Supramolecular Matrix Research Articles

Supramolecular catalyst with [FeCl4] unit boosting photoelectrochemical seawater splitting via water nucleophilic attack pathway

Propelled by the structure of water oxidation co-catalysts in natural photosynthesis, molecular co-catalysts have long been believed to possess the developable potential in artificial photosynthesis. However, the interfacial complexity between light absorber and molecular co-catalyst limits its structural stability and charge transfer efficiency. To overcome the challenge, a supramolecular scaffold with the [FeCl4] catalytic units is reported, which undergo a water-nucleophilic attack of the water oxidation reaction, while the supramolecular matrix can be in-situ grown on the surface of photoelectrode through a simple chemical polymerization to be a strongly coupled interface. A well-defined BiVO4 photoanode hybridized with [FeCl4] units in polythiophene reaches 4.72 mA cm−2 at 1.23 VRHE, which also exhibits great stability for photoelectrochemical seawater splitting due to the restraint on chlorine evolution reaction by [FeCl4] units and polythiophene. This work provides a novel solution to the challenge of the interface charge transfer of molecular co-catalyst hybridized photoelectrode.

Cellulose nanofibril-guided orienting response of supramolecular network enables superstretchable, robust, and antifatigue hydrogel

<p>Hydrogels featuring randomly networked matrix typically show poor mechanical strength owing to the weak interchain interactions of the matrix. Encouragingly, the stretchability and toughness of hydrogel materials along a certain direction were recently improved to an unprecedented level with the design of structured and oriented matrix, the realization of excellent and concurrently isotropic mechanical performance for hydrogels now become the next- research goal. Herein, a self-assembling process of poly(vinyl alcohol) (PVA) macromolecular chain and cellulose nanofibril (CNF) induced by the salting-out effect was reported, which allowed the formation of a strongly hydrogen-bonded PVA-CNF supramolecular matrix. The resulting hydrogel, in any direction, can show an ultra-high stretchability of 7,400% and a true tensile strength of 420 MPa through the orientation of the supramolecular matrix. The robustness of the supramolecular interaction between PVA and CNF was experimentally demonstrated by the fact that the hydrogel showed a high fracture energy (reaching up to 95.7 kJ m<sup>−2</sup>) and low notch sensitivity (fatigue threshold of 3,203 J m<sup>−2</sup>), even outperforming most state-of-the-art anisotropic hydrogels. These results highlight that constructing supramolecular interaction among various components of gel matrix holds great promise for the design of future gel materials with the extraordinary mechanical performance.</p>

Multicomponent Peptide-Based Hydrogels Containing Chemical Functional Groups as Innovative Platforms for Biotechnological Applications.

Multicomponent hydrogels (HGs) based on ultrashort aromatic peptides have been exploited as biocompatible matrices for tissue engineering applications, the delivery of therapeutic and diagnostic agents, and the development of biosensors. Due to its capability to gel under physiological conditions of pH and ionic strength, the low molecular-weight Fmoc-FF (Nα-fluorenylmethoxycarbonyl-diphenylalanine) homodimer is one of the most studied hydrogelators. The introduction into the Fmoc-FF hydrogel of additional molecules like protein, organic compounds, or other peptide sequences often allows the generation of novel hydrogels with improved mechanical and functional properties. In this perspective, here we studied a library of novel multicomponent Fmoc-FF based hydrogels doped with different amounts of the tripeptide Fmoc-FFX (in which X= Cys, Ser, or Thr). The insertion of these tripeptides allows to obtain hydrogels functionalized with thiol or alcohol groups that can be used for their chemical post-derivatization with bioactive molecules of interest like diagnostic or biosensing agents. These novel multicomponent hydrogels share a similar peptide organization in their supramolecular matrix. The hydrogels' biocompatibility, and their propensity to support adhesion, proliferation, and even cell differentiation, assessed in vitro on fibroblast cell lines, allows us to conclude that the hybrid hydrogels are not toxic and can potentially act as a scaffold and support for cell culture growth.

The Supramolecular Matrix Concept

It has been established that dilutions of a variety of substances, when exposed to vibration in the process of their preparation, acquire not only new structural characteristics in the form of nano-associates but also new physical properties, regardless of the presence of the initial substance. One of the most important properties of these dilutions is the ability to modify the physico–chemical and biological activity of the initial substance as well as exert non-contact, “distant”, effects. Here, we propose a novel hypothesis that the basis of modifying activity is the transformation of target molecules to a more harmonious (symmetrical) state supported by a supramolecular matrix, a structural unit of a structured space.

A Cyclodextrin Polymer as Supramolecular Matrix for Scalable Green Photooxygenation of Hydrophobic Substrates in Homogeneous Phase.

In the quest for new therapies targeting hypoxia, aromatic endoperoxides have intriguing potential as oxygen releasing agents (ORAs) able to free O2 in tissues upon suitable trigger. Four aromatic substrates were synthesized and the formation of their corresponding endoperoxides was optimized in organic solvent upon selective irradiation of Methylene Blue, a low-cost photocatalyst, producing the reactive singlet oxygen species. Complexation of the hydrophobic substrates within a hydrophilic cyclodextrin (CyD) polymer allowed their photooxygenation in homogeneous aqueous environment using the same optimized protocol upon dissolution in water of the three readily accessible reagents. Notably, reaction rates were comparable in buffered D2 O and organic solvent and, for the first time, the photooxygenation of highly hydrophobic substrates was achieved for millimolar solutions in non-deuterated water. Quantitative conversion of the substrates, straightforward isolation of the endoperoxides and recovery of the polymeric matrix were achieved. Cycloreversion of one ORA to the original aromatic substrate was observed upon thermolysis. These results hold great potential for the launch of CyD polymers both as reaction vessels for green, homogeneous photocatalysis and as carrier for the delivery of ORAs in tissues.

Multicomponent Hydrogel Matrices of Fmoc-FF and Cationic Peptides for Application in Tissue Engineering.

In the last years, peptide-based hydrogels are being increasingly used as suitable matrices for biomedical and pharmaceutical applications, including drug delivery and tissue engineering. Recently, the synthesis and the gelation properties of a small library of cationic peptides, containing a Lys residue at the C-terminus and derivatized with an Fmoc group or with the fluorenyl methoxycarbonyl-diphenylalanine (FmocFF) at the N-terminus are derived. Here, it is demonstrated that the combination of these peptides with the well-known hydrogelator FmocFF, in different weight/weight ratios, allows the achievement of seven novel self-sorted hydrogels, which share similar peptide organization of their supramolecular matrix. Rheological and relaxometric characterization highlight a different mechanical rigidity and water mobility in the gels as demonstrated by the storage modulus values (200 Pa < G' < 35 000Pa) and by relaxometry, respectively. In vitro studies demonstrate that most of the tested mixed hydrogels do not disturb significantly the cell viability (>95%) over 72 h of treatment. Moreover, in virtue to its capability to strongly favor adhesion, spreading and duplication of 3T3-L1 cells, one of the tested hydrogel may be eligible as synthetic extracellular matrix.

Solid-contact potentiometric sensors based on silver nanoparticles in the supramolecular matrix for the determination of halogenide ions

Determination of halogenide ions in pharmaceuticals and various waters is an actual task for the modern analytical chemistry. In the current work, solid-contact potentiometric sensor, based on the glassy carbon electrode covered with the layer of electropolymerized polyaniline and suspension of silver nanoparticles in the matrix of thiacalix[4]arene derivative bearing terminal catechol groups, has been described. The suspension was obtained by the chemical reduction of silver ions with the thiacalix[4]arene and drop casted on the polyaniline layer. The sensor showed potentiometric response to chloride-, bromide and iodide ions. For the simultaneous determination of iodide and bromide ions, a multi-sensor system, consisting of four electrodes with the different volumes of the suspension placed on the polyaniline layer, has been developed. The possibility of the response prediction within the simple additive model was found for the set of the iodide and bromide mixtures. In a similar manner, simultaneous determination of both ions in the variable mixtures has been performed. The multi-sensor system was tested during the determination of iodides in iodine containing pharmaceuticals and the determination of iodide and bromide ions in the artificial mineral water samples. Ionic chromatography was chosen as the comparison method. Sensors made it possible to determine from 0.1 μM to10 mMiodide and bromide ions in mixtures. The proposed approach and solid-contact potentiometric sensors can be used in the analysis of ion content of the waters and in control of the production and storage conditions of pharmaceuticals.

Squaramide-Based Supramolecular Materials Drive HepG2 Spheroid Differentiation.

A major challenge in the use of HepG2 cell culture models for drug toxicity screening is their lack of maturity in 2D culture. 3D culture in Matrigel promotes the formation of spheroids that express liver-relevant markers, yet they still lack various primary hepatocyte functions. Therefore, alternative matrices where chemical composition and materials properties are controlled to steer maturation of HepG2 spheroids remain desired. Herein, a modular approach is taken based on a fully synthetic and minimalistic supramolecular matrix based on squaramide synthons outfitted with a cell-adhesive peptide, RGD for 3D HepG2 spheroid culture. Co-assemblies of RGD-functionalized squaramide-based and native monomers resulted in soft and self-recovering supramolecular hydrogels with a tunable RGD concentration. HepG2 spheroids are self-assembled and grown (≈150µm) within the supramolecular hydrogels with high cell viability and differentiation over 21 days of culture. Importantly, significantly higher mRNA and protein expression levels of phase I and II metabolic enzymes, drug transporters, and liver markers are found for the squaramide hydrogels in comparison to Matrigel. Overall, the fully synthetic squaramide hydrogels are proven to be synthetically accessible and effective for HepG2 differentiation showcasing the potential of this supramolecular matrix to rival and replace naturally-derived materials classically used in high-throughput toxicity screening.

Supramolecular self-assembly of hydrogen bonded phenylenediboronic acid-alkoxy benzoic acids and their silver nanocomposites

Hydrogen bonded liquid crystals are functional soft materials that have attracted great research interest due to unique combination of their structural and dynamic properties. 1,4-Benzene diboronic acid (BDBA) was hydrogen bonded with mesogenic alkoxy benzoic acids (ABA) to form self-organized supramolecular structures, which exhibited nematic and smectic textures, confirmed using polarizing optical microscopy, differential scanning calorimetry and X-ray diffraction measurements. Uniform dispersion of 3% silver nanoparticles in the supramolecular matrix resulted in minor variations in the mesogenic behavior, but appreciable changes in the resistivity values were observed compared to the hydrogen-bonded BDBA-12ABA binary mixture.

Self-Assembly of Polymer End-Tethered Gold Nanorods into Two-Dimensional Arrays with Tunable Tilt Structures

We demonstrated a facile yet effective strategy for self-assembly of polymer end-tethered gold nanorods (GNRs) into tunable two-dimensional (2D) arrays with the assistance of supramolecules of hydrogen bonded poly(4-vinyl pyridine) (P4VP) and 3-n-pentadecylphenol (PDP). Well-ordered 2D arrays with micrometer size were obtained by rupturing the assembled supramolecular matrix with a selective solvent. The formation of long-range ordered 2D arrays during a drying process was observed via small-angle X-ray scattering. Interestingly, the packing structure of the ordered arrays strongly depends on the molecular weight (Mw) of the polymer ligands and the size of the GNRs. By increasing Mw of the polymer ligands, tilted arrays can be obtained. The average angle between GNRs and the surface normal direction of the layered 2D arrays changes from 0 to 37° with the increase in Mw of the polymer ligands. A mechanism for assembly behavior of dumbbell shapes with a soft shell structure has been proposed. The resulting GNR arrays with different orientations showed anisotropic surface-enhanced Raman scattering (SERS) performance. We showed that the vertically ordered GNR arrays exhibited ∼3 times higher SERS signals than the tilt ordered arrays. The results prove that the polymer end-tethered GNRs can be used as a building block for preparing the tilted 2D arrays with tunable physicochemical properties, which could have a wide range of potential applications in photonics, electronics, plasmonics, etc.

Multifunctional Organosulfonate Anions Self-Assembled with Organic Cations by Charge-Assisted Hydrogen Bonds and the Cooperation of Water

The present study focuses on the assembly of organo-cations with organo-anions in water. The anions, characterized by symmetric moieties (carbon-, adamantane-, or calixarene-based) functionalized with directional hydrogen bond (HB) acceptor functions (tetra-sulfonate moieties), are combined with planar guanidinium or terephtalimidamide cations as hydrogen bond donors, the purpose being to integrate water molecules into the lattice. The imbalance between the charge on the two components, and the considerable number of HB donor and acceptor sites, promotes the insertion of water into the structures. In the reported structures, a part of the water molecules serves as a structural linker between the anions and cations, while the remaining molecules cluster into channels and cavities in a loose association with the supramolecular matrix framework.

Fluorescently-tagged polyamines for the staining of siliceous materials

Siliceous frustules of diatom algae contain unique long-chain polyamines, including those having more than six nitrogen atoms. These polyamines participate in the formation of the siliceous frustules of the diatoms but their precise physiological role is not clear. The main hypotheses include formation of a polyamine and polyphosphate supramolecular matrix. We have synthesized novel fluorescent dyes from a synthetic oligomeric mixture of polyamines and the fluorophore 7-nitro-2,1,3-benzoxadiazole. The long polyamine chain ensures the high affinity of these dyes to silica, which allows their application in the staining of siliceous materials, such as valves of diatom algae and fossilized samples from sediments. The fluorescently stained diatom valves were found to be promising liquid flow tracers in hydrodynamic tests. Furthermore, complexation of the polyamine component of the dyes with carbonic polymeric acids results in changes to the visible spectrum of the fluorophore, which allows study of the stability of the complex vs the length of the polyamine chain. Using poly (vinyl phosphonic acid) as a model for phosphate functionality in silaffins (a potential matrix in the formation of biogenic silica) little complexation with the polyamine fluorophores was observed, bringing into question the role of a polyamine - polymeric phosphate matrix in biosilicification.

Programmable Supra-Assembly of a DNA Surface Adapter for Tunable Chiral Directional Self-Assembly of Gold Nanorods.

An important challenge in molecular assembly and hierarchical molecular engineering is to control and program the directional self-assembly into chiral structures. Here, we present a versatile DNA surface adapter that can programmably self-assemble into various chiral supramolecular architectures, thereby regulating the chiral directional "bonding" of gold nanorods decorated by the surface adapter. Distinct optical chirality relevant to the ensemble conformation is demonstrated from the assembled novel stair-like and coil-like gold nanorod chiral metastructures, which is strongly affected by the spatial arrangement of neighboring nanorod pair. Our strategy provides new avenues for fabrication of tunable optical metamaterials by manipulating the directional self-assembly of nanoparticles using programmable surface adapters.

Exact mass analysis of sulfur clusters upon encapsulation by a polyaromatic capsular matrix

Structural determination of inorganic clusters relies heavily on mass spectrometry because of, in most cases, their poor responsivities toward nuclear magnetic resonance, ultraviolet/visible, and infrared analyses. Nevertheless, mass spectrometry analysis of oligosulfurs (Sn), which are unique clusters with copious allotropic forms, usually displays their fragment peaks. Here we report that a polyaromatic capsule acts as a supramolecular matrix for the mass determination of the neutral sulfur clusters. Upon encapsulation, molecular ion peaks derived from the host–guest complexes including cyclic S6 and S8 clusters are exclusively detected by common electrospray ionization time-of-flight mass spectrometry analysis. Furthermore, mass spectrometry analysis of a cyclic S12 cluster, which is in situ prepared from two S6 clusters within the matrix upon light irradiation, is achieved by the same way. The present matrix can remarkably stabilize the otherwise labile S6 and S12 clusters in the polyaromatic shell not only under mass spectrometry conditions but also in an ambient solution state.

A Fast and Cost-Effective Detection of Melamine by Surface Enhanced Raman Spectroscopy Using a Novel Hydrogen Bonding-Assisted Supramolecular Matrix and Gold-Coated Magnetic Nanoparticles

A fast and cost-effective melamine detection approach has been developed based on surface enhanced Raman spectroscopy (SERS) using a novel hydrogen bonding-assisted supramolecular matrix. The detection utilizes Fe3O4/Au magnetic nanoparticles coated with 5-aminoorotic acid (AOA) as a SERS active substrate (Fe3O4/Au–AOA), and Rhodamine B (RhB) conjugated AOA as a Raman reporter (AOA–RhB). Upon mixing the reagents with melamine, a supramolecular complex [Fe3O4/Au–AOA•••melamine•••AOA–RhB] was formed due to the strong multiple hydrogen bonding interactions between AOA and melamine. The complex was separated and concentrated to a pellet by an external magnet and used as a supramolecular matrix for the melamine detection. Laser excitation of the complex pellet produced a strong SERS signal diagnostic for RhB. The logarithmic intensity of the characteristic RhB peaks was found to be proportional to the concentration of melamine with a limit of detection of 2.5 µg/mL and a detection linearity range of 2.5~15.0 µg/mL in milk. As Fe3O4 nanoparticles and AOA are thousands of times less expensive than the monoclonal antibody used in a traditional sandwich immunoassay, the current assay drastically cut down the cost of melamine detection. The current approach affords promise as a biosensor platform that cuts down sample pre-treatment steps and measurement expense.

Achieving 3-D Nanoparticle Assembly in Nanocomposite Thin Films via Kinetic Control

Nanocomposite thin films containing well-ordered nanoparticle (NP) assemblies are ideal candidates for the fabrication of metamaterials. Achieving 3-D assembly of NPs in nanocomposite thin films is thermodynamically challenging as the particle size gets similar to that of a single polymer chain. The entropic penalties of polymeric matrix upon NP incorporation leads to NP aggregation on the film surface or within the defects in the film. Controlling the kinetic pathways of assembly process provides an alternative path forward by arresting the system in nonequilibrium states. Here, we report the thin film 3-D hierarchical assembly of 20 nm NPs in supramolecules with a 30 nm periodicity. By mediating the NP diffusion kinetics in the supramolecular matrix, surface aggregation of NPs was suppressed and NPs coassemble with supramolecules to form new 3-D morphologies in thin films. The present studies opened a viable route to achieve designer functional composite thin films via kinetic control.

Non-Covalent Derivatives: Cocrystals and Eutectics.

Non-covalent derivatives (NCDs) are formed by incorporating one (or more) coformer molecule(s) into the matrix of a parent molecule via non-covalent forces. These forces can include ionic forces, Van der Waals forces, hydrogen bonding, lipophilic-lipophilic interactions and pi-pi interactions. NCDs, in both cocrystal and eutectic forms, possess properties that are unique to their supramolecular matrix. These properties include critical product performance factors such as solubility, stability and bioavailability. NCDs have been used to tailor materials for a variety of applications and have the potential to be used in an even broader range of materials and processes. NCDs can be prepared using little or no solvent and none of the reagents typical to synthetic modifications. Thus, NCDs represent a powerfully versatile, environmentally-friendly and cost-effective opportunity.

Amperometric Folic Acid Quantification Using a Supramolecular Tetraruthenated Nickel Porphyrin µ‐Peroxo‐Bridged Matrix Modified Electrode Associated to Batch Injection Analysis

AbstractA supramolecular Nickel (II) porphyrin complex containing four pyridyl‐bis(2,2′‐bipyridyl)chloro ruthenium meso substituents was submitted to successive voltammetric cycles in high alkaline media to produce a supramolecular matrix with Nickel centers linked by µ‐peroxo bridges, producing a highly stable thin film able to act as redox mediator for electrocatalytic oxidation of folic acid. The characterization of electrode surface material was performed by Scanning Electron Microscopy and Electrochemical Impedance Spectroscopy. The modified electrode was inserted into a batch injection electrochemical cell used for the rapid and precise quantification of folic acid in pharmaceutical products. The favorable hydrodynamic conditions provided by amperometry‐BIA association allowed a very high throughput with good linear range (1 to 200 µmol L−1) and low detection limit (7.37×10−7 mol L−1). The electrochemical method was applied to the quantification of folic acid in different tablet samples. The results were comparable with values indicated by the manufacturer and those found using high HPLC according to the Brazilian Pharmacopoeia; commercial samples were submitted to a procedure in order to remove lactose of tablets, since carbohydrates act as interfering species. This procedure together with the electrochemical method showed to be simple, rapid, efficient and an appropriate alternative for quantifying this compound in real samples.

A Multicomponent Gel for Nitric Oxide Photorelease with Fluorescence Reporting

AbstractAn engineered hydrogel platform has been developed, in the absence of any toxic solvents or reagents, by the supramolecular self‐assembly of three different components: a poly‐β‐cyclodextrin polymer, a hydrophobically modified dextran, and a photoactivatable bichromophoric molecular conjugate designed to photorelease nitric oxide (NO) with a fluorescent reporting function. The multivalent character of the interactions between the all components and the poor solubility of the conjugate in aqueous medium ensure the stability of the hydrogel and the lack of leaching of the photoactive cargo from the gel network under physiological conditions, even in the absence of protective coating agents. The photochemical properties of the molecular conjugate are retained in the supramolecular matrix, as demonstrated by the remote‐controlled release of NO upon visible light excitation simultaneously to the activation of a fluorescent reporting function, which allows easy monitoring of the photoreleased NO.

A NO photoreleasing supramolecular hydrogel with bactericidal action.

We have developed an engineered hydrogel formed, in the absence of any toxic solvents or reagents, by spontaneous self-assembly of three key components: a poly-β-cyclodextrin polymer (1), a hydrophobically modified dextran (2) and a nitric oxide (NO) photodonor bearing an adamantyl appendage (3). The formation of this supramolecular assembly is based on a "lock-and-key" mechanism in which the alkyl side chains of 2 and the adamantane moiety of 3 form inclusion complexes with the β-CD cavities of 1. The multivalent character of the interactions between all components and the insolubility of the NO photodonor in an aqueous medium ensure the stability of the hydrogel and the total lack of leaching of the photoactive component from the gel network under physiological conditions, even in the absence of protective coating agents. The photochemical properties of the NO photodonor are well preserved in the supramolecular matrix as demonstrated by the remote-controlled release of NO through visible light excitation and its transfer to a protein such as myoglobin. The utility of this NO photoreleasing platform is demonstrated in effective and strictly light-dependent bactericidal activity against the Gram-negative Escherichia coli bacterial colony suspension.