This study is aimed at booming intelligent catalysts, suggesting a bio-inspired polymer catalyst with substrate-sieving catalytic ability. By mimicking the hierarchical multi-level structures in biopolymers, this polymer catalyst was fabricated with metal nanoparticles and double "zipper" conformations individually made of polymeric hydrogen bonds and complexing interactions. Owing to the discrepant strength of both interactions against temperature, the double zipper conformations led to a hierarchical disruption of the two interactions and stepwise disaggregation of the polymeric networks and as a result the substrate-sieving catalytic ability. This catalyst didn't present effective catalysis at low temperatures because of the blocked networks. With the increasing temperatures, this catalyst would first present catalysis towards small molecules of substrate and then further towards bigger molecules of substrate, by virtue of the hierarchical disruption of the weaker hydrogen bonds and the stronger complexing interactions. In this way, this catalyst assumed the substrate-sieving catalytic ability. The protocol of this catalyst suggests a prospect to modulate the catalytic proceedings, particularly for complicated processes.
Research Article
Polymer Catalyst with Double "Zipper" Conformations for Formatting Substrate-Sieving Catalytic Ability
https://doi.org/10.21203/rs.3.rs-1504657/v1
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Intelligent catalysts
polymeric zipper conformations
substrate-sieving catalytic ability
There is much interest in intelligent catalysts and their tunable catalytic properties, given the extreme importance in modern chemical sectors [1,2]. The adoption of intelligent catalysts would allow the chemical processes underway to run in a designated manner, effectively decreasing the separation steps and increasing the catalytic performances. Marked by the sophisticated applications of poly(N-isopropylacrylamide)-based catalysts [3,4], striking progress has been made in the field over the years and currently a rapidly-increasing number and diversity of intelligent catalysts are springing up [5–7]. The connotation behind these intensive endeavors lies in the matter that these catalysts can adjust their physical morphology in real-time in response to the changing environment, which leads to modulative and administrative paradigms regarding catalytic applications. Despite the enchanting prospect, the actual adoption of these catalysts needn't lead to the desired high- performance catalysis and the modulative processes. The reason may be related to the practical catalytic processes which often involve in multi-component reactants and reaction proceedings [6–8], in which some reactions are desired to run first and then some others are desired to follow suit. This would require the intelligent catalyst that can run the catalytic processes with substrate-sieving catalytic ability and allows some reactions to be proceeded prior to some others. Unfortunately, it is not realistic to obtain such a catalyst from currently available outcomes. New methods and thoughts are needed.
Nature has been being human's tutor and teaching us about how to solve complicated scientific issues, and a volume of knowledge is already well established. Among the volume of knowledge are the biopolymers, which provide a promising answer to the struggling field of intelligent catalysts. Biopolymers (such as proteins) are often able to adapt to the changing environment, by virtue of their multi-level conformations made of diverse interactions such as hydrogen bonds, electrostatic interactions and Van der Waals's forces [9,10]. The relatively stronger interactions may shape the conformations to a greater extent while the weaker interactions act as synergism. A change in the environment would allow these interactions to hierarchically coalesce/disrupt and as a result exert environment-adaptable paradigms for these biopolymers and accordingly increase opportunities for survival [11]. With the changing environment (such as the increasing temperatures), the relatively weaker interactions would disaggregate first, followed by the stronger interactions [12,13]. In this way, these biopolymers assume the hierarchically-responsive properties. Although the established knowledge doesn't necessarily concern any catalytic applications, the multi-level conformations and the hierarchically-responsive properties at biopolymers share a prospect with developing intelligent catalysts capable of hierarchically-responsive catalytic ability.
Inspired by the principle in nature, here, we aim to address the current challenges in intelligent catalysts by developing a new catalyst that possesses substrate-sieving catalytic ability (which allows small molecules of substrate to be proceeded prior to big molecules of substrate). By mimicking the multi-level conformations in biopolymers, this polymer catalyst was fabricated with Ag nanoparticles and double "zipper" conformations individually made of polymeric hydrogen bonds (between PFA and PMBO331) and complexing interactions (between PFA and PVI) (herein, PFA is for poly(2-fluoroacrylic acid), PMBO331 means poly(3-methyl-3-butene-1-alcohol), and PVI stands for poly(1-vinylimidazole)). As outlined in Scheme 1, the discrepant strength of both interactions against temperature led to a hierarchical disruption of the two interactions and stepwise disaggregation of the polymeric networks and as a result the substrate-sieving catalytic ability (the microscopic decoding of the catalyst are presented in Section 2). At low temperatures, this catalyst wouldn't present effective catalysis because of the two interactions which blocked the polymeric networks. At medium temperatures, this catalyst may present efficient catalysis towards small molecules of substrate due to the disruption of the relatively weaker hydrogen bonds. At higher temperatures, this catalyst would further present catalysis towards bigger molecules of substrate in response to the open networks. In this way, this catalyst assumed the substrate-sieving catalytic ability. The design of this catalyst suggests opportunities to modulate the catalytic proceedings, particularly for complicated processes.
There are a few tentative discussions available regarding the microscopic mechanical properties of functional materials [14,15]. The microscopic world of materials and their motion keep within bounds of the Schrödinger equation
. (1)
To decode the proposed intelligent catalyst, the key relies on the polymeric interactions involved in the networks, i.e, the hydrogen bonds and the complexing interactions. Run with the confinement from energy barriers, the motion of one simple polymeric chain relative to the others can not go beyond the energy barriers. This natural law dictates these polymeric chains the microscopic motion subject to the potential barriers
. (2)
Here, d is the maximal distance borne among these polymeric chains (the further distance would incite a phase transition of the polymeric networks). This outline floats resulting from the effective interactions among these polymeric chains which fundamentally rely on the distance [16]. One polymeric chain excessively close to the others (r ≤ 0) would press the polymeric blocks and thus leads to a dramatically-increasing potential. One polymeric chain excessively faraway from the others (r ≥ d) would incite a phase transition of the polymeric networks, for which U0 must be surmounted. In conjunction with Eq. (2), solving Eq. (1) will show
. (3)
Here, µ and η are individually an integrated variable and a constant. Eq. (3) presents the physically- acceptable energy for the "bound" motion of these polymeric chains and which can be obtained from plotting cot µ against –[(η/µ)2-1]1/2. This will give the maximal value µm ≈ mπ →κ that shows
. (4)
Hence, the "bound" polymeric networks in the catalyst only become possible with Em ≤ U0. The higher energy will incite a phase transition of the polymeric networks which needs the extra energy
. (5)
Once the extra energy is compensated from a heat source (such as the catalytic solution), a phase transition of the polymeric networks would take place:
(6)
Here, Tc and T0 are individually the critical temperature for the phase transition and the ambient temperature, and ms and qs are the mass of the aqueous solution and the specific heat. Owing to the discrepant κ and m between hydrogen bonds and the complexing interactions in this catalyst, the increasing temperatures would result in a hierarchical disruption of the two interactions and stepwise disaggregation of the polymeric networks and as a result leads to the substrate-sieving catalytic ability. This catalyst wouldn't present effective catalysis at low temperatures because of the two interactions which blocked the polymeric networks. With the increasing temperatures, this catalyst would first present catalysis towards small molecules of substrate and then further towards bigger molecules of substrate, by virtue of the hierarchical disruption of the relatively weaker hydrogen bonds and the stronger complexing interactions. In this way, the catalyst assumed the substrate-sieving catalytic ability.
3.1. Preparation of polymer catalysts
All the chemicals used here were of analytical grade and commercial available from Sigma- Aldrich. The optimized ratio of functional monomers including 2-fluoroacrylic acid (FA), 3-methyl- 3-butene-1-alcohol (MBO331) and 1-vinyl imidazole (VI) were first dissolved in dimethylsulfoxide (8.0 mL) for full complexation (The details are presented in Section 4.1, where 0.89 g of FA, 0.54 g of MBO331 and 0.47 g of VI have been used). After being dispersed and degassed with sonication, azobisisobutyronitrile (0.01 g), N,N'-methylenebisacrylamide (0.015 g) and silver nitrate (0.32 g) were added. The mixture system was then kept at 70 oC for 3 hours' reaction. The embedded ionic silver was reduced with excess potassium borohydride. The resulting polymer catalyst was washed profusely with water and ethanol, and then dried in nitrogen. In this way, the proposed catalyst was prepared (mentioned hereafter as "AgPC-HCS", where Ag represents silver nanoparticles, PC for polymer catalysts, H for hydrogen bonds, C for complexing interactions, and S for responsive properties).
Given the hierarchical responsive properties and the stepwise catalytic ability at the proposed catalyst AgPC-HCS, four control groups lacking of either the former or the latter were comparably prepared (mentioned hereafter as "AgPC-N", "AgPC-HS", "AgPC-CS", and "PC-HCS"). Herein, AgPC-N was the non-responsive catalyst with the polymeric carrier wholly made of PVI. AgPC-HS and AgPC-CS were the catalysts only holding polymeric hydrogen bonds and the complexing interactions, prepared individually without using VI and PMBO331. PC-HCS was the polymer carrier of AgPC-HCS and prepared without using silver. In this way, the proposed catalyst and the control groups were prepared.
3.2. Characterization
The FTIR spectra of the above-prepared polymer catalysts were scanned using a Nicolet iS10 apparatus (USA). The energy dispersive X-ray spectra (EDS) were detected using a TESCAN MIRA3-XMU apparatus (Czech). The surface-plasma-resonance (SPR) spectra were recorded with a UV-2700 spectrophotometer (Japan). The SEM images were taken from a JSM-7800F field emission scanning electron microscope (Japan).
3.3. Thermosensitive transitions
The microscopically-mechanical decoding of the proposed catalyst revealed that two thermosensitive phase transitions may be included in the prepared catalysts (cf. Section 2). For this, dynamic light scattering (DLS) was used to trace the thermosensitive transitions. The catalyst specimens were soaked in water and the dynamically-changing sizes were scanned against temperature. By a comparison with non-responsive control groups, the thermosensitive transitions and their contributions to these prepared catalysts were thus shown [17,18].
3.4. Substrate-sieving catalytic properties
Vanillin (VA) and malachite green (MG) were used as the model compounds of substrate for the catalytic testing, given their discrepant sizes (MG is much larger than VA) and the common reduction properties [19,20]. The catalytic testing was implemented against temperature with a batch format, where the initial concentrations of the two substrates were both 0.06 µmoL mL− 1 (15 mL PBS; pH 7.0) (potassium borohydride, fourfold in contrast to both substrates). The amount of these prepared catalysts used in every testing was 0.05 mg mL− 1. The catalytic processes were detected with a spectrophotometer and the catalytic properties were achieved from the average of three runs. To avoid the possible effect of spontaneous reactions, the control processes which were proceeded in the absence of catalysts were also comparably implemented and the effect was deduced from the overall properties of these catalysts.
3.5. Hierarchically-accessing networks
As per the quantum theories (cf. Section 2), the increasing temperatures would lead to a hierarchical disruption of hydrogen bonds and the complexing interactions and as a result exerted hierarchically-accessing networks. As such, the electrochemical testing was implemented to trace the hierarchically-accessing networks [21]. The prepared catalysts that pre-adsorbed about 1 µmoL of substrates were settled in an electrochemical cell enveloped by a temperature-programmed apparatus (electrolyte: 10 mL PBS; pH 7.0). With eliminating diffusion from a sonication apparatus, the desorption processes of the absorbed substrates were detected in real-time by circularly scanning the system until the stable patterns was shown (200~ -600 mV; 1 mV s− 1).
4.1. Optimization of responsive interactions
As per the quantum theories (cf. Section 2), the interactions in the prepared catalysts are a key to the hierarchical responsive properties and the substrate-sieving catalytic ability. An excess at any one of these functional monomers would result in unsaturated interactions and mismatch association /disruption among these functional groups [22]. As such, the hydrogen bonds and the complexing interactions among these functional monomers were studies as a function of the ratios of these functional monomers. As shown in Fig. 1 and Fig. 2, the titration of one functional monomer to another one led to shifting UV spectra and the further titration eventually resulted in a saturation of the shifting spectra. The shifting UV spectra and their saturation may be due to the increasing interactions between the involved monomers, which led to a changing distribution of the electronic clouds (valence electrons) and eventually reached the saturation [23]. Individually with a 1.25 mol/mol ratio of MBO331/FA and a 1.02 mol/mol ratio of VI/FA, the hydrogen bonds and the complexing interactions reached saturations. As such, 9.92 mmol of FA (0.89 g) was adopted to prepare the proposed catalyst where 6.25 mmol of MBO331 (0.54 g) and 5.0 mmol of VI (0.47g) had been used. In this context, the further studies were implemented and shown below.
4.2. Characterization
The proposed catalyst AgPC-HCS consisted of silver nanoparticles and a polymeric carrier composite of PFA, PVI and PMBO331. By taking the complicated multi-component composition into account, these control groups at lack of one of these components were also detected together. As shown in Fig. 3, FTIR was first used to characterize the polymeric composition. Three main absorption bands (2950–3650 cm− 1, 1550–1780 cm− 1 and 1000–1450 cm− 1) and a few fingerprint bands were included in these spectra, spectroscopically relating to the stretching vibration of O-H (N-H), C = O and C-N (C-C) and their rotation [24]. The proposed catalyst AgPC-HCS exhibited actually all the main adsorption bands of these control groups, revealing the desired multi-component and composite composition. Figure 4 presents the EDS analysis on these prepared catalysts, which showed the corresponding chemical elements including C, N, O, F, Ag contained in these catalysts. The SPR spectra further supported the EDS analysis and raised the SPR bands of Ag nanoparticles at ~ 410 nm [25] (Fig. 5). Figure 6 presents the TEM images which revealed Ag nanoparticles which were well distributed in the polymeric carriers with a diameter of about 10 nm. In conjunction with the preparation processes (cf. Section 3.1), these polymer catalysts were prepared in the desired form.
4.3. Thermosensitive transitions
The microscopically-mechanical decoding of the proposed catalyst revealed that two thermosensitive phase transitions may be included in the prepared catalysts (cf. Section 2). As such, dynamic light scattering was implemented to detect the thermosensitive transitions. As shown in Fig. 7, AgPC-N, the non-responsive control group, did not show a substantive dependence on temperature due to the lack of responsive interactions in the polymeric networks. In contrast, these interaction-including catalysts exhibited the significant dependences upon temperatures. The thermosensitive transitions for AgPC-HS (containing only hydrogen bonds) and AgPC-CS (containing only complexing interactions) appeared at about 38 oC and 52 oC, revealing that the complexing interactions were stronger than hydrogen bonds. Below the individual thermosensitive transitions (Fig. 7a), AgPC-HS and AgPC-CS exhibited relatively a smaller size associating with the "bound" networks (cf. Section 2). With the temperatures higher than the thermosensitive transitions, AgPC-HS and AgPC-CS showed a much larger size associating with the open polymeric networks (cf. Section 2). It was noted that the proposed catalyst AgPC-HCS, along with PC-HCS, showed the combined responsive properties of both AgPC-HS and AgPC-CS and ran with two thermosensitive transitions, revealing the hierarchical dissociation of the two interactions and accordingly the stepwise disaggregation of the polymeric networks. These outcomes indicate that the hierarchical responsive properties have been projected into the proposed catalyst. In conjunction with the preparation of this catalyst (cf. Scheme 2), the hierarchical responsive properties potentially makes possible the substrate-sieving catalytic ability.
4.4. Catalytic properties and substrate-sieving ability
The catalytic properties of these prepared catalysts are presented in Fig. 8. By taking the hierarchical responsive properties into account, three representative temperatures (i.e., 30 oC, 45 oC and 60 oC) either higher or lower than the transition temperatures of AgPC-HCS (38 oC and 52 oC) (cf. Figure 7) were picked out for tracking the substrate-sieving ability. The purpose of picking out these temperatures was to make sure the responsive areas which can be cloaked. The non-responsive control group AgPC-N invariably presented higher activities towards MG than towards VA, a reason relating to the active physicochemical properties of MG in relation to VA [26]. PC-HCS did not provide substantive catalytic ability due to the lack of catalytic metal nanoparticles. With the increasing temperatures, it is worth noting that AgPC-HCS first ran like AgPC-HS and provided effective catalysis towards small molecules of VA, and then ran like AgPC-CS and further provided effective catalysis towards bigger molecules of MG. Specifically, at 30 oC, AgPC-HCS, AgPC-HS and AgPC-CS did not provide substantive catalysis due to the blocked networks (Fig. 8a). At 45 oC, AgPC-HCS ran like AgPC-HS and provided effective catalysis towards small molecules of VA (Fig. 8b). At 60 oC, AgPC-HCS further ran like AgPC-CS and extra provided effective catalysis towards bigger molecules of MG (Fig. 8c). These outcomes show that the desired substrate-sieving catalytic ability has been projected into the proposed catalyst AgPC-HCS. As explained in Section 2 and Section 4.3, these outcomes may be due to the hierarchical disruption of the two interactions and the stepwise disaggregation of the polymeric networks, which as a result led to the substrate-sieving catalytic ability.
4.5. Hierarchically-accessing networks
The microscopic decoding of the proposed catalyst revealed that two thermosensitive phase transitions may be included in the prepared catalysts (cf. Section 2), which as a result led to the hierarchically-accessing networks. As such, the electrochemical testing was implemented to track the hierarchically-accessing networks [21]. By taking the hierarchical responsive properties into account, 30 oC, 45 oC and 60 oC were picked out again for a comparative study. As shown in Fig. 9, the small molecule of VA that was absorbed onto AgPC-HCS provided a desorption-reduction peak at -447 mV at 30 oC (Fig. 8a). In contrast, this peak was switched to a small position (-355 mV) at 45 oC (Fig. 9b). There was not an actual change available for this peak at 60 oC (-347 mV) in contrast to that at 45 oC (-355 mV (Fig. 9c). The outcome was completely opposite regarding the bigger molecule of MG, in which MG that was absorbed onto AgPC-HCS at 30 oC and at 45 oC exhibited comparable desorption-reduction potentials (-359 mV vs. -351 mV; Fig. 9d and Fig. 9e). However, this peak at 60 oC was switched to a small position (-273mV) (Fig. 9f). AgPC-HCS provided a stronger interaction towards VA at relatively low temperatures but a stronger interaction towards MG at relatively higher temperatures. These outcomes reveal the hierarchically- accessing networks in AgPC-HCS which was accessible first for the small molecule of VA and then for the bigger molecule of MG.
To further address the hierarchically-accessing networks, Table 1 provides the desorption- reduction potentials obtained from all the prepared catalysts. With the increasing temperatures, the non-responsive AgPC-N did not provide a substantive change at the desorption-reduction potentials of both VA and MG. AgPC-HCS and PC-HCS provided a comparable change in the desorption- reduction potentials, regardless of the metal nanoparticles embedded in AgPC-HCS. With the increasing temperatures, AgPC-HCS first ran like AgPC-HS and provided a main switch of potential for the small molecule of VA (relative molecular mass: 152.15) and then ran like AgPC-CS and further provided a switch of potential for a bigger molecule of MG (relative molecular mass: 364.91). Once again, these outcomes reveal that the hierarchically-accessing networks in AgPC-HCS were the main reason behind the substrate-sieving catalytic ability. In conjunction with the microscopic decoding and the characterization of these catalysts (cf. Sections 2 and 4.2), the hierarchically-accessing networks in AgPC-HCS were essentially a result of the discrepant strength of hydrogen bonds and the complexing interactions, which endorsed a hierarchical disruption of the polymeric networks and as a result led to the substrate-sieving catalytic ability.
|
Polymer catalyst |
30 oC |
45 oC |
60 oC |
Delta (from 30 oC to 45 oC) |
Delta (from 45 oC to 60 oC) |
|||||
|---|---|---|---|---|---|---|---|---|---|---|
|
VA |
MG |
VA |
MG |
VA |
MG |
VA |
MG |
VA |
MG |
|
|
AgPC-N |
-351 |
-278 |
-348 |
-276 |
-346 |
-275 |
3 |
2 |
2 |
1 |
|
AgPC-HS |
-440 |
-349 |
-346 |
-274 |
-343 |
-271 |
94 |
75 |
3 |
3 |
|
AgPC-CS |
-444 |
-354 |
-439 |
-349 |
-348 |
-274 |
5 |
5 |
91 |
75 |
|
AgPC-HCS |
-447 |
-359 |
-355 |
-351 |
-347 |
-273 |
92 |
8 |
8 |
78 |
|
PC-HCS |
-446 |
-357 |
-353 |
-350 |
-345 |
-272 |
93 |
7 |
8 |
78 |
This study is to address the current challenges in intelligent catalysts, regarding the ambition to achieve control that allows some reactions to run prior to some others. This objective was reached by developing a bio-inspired polymer catalyst that possesses substrate-sieving catalytic ability. By mimicking the hierarchical multi-level structures in biopolymers, this catalyst was fabricated with metal nanoparticles and two zipper conformations individually made of polymeric hydrogen bonds and complexing interactions. Owing to the discrepant strength of both interactions against temperature, the double zipper conformations led to a hierarchical disruption of the two interactions and stepwise disaggregation of the polymeric networks and as a result the substrate- sieving catalytic ability. This catalyst didn't present effective catalysis at low temperatures because of the two interactions which blocked the polymeric networks. With the increasing temperatures, this catalyst first presented catalysis towards small molecules of substrate and then further towards bigger molecules of substrate, by virtue of the hierarchical disruption of the two interactions. In this way, the catalyst assumed the substrate-sieving catalytic ability. This study indicates that intelligent catalysts that possess substrate-sieving catalytic ability (which allows some reactions to run prior to some others) can be obtained with the bio-inspired proposal, which suggests opportunities to modulate the catalytic proceedings, particularly for complicated processes. The future advances will help facilitate the applications and boom in novel functional catalysts and catalytic materials.
Statement of interest
The authors declare no conflict of interest concerning in this study.
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Scheme 1 is available in the Supplementary Files section.
- Scheme1.png
Scheme 1. Technical outline for the proposed intelligent catalyst
