Discrete Actuation of Water-Responsive Crystalline Metal-Peptide Frameworks.

Engineering guest-responsive materials capable of controlled and precise sorption behavior and structural deformation in response to external stimuli is imperative for various applications. However, existing systems often exhibit complex, unpredictable dynamics, posing challenges for efficient control and utilization. Here, we design crystalline metal-peptide frameworks with tunable water-responsive (WR) dynamics by assembling glycine-threonine (Gly-Thr, GT) or glycine-serine (Gly-Ser, GS) peptides with zinc (Zn) ions, achieving either continuous or discrete threshold water-sorption-dependent phase transitions.

Pyrrole-Linked Benzimidazolyl Hydrazone Self-Assembly Forms HCl Channels and Induces Apoptosis in Cancer Cells.

Modulation of intracellular chloride ion concentration by artificially developed ion transporters has been known to induce apoptosis in cancer cells. However, most of these transporters cause harm to healthy cells as well, limiting their applicability in real biological systems. Here, we report a pyrrole-linked benzimidazolyl-hydrazone that self-assembles to form a nanochannel assembly across the lipid bilayer, enabling the selective translocation of HCl, a system rarely reported in the literature.

Self-Assembly Pathway Influence on Dehydropeptide-Based Gel Properties and Drug Release.

Low-molecular-weight peptide-based hydrogels formed through self-assembly have emerged as promising candidates for biomedical applications. While the self-assembly process is known to affect the network morphology, its impact on mechanical properties and drug delivery remains poorly understood. In this work, it is explored how different gelation conditions influence the morphology, properties, and drug release profiles of dehydropeptide-based gels.

Metal-Directed Self-Assembly of Minimal Heterochiral Peptides into Metallo-Supramolecular β-Helical Tubules for Artificial Transmembrane Water Channels.

Transmembrane selective transport of metabolites controls essential biological functions. During the last two decades, artificial channels have been developed and cyclic peptides have emerged as ideal platforms for efficient ion, sugar, and nucleic acid channel translocation. Despite these tremendous developments, cyclic peptides have eluded selective water transport.

Illuminating apoptosis: a visible light-activated chloride carrier for chloride transport and cell death.

Synthetic chloride carriers are known to induce chloride-mediated apoptosis inside cancer cells. One of the main disadvantages is the unfavorable cytotoxicity towards healthy cells due to the lack of selectivity. The use of stimuli, such as light, enzymes, ligands, , has enabled the selective activation of these systems in cancer cells.

A broad-spectrum antibacterial hydrogel based on the synergistic action of Fmoc-phenylalanine and Fmoc-lysine in a co-assembled state.

Multicomponent biomolecular self-assembly is fundamental for accomplishing complex functionalities of biosystems. Self-assembling peptides, amino acids, and their conjugates serve as a versatile platform for developing biomaterials. However, the co-assembly of multiple building blocks showing synergistic interplay between individual components and producing biomaterials with emergent functional attributes is much less explored.

A self-healing multispectral transparent adhesive peptide glass.

Despite its disordered liquid-like structure, glass exhibits solid-like mechanical properties. The formation of glassy material occurs by vitrification, preventing crystallization and promoting an amorphous structure. Glass is fundamental in diverse fields of materials science, owing to its unique optical, chemical and mechanical properties as well as durability, versatility and environmental sustainability.

Peptide hydrogen-bonded organic frameworks.

Hydrogen-bonded porous frameworks (HPFs) are versatile porous crystalline frameworks with diverse applications. However, designing chiral assemblies or biocompatible materials poses significant challenges. Peptide-based hydrogen-bonded porous frameworks (P-HPFs) are an exciting alternative to conventional HPFs due to their intrinsic chirality, tunability, biocompatibility, and structural diversity.

Metal-driven folding and assembly of a minimal β-sheet into a 3D-porous honeycomb framework.

In contrast to short helical peptides, constrained peptides, and foldamers, the design and fabrication of crystalline 3D frameworks from the β-sheet peptides are rare because of their high self-aggregation propensity to form 1D architectures. Herein, we demonstrate the formation of a 3D porous honeycomb framework through the silver coordination of a minimal β-sheet forming a peptide having terminal metal coordinated 4- and 3-pyridyl ligands.

Molecular Engineering of Ordered Piezoelectric Sulfonic Acid-Containing Assemblies.

Sulfonic acid-containing bioorganic monomers with wide molecular designability and abundant hydrogen bonding sites hold great potential to design diverse functional biocrystals but have so far not been explored for piezoelectric energy harvesting applications due to the lack of strategies to break the centrosymmetry of their assemblies. Here, a significant molecular packing transformation from centrosymmetric into non-centrosymmetric conformation by the addition of an amide terminus in the sulfonic acid-containing bioorganic molecule is demonstrated, allowing a high electromechanical response. The amide-functionalized molecule self-assembles into a polar supramolecular parallel β-sheet-like structure with a high longitudinal piezoelectric coefficient d = 15.

Photocontrolled activation of doubly -nitrobenzyl-protected small molecule benzimidazoles leads to cancer cell death.

Artificial biomimetic chloride anionophores have shown promising applications as anticancer scaffolds. Importantly, stimuli-responsive chloride transporters that can be selectively activated inside the cancer cells to avoid undesired toxicity to normal, healthy cells are very rare. Particularly, light-responsive systems promise better applicability for photodynamic therapy because of their spatiotemporal controllability, low toxicity, and high tunability.

Perspectives on recent advancements in energy harvesting, sensing and bio-medical applications of piezoelectric gels.

The development of next-generation bioelectronics, as well as the powering of consumer and medical devices, require power sources that are soft, flexible, extensible, and even biocompatible. Traditional energy storage devices (typically, batteries and supercapacitors) are rigid, unrecyclable, offer short-lifetime, contain hazardous chemicals and possess poor biocompatibility, hindering their utilization in wearable electronics. Therefore, there is a genuine unmet need for a new generation of innovative energy-harvesting materials that are soft, flexible, bio-compatible, and bio-degradable.

Exploring Helical Peptides and Foldamers for the Design of Metal Helix Frameworks: Current Trends and Future Perspectives.

Flexible and biocompatible metal peptide frameworks (MPFs) derived from short and ultra-short peptides have been explored for the storage of greenhouse gases, molecular recognition, and chiral transformations. In addition to short flexible peptides, peptides with specifically folded conformations have recently been utilized to fabricate a variety of metal helix frameworks (MHFs). The secondary structures of the peptides govern the structure-assembly relationship and thereby control the formation of three-dimensional (3D)-MHFs.

A Ferroelectric Aminophosphonium Cyanoferrate with a Large Electrostrictive Coefficient as a Piezoelectric Nanogenerator.

Hybrid materials possessing piezo- and ferroelectric properties emerge as excellent alternatives to conventional piezoceramics due to their merits of facile synthesis, lightweight nature, ease of fabrication and mechanical flexibility. Inspired by the structural stability of aminophosphonium compounds, here we report the first A BX type cyanometallate [Ph ( PrNH) P] [Fe(CN) ] (1), which shows a ferroelectric saturation polarization (P ) of 3.71 μC cm .

Nontoxic Artificial Chloride Channel Formation in Epithelial Cells by Isophthalic Acid-Based Small Molecules.

Artificial channels capable of facilitating the transport of Cl ions across cell membranes while being nontoxic to the cells are rare. Such synthetic ion channels can mimic the functions of membrane transport proteins and, therefore, have the potential to treat channelopathies by replacing defective ion channels. Here we report isophthalic acid-based structurally simple molecules 1 a and 2 a, which self-assemble to render supramolecular nanochannels that allow selective transport of Cl ions.

A bis-NHC-CAAC dimer derived dicationic diradical.

The isolation of carbon-centered diradicals is always challenging due to synthetic difficulties and their limited stability. Herein we report the synthesis of a -1,4-cyclohexylene bridged bis-NHC-CAAC dimer derived thermally stable dicationic diradical. The diradical character of this compound was confirmed by EPR spectroscopy.

Exploiting Minimalistic Backbone Engineered γ-Phenylalanine for the Formation of Supramolecular Co-Polymer.

Ordered supramolecular hydrogels assembled by modified aromatic amino acids often exhibit low mechanical rigidity. Aiming to stabilize the hydrogel and understand the impact of conformational freedom and hydrophobicity on the self-assembly process, two building blocks based on 9-fluorenyl-methoxycarbonyl-phenylalanine (Fmoc-Phe) gelator which contain two extra methylene units in the backbone, generating Fmoc-γPhe and Fmoc-(3-hydroxy)-γPhe are designed. Fmoc-γPhe spontaneously assembled in aqueous media forming a hydrogel with exceptional mechanical and thermal stability.

Atomic insight into short helical peptide comprised of consecutive multiple aromatic residues.

The occurrence of sequential multiple aromatic residues in a helical sequence is rare compared to the β-sheet rich structure. Here, using helix promoting α-aminoisobutyric acid (Aib) residues, we unravel atomistic details of the helical secondary structure formation and the super helical assembly of two heptapeptides composed of sequential five and six phenylalanine (Phe) residues.

Ferroelectricity and Piezoelectric Energy Harvesting of Hybrid ABX-Type Halogenocuprates Stabilized by Phosphonium Cations.

Perovskite-structured compounds containing organic cations and inorganic anions have gained prominence as materials for next-generation electronic and energy devices. Hybrid materials possessing ferro- and piezoelectric properties are in recent focus for mechanical energy harvesting (nanogenerator) applications. Here, we report the ferroelectric behavior of ABX-type halogenocuprate materials supported by heteroleptic phosphonium cations.

Stimuli-Responsive Anion Transport through Acylhydrazone-Based Synthetic Anionophores.

Photoswitchable acylhydrazone-based synthetic anionophores are reported. Single-crystal X-ray structure and H NMR titration studies confirmed the chloride binding in solid and solution states. The ion transport activity of was greatly attenuated through a phototriggered to photoisomerization process, and the photoisomerized deactivated state showed high kinetic stability due to an intramolecular hydrogen bond.

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph MeP] [Ni(NCS) ] Embedded in a Polymer Matrix.

Organic-inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion-containing A BX type organic-inorganic hybrid salt [Ph MeP] [Ni(NCS) ] (1) is now presented. P-E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.

Hydrogen-bonded organo-amino phosphonium halides: dielectric, piezoelectric and possible ferroelectric properties.

Molecular ferroelectric materials are an exciting class of materials for potential applications in energy and electronics. Herein, we report examples of hydrogen-bonded binary salts of diphenyl diisopropylamino phosphonium halides [Ph2(iPrNH)2P]·X [DPDP·X, X = Cl, Br, I] which show dielectric, piezoelectric and NLO properties and some potentially ferroelectric attributes at room temperature. The phosphonium bromide salt was prepared by bromination of the phosphine precursor Ph2PCl and its subsequent treatment with isopropyl amine.

Contrasting reactivity of (boryl)(aryl)lithium-amide with electrophiles: N- vs. p-aryl-C-nucleophilic substitution.

Herein we report two different reactivity modes of lithium(aryl)(boryl)amide, 4, when it is reacted with chlorosilanes such as SiCl4 and MeSiHCl2, and chlorophosphine, Ph2PCl. Thus, the reaction of lithium(aryl)(boryl)amide, 4, with MeSiHCl2 leads exclusively to an N-substitution product, 6. On the other hand, the reaction of 4 with SiCl4 and Ph2PCl proceeds completely differently affording exclusively p-aryl-C-substitution products, 5 and 7, respectively.

A Flexible Composite Mechanical Energy Harvester from a Ferroelectric Organoamino Phosphonium Salt.

A new binary organic salt diphenyl diisopropylamino phosphonium hexaflurophosphate (DPDP⋅PF ) was shown to exhibit a good ferroelectric response and employed for mechanical energy harvesting application. The phosphonium salt crystallizes in the monoclinic noncentrosymmetric space group Cc and exhibits an H-bonded 1D chain structure due to N-H⋅⋅⋅F interactions. Ferroelectric measurements on the single crystals of DPDP⋅PF gave a well-saturated rectangular hysteresis loop with a remnant (P ) polarization value of 6 μC cm .

NHC-stabilized 1-hydrosilaimine: synthesis, structure and reactivity.

A facile, straightforward synthesis of N-heterocyclic carbene (NHC)-stabilized 1-hydrosilaimine starting from a silicon(iv)-precursor is reported. It has been employed for the addition of an O-H bond of water under ambient conditions without any additional catalyst.