Urease-coupled systems and materials: design strategies, scope and applications.

Synthetic systems have co-opted urease, a crucial enzyme serving many biological functions, to recapitulate complex biological features. Therefore, the urease-urea feedback reaction network (FCRN) is reciprocated with soft materials to induce various animate-like features, including self-regulation, error correction, and decision-making capabilities, that are processed through a variety of non-linear functions. Although free-urease-based homogeneous systems are capable of adhering to many non-linear characteristics, they lack the ability to showcase the diffusion-controlled spatiotemporal phenomena.

Bistable Functions and Signaling Motifs in Systems Chemistry: Taking the Next Step Toward Synthetic Cells.

A key challenge in modern chemistry research is to mimic life-like functions using simple molecular networks and the integration of such networks into the first functional artificial cell. Central to this endeavor is the development of signaling elements that can regulate the cell function in time and space by producing entities of code with specific information to induce downstream activity. Such artificial signaling motifs can emerge in nonequilibrium systems, exhibiting complex dynamic behavior like bistability, multistability, oscillations, and chaos.

Anomalous Interlayer Exciton Diffusion in WS/WSe Moiré Heterostructure.

Stacking van der Waals crystals allows for the on-demand creation of a periodic potential landscape to tailor the transport of quasiparticle excitations. We investigate the diffusion of photoexcited electron-hole pairs, or excitons, at the interface of WS/WSe van der Waals heterostructure over a wide range of temperatures. We observe the appearance of distinct interlayer excitons for parallel and antiparallel stacking and track their diffusion through spatially and temporally resolved photoluminescence spectroscopy from 30 to 250 K.

Artificial Homeostasis Systems Based on Feedback Reaction Networks: Design Principles and Future Promises.

Feedback-controlled chemical reaction networks (FCRNs) are indispensable for various biological processes, such as cellular mechanisms, patterns, and signaling pathways. Through the intricate interplay of many feedback loops (FLs), FCRNs maintain a stable internal cellular environment. Currently, creating minimalistic synthetic cells is the long-term objective of systems chemistry, which is motivated by such natural integrity.

Influence of Atomic Relaxations on the Moiré Flat Band Wave Functions in Antiparallel Twisted Bilayer WS.

Twisting bilayers of transition metal dichalcogenides gives rise to a moiré potential resulting in flat bands with localized wave functions and enhanced correlation effects. In this work, scanning tunneling microscopy is used to image a WS bilayer twisted approximately 3° off the antiparallel alignment. Scanning tunneling spectroscopy reveals localized states in the vicinity of the valence band onset, which is observed to occur first in regions with S-on-S Bernal stacking.

Electrons Surf Phason Waves in Moiré Bilayers.

We investigate the effect of thermal fluctuations on the atomic and electronic structure of a twisted MoSe/WSe heterobilayer using a combination of classical molecular dynamics and density functional theory calculations. Our calculations reveal that thermally excited phason modes give rise to an almost rigid motion of the moiré lattice. Electrons and holes in low-energy states are localized in specific stacking regions of the moiré unit cell and follow the thermal motion of these regions.

pH-feedback systems to program autonomous self-assembly and material lifecycles.

pH-responsive systems have gained importance for the development of smart materials and for biomedical applications because they can switch between different states by simple acid/base triggers. However, such equilibrium systems lack the autonomous behaviour that is so ubiquitous in living systems that self-regulate out of equilibrium. As a contribution to the emerging field of autonomous chemical systems, we have developed pH-feedback systems (pH-FS) based on the coupling of acid- and base-producing steps in chemical reaction networks.

Tunable lattice thermal conductivity of twisted bilayer MoS.

We have studied the thermal conductivity () of layered MoS, a typical member of the transition metal dichalcogenide (TMDC) materials, using fully atomistic molecular dynamics simulations and Boltzmann transport equation (BTE) based first principles methods. We investigate the tuning of the thermal conductivity with the twist angle between two layers and found a decreasing trend of with the increase in the lattice constant of the moiré superlattice. The thermal conductivity at twist angle = 21.

Feedback and Communication in Active Hydrogel Spheres with pH Fronts: Facile Approaches to Grow Soft Hydrogel Structures.

Compartmentalized reaction networks regulating signal processing, communication and pattern formation are central to living systems. Towards achieving life-like materials, we compartmentalized urea-urease and more complex urea-urease/ester-esterase pH-feedback reaction networks into hydrogel spheres and investigate how fuel-driven pH fronts can be sent out from these spheres and regulated by internal reaction networks. Membrane characteristics are installed by covering urease spheres with responsive hydrogel shells.

Signaling in Systems Chemistry: Programing Gold Nanoparticles Formation and Assembly Using a Dynamic Bistable Network.

Living cells exploit bistable and oscillatory behaviors as memory mechanisms, facilitating the integration of transient stimuli into sustained molecular responses that control downstream functions. Synthetic bistable networks have also been studied as memory entities, but have rarely been utilized to control orthogonal functions in coupled dynamic systems. We herein present a new cascade pathway, for which we have exploited a well-characterized switchable peptide-based replicating network, operating far from equilibrium, that yields two alternative steady-state outputs, which in turn serve as the input signals for consecutive processes that regulate various features of Au nanoparticle shape and assembly.

Evolution of high-frequency Raman modes and their doping dependence in twisted bilayer MoS.

Twisted van der Waals heterostructures provide a new platform for studying strongly correlated quantum phases. The interlayer coupling in these heterostructures is sensitive to the twist angle (θ) and key to controllably tuning several interesting properties. Here, we demonstrate the systematic evolution of the interlayer coupling strength with twist angle in bilayer MoS using a combination of Raman spectroscopy and classical simulations.

A chemically fueled non-enzymatic bistable network.

One of the grand challenges in contemporary systems chemistry research is to mimic life-like functions using simple synthetic molecular networks. This is particularly true for systems that are out of chemical equilibrium and show complex dynamic behaviour, such as multi-stability, oscillations and chaos. We report here on thiodepsipeptide-based non-enzymatic networks propelled by reversible replication processes out of equilibrium, displaying bistability.

Open Prebiotic Environments Drive Emergent Phenomena and Complex Behavior.

We have been studying simple prebiotic catalytic replicating networks as prototypes for modeling replication, complexification and Systems Chemistry. While living systems are always open and function far from equilibrium, these prebiotic networks may be open or closed, dynamic or static, divergent or convergent to a steady state. In this paper we review the properties of these simple replicating networks, and show, via four working models, how even though closed systems exhibit a wide range of emergent phenomena, many of the more interesting phenomena leading to complexification and emergence indeed require open systems.

Bistability and Bifurcation in Minimal Self-Replication and Nonenzymatic Catalytic Networks.

Bistability and bifurcation, found in a wide range of biochemical networks, are central to the proper function of living systems. We investigate herein recent model systems that show bistable behavior based on nonenzymatic self-replication reactions. Such models were used before to investigate catalytic growth, chemical logic operations, and additional processes of self-organization leading to complexification.

Electrodeposited Lamellar Photoconductor Nanohybrids Driven by Peptide Self-Assembly.

Aromatic organic molecules serve as optoelectronic materials owing to their intrinsic optical and electronic properties. Herein, self-assembled lamellar nanostructures as photoconductor hybrids, which are obtained from naphthalene-2-methoxycarbonyl (Nmoc)-capped peptide amphiphiles, are described. Hybrid nanostructures are constructed in a controlled manner by an electrochemical deposition technique in combination with the inorganic Zn(OH) phase.

Lipase-catalyzed dissipative self-assembly of a thixotropic Peptide bolaamphiphile hydrogel for human umbilical cord stem-cell proliferation.

We report lipase-catalyzed inclusion of p-hydroxy benzylalcohol to peptide bolaamphiphiles. The lipase-catalyzed reactions of peptide bolaamphiphiles with p-hydroxy benzylalcohol generate dynamic combinatorial libraries (DCL) in aqueous medium that mimic the natural dissipative system. The peptide bolaamphiphile 1 (HO-WY-Suc-YW-OH) reacts with p-hydroxy benzylalcohol in the presence of lipase forming an activated diester building block.

Self-programmed nanovesicle to nanofiber transformation of a dipeptide appended bolaamphiphile and its dose dependent cytotoxic behaviour.

Nanostructural transition of a small peptide bolaamphiphile via molecular self-assembly is a challenging task. Here, we report the self-programmed morphological transformation from nanovesicles to nanofibers of a smart peptide bolaamphiphile in its self-assembling hydrogel state. The nanostructural transition occurs based on the structural continuity of the β-sheet structures.

In situ generation of redox active peptides driven by selenoester mediated native chemical ligation.

Redox active peptides are generated through selenoester mediated native chemical ligation (NCL). Distinct nanostructures, such as nanotubes to nanofibrillar architectures, were observed for self-assembling soft materials.

Lipase catalyzed inclusion of gastrodigenin for the evolution of blue light emitting peptide nanofibers.

We report lipase catalysed regioselective inclusion of gastrodigenin (p-hydroxybenzyl alcohol: HBA) to a peptide Nmoc-Leu-Trp-OH at physiological pH 7.4. The resultant Nmoc-Leu-Trp-HBA from a reaction cycle of dissipative self-assembly evolves into blue light emitting peptide nanofibers.

Peptide-Nanofiber-Supported Palladium Nanoparticles as an Efficient Catalyst for the Removal of N-Terminus Protecting Groups.

Sonication-induced tryptophan- and tyrosine-based peptide bolaamphiphile nanofibers have been used to synthesize and stabilize Pd nanoparticles under physiological conditions. The peptide bolaamphiphile self-assembly process has been thoroughly studied by using several spectroscopic and microscopic techniques. The stiffness of the soft hydrogel matrix was measured by an oscillatory rheological experiment.

Peptide self-assembly driven by oxo-ester mediated native chemical ligation.

We use the oxo-ester mediated native chemical ligation (NCL) reaction to generate a peptide self-assembly process to make supramolecular nanofibers and self-supporting gels.