Controlling Glycan Folding with Ionic Functional Groups DOI Creative Commons

Nishu Yadav,

Ana Poveda,

Yadiel Vázquez Mena

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 24, 2025

Glycans are intrinsically flexible molecules that can adopt many conformations. These often carry ionic functional groups influence glycan's conformational preferences, dynamics, and aggregation tendencies. Inspired by these mechanisms, we have engineered a glycan sequence whose secondary structure be precisely manipulated using groups. We strategically incorporated substituents into adopting hairpin conformation. Complementary stabilized the closed conformers, while repulsions shifted populations toward open forms. External stimuli, such as pH variations or enzyme addition, enabled us to dynamically control hairpin's opening closing. Additionally, changes in protonation states led aggregation, suggesting opportunities for creation of responsive glycan-based materials.

Язык: Английский

Oligo(phenyleneethynylene)s: Shape‐Tunable Building Blocks for Supramolecular Self‐Assembly DOI Creative Commons
Zulema Fernández, Luis Sánchez, Sukumaran Santhosh Babu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(18)

Опубликована: Фев. 29, 2024

Abstract Oligo(phenyleneethynylene)s (OPEs) have attracted widespread attention due to their remarkable (opto)electronic and photophysical properties, which enabled numerous applications. The versatile functionalization possibilities of OPEs make them unique candidates form various shape‐persistent geometries, including linear, triangular, rectangular, hexagonal macrocyclic. However, as a result this structural variety, it is oftentimes challenging correlate molecular design with self‐assembly properties. In minireview, we classified based on shapes correlated behavior in solution. Particularly, provide important insights into the aggregation propensity different how tune association strength using non‐covalent interactions. Our classification will enable better understanding structure‐property correlation OPEs, key develop supramolecular functional materials.

Язык: Английский

Процитировано

18
Chiral Nanostructures from Artificial Helical Polymers: Recent Advances in Synthesis, Regulation, and Functions DOI
Yuan Qiu,

Xilong Wei,

Jacky W. Y. Lam

и другие.

ACS Nano, Год журнала: 2025, Номер 19(1), С. 229 - 280

Опубликована: Янв. 4, 2025

Helical structures such as right-handed double helix for DNA and left-handed α-helix proteins in biological systems are inherently chiral. Importantly, chirality at the nanoscopic level plays a vital role their macroscopic chiral functionalities. In order to mimic functions of natural nanoarchitectures, variety nanostructures obtained from artificial helical polymers prepared, which can be directly observed by atomic force microscopy (AFM), scanning tunneling (STM), electron (SEM), transmission (TEM). This review mainly focuses on formation morphology regulation triggered polymer chain length, concentration, solvent, temperature, photoirradiation, chemical additives. addition, distinct including recognition, circularly polarized luminescence, drug release, cell imaging, antibiosis also discussed.

Язык: Английский

Процитировано

3
Chiral structures in azobenzene‐containing systems: Construction, regulation, and application DOI Creative Commons

Zixiang He,

Xiaoxiao Cheng, Zhao Wang

и другие.

Deleted Journal, Год журнала: 2024, Номер 2(2)

Опубликована: Май 1, 2024

Abstract Chirality is a fundamental property in nature, which essential for the existence and survival of living organisms. Smart responsive chiroptical materials have garnered increasing attention due to their unique structural characteristics potential applications. Among these, azobenzene (Azo), as typical photoresponsive chromophore, plays crucial role constructing controlling chiral structures. The cis ‐ trans isomerization, liquid crystallinity, other physicochemical properties allow wide range tunability stimuli‐responsive materials. Herein, we review research studies field chiral/achiral Azo building blocks multilevel generation well switching, summarize recent advances on applications structures from micro macro levels. Finally, aim provide an overview challenges new opportunities development novel smart

Язык: Английский

Процитировано

14
In situ thermoresponsive supramolecular assembly for switchable circularly polarized luminescence DOI

Menghan Pan,

Gong Zhang, Haotian Ma

и другие.

Science China Chemistry, Год журнала: 2024, Номер 67(7), С. 2362 - 2372

Опубликована: Май 27, 2024

Язык: Английский

Процитировано

14
Inducing and Switching the Handedness of Polyacetylenes with Topologically Chiral [2]Catenane Pendants DOI
Yu Wang, Xin Zhang,

Chang‐Bo Huang

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(37)

Опубликована: Июнь 5, 2024

Abstract To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed helical poly(phenylacetylenes) (PPAs) main chain topologically chiral [2]catenane pendants are described for first time. These with optically active [2]catenanes on side chains were synthesized by polymerization enantiomerically pure ethynyl site and/or point moiety. The information was successfully transferred to polyene backbones, leading preferred‐handed conformations, while introduction units has negligible effect overall helices. More interestingly, attributed unique dynamic feature pendants, these polymers revealed response behaviors solvents, temperature, sodium ions, resulting in fully reversible on/off induction. This work provides not only new design strategy novel chiroptical switches molecules but also platforms development smart materials.

Язык: Английский

Процитировано

7
M/P Helicity Switching and Chiral Amplification in Double-Helical Monometallofoldamers DOI Creative Commons

Kotaro Matsumura,

K. Kinjo,

Kotaro Tateno

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(30), С. 21078 - 21088

Опубликована: Июль 19, 2024

Short-stranded double-helical monometallofoldamers capable of M/P-switching were constructed by the complexation two strands, each with L-shaped units linked a 2,2′-bipyridine, Zn(II) cation. The helix terminals "double-helical form" folded π–π interactions can unfold in solution to equilibrate "open forms" that are favored at higher temperatures. Interestingly, helical chirality chiral side chains induced single-handed sense and controlled depending on achiral solvent stimuli. For instance, (M)-helicity was nonpolarized solvents (toluene, hexane, Et2O), whereas (P)-helicity Lewis basic (acetone, DMSO). Circular dichroism (CD) rotating-frame overhauser enhancement spectroscopy (ROESY) measurements revealed conformational change due interaction double helices helicity bias. These novel possessed stable structure exhibited switchable chiroptical properties (gabs ∼ 10–3–10–2). In addition, strand transfer amplification abilities through formation heteroleptic when mixed an strand.

Язык: Английский

Процитировано

7
Pathway-directed recyclable chirality inversion of coordinated supramolecular polymers DOI Creative Commons

Kuo Fu,

Yanli Zhao,

Guofeng Liu

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Ноя. 6, 2024

It remains challenging to elucidate the fundamental mechanisms behind dynamic chirality inversion of supramolecular assemblies with pathway complexity. Herein, metal coordination driven assembly systems based on pyridyl-conjugated cholesterol (PVPCC) and ions (Ag+ or Al3+) are established demonstrate pathway-directed, recyclable polymorphism. In Ag(I)/PVPCC system, a competitive leads Ag-Complex form either kinetically controlled polymer (Ag-SP I) thermodynamically favored Ag-SP II, accompanied by reversible chiroptical inversion. Conversely, Al(III)/PVPCC system displays solvent-assisted consecutive pathway: Al-Complex initially forms ethanol-containing Al-SP subsequently converts into ethanol-free I opposite performance upon thermal treatment. Moreover, stable in solid state enables potential circularly polarized luminescence encryption when is co-assembled thioflavin T. These findings provide guidance for modulation functionality materials applications information processing, data encryption, chiral spintronics. Elucidation complexity challenging. Here, authors report show that facilitate

Язык: Английский

Процитировано

7
Thermo/Light Dual-Responsive Helical Dendronized Poly(phenylacetylene)s DOI
Xueting Lu, Liangxuan Ren, Xiacong Zhang

и другие.

Macromolecules, Год журнала: 2024, Номер 57(12), С. 5915 - 5928

Опубликована: Июнь 4, 2024

Stimuli-responsive helical polymers form an intriguing class of materials that may find broad applications in chiroptical or switchable chiral devices. Here we report the synthesis a dendronized copolymers with poly(phenylacetylene) (PPA) backbones. These carry methoxy-terminated dendritic oligoethylene glycol (OEG) pendants and spiropyran moieties. Both block random were prepared to investigate effect structure on their stimuli-responsiveness helicities, as well supramolecular assemblies aqueous conditions. The exhibited typical thermoresponsive behavior through thermal dehydration OEGs tunable cloud point temperatures (Tcps). Polarity differences between hydrophilic OEG lipophilic PPA backbones afforded all radial amphiphilicity. In addition, for copolymers, polarity SP further provided axial Their unprecedented amphiphilic nature drove preferentially aggregate water even below Tcps. On heating across Tcps, thermally induced phase transitions resulted switches helicity. Photoisomerization moieties closed spirocyclic (SP) open merocyanine (MC) within copolymer matrices was dependent balance interactions OEGs, which did not exhibit obvious influence helicities. Supramolecular assembly tend extremely long fibers thicknesses about 25 nm, while anisotropic nanocubes dimensions around 400–600 nm observed from indicating topology plays important role modulating assemblies.

Язык: Английский

Процитировано

6
Self‐Assembled Nanohelixes Driven by Host‐Guest Interactions and Metal Coordination DOI Open Access

Xin‐Yue Lou,

Kun Zhang,

Yujie Bai

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Авг. 20, 2024

Abstract Helical nanostructures fabricated via the self‐assembly of artificial motifs have been a captivating subject because their structural aesthetics and multiple functionalities. Herein, we report facile construction self‐assembled nanohelix ( NH ) by leveraging an achiral aggregation‐induced emission (AIE) luminogen G pillar[5]arene H ), driven host–guest interactions metal coordination. Inspired “sergeants soldiers” effect “majority rule” principle, complexation between is employed to fixate twisted conformation for generation “contortion sites”, which further induced emergence helicity as 1D assemblies are formed Ag(I) coordination hexagonally packed into nano‐sized fibers. The strategy has proved feasible in both homogeneous heterogeneous syntheses. Along with formation , boosted luminescence enhanced productivity reactive oxygen species (ROS) afforded efficient restriction on indicating concurrent regulation ′s morphology photophysical properties supramolecular assembly. In addition, also exhibits capacity bacteria imaging photodynamic antibacterial activities against Staphylococcus aureus S. Escherichia coli E. ).

Язык: Английский

Процитировано

6
Size Control of Chiral Nanospheres Obtained via Nanoprecipitation of Helical Poly(phenylacetylene)s in the Absence of Surfactants DOI Creative Commons
Manuel Núñez‐Martínez, Manuel Fernández‐Míguez, Emilio Quiñoá

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(32)

Опубликована: Май 14, 2024

Abstract Nanostructuration of dynamic helical polymers such as poly(phenylacetylene)s (PPAs) depends on the secondary structure adopted by polymer and functional group used to connect chiral pendant PPA backbone. Thus, while PPAs with flexible scaffolds ( para ‐ meta ‐substituted, ω 1 <165°) generate nanoprecipitation low polydisperse nanospheres controllable size at different acetone/water mixtures, those a quasi‐static behavior presence an extended, almost planar ortho‐ substituted, >165°), aggregate into mixture spherical oval nanostructures whose is not controlled. Photostability studies show that poly(phenylacetylene) particles are more stable light irradiation than when dissolved macromolecularly. Moreover, photostability particle its screw sense excess. This fact, in combination encapsulation ability these particles, allows creation stimuli‐responsive nanocarriers, cargo can be delivered irradiation.

Язык: Английский

Процитировано

5