Hydrogen-Bonded Fibrous Nanotubes Assembled from Trigonal Prismatic Building Blocks DOI
Sayantan Mahapatra, Dingwen Qian, Ruihua Zhang

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(31), С. 21689 - 21699

Опубликована: Июль 29, 2024

In reticular chemistry, molecular building blocks are designed to create crystalline open frameworks. A key principle of chemistry is that the most symmetrical networks likely outcomes reactions, particularly when highly involved. The strategy synthesizing low-dimensional aims reduce explicitly symmetry blocks. Here we report spontaneous formation hydrogen-bonded fibrous structures from trigonal prismatic blocks, which were form three-dimensional on account their structures. Utilizing different microscopic and spectroscopic techniques, identify at early stages assembly process in order understand growth mechanism. incorporated preferentially longitudinal direction, giving rise anisotropic porous organic nanotubes. Entropy-driven provides micrometer-scale unidirectional nanotubes with high porosity. By combining experimental evidence theoretical modeling, have obtained a deep understanding nucleation processes. Our findings offer fundamental insight into design tubular evolve further transverse directions provide extended higher-order [nano- microfibers], ultimately leading large-scale interconnected fiber-like twists turns. work paves way for innovative designs networks.

Язык: Английский

Supramolecular umpolung: Converting electron-rich resorcin[4]arenes into potent CH-bonding anion receptors and transporters DOI Creative Commons
E. R. Abdurakhmanova, Debashis Mondal, Hanna Jędrzejewska

и другие.

Chem, Год журнала: 2024, Номер 10(6), С. 1910 - 1924

Опубликована: Март 27, 2024

CH hydrogen bonding receptors constitute an emerging class of anion sensors and transporters, which, owing to their high proteolytic pH resistance, are promising for biological applications. groups, however, considered as weak bond donors, requiring activation by strongly electron-withdrawing substituents. Accordingly, electron-rich aromatic rings have never been used this purpose thus far. In work, we demonstrate that resorcin[4]arenes, well known π-electron-rich cation receptors, can be converted into CH-bonding simple substitution with four nitro groups. Owing unique geometric features, tetranitroresorcin[4]arenes acquire large dipole moments (up 15.8 D) highly positive electrostatic potentials at the lower rim, leading remarkable affinities (Ka(Cl−) = 1.36 × 105 M−1 in THF). Moreover, show also seemingly innocent alkyl chains surrounding binding site enable transport activities (EC50 down 0.012 mol%) resistance competitive aqueous/organic media.

Язык: Английский

Процитировано

13
Phenol[4]arenes: Excellent Macrocyclic Precursors for Constructing Chiral Porous Organic Cages DOI

Fenglei Qiu,

Xinting Zhang,

Wenjing Wang

и другие.

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

Опубликована: Март 2, 2025

The development of new chiral building blocks for constructing complex architectures, such as macrocycles and cages, is both crucial challenging. Although concave-shaped calixarenes have been established versatile the synthesis cage compounds, there are no reports on cages constructed from calix[4]arene derivatives. Herein, we present a straightforward effective method gram-scale member macrocycle enantiomers, namely, phenol[4]arene (PC[4]A). As proof concept, functionalized these enantiomers into tetraformylphenol[4]arene (PC[4]ACHO) derivatives via Duff reaction to construct porous organic (CPOCs) using polyamine synthons. Specifically, employ two fluorescent amine synthons, bis(4-aminophenyl)phenylamine tris(4-aminophenyl)amine, assemble with PC[4]ACHO resulting in [2 + 4] lantern-shaped [6 8] truncated octahedral CPOCs, respectively. These structures unambiguously characterized by single-crystal X-ray diffraction circular dichroism (CD) spectroscopy. Notably, CPOCs exhibit internal diameters approximately 3.1 nm, cavity volume around 5300 Å3, high specific surface areas up 1300 m2 g-1 after desolvation, making them among largest reported. Additionally, investigations their sensing performance demonstrate that PC[4]A-based enable enantioselective recognition amino acids This work strongly suggests PC[4]A can serve an excellent block rational design materials practical applications.

Язык: Английский

Процитировано

1
3D-Printed Porous Supramolecular Sorbents for Cobalt Recycling DOI
Keldy S. Mason, Sheng-Yin Huang,

Samuel K. Emslie

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(6), С. 4078 - 4086

Опубликована: Фев. 1, 2024

Electronic waste recycling is a recognized global challenge that requires new strategies to bind and release critical materials selectively, such as cobalt present in lithium-ion batteries. To address this challenge, hierarchical 3D-printed porous polymer scaffolds bearing supramolecular receptors were prepared using vat photopolymerization their binding profiles examined function of matrix polarity. By combining high-resolution digital light processing (DLP) with polymerization-induced phase separation (PIPS), functional acrylic copolymer networks micrometer-level precision geometry nanometer-level pores generated. Covalent integration methacrylate-functionalized bisdicyclohexyl acetamide (BDCA-MA) receptor enabled cobalt(II) chloride (CoCl2) via solvent polarity switch mechanism involving change from ethanol water. The structures proved reusable shown by sustained high efficiency over five cycles. This platform represents "green" energy conscious method for future electronic recycling.

Язык: Английский

Процитировано

6
Streamlining the automated discovery of porous organic cages DOI Creative Commons
Annabel R. Basford, Steven Bennett, Muye Xiao

и другие.

Chemical Science, Год журнала: 2024, Номер 15(17), С. 6331 - 6348

Опубликована: Янв. 1, 2024

Efficiently merging low-cost high-throughput screening and characterisation, automated data analysis, computational modelling, cagey – a custom database analysis tool, enhances large-scale curation accelerates discovery of organic cages.

Язык: Английский

Процитировано

6
Expedient Decagram-Scale Synthesis of Robust Organic Cages That Bind Sulfate Strongly and Selectively in Water DOI

Émer M. Foyle,

Rosemary J. Goodwin,

C. Cox

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 23, 2024

Selective anion recognition remains a key challenge in supramolecular chemistry: only very small number of systems that can function water are known, and these nearly always preferentially bind hydrophobic anions. In this work, we report three robust hexa-cationic cages be prepared on scales up to 14 g two simple high-yielding steps from commercially available materials. One displays unusually strong sulfate binding (

Язык: Английский

Процитировано

6
Modular Strategy for Constructing para-Cage[n]arenes, meta-Cage[n]arenes, and meta-Bimacrocyclic-Arenes DOI
Gang Wu, Sheng‐Yi Zhuang, Jiabin Xing

и другие.

Organic Letters, Год журнала: 2024, Номер 26(10), С. 2007 - 2012

Опубликована: Март 5, 2024

Here, we present a versatile modular strategy for crafting novel covalent organic cages (para-cage[n]arenes and meta-cage[n]arenes, n = 3,4) bimacrocycles (meta-bimacrocyclic-arenes) with stable backbones modifiable rims. These structures can be synthesized from commercially available aromatic multialdehydes in three-step process: quantitative bromination, Suzuki–Miyaura reaction (yielding over 60%), rapid one-pot Friedel–Crafts paraformaldehyde. Notably, the cage[n]arenes exhibit well-defined prismatic shape, bimacrocyclic-arenes display both dimeric monomeric configurations.

Язык: Английский

Процитировано

5
Highly Selective Removal of Perchlorate from Water: Roles of Unconventional Hydrogen Bond and Hydrophobic Cavity DOI Creative Commons

Jian Ao,

Lingjun Bu, Yangtao Wu

и другие.

Engineering, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Molecular recognition in water by synthetic hydrogen-bonding receptors DOI
Canjia Zhai,

Alexander Mariscal,

Wenqi Liu

и другие.

Trends in Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Proline-based tripodal cages with guest-adaptive features for capturing hydrophilic and amphiphilic fluoride substances DOI Creative Commons
Bo Huang, Sihao Li,

Cong Pan

и другие.

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Апрель 4, 2025

Proteins exhibit remarkable molecular recognition by dynamically adjusting their conformations to selectively interact with ligands at specialized binding sites. To bind hydrated ligands, proteins leverage amino acid residues similar water affinities as the substrate, minimizing energy required strip molecules from hydrophilic substrates. In synthetic receptor design, replicating this sophisticated adaptability remains a challenge, most artificial receptors are optimized desolvated substances. Here, we show that proline-based can mimic conformational dynamics of achieve selective and amphiphilic fluoride substances in aqueous environments. This finding highlights critical role flexibility strategic hydrophilicity enhancing ligand affinity water. Moreover, it establishes new framework for designing versatile tunable hydrophobicity profiles.

Язык: Английский

Процитировано

0
Probing the Reversible Binding of Anionic Reactive Sulfur and Nitrogen Species in Imidazolium Receptors with Directional C–H Hydrogen Bonds DOI
Amanda G. Davis, Lev N. Zakharov, Michael D. Pluth

и другие.

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 9, 2025

H2S and NO are physiologically important signaling molecules with complex roles in biology intermolecular crosstalk. Although these species often referred to as neutral on paper, they primarily found anionic and/or oxidized forms aerobic solutions HS- or NO2-/NO3-, respectively. Despite the prominence of anions biology, particularly NO2-, few investigations have focused molecular recognition reversible binding species. Using a library imidazolium receptors C-H hydrogen bonding interactions, we investigate influences affinity through modulation charge, multiplicity, preorganization, while also investigating how anion volume impacts binding. These factors probed by solution-state titration experiments solid-state X-ray crystallographic data showing specific interactions involved guest Both NMR crystallography support importance abundance C-H···X- facilitating well conformational changes upon recognition.

Язык: Английский

Процитировано

0