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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 WS2/WSe2 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. While the measured exciton diffusivity decreases with temperature, it surprisingly plateaus below 90 K. Our observations cannot be explained by classical models like hopping in the moiré potential. A combination of ab initio theory and molecular dynamics simulations suggests that low-energy phonons arising from the mismatched lattices of moiré heterostructures, also known as phasons, play a key role in describing and understanding this anomalous behavior of exciton diffusion. Our observations indicate that the moiré potential landscape is dynamic down to very low temperatures and that the phason modes can enable efficient transport of energy in the form of excitons.

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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. The design, kinetic optimization, and analysis of FCRNs to exhibit functions akin to those of a cell still pose significant challenges. Indeed, reaching synthetic homeostasis is essential for engineering synthetic cell components. However, maintaining homeostasis in artificial systems against various agitations is a difficult task. Several biological events can provide us with guidelines for a conceptual understanding of homeostasis, which can be further applicable in designing artificial synthetic systems. In this regard, we organize our review with artificial homeostasis systems driven by FCRNs at different length scales, including homogeneous, compartmentalized, and soft material systems. First, we stretch a quick overview of FCRNs in different molecular and supramolecular systems, which are the essential toolbox for engineering different nonlinear functions and homeostatic systems. Moreover, the existing history of synthetic homeostasis in chemical and material systems and their advanced functions with self-correcting, and regulating properties are also emphasized.

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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 WS2 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. In contrast, density functional theory calculations on twisted bilayers that have been relaxed in vacuum predict the highest-lying flat valence band to be localized in regions of AA' stacking. However, agreement with experiment is recovered when the calculations are performed on bilayers in which the atomic displacements from the unrelaxed positions have been reduced, reflecting the influence of the substrate and finite temperature. This demonstrates the delicate interplay of atomic relaxations and the electronic structure of twisted bilayer materials.

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Living organisms are replete with rhythmic and oscillatory behavior at all levels, to the extent that oscillations have been termed as a defining attribute of life. Recent studies of synthetic oscillators that mimic such functions have shown decayed cycles in batch-mode reactions or sustained oscillatory kinetics under flow conditions. Considering the hypothesized functionality of peptides in early chemical evolution and their central role in current bio-nanotechnology, we now reveal a peptide-based oscillator. Oscillatory behavior was achieved by coupling coiled-coil-based replication processes as positive feedback to controlled initiation and inhibition pathways in a continuously stirred tank reactor (CSTR). Our results stress that assembly into the supramolecular structure and specific interactions with the replication substrates are crucial for oscillations. The replication-inhibition processes were first studied in batch mode, which produced a single damped cycle. Thereafter, combined experimental and theoretical characterization of the replication process in a CSTR under different flow and environmental (pH, redox) conditions demonstrated reasonably sustained oscillations. We propose that studies in this direction might pave the way to the design of robust oscillation networks that mimic the autonomous behavior of proteins in cells (e.g., in the cyanobacterial circadian clock) and hence hint at feasible pathways that accelerated the transition from simple peptides to extant enzymes.

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We investigate the effect of thermal fluctuations on the atomic and electronic structure of a twisted MoSe2/WSe2 heterobilayer using a combination of classical molecular dynamics and ab initio 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. In other words, charge carriers surf phason waves that are excited at finite temperatures. We also show that such surfing survives in the presence of a substrate and frozen potential. This effect has potential implications for the design of charge and exciton transport devices based on moiré materials.

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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. The resulting autonomous nonlinear pH curves can be coupled with a variety of pH-sensitive building blocks to program the lifecycles of the associated transient state at the level of self-assemblies and material systems. In this article, we discuss the different generations of such pH-feedback systems, the principles of their coupling to self-assemblies with lifecycles and highlight emerging concepts for the design of autonomous functional materials. The specificity, robustness, and flexible operation of such pH-FS can also be used to realize chemo-structural and chemo-mechanical feedbacks that extend the behaviour of such materials systems toward complex and functional life-like systems.

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We have studied the thermal conductivity (κ) of layered MoS2, 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 κ with the increase in the lattice constant of the moiré superlattice. The thermal conductivity at twist angle θ = 21.78° is found to be 72.03 W m-1 K-1 and for an angle of 2.87°, it reaches 54.48 W m-1 K-1, leading to a 32% reduction in the thermal conductivity. We use first principles calculations based on the BTE for phonons to give a microscopic origin of the decrease in thermal conductivity through anharmonic phonon scattering events and also reaffirm the MD simulation results for the monolayer and bilayer.

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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. We then encapsulate the two networks (urea-urease and ester-esterase) separately into different hydrogel spheres to devise communication, pattern formation and attraction. Moreover, these pH fronts and patterns can be used for self-growing hydrogels, and for developing complex geometries from non-injectable hydrogels without 3D printing tools. This study opens possibilities for compartmentalized feedback reactions and their use in next generation materials fabrication.

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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. This study further sheds light on how bridging together the fields of systems chemistry and nanotechnology may open up new opportunities for the dynamically controlled design of functional materials.

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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 MoS2 using a combination of Raman spectroscopy and classical simulations. At zero doping, we observe a monotonic increase in the separation between the A1g and E2g1 mode frequencies as θ decreases from 10°â†’ 1°, and the separation approaches that of a bilayer at small twist angles. Furthermore, using doping dependent Raman spectroscopy, we reveal the θ dependent softening and broadening of the A1g mode, whereas the E2g1 mode remains unaffected. Using first principles based simulations, we demonstrate large (weak) electron-phonon coupling for the A1g (E2g1) mode, which explains the experimentally observed trends. Our study provides a non-destructive way to characterize the twist angle and the interlayer coupling and establishes the manipulation of phonons in twisted bilayer MoS2 (twistnonics).

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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. Accordingly, we present quantitative analyses of the bistable behaviour, featuring a phase transition from the simple equilibration processes taking place in reversible dynamic chemistry into the bistable region. This behaviour is observed only when the system is continuously fueled by a reducing agent that keeps it far from equilibrium, and only when operating within a specifically defined parameter space. We propose that the development of biomimetic bistable systems will pave the way towards the study of more elaborate functions, such as information transfer and signalling.

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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.

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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. By solving for their steady-state solutions by using various analytical and numerical methods, we analyze how and when these systems yield bistability and bifurcation and discover specific cases and conditions producing bistability. We demonstrate that the onset of bistability requires at least second-order catalysis and results from a mismatch between the various forward and reverse processes. Our findings may have far-reaching implications in understanding early evolutionary processes of complexification, emergence, and potentially the origin of life.

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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. The activated diester building block self-assembles to produce nanofibrillar thixotropic hydrogel. The subsequent hydrolysis results in the dissipation of energy to form nonassembling bolaamphiphile 1 with collapsed nanofibers. The thixotropic DCL hydrogel matrix is used for 3D cell culture experiments for different periods of time, significantly supporting the cell survival and proliferation of human umbilical cord mesenchymal stem cells.

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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)2 phase. Inorganic Zn(OH)2 layers turn into semiconductor ZnO layers upon annealing at 150 °C and lamellar nanostructures are formed in a periodic manner. Synergistic effects of hydrogen bonding and π-π stacking interactions of aromatic peptide amphiphiles are the driving force for the formation of self-assembled lamellar nanostructures. Morphological, structural, and optical studies of such lamellar hybrid nanostructures are reported. Photoconduction of these hybrid nanostructures is also examined in detail.

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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.

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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.

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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. FTIR and circular dichroism (CD) experiments revealed a hydrogen-bonded ß-sheet conformation of peptide bolaamphiphile molecules in a gel-phase medium. The π-π stacking interactions also played a crucial role in the self-assembly process, which was confirmed by fluorescence spectroscopy. Electron (SEM and TEM) and atomic force microscopy (AFM) studies showed that the peptide bolaamphiphile molecules self-assemble into nanofibrillar structures. Pd nanoparticles were synthesized in the hydrogel matrix in which redox-active tryptophan and tyrosine residues reduce the metal ions to metal nanoparticles. The size of the Pd nanoparticles are in the range of 3-9 nm, and are stabilized by peptide nanofibers. The peptide-nanofiber-supported Pd nanoparticles have shown effective catalytic activity for the removal of N-terminus protecting groups of amino acids and peptides.

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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 ß-sheet structures. Spectroscopic studies confirmed the different molecular arrangements of the two different nanostructures. Furthermore, the smart bolaamphiphile shows a dose-dependent cytotoxicity and cell-proliferation behaviour.

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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.

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