Amide-based organic cage cavities are, in principle, ideal enzyme active site mimics. Yet, cage-promoted organocatalysis has remained elusive, large part due to synthetic accessibility of robust and functional scaffolds. Herein, we report the acyl transfer catalysis properties robust, hexaamide cages solvent. Cage structural variation reveals that esterification with an anhydride carrier occurs only bifunctional featuring internal pyridine motifs two crucial antipodal carboxylic acid groups....

Organic(porous) and metal–organic cages are promising biomimetic platforms with diverse applications spanning recognition, sensing, catalysis. The key to the emergence of these functions is presence well-defined inner cavities capable binding a wide range guest molecules modulating their properties. However, despite myriad cage architectures currently available, rational design structurally functional specific host–guest properties remains challenging. Efficiently predicting such critical...

Organic(porous) and metal-organic cages are promising biomimetic platforms with diverse applications spanning recognition, sensing catalysis. The key to the emergence of these functions is presence well-defined inner cavities capable binding a wide range guest molecules modulating their properties. However, despite myriad cage architectures currently available, rational design structurally functional specific host–guest properties remain challenging. Efficiently predicting such critical for...

Cage catalysis continues to create significant interest, yet catalyst function remains poorly understood. Herein, we report mechanistic insights into coordination-cage-catalyzed Michael addition using kinetic and computational methods. The study has been enabled by the detection of identifiable intermediates, which allow evolution different cage species be monitored modeled alongside reactants products. investigations show that overall acceleration results from two distinct effects. First,...

Imide-based chlorinating reagents are mild and easy to use yet can lack the reactivity of charged chlorenium-ion donors. Here, we present a simple strategy for increasing these neutral species by encapsulation inside cationic coordination cage. Using this approach, demonstrate that two different-sized Pd2L4 cages catalyze chlorolactonization chlorocycloetherification reactions acid alcohol functionalized α β-substituted styrene substrates with either 1,3-dichloro-5,5-dimethylhydantoin...

Abstract Here, transient supramolecular hydrogels that are formed through simple aging‐induced seeded self‐assembly of molecular gelators reported. In the involved system, multicomponent from a mixture precursor molecules and, typically, can spontaneously self‐assemble into thermodynamically more stable multilevel self‐sorting process. present work, it is surprisingly found one capable self‐assembling nano‐sized aggregates upon gentle aging treatment. Importantly, these tiny serve as seeds...

Coarse-grained molecular dynamics simulations are employed to obtain a detailed view of the formation long-range ordered lamellar structures physisorbed self-assembling long functionalized alkanes on graphite. During self-assembly, two processes take place: Langmuir preferential adsorption and rearrangement surface. The starts with nucleation, in which molecules create an domain. nucleation mechanism is temperature dependent. At lower independent, small stable nuclei seed emergence domains....

We report on the biocatalytic activation of a self-assembling (unprotected) tripeptide to stabilize oil-in-water emulsions on-demand. This is achieved by conversion phosphorylated precursor into hydrogelator using alkaline phosphatase (AP) as trigger. The rate conversion, controlled amount enzyme used, shown play key role in dictating morphology nanofibrous networks produced. When these amphiphilic tripeptides are used biphasic mixtures, nanofibers self-assemble not only at aqueous/organic...

Metal ions play a central, functional, and structural role in many molecular structures, from small catalysts to metal-organic frameworks (MOFs) proteins. Computational studies of these systems typically employ classical or quantum mechanical approaches combination both. Among models, only the covalent metal model reproduces both geometries charge transfer effects but requires time-consuming parameterization, especially for supramolecular containing repetitive units. To streamline this...

Fluorescence correlation spectroscopy (FCS) is frequently used to study the processes of restricted diffusion. The most important quantity determine size structures that hinder Brownian motion molecules. We three qualitatively different models diffusion, widely applied in biophysics and material science: Diffusion constrained by elastic force (i), walking confined diffusion (ii), hop (iii). They cover diversity statistical behaviors, from purely Gaussian (i) sharply non-Gaussian on...

In recent years, computational methods have become an essential element of studies focusing on the self-assembly process. Although they provide unique insights, face challenges, from which two are most often mentioned in literature: temporal and spatial scale self-assembly. A less issue, but not important, is choice force-field. The repetitive nature supramolecular structure results many similar interactions. Consequently, even a small deviation these interactions can lead to significant...

Metal ions play a central functional and structural role in many molecular structures, from small catalysts to metal-organic frameworks (MOFs) proteins. Computational studies of these systems typically employ classical or quantum mechanical approaches combination both. Among models, only the covalent metal model reproduces both geometries charge transfer effects but requires time-consuming parametrization, especially for supramolecular containing repetitive units. To streamline this process,...

Reported here is a 2D, interfacial microcompartmentalization strategy governed by 3D phase separation. In aqueous polyethylene glycol (PEG) solutions doped with biotinylated polymers, the polymers spontaneously accumulate in layer between oil-surfactant-water interface and adjacent polymer phase. two-phase systems, these first accumulated separating two then selectively migrated to oil-PEG layer. By using varying photopolymerizable groups crosslinking rates, kinetic control capture of...

Ostwald ripening can improve the long-range order of self-assembled monolayers by growth large domains and disassembly smaller ones. Here, coarse-grained molecular dynamics simulations are used to study stable assembly coarsening defects physisorbed long-chain functionalized alkanes. Our results show that partial desorption from surface one or more adsorbent molecules is essential process allows other rearrange on thereby alignment. We also faster at higher temperature because rate higher.

TBC

In this thesis, we explore the application of various molecular simulations techniques to give insights into self-assembly supramolecular systems. Chapter 1 explains importance simulation study selfassembly process. chapter 2 a derivative 1,3,5-triamidocyclohexane (CTA) using common techniques: from randomly distributed molecules and final structure. The results show choice force-field limitations conventional dynamics processes which occur on long timescale. 3 tackle timescale issue by an...

Abstract Reported here is a 2D, interfacial microcompartmentalization strategy governed by 3D phase separation. In aqueous polyethylene glycol (PEG) solutions doped with biotinylated polymers, the polymers spontaneously accumulate in layer between oil‐surfactant‐water interface and adjacent polymer phase. two‐phase systems, these first accumulated separating two then selectively migrated to oil‐PEG layer. By using varying photopolymerizable groups crosslinking rates, kinetic control capture...