Insights into chemically-fueled supramolecular polymers

Sharko, Anastasiia; Livitz, Dimitri; Piccoli, Serena De; Bishop, Kyle J. M.; Hermans, Thomas M.

doi:10.26434/chemrxiv-2022-jd607

Cited by 4 publications

(4 citation statements)

References 76 publications

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“…48 Many dynamic assembly processes with attractive features such as programmed reactors or delivery vehicles have been reported where the surfactant assembly was triggered by ATP and their corresponding dissociation to AMP or adenosine + inorganic phosphate (3Pi) by using enzymes such as ATPase or phosphatase. 36,37 In our case, we also expected to observe no additional assembly of the GNP by introducing the enzyme ALP into the system, as ALP is known to dissociate ATP to adenosine + 3 Pi. To this end, we monitored aggregation kinetics by following the A 620 /A 520 ratio over the course of 80 min in 15 mM tris-HCl buffer, pH 9, at 25 °C.…”

Section: Resultsmentioning

confidence: 81%

Self-Regulatory Micro- and Macroscale Patterning of ATP-Mediated Nanobioconjugate

Shandilya

Maiti

2023

ACS Nano

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Directional interactions and the assembly of a nanobioconjugate in clusters at a specific location are important for patterning and microarrays in biomedical research. Herein, we report that self-assembly and spatial control in surface patterning of the surfactant-functionalized nanoparticles can be governed in micro-and macroscale environments by two factors, synergistic enzyme−substrate−nanoparticle affinity and the phoretic effect. First, we show that aggregation of cationic gold nanoparticles (GNP) can be modulated by multivalent anionic nanoparticle binding of an adenosine-based nucleotide and enzyme, alkaline phosphatase. We further demonstrate two different types of their autonomous aggregation pattern: (i) by introducing an enzyme gradient that modulates the synergistic nonequilibrium interactivity of the nanoparticle, nucleotide, and enzyme both in microfluidic conditions and at the macroscale; and (ii) the surface deposition pattern from evaporating droplets via the coffee ring effect. Here, temporal control over the width and site of the patterning area inside the microfluidic channel under catalytic and noncatalytic conditions has also been demonstrated. Finally, we show a change in capillary phoresis parameters responsible for the coffee ring due to introduction of ATP-loaded GNP in the blood serum, showing applicability in low-cost disease diagnostics. Overall, an enzyme-actuated surface nanobiopatterning method has been demonstrated that has potential application in controlled micro-and macroscale area patterning with a diverse cascade catalytic surface and spatiotemporal multisensory-based application.

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Section: Resultsmentioning

confidence: 81%

Self-Regulatory Micro- and Macroscale Patterning of ATP-Mediated Nanobioconjugate

Shandilya

Maiti

2023

ACS Nano

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“…Continuously fueling soft matter to yield sustained non-equilibrium steady states is challenging because these solutions cannot be stirred without affecting the assemblies. Moreover, waste accumulation often poisons the self-assembling systems (36,43). Therefore, we developed new aqueous microreactors in which fuel can continuously diffuse (Fig.…”

Section: Figure 2 Chemically Fueled Droplets Under Batch-fueling a Ch...mentioning

confidence: 99%

Liquid spherical shells are a non-equilibrium steady state

Bergmann

Bauermann

Bartolucci

et al. 2023

Preprint

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Liquid-liquid phase separation is the process in which two immiscible liquids demix. This spontaneous phenomenon yields spherical droplets that eventually coarsen to one large, stable droplet governed by the principle of minimal free energy. In chemically fueled phase separation, the formation of phase-separating molecules is coupled to a fuel-driven, non-equilibrium reaction cycle. Chemically fueled phase separation yields dissipative structures sustained by a continuous fuel conversion. Such dissipative structures are ubiquitous in biology but poorly understood as they are governed by non-equilibrium thermodynamics. Here, we bridge the gap between passive, close-to-equilibrium, and active, dissipative structures with chemically fueled phase separation. We observe that spherical, active droplets can transition into a new morphology, i.e., a liquid, spherical shell of droplet material. A spherical shell would be highly unstable at equilibrium. Only by continuously converting chemical energy, this dissipative structure can be sustained. We demonstrate the transition mechanism, which is related to the activation of a product outside of the droplet, and the deactivation within the droplets leading to gradients of droplet material. We characterize how far out of equilibrium the spherical shell state is and the chemical power necessary to sustain it. Our work suggests new avenues for assembling complex stable morphologies, which might already be exploited to form membraneless organelles by cells.

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“…A distinct feature of natural shunts is that they offer control over product speciation in response to external stimuli or the organism's internal needs. [7][8][9][10] Although the field of Systems Chemistry has developed numerous artificial reaction networks of various complexity, [11][12][13][14][15][16][17][18][19][20] shunts are exceedingly rare in synthetic reaction cycles.…”

Section: Introductionmentioning

confidence: 99%

Redox-controlled shunts in a synthetic chemical reaction cycle

Sharko

Spitzbarth

Hermans

et al. 2023

Preprint

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Shunts, alternative pathways in chemical reaction networks, are ubiquitous in Nature, enabling adaptability to external and internal stimuli. We introduce a chemical reaction network (CRN) in which the recovery of a Michael-accepting species is driven by oxidation chemistry. Using weak oxidants can enable access to two shunts within this CRN with different kinetics and a reduced number of side reactions compared to the main cycle that is driven by strong oxidants. Further, we introduce a strategy to recycle one of the main products under flow conditions to partially reverse the CRN and control product speciation throughout time. These findings introduce new levels of control over artificial CRNs, driven by redox chemistry, narrowing the gap between synthetic and natural systems.

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Insights into chemically-fueled supramolecular polymers

Cited by 4 publications

References 76 publications

Self-Regulatory Micro- and Macroscale Patterning of ATP-Mediated Nanobioconjugate

Self-Regulatory Micro- and Macroscale Patterning of ATP-Mediated Nanobioconjugate

Liquid spherical shells are a non-equilibrium steady state

Redox-controlled shunts in a synthetic chemical reaction cycle

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