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The intricate interplay between self‐assembly and phase separation orchestrates biomolecular organization inside cells, thereby dictating the formation of vital structures such as protein assemblies and membraneless organelles (MLOs). However, in the context of supramolecular polymerization, these fundamental processes have traditionally been studied separately. This study reevaluates the supramolecular polymerization process to unveil the presence of phase‐separated droplet state. Utilizing the well‐studied benzene‐1,3,5‐tricarboxamide (BTA) supramolecular motif, we explore its thermally driven liquid‐liquid phase separation (LLPS). Thermodynamic and kinetic analysis, employing temperature‐dependent spectroscopic and microscopic techniques, elucidates the distinct BTA states and their evolution towards the thermodynamic fiber state. This research sheds light on the existence of hidden phases of supramolecular monomers, emphasizing the delicate balance of non‐covalent interactions among monomers and with solvents in governing self‐assembly vs. phase separation. This is particularly important in comprehending phase separation in the biological realm such as in MLOs, and for applications such as condensate‐modifying therapeutics. [ABSTRACT FROM AUTHOR]

Multicomponent supramolecular polymers offer versatile dynamic and functional properties; however, the influence of the monomer chemical structures on their structure-dynamics-function relationship remains unclear. In this study, we investigated the subtle variations in monomer interactions using one monomer and its two dopant derivatives, with functionalization away from the self-assembling core. We systematically investigated their multicomponent supramolecular polymers using a combination of spectroscopy and super-resolution microscopy. Our results highlight the significant impact of the supplementary intermolecular interactions, resulting from the functional motifs located away from the core and present in small quantities, on the microstructure and dynamics. Thus, a comprehensive approach, combining spectroscopy, microscopy, and well-designed experiments, is essential for assessing multicomponent supramolecular polymers. These findings have implications for the rational design of functional multicomponent supramolecular materials. [ABSTRACT FROM AUTHOR]

Polyaniline films are under extensive consideration for applications in sensors, memory devices, displays, biomedicals, etc., owing to their unique optical and electronic functional states that are switchable in response to external stimuli. The application arena of these materials could be enhanced by creating active, adaptive, and autonomous systems with preprogramable spatiotemporal control over the functional states. Here, we present a simple approach to achieve autonomous temporal regulation of polyaniline films' optical and electrical states by integrating enzyme-catalyzed biochemical reaction. The enzymatic reaction produces a feedback-induced transient pH profile, and correspondingly, the functional states of polyaniline films give rise to a similar switching profile, whose lifetime could be preprogrammed via enzyme concentration. This autonomous, temporally regulated polymer film system represents an advancement to the existing switchable materials that operate at equilibrium. [ABSTRACT FROM AUTHOR]

The clinical use of irinotecan (IRI), one of the most commonly used antitumor drugs for colon cancer, is limited by its numerous side effects, and it also lacks selectivity and specificity for tumor cells. When conjugated with fullerenes and biotin, this drug may serve as a drug of choice to reduce these side effects. Fullerenes are an allotropic form of carbon with a closed cage-like structure that can act as a drug carrier, and the presence of biotin makes it a promising targeting agent. In this work, we performed release as well as toxicity comparison studies between pure irinotecan and fullerene-biotin-conjugated irinotecan. The release studies were performed by HPLC (High Performance Liquid Chromatography), while the toxicity studies were performed on a model of colon tumors in gopher rats. All animals were divided into four groups, namely normal, control, test and standard groups. Biochemical parameters and histopathological studies were performed to compare the acute toxicity of irinotecan and the conjugate (C60-PEIbiotin/IRI). It was found that IRI alone was unable to reduce the toxicity caused by DMH (1,2-dimethylhydrazine), whereas its conjugate was able to significantly reduce the toxic effects, which was also evident in the histopathological studies. Therefore, the study suggests that the administration of conjugated IRI reduces toxicity and proves to be a potential candidate for a preventive chemo effect. [ABSTRACT FROM AUTHOR]

Adenosine triphosphate (ATP) is a molecular unit of energy that drives various processes in the cellular environment. In this Minireview, we discuss the potential of physical and chemical properties of ATP for the development of bio‐inspired, synthetic ATP‐induced supramolecular systems with dynamic, stimuli‐responsive and active assembly characteristics. Molecular design rules for ATP‐induced assemblies with various architectures and their stimuli‐responsive structural and functional response are categorized. Special attention is given to the immense potential of ATP‐fuelled designs in the nascent field of transient/non‐equilibrium supramolecular polymerization for the synthesis of lifelike temporally programmable soft materials. Finally, the existing dearth and fate of ATP‐driven systems for future challenges are discussed. [ABSTRACT FROM AUTHOR]

Adenosine triphosphate (ATP) is a molecular unit of energy that drives various processes in the cellular environment. In this Minireview, we discuss the potential of physical and chemical properties of ATP for the development of bio‐inspired, synthetic ATP‐induced supramolecular systems with dynamic, stimuli‐responsive and active assembly characteristics. Molecular design rules for ATP‐induced assemblies with various architectures and their stimuli‐responsive structural and functional response are categorized. Special attention is given to the immense potential of ATP‐fuelled designs in the nascent field of transient/non‐equilibrium supramolecular polymerization for the synthesis of lifelike temporally programmable soft materials. Finally, the existing dearth and fate of ATP‐driven systems for future challenges are discussed. [ABSTRACT FROM AUTHOR]

Transient supramolecular self‐assembly has evolved as a tool to create temporally programmable smart materials. Yet, so far single‐component self‐assembly has been mostly explored. In contrast, multicomponent self‐assembly provides an opportunity to create unique nanostructures exhibiting complex functional outcomes, newer and different than individual components. Even two‐component can result in multiple organizations, such as self‐sorted domains or co‐assembled heterostructures, can occur, thus making it highly complex to predict and reversibly modulate these microstructures. In this study, we attempted to create active bicomponent nanoparticle assemblies of orthogonally pH‐responsive‐group‐functionalized gold and cadmium selenide nanoparticles with temporal microstructural control on their composition (self‐sorted or co‐assembly) in order to harvest their emergent transient photocatalytic activity by coupling to temporal changes in pH. Moving towards multicomponent systems can deliver next level control in terms of structural and functional outcomes of supramolecular systems. [ABSTRACT FROM AUTHOR]

Dissipative systems, that constantly consume energy for sustenance, are ubiquitous and essential to life. In synthetic systems, the phenomenon promises emergent properties and different structure from the ones existing at thermodynamic equilibrium. It can create reconfigurable and temporally programmable life‐like smart materials. In this study, we attempt to create reconfigurable, temporally programmable self‐assembly using the redox chemistry of a core‐substituted naphthalene diimide derivative. As a result, transient reconfiguration of supramolecular assembly from vesicle to sheet along with transient fluorescence switching with fuel‐dependent lifetime is attained. We believe that such a design strategy can advance the synthesis of active, adaptive and autonomous materials. [ABSTRACT FROM AUTHOR]

Viologen based covalent organic polymer (COP) interfaced with graphene at the nanoscale showed pseudocapacitive energy storage associated with redox‐active moieties. The positively charged viologen moieties endow charge storage as well as easy wetting of the electrode. The non‐conducting COP grown over conducting graphene enhances its performance by extensive interface formation. All the redox states of viologen moieties can be reversibly attained without significant polarization when it is interfaced with graphene. However, the COP (devoid of graphene) shows irreversible/pseudo‐reversible behavior due to lack of electron conducting pathways. The intimate and dense conducting pathways in graphene‐COP composites facilitates the charge transfer across interface leading to effective and reversible participation of redox moieties across the entire range over 1000 cycles. Also, we show that the strategy being universal in nature and aid in electron transfer in dense 3D networks which lacks traditional π‐π stacking of 2D crystalline networks (COF). [ABSTRACT FROM AUTHOR]

Aim: Rhodiola imbricata is an endangered medicinal plant of the trans-Himalayan Leh-Ladakh region belonging to the family Crassulaceae. An efficient propagation and regeneration system via direct shoot organogenesis from leaf explant and evaluation of cinnamyl alcohol (Secondary metabolite) was established in this study. Material and Methods: In vitro grown leaves were inoculated using Murashige and Skoog (MS) medium supplemented with (alpha)- naphtalene acetic acid (NAA) in combination with 6- benzyladenine (BAP) for callus proliferation and regeneration. Results: The highest percentage of rhizogenous callus was induced in medium containing NAA (10.0-15.0 μM). The highest percentage of shoot formation from leaf derived callus was obtained in the medium containing of NAA (5.0 μM) and BAP (2.5 μM) as well as in NAA (1.0 μM), BAP (5.0 μM) (38.88% and 37.49%) respectively. Rooting of regenerated shoots were effective when a lower concentration of NAA (0.5 μM) was used alone. A maximum number of roots (22.0) and higher length (0.6 cm) was observed. The in-vitro plantlets with well-developed shoots and roots were acclimatized successfully to natural field conditions with a survival rate of over 80%. Cinnamyl alcohol (Secondary metabolite) evaluation was also done for the very first time and an upregulation of 49.6% and 30.6% were observed in in-vitro roots and shoots when compared with mother root and shoot respectively. Hence, it was proved that the content of secondary metabolites obtained from in-vitro raised plants is higher than mother plant. Conclusion : These results may lay a foundation for genetic improvement and can be used to determine sequential level of targeted secondary metabolites through cell culture in Rhodiola imbricata. [ABSTRACT FROM AUTHOR]

Chirality-driven self-sorting is envisaged to efficiently control functional properties in supramolecular materials. However, the challenge arises because of a lack of analytical methods to directly monitor the enantioselectivity of the resulting supramolecular assemblies. Presented herein are two fluorescent core-substituted naphthalene-diimide-based donor and acceptor molecules with minimal structural mismatch and they comprise strong self-recognizing chiral motifs to determine the self-sorting process. As a consequence, stereoselective supramolecular polymerization with an unprecedented chirality control over energy transfer has been achieved. This chirality-controlled energy transfer has been further exploited as an efficient probe to visualize microscopically the chirality driven self-sorting. [ABSTRACT FROM AUTHOR]

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Synthetic manifestations of supramolecular chirality have extensively drawn inspiration from naturally occurring systems. Even though in biological systems conformational changes are dissipative, synthetic systems that change conformation under non-equilibrium conditions have still not been established. Herein, we attempt to alleviate this scenario by reporting a synthetic supramolecular system that undergoes temporal changes in its helical conformation as an active system at the expense of a biologically relevant chemical fuel, ATP. Use of enzymes working in tandem provides transient and switchable helices with modular lifetime and stereomutation rates. [ABSTRACT FROM AUTHOR]

Synthetic manifestations of supramolecular chirality have extensively drawn inspiration from naturally occurring systems. Even though in biological systems conformational changes are dissipative, synthetic systems that change conformation under non-equilibrium conditions have still not been established. Herein, we attempt to alleviate this scenario by reporting a synthetic supramolecular system that undergoes temporal changes in its helical conformation as an active system at the expense of a biologically relevant chemical fuel, ATP. Use of enzymes working in tandem provides transient and switchable helices with modular lifetime and stereomutation rates. [ABSTRACT FROM AUTHOR]

Temporal control over self-assembly process is a desirable trait in the quest towards adaptable and controllable materials. The ability to devise synthetic ways to control the growth, as well as decay of materials has long been a property which only the biological systems could perform seamlessly. A common synthetic strategy which works on the biological principles such as chemical fuel-driven control over temporal self-assembly profile has not been completely realized synthetically. Here we show, we filled this dearth by showing that a chemical fuel driven self-assembling system can not only be grown in a controlled manner, but it can also result in precise control over the assembly and disassembly kinetics. Herein, we elaborate strategies which clearly show that once a chemical fuel driven self-assembly is established it can be made receptive to multiple molecular cues such that the inherent growth and decay characteristics are programmed into the ensemble. Temporal control over self-assembly processes is a desirable trait for discovering adaptable and controllable materials. Here the authors show that a chemical fuel driven system can not only self-assemble in a controlled manner, but can also result in precise control over the assembly and disassembly kinetics. [ABSTRACT FROM AUTHOR]