Spatially Localized Entropy-Driven Evolution of Nucleic Acid-Based Constitutional Dynamic Networks for Intracellular Imaging and Spatiotemporal Programmable Gene Therapy

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(30), P. 20685 - 20699

Published: July 16, 2024

The primer-guided entropy-driven high-throughput evolution of the DNA-based constitutional dynamic network, CDN, is introduced. entropy gain associated with process provides a catalytic principle for amplified emergence CDN. concept applied to develop programmable, spatially localized DNA circuit effective in vitro and vivo theranostic, gene-regulated treatment cancer cells. consists tetrahedron core modified at its corners four tethers that include encoded base sequences exhibiting capacity emerge assemble into [2 × 2] Two are caged by pair siRNA subunits, blocking mute, dynamically inactive configuration. In presence miRNA-21 as primer, subunits displaced, resulting release siRNAs silencing HIF-1α mRNA fast reconfiguration CDN is, however, engineered be reconfigured miRNA-155 an equilibrated mixture enriched DNAzyme component, catalyzing cleavage EGR-1 mRNA. nanostructure stimulates enhanced permeation miRNA-triggered leads cooperative bis-gene-silencing mRNAs, selective apoptosis breast cells inhibition tumors tumor bearing mice.

Language: Английский

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DNA-empowered synthetic cells as minimalistic life forms

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(6), P. 454 - 470

Published: May 15, 2024

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(14)

Published: Jan. 16, 2024

Abstract 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 environment. Currently, creating minimalistic synthetic cells is long‐term objective systems chemistry, which motivated by natural integrity. The design, kinetic optimization, analysis to exhibit functions akin those cell still pose significant challenges. Indeed, reaching homeostasis essential engineering components. However, maintaining in artificial against agitations difficult task. Several events can provide us with guidelines conceptual understanding homeostasis, be further applicable designing systems. In this regard, we organize our review driven at different length scales, including homogeneous, compartmentalized, soft material First, stretch quick overview molecular supramolecular systems, toolbox nonlinear homeostatic Moreover, existing history their advanced self‐correcting, regulating properties also emphasized.

Language: Английский

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Color‐Tunable White Circularly Polarized Electroluminescence Triggered Using Chiral Co‐Assembly‐Sensitized Strategy

Laser & Photonics Review, Journal Year: 2024, Volume and Issue: 18(11)

Published: June 26, 2024

Abstract White circularly polarized organic light‐emitting diodes (CP‐WOLEDs) are central to prospective 3D displays and lighting sources. However, owing the unwanted charge trapping effect inefficient chirality transfer, development of CP‐WOLEDs with a high color rendering index (CRI) large dissymmetry factor ( g EL ) is challenging. Herein, pioneering strategy chiral co‐assembly‐sensitized luminescence (CCS‐CPL) proposed for improving performance white electroluminescence (CP‐EL). Chiral co‐assembled sensitizers (( S ‐/ R ‐Cz) 0.2 ‐( I ‐P) 0.8 smartly developed using π – stacking interactions between binaphthyl derivatives achiral conjugated pyrene‐based polymer in molar ratio 1:4. Using on aggregation‐induced emission (AIE) dyes emitting layers (EMLs) OLEDs, full‐color AIE‐active can be sensitized by co‐assembly . The color‐tunable CP‐EL achieved at CIE coordinates (0.33, 0.33) an ultrahigh CRI 93 value up 0.071. This study thus provides valuable guidance CCS‐type CP‐WOLEDs.

Language: Английский

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Covalent Dynamic DNA Networks to Translate Multiple Inputs into Programmable Outputs

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 5, 2025

Inspired by naturally occurring protein dimerization networks, in which a set of proteins interact with each other to achieve highly complex input-output behaviors, we demonstrate here fully synthetic DNA-based network that enables programmable computations. Our consists DNA oligonucleotide monomers modified reactive moieties can covalently bond form dimer outputs an all-to-all or many-to-many fashion. By designing input strands specifically sequester monomers, control the size reaction and thus fine-tune yield output predictable manner. Thanks programmability specificity DNA–DNA interactions, show this approach be used different using inputs. The is also versatile networks based on two distinct covalent reactions: thiol–disulfide strain-promoted azide–alkyne cycloaddition (SPAAC) reactions. Finally, functional output, ultimately controlling assembly disassembly nanostructures. dynamic shown provide way convert multiple inputs into broader range functions, including ones mimic those living cells.

Language: Английский

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Exchanging and Releasing Information in Synthetic Digital Polymers Using a Strand-Displacement Strategy

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6456 - 6460

Published: Jan. 29, 2024

Toehold-mediated strand displacement (TMSD) was tested as a tool to edit information in synthetic digital polymers. Uniform DNA-polymer biohybrid macromolecules were first synthesized by automated phosphoramidite chemistry and characterized HPLC, mass spectrometry, polyacrylamide gel electrophoresis (PAGE). These precursors diblock structures containing poly(phosphodiester) (PPDE) segment covalently attached single-stranded DNA sequence. Three types of biohybrids prepared herein: substrate an accessible toehold well input output macromolecules. The the contained noncoded PPDE homopolymers, whereas macromolecule digitally encoded segment. After hybridization with output, incubation presence led efficient TMSD release can therefore be used erase or rewrite self-assembled superstructures. Furthermore, it found this work that conjugation single strands segments chosen lengths greatly facilitates characterization PAGE visualization process.

Language: Английский

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Reactive Brownian Dynamics of Chemically Fueled Droplets: Roles of Attraction and Deactivation Modes

The Journal of Physical Chemistry B, Journal Year: 2025, Volume and Issue: 129(2), P. 626 - 636

Published: Jan. 6, 2025

The self-assembly of biological membraneless organelles can be mimicked by active droplets resulting from chemically fueled microphase separation. However, how the nonequilibrium, transient structure these controlled through physicochemical input parameters is not yet well understood. In our work, a two-state chemical reaction and subsequent droplet growth decay are modeled with reactive Brownian dynamics simulation in two spatial dimensions. model, particles that activated via consumption fuel become attractive accumulate into droplets. A local-density-dependent distinction droplet's 'internal' 'external' allows for structural feedback giving further control over deactivation process. shows only external slows down stabilizes droplets, whereas internal lead to temporary encapsulation deactivated (in nonequilibrium 'core–shell' structures) where serve as an outer shell. Additionally, role hydrophobicity resembled attraction energy ε dependency formation on various investigated. For example, high finite-size crystalline while other parameter choices indicate bimodal size distributions at specific times. Similarities differences related experiments discussed.

Language: Английский

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Transient colloidal crystals fueled by electrochemical reaction products

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Feb. 28, 2025

Conventional electric field directed colloidal assembly enables fabricating ordered structures but lacks temporal control over state. Chemical reaction networks have been discovered that transiently assemble colloids; however, they slow dynamics (hrs – days) and poor tunability, utilize complex reagents, produce kinetically trapped states. Here we demonstrate transient crystals autonomously form, breakup, reconstitute in response to an electrochemical network driven by a time invariant electrical stimulus. Aqueous mixtures of micron sized colloids para-benzoquinone (BQ) were subjected superimposed oscillatory steady potentials, i.e., multimode induce electrokinetic flows around proton-coupled BQ redox reactions. Transient states coincided with electrochemically generated pH spikes near the cathode. We wide tunability state lifetimes two orders magnitude modifying potential electrode separation. An transport model showed interaction advancing acidic alkaline fronts from anodic oxidation cathodic reduction caused transients. present theoretical experimental evidence indicates mediated competition between opposing scale electrohydrodynamic electroosmotic flows, latter which is dependent. methods for struggle This study demonstrates disassemble, reassemble network, achieving using potentials.

Language: Английский

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Bioinspired Nucleic Acid-Based Bandpass Filters and Their Concentration-Adaptive Functions

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 3, 2025

Natural signaling networks can act as bandpass filters to interpret external stimuli within defined concentration ranges for differential cellular activities. Replicating such a filtering mechanism by synthetic poses significant challenge. Herein, we introduce modular design of nucleic acid-based multilayer threshold-gated incoherent feedforward multiband produce mutually exclusive responses input ranges. In these networks, acids demonstrate triple functionality acting entities discern levels, serving network nodes assemble loops nonlinear signal processing, and functioning transduction units coupling downstream functional modules. These enable the fine-tuning performance in terms band position, bandwidth, cascades, responses. A mathematical simulation model allows us predict behaviors under various conditions. Also, are integrated with upstream conversion modules process information on molecules beyond acids, adenosine its derivatives. Furthermore, connections allow system regulate processes manner, realizing concentration-adaptive DNAzyme biocatalysis, tristate logic operations, RNA transcription, DNA condensate formation. findings underscore potential enzyme-free reaction complex processing lay solid foundation developing chemical material systems highly adaptive autonomous behaviors.

Language: Английский

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Developmental assembly of multi-component polymer systems through interconnected synthetic gene networks in vitro

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Oct. 3, 2024

Language: Английский

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