Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Multistep sequence-controlled supramolecular polymerization by the combination of multiple self-assembly motifs

ABSTRACT: Summary The precise sequence control of polymer chain is an important research topic of polymer chemistry. Although some methods such as iterative synthesis and supramolecular polymerization have been developed to fabricate sequence-controllable polymer, it is still a great challenge to consecutively prepare multiple supramolecular polymers with different sequence structures. In this work, through the reasonable utilization of assembly motifs, we integrated multiple host-guest recognitions and metal coordination interactions to prepare different sequence-controlled supramolecular polymers by a multistep assembly strategy. This research provides inspiration for the design and preparation of supramolecular polymers with different sequence structures. Graphical abstract Highlights • Multiple supramolecular polymers were prepared by a multistep assembly strategy• Supramolecular polymers with different structures show different stimuli responsiveness• Different supramolecular polymer materials show different fluorescence emission Polymer chemistry; Supramolecular chemistry; Molecular self-assembly

SUBMITTER: Li H

PROVIDER: S-EPMC9932128 | biostudies-literature | 2023 Jan

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Biomimetic temporal self-assembly via fuel-driven controlled supramolecular polymerization.

Project description:Temporal control of supramolecular assemblies to modulate the structural and transient characteristics of synthetic nanostructures is an active field of research within supramolecular chemistry. Molecular designs to attain temporal control have often taken inspiration from biological assemblies. One such assembly in Nature which has been studied extensively, for its well-defined structure and programmable self-assembly, is the ATP-driven seeded self-assembly of actin. Here we show, in a synthetic manifestation of actin self-assembly, an ATP-selective and ATP-fuelled, controlled supramolecular polymerization of a phosphate receptor functionalised monomer. It undergoes fuel-driven nucleation and seeded growth that provide length control and narrow dispersity of the resultant assemblies. Furthermore, coupling via ATP-hydrolysing enzymes yielded its transient characteristics. These results will usher investigations into synthetic analogues of important biological self-assembly motifs and will prove to be a significant advancement toward biomimetic temporally programmed materials.

| S-EPMC5878180 | biostudies-literature

Chirality-controlled polymerization-induced self-assembly.

Project description:Recent studies have shown that biodegradable nanoparticles can be efficiently prepared with polymerization of N-carboxyanhydrides-induced self-assembly (NCA-PISA). However, thus far, the effect of chiral monomer ratio on such NCA-PISA formulations and the resulting nanoparticles has not yet been fully explored. Herein, we show, for the first time, that the morphology, secondary structure, and biodegradation rate of PISA nanoparticles can be controlled by altering the chiral ratio of the core-forming monomers. This chirality-controlled PISA (CC-PISA) method allowed the preparation of nanoparticles that are more adjustable and applicable for future biomedical applications. Additionally, the complex secondary peptide structure (ratio of α-helix to β-sheet) and π-π stacking affect the polymer self-assembly process. More specifically, a PEG45 macro-initiator was chain-extended with l- and d-phenylalanine (l- and d-Phe-NCA) in various molar ratios in dry THF at 15 wt%. This ring-opening polymerization (ROP) allowed the preparation of homo- and hetero-chiral Phe-peptide block copolymers that self-assembled in situ into nanoparticles. For homo-chiral formulations, polymers self-assembled into vesicles once a sufficiently high phenylalanine degree of polymerization (DP) was obtained. Hetero-chiral formulations formed larger nanoparticles with various morphologies and, much to our surprise, using an equal enantiomer ratio inhibited PISA and led to a polymer solution instead. Finally, it was shown that the enzymatic biodegradation rate of such PISA particles is greatly affected by the polymer chirality. This PISA approach could be of great value to fabricate nanoparticles that exploit chirality in disease treatment.

| S-EPMC9728572 | biostudies-literature

Organobase triggered controlled supramolecular ring opening polymerization and 2D assembly.

Project description:A carboxylic acid appended naphthalene-diimide (NDI) derivative spontaneously aggregates in decane to generate a kinetically controlled product with irregular fibrillar morphology. By fine-tuning the sample preparation conditions, the carboxylic acid group can be trapped by intra-molecular H-bonds with the adjacent imide carbonyl, which retards the spontaneous aggregation. In the presence of a catalytic amount of a non-nucleophilic organic base (DBU or DMAP), the meta-stable monomer exhibits supramolecular polymerization through a thermodynamically controlled pathway involving simultaneous H-bonding and π-stacking and generates ultra-thin 2D nano-sheets. DMAP/DBU helps in ring-opening of the intra-molecularly H-bonded monomer and in situ breeds the free acid, which, beyond a critical concentration, initiates controlled supramolecular ring opening polymerization (SROP) via the chain-growth mechanism. The 2D polymer acts as a macro-initiator for subsequent two cycles of SROP and produces laterally extended ultra-thin nano-sheets.

| S-EPMC6764260 | biostudies-literature

'Sacrificial' supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads.

Project description:Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of 'sacrificial' aryl-perfluoroaryl supramolecular synthons to synthesize sp3-hybridized nanothreads from sp2-enriched reactants. Our strategy features A-B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous -OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto-enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

| S-EPMC8162754 | biostudies-literature

Reverse Sequence Polymerization-Induced Self-Assembly in Aqueous Media.

Project description:We report a new aqueous polymerization-induced self-assembly (PISA) formulation that enables the hydrophobic block to be prepared first when targeting diblock copolymer nano-objects. This counter-intuitive reverse sequence approach uses an ionic reversible addition-fragmentation chain transfer (RAFT) agent for the RAFT aqueous dispersion polymerization of 2-hydroxypropyl methacrylate (HPMA) to produce charge-stabilized latex particles. Chain extension using a water-soluble methacrylic, acrylic or acrylamide comonomer then produces sterically stabilized diblock copolymer nanoparticles in an aqueous one-pot formulation. In each case, the monomer diffuses into the PHPMA particles, which act as the locus for the polymerization. A remarkable change in morphology occurs as the ≈600 nm latex is converted into much smaller sterically stabilized diblock copolymer nanoparticles, which exhibit thermoresponsive behavior. Such reverse sequence PISA formulations enable the efficient synthesis of new functional diblock copolymer nanoparticles.

| S-EPMC9541501 | biostudies-literature

In situ supramolecular polymerization-enhanced self-assembly of polymer vesicles for highly efficient photothermal therapy.

Project description:Vesicular photothermal therapy agents (PTAs) are highly desirable in photothermal therapy (PTT) for their excellent light-harvesting ability and versatile hollow compartments. However, up to now, the reported vesicular PTAs are generally self-assembled from small molecules like liposomes, and polymer vesicles have seldom been used as PTAs due to the unsatisfactory photothermal conversion efficiency resulting from the irregular packing of chromophores in the vesicle membranes. Here we report a nano-sized polymer vesicle from hyperbranched polyporphyrins with favorable photothermal stability and extraordinarily high photothermal efficiency (44.1%), showing great potential in imaging-guided PTT for tumors through in vitro and in vivo experiments. These excellent properties are attributed to the in situ supramolecular polymerization of porphyrin units inside the vesicle membrane into well-organized 1D monofilaments driven by π-π stacking. We believe the supramolecular polymerization-enhanced self-assembly process reported here will shed a new light on the design of supramolecular materials with new structures and functions.

| S-EPMC7138818 | biostudies-literature

Using sequence data to predict the self-assembly of supramolecular collagen structures.

Project description:Collagen fibrils are the major constituents of the extracellular matrix, which provides structural support to vertebrate connective tissues. It is widely assumed that the superstructure of collagen fibrils is encoded in the primary sequences of the molecular building blocks. However, the interplay between large-scale architecture and small-scale molecular interactions makes the ab initio prediction of collagen structure challenging. Here, we propose a model that allows us to predict the periodic structure of collagen fibers and the axial offset between the molecules, purely on the basis of simple predictive rules for the interaction between amino acid residues. With our model, we identify the sequence-dependent collagen fiber geometries with the lowest free energy and validate the predicted geometries against the available experimental data. We propose a procedure for searching for optimal staggering distances. Finally, we build a classification algorithm and use it to scan 11 data sets of vertebrate fibrillar collagens, and predict the periodicity of the resulting assemblies. We analyzed the experimentally observed variance of the optimal stagger distances across species, and find that these distances, and the resulting fibrillar phenotypes, are evolutionary well preserved. Moreover, we observed that the energy minimum at the optimal stagger distance is broad in all cases, suggesting a further evolutionary adaptation designed to improve the assembly kinetics. Our periodicity predictions are not only in good agreement with the experimental data on collagen molecular staggering for all collagen types analyzed, but also for synthetic peptides. We argue that, with our model, it becomes possible to design tailor-made, periodic collagen structures, thereby enabling the design of novel biomimetic materials based on collagen-mimetic trimers.

| S-EPMC9463645 | biostudies-literature

Versatile small-molecule motifs for self-assembly in water and the formation of biofunctional supramolecular hydrogels.

Project description:This feature article introduces new structural motifs (referred as "samogen") that serve as the building blocks of hydrogelators for molecular self-assembly in water to result in a series of supramolecular hydrogels. Using a compound that consists of two phenylalanine residues and a naphthyl group (also abbreviated as NapFF (1) in this text) as an example of the samogens, we demonstrated the ability of the samogens to convert bioactive molecules into molecular hydrogelators that self-assemble in water to result in nanofibers. By briefly summarizing the properties and applications (e.g., wound healing, drug delivery, controlling cell fate, typing bacteria, and catalysis) of these molecular hydrogelators derived from the samogens, we intend to illustrate the basic requirements and promises of the small-molecule hydrogelators for applications in chemistry, materials science, and biomedicine.

| S-EPMC3019246 | biostudies-literature

Multistep hierarchical self-assembly of chiral nanopore arrays.

Project description:A series of simple hierarchical self-assembly steps achieve self-organization from the centimeter to the subnanometer-length scales in the form of square-centimeter arrays of linear nanopores, each one having a single chiral helical nanofilament of large internal surface area and interfacial interactions based on chiral crystalline molecular arrangements.

| S-EPMC4209994 | biostudies-literature

Supramolecular polymerization of electronically complementary linear motifs: anti-cooperativity by attenuated growth.

Project description:Anti-cooperative supramolecular polymerization by attenuated growth exhibited by self-assembling units of two electron-donor benzo[1,2-b:4,5-b']dithiophene (BDT) derivatives (compounds 1a and 1b) and the electron-acceptor 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) (compound 2) is reported. Despite the apparent cooperative mechanism of 1 and 2, AFM imaging and SAXS measurements reveal the formation of small aggregates that suggest the operation of an anti-cooperative mechanism strongly conditioned by an attenuated growth. In this mechanism, the formation of the nuclei is favoured over the subsequent addition of monomeric units to the aggregate, which finally results in short aggregates. Theoretical calculations show that both the BDT and BODIPY motifs, after forming the initial dimeric nuclei, experience a strong distortion of the central aromatic backbone upon growth, which makes the addition of successive monomeric units unfavourable and impedes the formation of long fibrillar structures. Despite the anti-cooperativity observed in the supramolecular polymerization of 1 and 2, the combination of both self-assembling units results in the formation of small co-assembled aggregates with a similar supramolecular polymerization behaviour to that observed for the separate components.

| S-EPMC8694371 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data