Revealing the effect of stereocontrol on intermolecular interactions between abiotic, sequence-defined polyurethanes and a ligand DOI Creative Commons

Maksymilian Szatko,

Weronika Forysiak, Sara Kozub

et al.

Published: April 29, 2024

The development of precision polymer synthesis has facilitated access to a diverse library abiotic structures, wherein chiral monomers are positioned at specific locations within macromolecule chains. These structures anticipated exhibit folding characteristics similar biotic macromolecules and possess comparable functionalities. However, the extensive sequence space numerous variables make selecting with desired function challenging. Therefore, revealing sequence-function dependencies developing practical tools necessary analyze their conformation molecular interactions. In this study, we investigate effect stereochemistry, which dictates spatial location backbone pendant groups, on interaction between sequence-defined oligourethanes bisphenol A ligands. Various methods explored receptor-like properties model oligomers ligand. accuracy dynamics simulations experimental techniques is assessed uncover impact discrete changes in stereochemical arrangements structure resulting complexes binding strength. Detailed computational investigations providing atomistic details show that formed demonstrate significant structural diversity depending stereocenters, thus affecting oligomer-ligand Among tested techniques, fluorescence spectroscopy data, fitted Stern-Volmer equation, consistently aligned calculations, validating developed simulation methodology. methodology opens way engineer functionality explore applications, e.g., as sensory materials.

Language: Английский

Sequence- and stereo-defined macromolecules: Properties and emerging functionalities DOI
Róża Szweda

Progress in Polymer Science, Journal Year: 2023, Volume and Issue: 145, P. 101737 - 101737

Published: Aug. 16, 2023

Language: Английский

Citations

17
Revealing the Effect of Stereocontrol on Intermolecular Interactions between Abiotic, Sequence-Defined Polyurethanes and a Ligand DOI Creative Commons

Maksymilian Szatko,

Weronika Forysiak, Sara Kozub

et al.

ACS Biomaterials Science & Engineering, Journal Year: 2024, Volume and Issue: 10(6), P. 3727 - 3738

Published: May 28, 2024

The development of precision polymer synthesis has facilitated access to a diverse library abiotic structures wherein chiral monomers are positioned at specific locations within macromolecular chains. These anticipated exhibit folding characteristics similar those biotic macromolecules and possess comparable functionalities. However, the extensive sequence space numerous variables make selecting with desired function challenging. Therefore, revealing sequence–function dependencies developing practical tools necessary analyze their conformations molecular interactions. In this study, we investigate effect stereochemistry, which dictates spatial location backbone pendant groups, on interaction between sequence-defined oligourethanes bisphenol A ligands. Various methods explored receptor-like properties model oligomers ligand. accuracy dynamics simulations experimental techniques is assessed uncover impact discrete changes in stereochemical arrangements resulting complexes binding strengths. Detailed computational investigations providing atomistic details show that formed demonstrate significant structural diversity depending stereocenters, thus affecting oligomer–ligand strength. Among tested techniques, fluorescence spectroscopy data, fitted Stern–Volmer equation, consistently aligned calculations, validating developed simulation methodology. methodology opens way engineer structure functionality explore applications, e.g., as sensory materials.

Language: Английский

Citations

4
Carbamate‐Functionalized NLOphores via a Formal [2+2] Cycloaddition‐Retroelectrocyclization Strategy DOI Creative Commons
İpek Savaş, M. Çelik, Alberto Barsella

et al.

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 23, 2025

This study introduces a new donor group capable of activating click-type [2+2] cycloaddition-retroelectrocyclizations, generally known for their limited scope. Target chromophores were synthesized using isocyanate-free urethane synthesis. The developed synthetic method allows the tuning optical properties by modifying groups, acceptor units, and side chains. charge transfer (CT) bands exhibit λmax values ranging from 363 to 692 nm. CT observed have been supported solvatochromism protonation experiments. compounds positive solvatochromism. Due potential as NLOphore candidates, stability investigated both experimentally through TGA theoretically calculating parameters such frontier orbital energy differences, electronegativity, global hardness/softness. TD-DFT calculations used elucidate nature electronic transitions, revealing that correspond arising HOMO-to-LUMO excitations. NLO DFT methods EFISHG technique. Both results are shown be in agreement with HOMO-LUMO differences. experimental μβ selected molecules range 470×10-48 5400×10-48 esu.

Language: Английский

Citations

0
Design and Construct Cyclic Carbonate Functionalized Chitosan‐Based Hydrogel Enabling Photodecarboxylase Immobilization with Enhanced Stability and Reusability DOI Open Access

Jianle Zhou,

Xiongliang He,

Yanyan Ye

et al.

Advanced Sustainable Systems, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 26, 2025

Abstract Fatty acid photodecarboxylase (FAP) plays a crucial role in the green production of biofuel and other valuable biochemicals. However, reusability immobilized FAP has been limited due to inadequate durability. Here, porous, translucent chitosan hydrogel sphere carrier functionalized with cyclic carbonate group enhance is presented. Based on arrangement basic amino residues surface FAP, bis(cyclic carbonate) containing flexible chain from CO 2 designed synthesized. This compound used modify porous hydrogels obtained via template‐etching process. then covalently within framework through reaction remaining groups, as evidenced by quartz crystal microbalance analysis. The modified carrier, PH3‐BC‐II, significantly improves activity achieving maximum conversion 70.0%, enzyme loading 125.3 mg g −1 (dry carrier). Furthermore, PH3‐BC‐II retains >50% its initial after eight consecutive cycles (total runtime 24 h) at high fatty substrate concentrations. study provides an effective strategy for constructing stable (photo)enzymes sustainable materials.

Language: Английский

Citations

0
Computational Study on the Pd-Catalyzed Pathway for the Formation of (R)-Methyl-(2-Hydroxy-1-Phenylethyl)Carbamate DOI Creative Commons
Silvia González, Consuelo Mendoza Herrera, Lydia María Pérez Díaz

et al.

Molecules, Journal Year: 2025, Volume and Issue: 30(8), P. 1781 - 1781

Published: April 16, 2025

The formation of (R)-methyl-(2-hydroxy-1-phenylethyl)carbamate through Pd(PPh3)4-catalyzed synthesis was investigated using computational methods to elucidate the reaction pathway and energetic feasibility. Density functional theory (DFT) calculations confirmed that direct between (R)-(-)-2-phenylglycinol methyl chloroformate is not spontaneous, requiring a catalyst proceed efficiently. study proposes detailed mechanistic involving ligand dissociation, intermediate formation, hydrogenation. role Pd(PPh3)4 examined, demonstrating its ability stabilize intermediates facilitate key transformations, such as dehydrogenation chlorine elimination. Two pathways were identified, with Pathway 1 exhibiting net energy –84.7 kcal/mol 2 showing an initial positive 90.1 kcal/mol. However, regeneration in ultimately reduces total –238.7 kcal/mol, confirming feasibility both routes. Computational results align experimental NMR data, supporting proposed intermediates. These findings provide valuable insights into optimization, suggesting modifications or alternative palladium-based catalysts could enhance efficiency. This advances understanding Pd-catalyzed carbamate offers basis for future investigations.

Language: Английский

Citations

0
Revealing the effect of stereocontrol on intermolecular interactions between abiotic, sequence-defined polyurethanes and a ligand DOI Creative Commons

Maksymilian Szatko,

Weronika Forysiak, Sara Kozub

et al.

Published: April 29, 2024

The development of precision polymer synthesis has facilitated access to a diverse library abiotic structures, wherein chiral monomers are positioned at specific locations within macromolecule chains. These structures anticipated exhibit folding characteristics similar biotic macromolecules and possess comparable functionalities. However, the extensive sequence space numerous variables make selecting with desired function challenging. Therefore, revealing sequence-function dependencies developing practical tools necessary analyze their conformation molecular interactions. In this study, we investigate effect stereochemistry, which dictates spatial location backbone pendant groups, on interaction between sequence-defined oligourethanes bisphenol A ligands. Various methods explored receptor-like properties model oligomers ligand. accuracy dynamics simulations experimental techniques is assessed uncover impact discrete changes in stereochemical arrangements structure resulting complexes binding strength. Detailed computational investigations providing atomistic details show that formed demonstrate significant structural diversity depending stereocenters, thus affecting oligomer-ligand Among tested techniques, fluorescence spectroscopy data, fitted Stern-Volmer equation, consistently aligned calculations, validating developed simulation methodology. methodology opens way engineer functionality explore applications, e.g., as sensory materials.

Language: Английский

Citations

1