Supramolecular Assemblies Research Articles

Exploring Through-Space Charge Transfer-Mediated Optoelectrochemical Properties of Dual-State Luminescent Aliphatic Polymers and Optoelectronic Responses toward Metal Ions.

Herein, natural-synthetic hybrid dual-state luminescent conducting polymers (DLCPs/DLCP1-DLCP8) possessing significant optoelectrochemical properties are strategically developed by the polymerization of prop-2-enamide, cis-butenedioic acid, 2-acrylamido-2-methylpropane-1-sulfonic acid, and in situ-generated 2-(3-acrylamidopropanamido)-2-methylpropane-1-sulfonic acid alongside the grafting of gum tragacanth. The spectroscopic data of aliphatic DLCPs affirm DLCP7 as the most stable supramolecular assembly endowing optoelectronic properties. Computational calculations identified -C(═O)NH-, -C(═O)OH, -OH, and -SO3H as subluminophores. The absorption spectra, excitation wavelength-/solvent-polarity-/concentration-dependent luminescence, solid state luminescence, aggregation-induced enhanced luminescence, and time-correlated single photon count (TCSPC) studies confirm the occurrence of aggregation-mediated intramolecular through-space charge transfer (ITSCT) in the excited state of DLCP7. Mulliken charge, natural bond orbital, dipole moments, and electronic potential surface analyses confirm the charge donor-acceptor system in DLCP7. Furthermore, the selective optoelectronic response of DLCP7 toward Ca2+/Cu(II) at 438/574 nm is explored using ultraviolet-visible spectra, TCSPC analyses, a dynamic light scattering study, and computational investigations. The chelation-enhanced luminescence and ITSCT inhibition are responsible for turn-on and turn-off detections of Ca2+ and Cu(II), respectively. Cu(II) → Cu(I) reduction in a DLCP7 solution is inferred from electrochemical and spectroscopic analyses. The conductivities of 9.65 × 10-5 S cm-1 (solid state) and 44.35 × 10-5 S cm-1 (solution) in DLCP7 are validated by current-voltage and electrochemical impedance measurements. Again, strong electronic conductivities of 43.89 × 10-5 S cm-1 (solid state)/53.34 × 10-5 S cm-1 (solution) and 45.42 × 10-5 S cm-1 (solid state)/64.81 × 10-5 S cm-1 (solution) are observed in Ca2+-DLCP7 and Cu(II)-DLCP7, respectively.

Charge Transfer Plasmons Enabled by Supramolecular Plug: From Optoelectronic Switching to Enhanced Chiral Sensing.

Miniaturization and integration of plasmonic nanodevices are fundamentally limited by quantum tunneling, which leads to quantum plasmonics with reduced local E-field intensity. Despite significant efforts devoted to modeling and deterring the detrimental effect of quantum plasmonics, the modulation and application of electron transport through the subnanometer gaps seems rarely exploited due to the limited tunability of conventional quantum materials. Here, we establish a supramolecular plasmonic system made of pillar[5]arene complexes and plasmonic resonators (nanoparticle-on-mirror, NPoM). The supramolecular assemblies significantly enhance the gap conductance of NPoM, which results in a blue-shift of the coupled plasmons. Plasmonic hot-electron transport with laser excitation further modulates the gap plasmons, which are fully reversible and beneficial for enhanced chiroptic sensing. Such a conductive supramolecular plasmonic system not only suggests an optoelectronic switching strategy for charge transfer plasmons but also provides a superior sensing platform for single molecules.

Recombinant Fibrous Protein Gels as Rheological Modifiers in Skin Ointments.

Rheological modifiers are an important component in the development of skin cream (SC) chassis for personal skin care products (PSCPs). The viscous behavior of a PSCP is critical to its effectiveness where its uniformity and material strength impact its processing, storage, and delivery of active ingredients. Due to the mildly acidic environment of the skin, PSCPs require a SC that will assist in maintaining their material strength at low pHs. We have investigated a coiled-coil protein hydrogel system for the ability to possess pH-responsiveness, where physical cross-linking and material strength is controlled by pH relative to the isoelectric point (pI) of the protein. We recently designed a coiled-coil protein hydrogel variant, Q5, which possesses a relatively low pI that we hypothesized to have improved supramolecular assembly into a hydrogel at acidic conditions. We demonstrate that Q5 can retain a partial solution-to-gel transition at pH 6.0 and acts as a soft hydrogel by rheology. We further tested Q5 to act as a rheological modifier in a standard SC at pH 6.0 and pH 8.0 to test conditions mediated by pH changes in the skin environment. Q5 reveals the ability to uniquely increase material strength at low pH in comparison to a standard rheological modifier like hydroxyethyl cellulose (HEC), suggesting modular protein-based coiled-coil rheological modifiers can be used in PSCPs.

Supramolecular cyclodextrin complexes of biologically active nitrogen heterocycles

The review is devoted to the rapidly developing field of modern supramolecular chemistry - cyclodextrin complexes of biologically active nitrogen heterocycles, such as piperidines, piperazines, morpholines and pyridines. Interest in cyclodextrin complexes is growing due to the search and construction of supramolecular assemblies for targeted drug delivery. The latter is achieved as a result of supramolecular self-assembly, based on the principles of molecular recognition, and is one of the areas of modern chemistry, leading to the creation of new materials with new properties. This review fully demonstrates the ongoing scientific and practical interest in the problem of encapsulation with cyclodextrins, including nanoencapsulation. Encapsulation with cyclodextrins provides a wide range of advantages: obtaining solid dosage forms from liquid ones, stabilizing and protecting active substances from the adverse effects of external factors, increasing solubility, increasing bioavailability, reducing toxicity, prolonging action, etc. The presented review includes recent advances in the field of supramolecular complexes of biologically active nitrogen heterocycles with cyclodextrins and concludes with a discussion and identification of future promising directions for research. The review presents the results of supramolecular self-assembly of biologically active azaheterocycles with cyclodextrins.

One‐Step Synthesis of Melem‐Based Supramolecular Assemblies and Their Photocatalytic Properties

In this work, melem‐based supramolecular assemblies were obtained in one step by thermal treatment of melamine in an autoclave in the presence of sodium chloride. The detailed analysis showed that the obtained powder consists of two phases: poorly crystalline Na‐PHI flakes and rod‐shaped melem hydrate single crystals (several micrometers long and ~300‐500 nm wide). Melem hydrate crystals absorb light in the visible range (Eg = 2.7 eV) and demonstrate photocatalytic activity in the reaction of partial oxidation of benzyl alcohol to benzaldehyde by air under visible light with high selectivity for the target product. At 60% conversion of benzyl alcohol, the selectivity of benzaldehyde formation is above 95%.

Planar Chiral Charge‐Transfer Cyclophanes: Convenient Synthesis, Circularly Polarized Light‐Responsive Photothermal Conversion and Supramolecular Chiral Assembly

We report herein a series of macrocycles in which the densely π‐stacked charge‐transfer (CT) donor/acceptor with naphthalenediimides (NDIs) or perylene diimide (PDI) as acceptor moiety pairing various donor moieties are locked by covalent bond. The X‐ray crystallography of C8BDT‐NDI reveals a short intramolecular π‐stacking distance around 3.4 Å and the existence of intermolecular donor/acceptor π‐stacking (3.7 Å). The intramolecular CT is highly dependent on the electron‐donating ability of donor moiety and replacing carbazole (C8KZ) with benzo[1,2‐b:4,5‐b']dithiophene (C8BDT) or dihydroindolo[3,2‐b]indole (C8DN) redshift CT absorption into NIR region. Notably, both C8BDT‐NDI and C8DN‐NDI demonstrate excellent photothermal performance, which is a result of the active non‐radiative pathways. Interestingly, the different molecular symmetry between donor and acceptor moiety endows C8BDT‐NDI and C8DN‐NDI with intrinsic planar chirality. The enantiomeric C8BDT‐NDI shows chiral selectivity for incident light, i.e., when irradiated by left‐circularly polarized light, (R)‐C8BDT‐NDI is more sensitive and a higher maximum stable temperature is achieved. While, enantiomeric C8DN‐NDI pack with different orientations forming M‐ and P‐handedness helix, respectively, demonstrating molecular planar chirality being transferred and amplified through molecular assembly. These results provide insight into the intramolecular charge transfer in enforced D/A π‐stacks in which CT interactions and planar chirality would be engineered through structural control.

Chiral Hydrogel Nerve Conduit Boosts Peripheral Nerve Regeneration via Regulation of Schwann Cell Reprogramming.

The Schwann cell (SC) is essential in peripheral nerve regeneration by reprogramming into a stem-like "repair Schwann cell" (rSC) phenotype; however, maintaining the rSC stemness remains an unmet challenge. Chirality is a fundamental factor controlling cell fate, and its potential role in regulation of SC reprogramming has long been ignored and remains poorly understood. Herein, inspired by natural chiral components in the SC microenvironment, chiral hydrogel nerve conduits are prepared by supramolecular assembly of l/d-phenylalanine derivatives (l/d-Phe) in polymeric chitosan-gelatin conduits. Right-handed l-Phe fibers within hydrogel conduits maintain the stemness of rSC through enhanced stereoselective interaction between collagen IV and l-Phe fibers triggered by collagen IV-Integrin α1β1, MAPK, and YAP/TAZ signaling pathways and finally activate the key regulator of SC reprogramming, the c-Jun pathway. In the rat model of a sciatic nerve defect, the l-Phe hydrogel nerve conduit significantly enhances nerve regeneration, exhibiting markedly improved histological, electrophysiological, and functional outcomes. The findings reveal the chirality-dependent regulation of SC reprogramming in a pioneering way, offering potential strategies for nerve regeneration therapies.

Chiral Self-Assembly of Twisted Prisms, Cuboids, and Polyhedral Capped Cages with Tartrate Ligands.

Homochiral triangular prisms, cuboid cages, and capped polyhedral cages are successfully synthesized via coordination-driven self-assembly. Typical tartrate ligands demonstrated notable torsional flexibility and variable coordination numbers, allowing for diverse coordination patterns, including saturated chelation and terminal mono-coordination with half-sandwich rhodium and iridium fragments. The ligand lengths, molar ratios, and metal vertices are meticulously designed and fine-tuned to yield chiral cages with entirely distinct architectures. Tartrate ligand exhibits abundant hydrogen bonding interactions and chiral induction capabilities, these supramolecular assemblies are characterized by single-crystal X-ray diffraction, nuclear magnetic resonance, and circular dichroism spectroscopy. An efficient method is developed for constructing chiral structurally versatile cage-like entities, facilitating self-assembly in complicated multi-component systems.

Amino Acid-Derived Supramolecular Assembly and Soft Materials.

Amino acids (AAs), serving as the primary monomer of peptides and proteins, are widely present in nature. Benefiting from their inherent advantages, such as chemical diversity, low cost, ease of modification, chirality, biosafety, and bio-absorbability, AAs have been extensively exploited to create self-assembled nanostructures and supramolecular soft materials. In this review article, we systematically describe the recent progress regarding amino acid-derived assembly and functional soft materials. A brief background and several classified assemblies of AAs and their derivatives (chemically modified AAs) are summarized. The key non-covalent interactions to drive the assembly of AAs are emphasized based on the reported systems of self-assembled and co-assembled AAs. We discuss the molecular design of AAs and the general rules behind the hierarchical nanostructures. The resulting soft materials with interesting properties and potential applications are demonstrated. The conclusion and remarks on AA-based supramolecular assemblies are also presented from the viewpoint of chemistry, materials, and bio-applications.

Structural insights into supramolecular interactions in isostructural salts of 2,4,6-triaminopyrimidinium with various heterocyclic carboxylates.

2,4,6-Triaminopyrimidine is an interesting and challenging molecule due to the presence of multiple hydrogen-bond donors and acceptors. Its noncovalent interactions with a variety of carboxylic acids provide several supramolecular aggregates with frequently occurring molecular synthons. The present work focuses on the supramolecular interactions of 2,4,6-triaminopyrimidinium 3-(indol-3-yl)propionate-3-(indol-3-yl)propionic acid (1/1), C4H8N5+·C11H10NO2-·C11H11NO2, (I), 2,4,6-triaminopyrimidinium 2-(indol-3-yl)acetate, C4H8N5+·C10H8NO2-, (II), 2,4,6-triaminopyrimidinium 5-bromothiophene-2-carboxylate, C4H8N5+·C5H2BrO2S-, (III), and 2,4,6-triaminopyrimidinium 5-chlorothiophene-2-carboxylate, C4H8N5+·C5H2ClO2S-, (IV). All four salts exhibit robust homomeric and heteromeric R22(8) ring motifs. Salts (I) and (II) develop sextuple [in (I)] and quadruple [in (I) and (II)] hydrogen-bonded arrays through fused-ring motifs. Salt (II) exhibits a rosette-like architecture. Salt (IV) is isostructural and isomorphous with salt (III), exhibiting an identical crystal structure with a different composition and an identical supramolecular architecture. In salts (III) and (IV), a linear hetero-tetrameric motif is formed and, in addition, both salts exhibit halogen-π interactions which enhance the crystal stability. All four salts develop a supramolecular hydrogen-bonded pattern facilitated by several N-H...O and N-H...N hydrogen bonds with multiple furcated donors and acceptors.

Oligo-Adenine Derived Secondary Nucleic Acid Frameworks: From Structural Characteristics to Applications.

Oligo-adenine (polyA) is primarily known for its critical role in mRNA stability, translational status, and gene regulation. Beyond its biological functions, extensive research has unveiled the diverse applications of polyA. In response to environmental stimuli, single polyA strands undergo distinctive structural transitions into diverse secondary configurations, which are reversible upon the introduction of appropriate counter-triggers. In this review, we systematically summarize recent advances of noncanonical structures derived from polyA, including A-motif duplex, A-cyanuric acid triplex, A-coralyne-A duplex, and T ⋅ A-T triplex. The structural characteristics and mechanisms underlying these conformations under specific external stimuli are addressed, followed by examples of their applications in stimuli-responsive DNA hydrogels, supramolecular fibre assembly, molecular electronics and switches, biosensing and bioengineering, payloads encapsulation and release, and others. A detailed comparison of these polyA-derived noncanonical structures is provided, highlighting their distinctive features. Furthermore, by integrating their stimuli-responsiveness and conformational characteristics, advanced material development, such as pH-cascaded DNA hydrogels and supramolecular fibres exhibiting dynamic structural transitions adapting environmental cues, are introduced. An outlook for future developments is also discussed. These polyA derived, stimuli-responsive, noncanonical structures enrich the arsenal of DNA "toolbox", offering dynamic DNA frameworks for diverse future applications.

Constructing Molecular Networks on Metal Surfaces through Tellurium-Based Chalcogen-Organic Interaction.

On-surface molecular self-assembly presents an important approach to the development of low-dimensional functional nanostructures and nanomaterials. Traditional strategies primarily exploit hydrogen bonding or metal coordination, yet the potential of chalcogen bonding (ChB) for on-surface self-assemblies remains underexplored. Here, we explore fabricating molecular networks via tellurium (Te)-directed chalcogen-organic interactions. Employing carbonitrile molecules as molecular building blocks, we have achieved extended 2D networks exhibiting a 4-fold binding motif on Au(111), marking a notable difference from the conventional coordinative interaction involving transition metals. Our findings, supported by density functional theory (DFT) and scanning tunneling spectroscopy (STS), show that the Te-carbonitrile interaction exhibits lower stability compared to the metal-organic coordination, and the construction of the Te-directed molecular networks does not alter the electronic properties of the involved molecules. Introducing chalcogen-directed interactions may expand the spectrum of strategies in supramolecular assembly, contributing to the design of advanced molecular architectures for nanotechnological applications.

Structural investigation, DNA/Mpox/COVID-19 molecular docking, and biological assays of two novel Co(II) and Cu(II) complexes derived from tri- and bi-dentate pyridyl-functionalized phosphoramide ligand [Ph]P(O)[NH-2Py]2

Phosphoramides have recently gained significant attention in medical and pharmaceutical research due to their diverse biological applications, including anticancer and antiviral drugs. Here, novel phosphoramide complexes [Co(II){(O)P[NH-2Py]2[Ph]}2][CoCl4] (1) and [Cu(II){(O)P[O][NH-2Py][Ph]}2{OH2}].2H2O (2) derived from [Ph]P(O)[NH-2Py]2 were synthesized and characterized by FT-IR, CHN elemental analysis and single crystal X-ray diffraction. In these discrete chelate complexes the phosphoramide [Ph]P(O)[NH-2Py]2 moiety acts as a flexible tridentate O,N,N-donor ligand for 1 or bidentate N,O-donor ligand for 2. The metal cation has a hexa-coordinate M(N)4(O)2 environment adopting a distorted octahedral geometry for 1 and a penta-coordinate M(N)2(O)3 environment with a distorted square pyramidal geometry for 2. The supramolecular assemblies have 1D linear arrangements along the [201] axis formed via NH…Cl hydrogen bond interactions for 1 and 2D arrangements parallel to the ab plane formed via classical NH…O and OH…O hydrogen bonds for 2. The in vitro anticancer activity of 1 and 2 was assessed against MDA-MB-231 breast cancer cell line showing a good inhibitory effect for both compounds, especially for the Cu(II) complex 2 with a IC50 of 29 ± 2.1 nmolar. Antioxidant and anti-hemolytic potential of 1 and 2 was experimentally evaluated using the DPPH technique showing suitable performance for both compounds. The binding capacity of 1 and 2 to DNA was investigated using molecular docking simulations showing a good correlation with the experimental in vitro results. The results reveal mixed modes of interactions between the compounds with the DNA receptor confirming a suitable DNA-binding ability for both 1 and 2. In silico molecular docking technique was also employed to provide a detailed prediction of the binding affinity of the studied compounds for SARS-CoV-2 (−6.5 kcal/mol) and Monkeypox (−8.4 kcal/mol)) which competes with current effective drugs.

Boosting chondrocyte bioactivity with ultra-sulfated glycopeptide supramolecular polymers

Although autologous chondrocyte transplantation can be effective in articular cartilage repair, negative side effects limit the utility of the treatment, such as long recovery times, poor engraftment or chondrogenic dedifferentiation, and cell leakage. Peptide-based supramolecular polymers have emerged as promising bioactive systems to promote tissue regeneration through cell signaling and dynamic behavior. We report here on the development of a series of glycopeptide amphiphile supramolecular nanofibers with chondrogenic bioactivity. These supramolecular polymers were found to have the ability to boost TGFβ-1 signaling by displaying galactosamine moieties with differing degrees of sulfation on their surfaces. We were also able to encapsulate chondrocytes with these nanostructures as single cells without affecting viability and proliferation. Among the monomers tested, assemblies of trisulfated glycopeptides led to elevated expression of chondrogenic markers relative to those with lower degrees of sulfation that mimic chondroitin sulfate repeating units. We hypothesize the enhanced bioactivity is rooted in specific interactions of the supramolecular assemblies with TGFβ-1 and its consequence on cell signaling, which may involve elevated levels of supramolecular motion as a result of high charge in trisulfated glycopeptide amphiphiles. Our findings suggest that supramolecular polymers formed by the ultra-sulfated glycopeptide amphiphiles could provide better outcomes in chondrocyte transplantation therapies for cartilage regeneration. Statement of significanceThis study prepares glycopeptide amphiphiles conjugated at their termini with chondroitin sulfate mimetic residues with varying degrees of sulfation that self-assemble into supramolecular nanofibers in aqueous solution. These supramolecular polymers encapsulate chondrocytes as single cells through intimate contact with cell surface structures, forming artificial matrix that can localize the growth factor TGFβ-1 in the intercellular environment. A high degree of sulfation on the glycopeptide amphiphile is found to be critical in elevating chondrogenic cellular responses that supersede the efficacy of natural chondroitin sulfate. This work demonstrates that supramolecular assembly of a unique molecular structure designed to mimic chondroitin sulfate successfully boosts chondrocyte bioactivity by single cell encapsulation, suggesting a new avenue implementing chondrocyte transplantation with supramolecular nanomaterials for cartilage regeneration.

Smart β-cyclodextrin-dominated helical supramolecular dendritic assemblies improve the foliar affinity and biofilm disruption for treating alarming bacterial diseases

Recent outbreaks of alarming bacterial diseases have significantly impacted global agricultural productivity. Conventional bactericides exhibit certain limitations in efficiently impeding biofilm formation and annihilating biofilm-dispersed pathogens, and often expose to high off-target movement during foliar spraying. Here, we produce an innovative helical dendrimer-like supramolecular material (PhA28@β-CD) assembled by a bioactive small-molecule 2-chlorophenylisopropanolamine (PhA28) and β-cyclodextrin (β-CD) through host-guest recognition principle. In this system, the advisable optimization by a macrocyclic oligosaccharide—β-CD significantly enhances the water-solubility, biocompatibility, and bioavailability of PhA28. At a low-dose of 6.8 μg/mL, PhA28@β-CD discloses an outstanding biofilm disruption rate of 82.4 %, notably exceeding that of PhA28 (60.6 %), which thereby reduces the biofilm-associated virulence. Meanwhile, the self-assembled PhA28@β-CD possesses superior wetting and dispersing properties on hydrophobic leaves, leading to effective foliar deposition and prolong retention of active components. In vivo studies reveal that PhA28@β-CD exhibits superior curative (66.0 %) and protective (72.6 %) activities against citrus canker at 200 μg/mL, markedly surpassing those of the existing bactericide thiodiazole‑copper (46.8 % and 52.2 %) and single PhA28. This material also has broad-spectrum control efficiency (53.0 % ~ 59.5 %) against rice bacterial blight. This research lays the groundwork for developing carbohydrate-optimized multifunctional dendrimer-like assemblies aimed at disrupting biofilms and improving sustained bioavailability to combat bacterial diseases.

A Foldaxane-Based Supramolecular Muscle-Like Switch.

[cn]daisy chain molecular muscle architectures are self-assemblies of hermaphrodite monomers, which usually contain a macrocycle unit linked to a molecular thread that contains sites of interactions - i. e. molecular stations - for the macrocycle. In these multiply threaded structures, altering with control the affinity between macrocycles and stations allows for contraction and extension of the molecule, which is reminiscent of the operation of a muscle. Besides, the field that consists of combining helix and template-containing rods to design foldaxane supramolecular assemblies is still underexplored. By using foldamer units as surrogates for macrocycles, Gan et al. reported the first supramolecular muscle-like foldamer-containing switch that can adopt, after chemical stimulus, either a contracted co-conformational state or a degenerate-like state for which a slow exchange occurred between the contracted and the stretched state.

Synergistic effect of hydrogen bonding and C–H…π interactions to modulate the supramolecular assemblies of isobenzofuranones: X-ray crystallography, DFT analysis and antihyperglycemic potential

This manuscript reports the synthesis, X-ray characterization and antihyperglycemic potential of two isobenzofuranone derivatives. The Suzuki-Miyaura cross-coupling of 5-bromoisobenzofuran-1(3H)-one with phenylboronic acid and p-tolylboronic acid under the action of palladium catalysis afforded the desired compounds in good yields. The structures were fully established using FTIR and NMR spectroscopy and X-ray crystallography. The study further delves into the synergistic effects of hydrogen bonding and C–H…π interactions on the supramolecular assemblies of isobenzofuranones, leveraging a holistic approach that combines X-ray crystallography, Density Functional Theory (DFT) analysis, and evaluation of antihyperglycemic activity. Focusing on two isobenzofuranone derivatives, we meticulously elucidate their structural features and how noncovalent interactions shape their crystal packing. Our exploration extends to assessing the antihyperglycemic potential of these compounds, underpinned by α-glucosidase inhibitory assays and augmented by molecular docking analysis. Compound 3b showed the best potency with an IC50 value of 13 ± 0.01 µM which is 67-folds strong inhibition than acarbose (IC50 = 870.2 ± 1.54 µM). Furthermore, the admetSAR and ProTox-II demonstrated that compound 3b follows the druggable criteria with a safe toxicity profile. Overall, these findings highlight the pivotal role of noncovalent interactions in modulating the supramolecular architectures of isobenzofuranones, thereby offering insights into their therapeutic potential against diabetes mellitus.

Time-varying stimuli that prolong IKK activation promote nuclear remodeling and mechanistic switching of NF-κB dynamics.

Temporal properties of molecules within signaling networks, such as sub-cellular changes in protein abundance, encode information that mediate cellular responses to stimuli. How dynamic signals relay and process information is a critical gap in understanding cellular behaviors. In this work, we investigate transmission of information about changing extracellular cytokine concentrations from receptor-level supramolecular assemblies of IκB kinases (IKK) downstream to the nuclear factor κB (NF-κB) transcription factor (TF). In a custom robot-controlled microfluidic cell culture, we simultaneously measure input-output (I/O) encoding of IKK-NF-κB in dual fluorescent-reporter cells. When compared with single cytokine pulses, dose-conserving pulse trains prolong IKK assemblies and lead to disproportionately enhanced retention of nuclear NF-κB. Using particle swarm optimization, we demonstrate that a mechanistic model does not recapitulate this emergent property. By contrast, invoking mechanisms for NF-κB-dependent chromatin remodeling to the model recapitulates experiments, showing how temporal dosing that prolongs IKK assemblies facilitates switching to permissive chromatin that sequesters nuclear NF-κB. Remarkably, using simulations to resolve single-cell receptor data accurately predicts same-cell NF-κB time courses for more than 80% of our single cell trajectories. Our data and simulations therefore suggest that cell-to-cell heterogeneity in cytokine responses are predominantly due to mechanisms at the level receptor-associated protein complexes.

Preparation of cucurbit[5]uril - Ln3+ - based supramolecular assemblies and its effective detection of L-Tryptophan

Preparation of cucurbit[5]uril - Ln3+ - based supramolecular assemblies and its effective detection of L-Tryptophan

Supramolecular Architectures of Dendritic Polymers Provide Irreversible Inhibitor to Block Viral Infection.

In Nature, most known objects can perform their functions only when in supramolecular self-assembled from, e.g. protein complexes and cell membranes. Here, a dendritic polymer is presented that inhibits severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) with an irreversible (virucidal) mechanism only when self-assembled into a Two-dimmensional supramolecular polymer (2D-SupraPol). Monomeric analogs of the dendritic polymer can only inhibit SARS-CoV-2 reversibly, thus allowing for the virus to regain infectivity after dilution. Upon assembly, 2D-SupraPol shows a remarkable half-inhibitory concentration (IC50 30nM) in vitro and in vivo in a Syrian Hamster model has a good efficacy. Using cryo-TEM, it is shown that the 2D-SupraPol has a controllable lateral size that can be tuned by adjusting the pH and use small angle X-ray and neutron scattering to unveil the architecture of the supramolecular assembly. This functional 2D-SupraPol, and its supramolecular architecture are proposed, as a prophylaxis nasal spray to inhibit the virus interaction with the respiratory tract.