 and catalyst 5 (both 10 mol%) the
reaction of 6 and 7 (both 13.4 mM) afforded no addition product
8 at a temperature below 50 °C. Clearly, product formation is
precluded due to the strong interaction between porphyrin 4 and
N-methylpyrrolidine (5) (log K = 4.01 ± 0.12) (SI, Figure S74).
Only at temperatures above 50 °C the equilibrium is shifted so
much that liberated 5 causes perceptible product formation
(Figure 3). Contrastingly, in absence of inhibitor 4, at 50 °C the
model reaction furnished (66 ± 2)% of product 8.
Figure 4. Temperature T14% (14% yield of product 8 is generated at T14%
)
depends on the sliding speed of the machinery.
Figure 3. Yields of the conjugate addition between 6 and 7 (both 1.34 × 10−2
M) with catalyst 5 (1.34 × 10−3 M) in presence of 4 (1.34 × 10−3 M) or DS1-DS3
(1.34 × 10−3 M) after 4 hours.
a) Compounds 5 (=cat), 6, 7 and DS1-DS3 at 10:100:100:10 ratio in CDCl3 for 4 h. Sliding
speeds were calculated from the activation data.
Obviously temperatures T14% are influenced by both the dynamic
release and the inherent effect of the temperature on the
catalytic reaction. To solely evaluate the effect of machine speed
at a defined temperature, we determined the equilibrium amount
of catalyst released into solution at 50 °C. As reference, we
investigated the model reaction (catalyst 5 + substrates 6 + 7)
varying the amounts of 5 (2-10 mol%). As expected, the yield is
almost linearly increased with augmented amounts of 5 (Figure
5A). A comparison with the yields that are obtained in the
presence of DS1-DS3 at 50 °C shows that 29% of 5 (with 10
mol% being the total amount) was available in solution with DS1,
48% with DS2 and 76% with DS3. Thus with increasing speed
the amount of liberated catalyst is largely increased at a given
temperature (Figure 5B).
Subsequently, the catalytic activity of the three-component
machinery 5D(S1-S3) was evaluated under reference
conditions. Hereunto we mixed 5, 6, 7 and the aggregates DS1,
DS2 or DS3 in an NMR tube at 10:100:100:10 ratio in CDCl3.
Keeping the same conditions as for the model reaction (same
concentrations, 4 h reaction time) we observed distinct yields for
each individual slider-on-deck system with regard to the addition
reaction. In presence of 5DS1 the conjugate addition
discernibly occurred already at 40 °C, while at 50 °C (taken as
reference) it furnished (18 ± 2)% (Figure 3) of 8. For 5DS2 the
reaction already started at 35 °C; at 50 °C thiol adduct 8 was
afforded in (32 ± 2)%. The catalytic machinery 5DS3 led to an
even faster acceleration of the conjugate addition reaction: the
transformation started already at a temperature of 30 °C while at
50 °C it eventually exhibited (50 ± 2%) yield of 8 (Figure 3). All
product yields are caused kinetically, as product 8 is formed
irreversibly at 50 °C. A control experiment in absence of 5 shows
that the aggregates DS1, DS2 or DS3 themselves are
catalytically inactive (SI, Figure S69).
Figure 5. (A) Yields of the model reaction between 6 and 7 at 50 °C (4 h)
using variable amounts of 5. The yields (18%, 32%, and 50%) are those of the
corresponding reactions with the catalytic machinery 5(DS1-DS3). (B) Data
for the catalytic machinery.
a) Exchange frequencies k50 at 50 °C were calculated from the activation data.
The present findings suggest that the dynamics of the catalytic
three-component machinery 5D(S1-S3) is correlated to the
speed of the organocatalytic addition reaction. As the speeds of
DS1 and 5DS1 are identical within error limits (SI, Figure
S84), we use the kinetic data from Figure 2B for the three-
component-machinery as well. As an indirect measure of the
catalytic activity of 5D(S1-S3) we use the temperatures T14% at
From the data it is evident that, among the three machinery
aggregates, 5DS3 displays the highest catalytic activity due to
the release of 76% of the available catalyst 5 from the ZnPor
binding site into solution. The other ones 5DS2 and 5DS1
show lower yields of 8 and less release of 5 as a consequence
of their reduced sliding speed. An interesting detail is the fact
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10.1002/anie.201709644
Angewandte Chemie International Edition
COMMUNICATION
that the data allow us to extrapolate to both zero and infinite
operating speed. At infinite exchange frequency the system
would be expected to furnish the same yield as the model
reaction at 50 °C in absence of porphyrin 4, which would mean
66% of 8. In contrast at zero sliding speed, the full inhibitory
action of the ZnPor unit should be sensed, thus a yield of 0% is
expected (0% yield was observed in the model reaction in
presence of 4 at 50 °C). Remarkably, the release of catalyst is
the more pronounced, the higher the sliding speed and the
weaker the thermodynamic binding within the slider-on-deck
systems.[35] Thus liberation has to be a kinetic phenomenon!
[6]
[7]
[8]
[9]
P. K. Biswas, S. Saha, Y. Nanaji, A. Rana, M. Schmittel, Inorg. Chem.
2017, 56, 6662-6670.
S. K. Samanta, A. Rana, M. Schmittel, Angew. Chem. Int. Ed. 2016, 55,
2267-2272.
C. Cheng, P. R. McGonigal, S. T. Schneebeli, H. Li, N. A. Vermeulen, C.
Ke, J. F. Stoddart, Nat. Nanotechnol. 2015, 10, 547-553.
M. Nishikawa, S. Kume, H. Nishihara, PCCP 2013, 15, 10549-10565.
[10] S. K. Samanta, M. Schmittel, J. Am. Chem. Soc. 2013, 135, 18794-
18797.
[11] S. Hiraoka, Y. Hisanaga, M. Shiro, M. Shionoya, Angew. Chem. Int. Ed.
2010, 49, 1669-1673.
[12] D. P. Ferris, Y.-L. Zhao, N. M. Khashab, H. A. Khatib, J. F. Stoddart, J.
I. Zink, J. Am. Chem. Soc. 2009, 131, 1686-1688.
The most likely explanation for the observed effect is a neighbor-
group participation, analogous to the proximity effect. Due to the
foot of the slider visiting all ZnPor stations on the deck, it
displaces catalyst 5 bound to the third ZnPor unit of DS1-DS3 in
an SN2-type reaction. Notoriously, ZnPor can only bind strongly
to one additional ligand.[36] This SN2-displacement increases the
[13] S. Hiraoka, E. Okuno, T. Tanaka, M. Shiro, M. Shionoya, J. Am. Chem.
Soc. 2008, 130, 9089-9098.
[14] S. V. Bhosale, C. Chong, C. Forsyth, S. J. Langford, C. P. Woodward,
Tetrahedron 2008, 64, 8394-8401.
[15] H. Kai, S. Nara, K. Kinbara, T. Aida, J. Am. Chem. Soc. 2008, 130,
6725-6727.
dissociation speed (kdiss
)
of catalyst
5
from DS1-DS3.
[16] S. Silvi, A. Arduini, A. Pochini, A. Secchi, M. Tomasulo, F. M. Raymo,
M. Baroncini, A. Credi, J. Am. Chem. Soc. 2007, 129, 13378-13379.
[17] S. Hiraoka, M. Shiro, M. Shionoya, J. Am. Chem. Soc. 2004, 126,
1214-1218.
Reciprocally, the association (kass) of liberated 5 back to DS1-
DS3 should be slowed down due to the dynamic loading of all
ZnPor platforms with the slider. In sum, both effects lower the
binding constant K5(DS1-DS3) = kass/kdiss and thereby increase the
concentration of liberated catalyst 5 in solution.
[18] R. Hernandez, H.-R. Tseng, J. W. Wong, J. F. Stoddart, J. I. Zink, J.
Am. Chem. Soc. 2004, 126, 3370-3371.
[19] Z. He, W. Jiang, C. A. Schalley, Chem. Soc. Rev. 2015, 44, 779-789.
[20] M. L. Saha, M. Schmittel, Org. Biomol. Chem. 2012, 10, 4651-4684.
[21] M. M. Safont-Sempere, G. Fernández, F. Würthner, Chem. Rev. 2011,
111, 5784-5814.
In conclusion it can be stated that three two-component slider-
on-desk systems were presented, in which the adjustment of the
binding strength of the slider’s foot to the ZnPor determines the
speed of the sliding motion. Addition of N-methylpyrrolidine (5)
as organocatalyst to DS1-DS3 generates catalytic machinery
consisting of three components. In 5D(S1-S3) the liberation of
the catalyst and the yield of the organocatalytic reaction are
unmistakably coupled to the machine speed. The liberation
results from a proximity effect which is remotely related to the
dynamic allosteric effect.[37,38] Coupling of an output (catalysis) to
the speed of a mechanical motion is a characteristic feature of
machinery. As nature is using nanomechanical motions for some
of its most demanding catalytic processes [39] it should be a great
incentive to study further links between motion and catalytic
activity in nanomechanical machinery.
[22] S. F. M. van Dongen, S. Cantekin, J. A. A. W. Elemans, A. E. Rowan, R.
J. M. Nolte, Chem. Soc. Rev. 2014, 43, 99-122.
[23] S. Erbas-Cakmak, D. A. Leigh, C. T. McTernan, A. L. Nussbaumer,
Chem. Rev. 2015, 115, 10081-10206.
[24]
A. J. McConnell, C. S. Wood, P. P. Neelakandan, J. R. Nitschke,
Chem. Rev. 2015, 115, 7729-7793.
[25] M. Xue, Y. Yang, X. Chi, X. Yan, F. Huang, Chem. Rev. 2015, 115,
7398-7501.
[26] J. C. M. Kistemaker, P. Stacko, J. Visser, B. L. Feringa, Nat. Chem.
2015, 7, 890-896.
[27] M. Schmittel, Chem. Commun. 2015, 51, 14956-14968.
[28] J.-P. Sauvage, Angew. Chem. Int. Ed. 2017, 56, 11080.- 11093.
[29] J. F. Stoddart, Angew. Chem. Int. Ed. 2017, 56, 11094 –11125.
[30] C. Burkhart, G. Haberhauer, Eur. J. Org. Chem. 2017, 1308- 1317.
[31] S. R. Domingos, A. Cnossen, W. J. Buma, W. R. Browne, B. L. Feringa,
M. Schnell, Angew. Chem. Int. Ed. 2017, 56, 11209- 11212.
[32] A. Goswami, I. Paul, M. Schmittel, Chem. Commun. 2017, 53, 5186-
5189.
Acknowledgement
We are grateful to Deutsche Forschungsgemeinschaft (SCHM
647/20-1) and the University of Siegen for financial support.
[33] L. K. S. von Krbek, C. A. Schalley, P. Thordarson, Chem. Soc. Rev.
2017, 46, 2622-2637.
[34] N. Mittal, S. Pramanik, I. Paul, S. De, M. Schmittel, J. Am. Chem. Soc.
2017, 139, 4270-4273.
Keywords: Supramolecular machinery, Speed, Catalysis,
[35] Control experiments with the non-dynamic analogs D‘S1-D‘S3 confirm
the relevance of sliding dynamics for the product yields, see SI, Figure
S88.
Multicomponent-Assembly, Self-sorting
[36] L. Favereau, A. Cnossen, J. B. Kelber, J. Q. Gong, R. M. Oetterli, J.
Cremers, L. M. Herz, H. L. Anderson, J. Am. Chem. Soc. 2015, 137,
14256-14259.
[1]
[2]
T. H. Kim, P. Mehrabi, Z. Ren, A. Sljoka, C. Ing; A. Bezginov, L. Ye, R.
Pomès, R. S. Prosser, E. F. Pai, Science 2017, 355, eaag2355.
L. Y. P. Luk, E. J. Loveridge, R. K. Allemann, Phys. Chem. Chem. Phys.
2015, 17, 30817-30827.
[37] J. Guo, H.-X. Zhou, Chem. Rev. 2016, 116, 6503-6515.
[38] C. Kremer, A. Lützen, Chem. Eur. J. 2013, 19, 6162-6196.
[39] M. Yoshida, E. Muneyuki, T. Hisabori, Nature Rev. Mol. Cell Biol. 2001,
2, 669–677.
[3]
[4]
D. Y. Zhang, E. Winfree, J. Am. Chem. Soc. 2008, 130, 13921-13926.
M. Larion, A. L. Hansen, F. Zhang, L. Bruschweiler-Li, V. Tugarinov, B.
G. Miller, R. Brüschweiler, Angew. Chem. Int. Ed. 2015, 54, 8129-8132.
A. Warshel, R. P. Bora, J. Chem. Phys. 2016, 144, 180901-180916.
[5]
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