Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts DOI
Matthew A. Sanders, Supraja S. Chittari,

Jack R. Foley

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 17404 - 17413

Опубликована: Июнь 12, 2024

Complex interactions between noncoordinating residues are significant yet commonly overlooked components of macromolecular catalyst function. While these have been demonstrated to impact binding affinities and catalytic rates in metalloenzymes, the roles similar structural elements synthetic polymeric catalysts remain underexplored. Using a model Suzuki-Miyuara cross-coupling reaction, we performed series systematic studies probe interconnected effects metal-ligand cross-links, electrostatic interactions, local rigidity polymer catalysts. To achieve this, novel bifunctional triphenylphosphine acrylamide (BisTPPAm) monomer was synthesized evaluated alongside an analogous monofunctional (TPPAm). In copolymer catalysts, increased initial reaction were observed for copolymers untethered by Pd complexation (BisTPPAm-containing) compared Pd-cross-linked (TPPAm-containing). Further, incorporating through secondary structure-like revealed nonmonotonic relationships composition rate, demonstrating potential tunable behavior secondary-sphere interactions. Finally, rigorous cheminformatics featurization strategies statistical modeling, quantitated chemical descriptors substrate conditions on performance. Collectively, results provide insights into among composition, structure, function protein-mimetic copolymers.

Язык: Английский

Dynamic Implications of Noncovalent Interactions in Amphiphilic Single-Chain Polymer Nanoparticles DOI

Peter A. Dykeman-Bermingham,

Laura R. Stingaciu, Changwoo Do

и другие.

ACS Macro Letters, Год журнала: 2024, Номер 13(7), С. 889 - 895

Опубликована: Июль 3, 2024

Single-chain polymer nanoparticles (SCNPs) combine the chemical diversity of synthetic polymers with intricate structure biopolymers, generating versatile biomimetic materials. The mobility chain segments at length scales similar to secondary structural elements in proteins is critical SCNP and thus function. However, influence noncovalent interactions used form SCNPs (e.g., hydrogen-bonding secondary-like structure) on these conformational dynamics challenging quantitatively assess. To isolate effects dynamics, we synthesized a series amphiphilic copolymers containing dimethylacrylamide monomers capable forming different interactions: (1) di(phenylalanine) acrylamide that forms intramolecular β-sheet-like cross-links, (2) phenylalanine hydrogen-bonds but lacks defined local structure, (3) benzyl has lowest propensity for hydrogen-bonding. Each formed folded structures comparable those intrinsically disordered proteins, as observed by size exclusion chromatography small angle neutron scattering. polymers, characterized combination dynamic light scattering spin echo spectroscopy, was well described using Zimm internal friction (ZIF) model, highlighting role each interaction additively restrict relaxations SCNPs. These results demonstrate utility scale control guiding design functional materials refined binding sites tunable kinetics.

Язык: Английский

Процитировано

3
Amphiphilic block copolymer conjugated with cell-penetrating-peptides derived from Influenza A H1N1 virus as a biocompatible scaffold for enhanced cell-uptake DOI Creative Commons

Carolina Ventura‐Hunter,

David Pretzel, Caroline Gubser Keller

и другие.

European Polymer Journal, Год журнала: 2025, Номер unknown, С. 113876 - 113876

Опубликована: Март 1, 2025

Язык: Английский

Процитировано

0
FRET‐Based Investigation of the Dynamics of Peptide‐Folded Single Chain Nanoparticles Inside Cancer Cells DOI Creative Commons

Shegufta Farazi,

Radhika Raveendran,

Alexander Macmillan

и другие.

Macromolecular Rapid Communications, Год журнала: 2025, Номер unknown

Опубликована: Май 21, 2025

Abstract Single chain nanoparticles (SCNPs) prepared using diphenylalanine ( L FF) as crosslinker have recently been proposed protein‐inspired drug delivery carriers. The aim of this work is to learn more about the stability these peptide‐based supramolecular systems in biological environments Förster resonance energy transfer and fluorescence lifetime imaging microscopy (FRET‐FLIM). Two self‐folding poly( N,N ‐dimethyl acrylamide) PDMA with 10 mol.% pendant FF, labeled at omega end cyanine dyes Cy5 Cy3, respectively, are formed into SCNPs sizes below nm. particles found be stable water do not aggregate a cellular environment (MCF‐7 breast cancer cells). uptaken by cells slightly faster than control nanoparticle same polymers (≈100 nm cell culture media) similar total uptake after 1 h. Temperature‐dependent studies demonstrate that while larger dependent on endocytosis for uptake, can cross membrane via diffusion. This study demonstrates value FRET‐FLIM understanding behavior self‐assembled vitro provides additional evidence alternate pathways access over traditional based

Язык: Английский

Процитировано

0
Quasi‐Chromophores Segregated by Single‐Chain Nanoparticles of Fluorinated Zwitterionic Random Copolymers Showing Remarkably Enhanced Fluorescence Emission Capable of Fluorescent Cell Imaging DOI
Yongming Zeng, Tianchi Xu,

Weizhi Chen

и другие.

Macromolecular Rapid Communications, Год журнала: 2024, Номер 45(11)

Опубликована: Март 13, 2024

Abstract Organic and polymer fluorescent nanomaterials are a frontier research focus. Here in this work, series of fluorinated zwitterionic random copolymers end‐attached with quasi‐chromophoric group pyrene or tetraphenylethylene (TPE) well synthesized via atom transfer radical polymerization activators regenerated by electron (ARGET ATRP). Those total degree 100 200 able to produce single‐chain nanoparticles (SCNPs) through intra‐chain self‐folding assembly quite uniform diameters the range 10–20 nm as characterized dynamic light scattering transmission microscopy. By virtue segregation confinement effect, both SCNPs functionalized TPE capable emitting fluorescence, tethered exhibiting stronger fluorescence emission reaching highest quantum yield ≈20%. Moreover, such kind manifest low cytotoxicity good cell imaging performance for Hela cells. The creation covalently attached one quasi‐chromophore end copolymer provides an alternative strategy preparing polymeric luminescence nanomaterials, promisingly serving new type nanoprobes biological applications.

Язык: Английский

Процитировано

1
Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts DOI Creative Commons
Matthew A. Sanders, Supraja S. Chittari,

Jack R. Foley

и другие.

Опубликована: Апрель 15, 2024

Complex interactions between non-coordinating residues are significant yet commonly overlooked components of macromolecular catalyst function. While these have been demonstrated to impact binding affinities and catalytic rates in metalloenzymes, the roles similar structural elements synthetic polymeric catalysts remain underexplored. Using a model Suzuki-Miyuara cross-coupling reaction, we performed series systematic studies probe interconnected effects metal-ligand cross-links, electrostatic interactions, local rigidity polymer catalysts. To achieve this, novel bi-functional triphenylphosphine acrylamide (BisTPPAm) monomer was synthesized evaluated alongside an analogous monofunctional (TPPAm). In copolymer catalysts, increased initial reaction were observed for copolymers untethered by Pd complexation (BisTPPAm-containing) as compared Pd-cross-linked (TPPAm-containing). Further, incorporating through secondary structure-like revealed nonmonotonic relationships composition rate, demonstrating potential tunable behavior sphere interactions. Finally, rigorous cheminformatics featurization strategies statistical modeling, quantitated chemical descriptors substrate conditions on performance. Collectively, results provide insights into composition, structure, function protein-mimetic copolymers.

Язык: Английский

Процитировано

1
Macromolecular Function Emerging from Intramolecular Peptide Stapling of Synthetic Polymers DOI

Henrik Kalmer,

Federica Sbordone, John C. McMurtrie

и другие.

Macromolecular Rapid Communications, Год журнала: 2024, Номер unknown

Опубликована: Окт. 22, 2024

Abstract Protein function results from the precise folding of polypeptides into bespoke architectures. Taking inspiration nature, field single‐chain nanoparticles (SCNPs), intramolecularly crosslinked synthetic polymers, emerged. In contrast to SCNPs is generally defined by parent polymer or applied crosslinker, rather than crosslinking process itself. This work explores cyanopyridine–aminothiol click reaction crosslink peptide‐decorated polymers intra‐macromolecularly endow resulting with emerging functionality, conversion N‐terminal cysteine units pyridine‐thiazolines. Dimethylacrylamide based different cysteine‐terminated amino acid sequences tethered their sidechains are investigated ( P1 (C), P2 (GDHC), P3 (GDSC)) and SCNPs. Since deprotection yields disulfide‐based SCNPs, a direct comparison between disulfide pyridine‐thiazolines possible. revealed two properties pyridine‐thiazoline SCNPs: 1) The formation gave rise metal binding sites within SCNP, which complexed iron. 2) Depending on peptide sequence in precursor polymer, hydrolytic activity either increased (GDHC) decreased (GDSC) upon compared identical crosslinks.

Язык: Английский

Процитировано

0
Leveraging Triphenylphosphine-Containing Polymers to Explore Design Principles for Protein-Mimetic Catalysts DOI
Matthew A. Sanders, Supraja S. Chittari,

Jack R. Foley

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(25), С. 17404 - 17413

Опубликована: Июнь 12, 2024

Complex interactions between noncoordinating residues are significant yet commonly overlooked components of macromolecular catalyst function. While these have been demonstrated to impact binding affinities and catalytic rates in metalloenzymes, the roles similar structural elements synthetic polymeric catalysts remain underexplored. Using a model Suzuki-Miyuara cross-coupling reaction, we performed series systematic studies probe interconnected effects metal-ligand cross-links, electrostatic interactions, local rigidity polymer catalysts. To achieve this, novel bifunctional triphenylphosphine acrylamide (BisTPPAm) monomer was synthesized evaluated alongside an analogous monofunctional (TPPAm). In copolymer catalysts, increased initial reaction were observed for copolymers untethered by Pd complexation (BisTPPAm-containing) compared Pd-cross-linked (TPPAm-containing). Further, incorporating through secondary structure-like revealed nonmonotonic relationships composition rate, demonstrating potential tunable behavior secondary-sphere interactions. Finally, rigorous cheminformatics featurization strategies statistical modeling, quantitated chemical descriptors substrate conditions on performance. Collectively, results provide insights into among composition, structure, function protein-mimetic copolymers.

Язык: Английский

Процитировано

0