New Insights on Solvent-Induced Changes in Refractivity and Specific Rotation of Poly(propylene oxide) Systems Extracted from Channeled Spectra DOI Open Access

Alexandru Zara,

Raluca Marinica Albu, Iuliana Stoica

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(9), P. 4682 - 4682

Published: April 25, 2024

Investigation of chiroptical polymers in the solution phase is paramount for designing supramolecular architectures photonic or biomedical devices. This work devoted to case study poly(propylene oxide) (PPO) optical activity several solvents: benzonitrile, carbon disulfide, chloroform, ethyl acetate, and p-dioxane. To attain information on interactions these systems, rheological testing was undertaken, showing distinct variations parameters as a function solvent type. These aspects are also reflected refractive index dispersive behavior, from which linear non-linear properties extracted. determine circular birefringence specific rotation PPO solutions, alternative method channeled spectra employed. The spectral data were correlated with molecular modeling structural unit selected solvents. Density functional theory (DFT) computational indicated that torsional potential energy—related O1-C2-C3-O4 dihedral angle polymer repeating unit—was hindered solvation environments characterized by high polarity ability interact via hydrogen bonding. agreement characterization samples, lower solutions acetate Also, shape rotatory dispersion curves slightly modified solvents compared other ones.

Language: Английский

Torsional Strain Enabled Ring‐Opening Polymerization towards Axially Chiral Semiaromatic Polyesters with Chemical Recyclability DOI
Qing Cao,

Yi‐Min Tu,

Hua‐Zhong Fan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 15, 2024

Abstract The development of new chemically recyclable polymers via monomer design would provide a transformative strategy to address the energy crisis and plastic pollution problem. Biaryl‐fused cyclic esters were targeted generate axially chiral polymers, which impart material performance. To overcome non‐polymerizability biaryl‐fused DBO, ester Me‐DBO installed with dimethyl substitution was prepared enable its polymerizability enhancing torsional strain. Impressively, readily went through well‐controlled ring‐opening polymerization, producing polymer P(Me‐DBO) high glass transition temperature ( T g >100 °C). Intriguingly, mixing these complementary enantiopure containing axial chirality promoted transformation from amorphous crystalline material, affording semicrystalline stereocomplex melting more than 300 °C. capable depolymerizing back in efficiency, highlighting an excellent recyclability.

Language: Английский

Citations

10
Chiral polymer micro/nano-objects: evolving preparation strategies in heterogeneous polymerization DOI Creative Commons
Dongdong Liu,

Jinyan Zhao,

Xi Zhao

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 13, 2024

Language: Английский

Citations

5
Induced Chirality in Canthaxanthin Aggregates Reveals Multiple Levels of Supramolecular Organization DOI Creative Commons
Monika Halat, Grzegorz Zając, Valery Andrushchenko

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 22, 2024

Carotenoids tend to form supramolecular aggregates via non-covalent interactions where the chirality of individual molecules is amplified macroscopic level. We show that this can also be achieved for non-chiral carotenoid monomers interacting with polysaccharides. The induction in canthaxanthin (CAX), caused by heparin (HP) and hyaluronic acid (HA), was monitored chiroptical spectroscopy. Electronic circular dichroism (ECD) Raman optical activity (ROA) spectra indicated presence multiple formations, such as H- J-type aggregates. This consistent molecular dynamics (MD) density functional theory (DFT) simulations structures their spectroscopic response.

Language: Английский

Citations

4
Regulating the Chirality of the Superhelices Self-Assembled from Block Copolymer/Homopolymer Binary Systems by the Mixing Ratio of the Polymers DOI
Kexin Cao,

Yue Du,

Jiaping Lin

et al.

Macromolecules, Journal Year: 2024, Volume and Issue: 57(14), P. 6514 - 6521

Published: July 11, 2024

Language: Английский

Citations

4
Using Achiral Monomers to Synthesize Organometallic Chiral Copolymers on an Achiral Surface DOI
Yuchen Bai, Zhongyi Wu, Yuxuan Lin

et al.

ACS Nano, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Preparing chiral polymers by using achiral building blocks in an reaction environment is very demanding because this strategy avoids the use of expensive reagents. Here, a surface-confined and sequence-controlled copolymer synthesized organometallic reactions between precursors 4,4″-dibromo-1,1′:3′,1′′-terphenyl 1-ethynyl-4-[2-(4-ethynylphenyl)ethynyl]benzene on Ag(111) surface. Combined scanning tunneling microscopy density functional theory explorations show that terminal alkyne aromatic bromide undergo dehydrogenated debrominated metalations with surface Ag adatoms to yield polymeric products. Despite substrate employed, [phenyl–Ag–alkynyl–Ag–phenyl–Ag]n adsorption configuration stands out from various competitors become dominant copolymeric product. Mechanistic analysis reveals such selectivity originates precise control both sequence product during its growth, where interpolymer interactions play pivotal role. These also drive enantioselective assembly copolymers form domains, which achieves chirality transfer single-molecular supramolecular level. findings demonstrate power chemistry creating nanostructures precursors, may help achieve functionalization.

Language: Английский

Citations

0
Highly Photoelectrical responsive and Controllable Supramolecular Helical Assemblies with Dual Functionalities as Photo-Organocatalysts DOI

Yahao Ren,

Duo Wei, Wei Yang

et al.

Colloids and Surfaces A Physicochemical and Engineering Aspects, Journal Year: 2025, Volume and Issue: unknown, P. 136968 - 136968

Published: April 1, 2025

Language: Английский

Citations

0
Chiral Polymer-induced Hydroxyapatite for Promoting Bone Regeneration DOI Creative Commons
Zongying Zhang, Bing Liang, Dan Wang

et al.

Materials Today Bio, Journal Year: 2025, Volume and Issue: 31, P. 101460 - 101460

Published: Jan. 5, 2025

Chirality is one of the basic characteristics living matter, yet effect chiral polymers on osteogenesis seldom studied. Thus, it necessary to deeply recognize behaviors in osteogenic processes, which can be beneficial for development bone repair materials. In this work, hydroxyapatite (HAP) was constructed simply using poly(levorotatory/dextral-tartaric acid) as guest transfer system. We studied influence HAPs migration and differentiation pre-osteoblasts, angiogenesis endothelial cell vitro. The results showed that poly(levorotatory-tartaric acid)-induced HAP did promote vascular remodeling exhibited excellent impact osteogenetic by improving related gene protein expression, whereas no significant change observed poly(dextral-tartaric or poly(racemic-tartaric induced HAP, respectively. This study highlighted effects potential, laid groundwork biomaterials regeneration.

Language: Английский

Citations

0
“Gear-driven”-type chirality transfer of tetraphenylethene-based supramolecular organic frameworks for peptides in water DOI Creative Commons
Chaochao Yan,

Qingfang Li,

Kaige Wang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(10), P. 3758 - 3766

Published: Jan. 1, 2024

Chirality transfer for natural chiral biomolecules can reveal the indispensable role of structures in life and be used to develop chirality-sensing biomolecular recognition. Here, we report synthesis characterization a series achiral supramolecular organic frameworks (SOF-1, SOF-2, SOF-3), constructed from cucurbit[8]uril (CB[8]) tetraphenylethene (TPE) derivatives (1, 2, 3), respectively, as platforms explore their chirality mechanism peptides water. Given right-handed (P) left-handed (M) rotational conformation TPE units selective binding CB[8] aromatic amino acids, these SOFs selectively triggered water by containing N-terminal tryptophan (W) phenylalanine (F) residues into P- or M-rotational conformation, exhibiting significantly different circular dichroism (CD) spectra. Although various have same l-type configuration, they induce positive CD signals SOF-1 negative SOF-2 SOF-3, respectively. Based on structural analysis linkage between SOFs, "gear-driven"-type has been proposed visually illustrate multiple-step process recognition site CB[8]'s cavity units. Furthermore, utilizing characteristic generated through transfer, serve chiroptical sensor arrays effectively recognize distinguish based distinctive

Language: Английский

Citations

1
Torsional Strain Enabled Ring‐Opening Polymerization towards Axially Chiral Semiaromatic Polyesters with Chemical Recyclability DOI
Qing Cao,

Yi‐Min Tu,

Hua‐Zhong Fan

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Feb. 15, 2024

Abstract The development of new chemically recyclable polymers via monomer design would provide a transformative strategy to address the energy crisis and plastic pollution problem. Biaryl‐fused cyclic esters were targeted generate axially chiral polymers, which impart material performance. To overcome non‐polymerizability biaryl‐fused DBO, ester Me‐DBO installed with dimethyl substitution was prepared enable its polymerizability enhancing torsional strain. Impressively, readily went through well‐controlled ring‐opening polymerization, producing polymer P(Me‐DBO) high glass transition temperature ( T g >100 °C). Intriguingly, mixing these complementary enantiopure containing axial chirality promoted transformation from amorphous crystalline material, affording semicrystalline stereocomplex melting more than 300 °C. capable depolymerizing back in efficiency, highlighting an excellent recyclability.

Language: Английский

Citations

1
Tailoring topology and bio-interactions of triazine frameworks DOI Creative Commons

Sara Bagheri,

Mohsen Adeli, Abedien Zabardasti

et al.

Scientific Reports, Journal Year: 2024, Volume and Issue: 14(1)

Published: June 26, 2024

The construction of covalent organic frameworks with special geometery and optical properties is high interest, due to their unique physicochemical biological properties. In this work, we report on a new method for the triazine defined topologies using coordination chemistry. Ball milling wet chemical reactions between cyanuric chloride melamine were directed in spatial arrangements opposite activity. Cobalt was used as directing agent drive into morphologies, enantiorecognition ability that manifested activities against bacteria, demonstrated way materials specific interactions at biointerfaces.

Language: Английский

Citations

1