Photo-Controllable Förster Resonance Energy Transfer Based on Dynamic Chiral Self-Assembly of Sequence-Defined Amphiphilic Alternating Azopeptoids.

Endowing biomimetic sequence-controlled polymers with chiral functionality to construct stimuli-responsive chiral materials offers a promising approach for innovative chiroptical switch, but it remains challenging. Herein, it is reported that the self-assembly of sequence-defined chiral amphiphilic alternating azopeptoids to generate photo-responsive and ultrathin bilayer peptoidosomes with a vesicular thickness of ≈1.50 nm and a diameter of around ≈290 nm.

Robust Multifunctional Ultrathin 2 Nanometer Organic Nanofibers.

Ultrathin organic nanofibers (UTONFs) represent an emerging class of nanomaterials as they carry a set of favorable attributes, including ultrahigh specific surface area, lightweight, and mechanical flexibility, over inorganic counterparts, for use in biomedicine and nanotechnology. However, precise synthesis of uniform UTONFs (diameter ≤ 2 nm) with tailored functionalities remained challenging. Herein, we report robust multifunctional UTONFs using hydrophobic interaction-driven self-assembly of amphiphilic alternating peptoids containing hydrophobic photoresponsive azobenzene and hydrophilic hydroxyl moieties periodically arranged along the peptoid backbone.

Designable Photo-Responsive Micron-Scale Ultrathin Peptoid Nanobelts for Enhanced Performance on Hydrogen Evolution Reaction.

The development of high-reactive single-atom catalysts (SACs) based on long-range-ordered ultrathin organic nanomaterials (UTONMs) (i.e., below 3 nm) provides a significant tactic for the advancement in hydrogen evolution reactions (HER) but remains challenging.

Small-molecule nanoprodrug with high drug loading and EGFR, PI3K/AKT dual-inhibiting properties for bladder cancer treatment.

Bladder cancer (BCa) is one of the most common malignancies worldwide. Although multiple efforts have been made, the 5-year survival rate of patients with BCa remains unchanged in recent years. Overexpression of the epidermal growth factor receptor (EGFR) is found in ≈74% of BCa tissue specimens; however, current EGFR-based targeted therapies show little benefit for BCa patients, as the EGFR downstream pathways appear to be circumvented by other receptor tyrosine kinases (RTKs).

Sustainable sepiolite-based composites for fast clotting and wound healing.

Uncontrolled bleeding and bacterial coinfection are the major causes of death after an injury. Fast hemostatic capacity, good biocompatibility, and bacterial coinfection inhibition pose great challenges to hemostatic agent development. A prospective sepiolite/Ag nanoparticles (sepiolite@AgNPs) composite has been prepared by using natural clay sepiolite as template.

Light-Induced Reversible Hierarchical Self-Assembly of Amphiphilic Diblock Copolymers into Microscopic Vesicles with Tunable Optical and Nanocarrier Properties.

In contrast to the conventional hierarchical self-assembly process, effective methods to enable reversible hierarchical self-assembly of block copolymers are comparatively few and limited in scope. Herein, we report, for the first time, a simple yet robust strategy for light-induced reversible hierarchical self-assembly of an amphiphilic diblock copolymer, poly(4-vinylpyridine)--poly[6-[4-(4-butyloxyphenylazo)phenoxy]hexyl methacrylate] (denoted P4VP--PAzoMA). The hierarchical structures are constructed via a two-step self-assembly process (first-level reverse micelles, second-level compound micelles, and rearrangement into micrometer-sized vesicles) driven by use of solvent.

Theranostic Activity of Nitric Oxide-Releasing Carbon Quantum Dots.

The synthesis and anticancer cell activity of nitric oxide (NO)-releasing carbon quantum dots (CQDs) are described as potential theranostics. A series of secondary amine-modified CQDs were prepared using a hydrothermal method to modify β-cyclodextrin with hydroxyl and primary amine terminal functional groups. Subsequent reaction of the CQDs with NO gas under alkaline conditions yielded -diazeniumdiolate NO donor-modified CQDs with adjustable NO payloads (0.

Bioinspired Peptoid Nanotubes for Targeted Tumor Cell Imaging and Chemo-Photodynamic Therapy.

Substantial progress has been made in applying nanotubes in biomedical applications such as bioimaging and drug delivery due to their unique architecture, characterized by very large internal surface areas and high aspect ratios. However, the biomedical applications of organic nanotubes, especially for those assembled from sequence-defined molecules, are very uncommon. In this paper, the synthesis of two new peptoid nanotubes (PepTs1 and PepTs2) is reported by using sequence-defined and ligand-tagged peptoids as building blocks.

Hierarchical Assembly of Peptoid-Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution.

Herein we show that by appending bulky β-cyclodextrin (CD) groups onto sheet-forming peptoids, we obtain cylindrical micelles that further assembly into membranes and intertwined ribbons on substrates in aqueous solution, depending on the choice of solution and substrate conditions. In situ atomic force microscopy (AFM) shows that micelle assembly occurs in two steps, starting with "precursor" particles that transform into worm-like micelles, which extend and coalesce to form the higher order structures with a rate and a degree of cooperativity dependent on pH and Ca concentration. After co-assembly with hydrophobic 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole (NBD) donors that occupy the hydrophobic core, followed by exposure to hydrophilic Rhodamine B as acceptors that insert into cyclodextrin, the micelles exhibit highly efficient Förster resonance energy transfer efficiency in aqueous solution, thereby mimicking natural light harvesting systems.

Crystalline Facet-Directed Generation Engineering of Ultrathin Platinum Nanodendrites.

In this work, we successfully prepare two-dimensional ultrathin single-crystalline platinum nanodendrites (PtNDs) with precisely controlled generation (size) through a surfactant-directed solution-phase synthesis. The amphiphilic surfactant of CH-N(CH)CHCOOH (Br) acts as the structure-directing template and facet-capping agent simultaneously to kinetically engineer in-the-plane epitaxial growth of Pt nanocrystals along selectively exposed {111} facets into ultrathin PtNDs. A novel formation mechanism defined as crystalline facet-directed step-by-step in-the-plane epitaxial growth, similar to the synthesis of organic dendrimers, is proposed on the basis of the nanostructure and crystalline evolution of PtNDs.

Solid-phase synthesis of three-armed star-shaped peptoids and their hierarchical self-assembly.

Due to the branched structure feature and unique properties, a variety of star-shaped polymers have been designed and synthesized. Despite those advances, solid-phase synthesis of star-shaped sequence-defined synthetic polymers that exhibit hierarchical self-assembly remains a significant challenge. Hence, we present an effective strategy for the solid-phase synthesis of three-armed star-shaped peptoids, in which ethylenediamine was used as the centric star pivot.

Nitric oxide diffusion through cystic fibrosis-relevant media and lung tissue.

A simplified diffusion cell methodology was employed to measure the diffusion coefficient of nitric oxide (NO) through phosphate buffered saline (PBS) and artificial sputum medium (ASM)-an in vitro analog for airway mucus. Diffusion through the proteinaceous ASM yielded a significantly lower diffusion coefficient compared to PBS, which is attributed to both the physical obstruction by the mucin mesh and reactive nature of NO radicals towards the biological compounds in ASM. To further confirm that ASM was restricting NO from diffusing freely, a macromolecular propylamine-modified cyclodextrin donor (CD-PA) was employed to release the NO more slowly.

Efficient Cytosolic Delivery Using Crystalline Nanoflowers Assembled from Fluorinated Peptoids.

The design and synthesis of biocompatible nanomaterials as cargoes for the intracellular delivery of therapeutic proteins or genes have attracted intense attention because of their potential for use in therapeutics. Despite the advances in this area, very few nanomaterials can be efficiently delivered to the cytosol. To address these challenges, crystalline nanoflower-like particles are designed and synthesized from fluorinated sequence-defined peptoids; the crystallinity and fluorination of these particles enable highly efficient cytosolic delivery with minimal cytotoxicity.

Nitric Oxide-Releasing Cyclodextrins.

A series of secondary amine-modified cyclodextrin (CD) derivatives was synthesized with diverse exterior terminal groups (i.e., hydroxyl, methyl, methoxyl, and primary amine).

Hierarchical C/SiO /TiO ultrathin nanobelts as anode materials for advanced lithium ion batteries.

TiO-based nanomaterials are demonstrated to be a promising candidate for next generation lithium ion batteries due to their stable performance and easy preparation. However, their inherent low capacity impedes their wide application compared to commercial carbon nanomaterials. Here we present a unique in situ grafting-graphitization method to achieve a ternary nanocomposite of C/SiO /TiO ultrathin nanobelts with a core-shell heterostructure.

Tunable assembly of biomimetic peptoids as templates to control nanostructure catalytic activity.

Nanostructured materials present new opportunities to achieve sustainable catalytic reactivity. Fabrication and organization of these catalytic particles for enhanced reactivity remain challenging due to limited synthetic and organization strategies. Biomimetic approaches represent new avenues to address such challenges.

Natural assembly of a ternary Ag-SnS-TiO photocatalyst and its photocatalytic performance under simulated sunlight.

Natural assembly method was utilized to prepare a novel ternary Ag-SnS-TiO nanocomposite, in which TiO nanobelts were used as templates. The co-loading of Ag and SnS nanoparticles endows TiO nanobelts with enhanced photocatalytic capability, resulting from the broadened light absorption spectra and decreased band gaps. Comparing with raw TiO nanobelts and commercial Degussa P25, an improvement in photodegradation of simulated organic pollutants was successfully demonstrated due to the decreasing recombination of photogenerated electron-hole pairs.

Designable and dynamic single-walled stiff nanotubes assembled from sequence-defined peptoids.

Despite recent advances in the assembly of organic nanotubes, conferral of sequence-defined engineering and dynamic response characteristics to the tubules remains a challenge. Here we report a new family of highly designable and dynamic nanotubes assembled from sequence-defined peptoids through a unique "rolling-up and closure of nanosheet" mechanism. During the assembly process, amorphous spherical particles of amphiphilic peptoid oligomers crystallize to form well-defined nanosheets before folding to form single-walled nanotubes.

Preparation of anion-exchangeable polymer vesicles through the self-assembly of hyperbranched polymeric ionic liquids.

This work reports the self-assembly of anion-exchangeable vesicles from an amphiphilic hyperbranched polymeric ionic liquid (HBPIL). By a simple one-step anion exchange with methyl orange, the obtained HBPILs could self-assemble into pH-indicative and colorful vesicles in water with color changes directly visible to the naked eye in response to solution pH. In addition, by another step of anion exchange with bovine serum albumin (BSA), the BSA-coated vesicles could also be readily prepared.

Dissipative particle dynamics simulation study on vesicles self-assembled from amphiphilic hyperbranched multiarm copolymers.

Hyperbranched multiarm copolymers (HMCs) have been shown to hold great potential as precursors in self-assembly, and many impressive supramolecular structures have been prepared through the self-assembly of HMCs in solution. However, theoretical studies on the corresponding self-assembly mechanism have been greatly lagging behind. Herein, we report the self-assembly of normal or reverse vesicles from amphiphilic HMCs by dissipative particle dynamics (DPD) simulation.

Three-component vesicle aggregation driven by adhesion interactions between Au nanoparticles and polydopamine-coated nanotubes.

Large-scale and robust vesicle aggregates were obtained through molecular recognition among cell-sized polymer vesicles, carbon nanotubes and AuNPs, driven by adhesion interactions between Au and polydopamine. Vesicle fusion was effectively avoided in this three-component vesicle aggregation process.

A supramolecular Janus hyperbranched polymer and its photoresponsive self-assembly of vesicles with narrow size distribution.

Herein, we report a novel Janus particle and supramolecular block copolymer consisting of two chemically distinct hyperbranched polymers, which is coined as Janus hyperbranched polymer. It is constructed by the noncovalent coupling between a hydrophobic hyperbranched poly(3-ethyl-3-oxetanemethanol) with an apex of an azobenzene (AZO) group and a hydrophilic hyperbranched polyglycerol with an apex of a β-cyclodextrin (CD) group through the specific AZO/CD host-guest interactions. Such an amphiphilic supramolecular polymer resembles a tree together with its root very well in the architecture and can further self-assemble into unilamellar bilayer vesicles with narrow size distribution, which disassembles reversibly under the irradiation of UV light due to the trans-to-cis isomerization of the AZO groups.

A facile method for fabricating TiO2@mesoporous carbon and three-layered nanocomposites.

Herein, we report a new and facile method for fabricating TiO(2)@mesoporous carbon hybrid materials. Uniform polydopamine (PDA) layers were coated onto the surface of titanate nanotubes (TNTs) and TiO(2) nanorods (TNDs) through the spontaneous adhesion and self-polymerization of dopamine during the dipping process. Core-shell mesoporous carbon nanotubes with TiO(2) nanorods or nanoparticles encapsulated inside (TiO(2)@MC) were then obtained by transforming PDA layers into carbonaceous ones through calcination in nitrogen at 800 °C.

Biocompatible or biodegradable hyperbranched polymers: from self-assembly to cytomimetic applications.

Self-assembly of amphiphilic hyperbranched polymers (HBPs) is a newly emerging research area and has attracted increasing attention due to the great advantages in biomedical applications. This tutorial review focuses on the self-assembly of biocompatible or biodegradable amphiphilic HBPs and their cytomimetic applications, and specialities or advantages therein owing to the hyperbranched structure have also been summarized. As shown here, various supramolecular structures including micelles, vesicles, tubes, fibers and films have been prepared through the primary self-assembly processes.