ACS Nano
·
2025
·
IF 16
Yanyan Zhang,Huimin Zheng,Yu Zhao,Cong Du,Jian Zhang,Jinying Liu,Shengjie Jiang,Yan Wei,Chuan-Liang Feng
Chirality is a pivotal determinant in stem cell differentiation, yet discerning the individual effects of chirality across different scales within native three-dimensional (3D) environments remains challenging. Here, a strategy is employed using nanostructures with controlled chirality to precisely assess the impact of molecular and supramolecular chirality on mesenchymal stem cell (MSC) osteogenic differentiation. We synthesized two pairs of enantiomers, l/d-phenylalanine (l/D-Phe) and l/d-1-naphthylalanine (L/D-1-Nap) derivatives, which could form four distinct chiral fibrous hydrogels with different molecular and supramolecular chiralities: L-supP and D-supP (supP indicates supramolecular right-handed helix), and L-supM and D-supM (supM denotes supramolecular left-handed helix). Both experimental and computational analyses reveal that the supramolecular supM/supP helicity is governed by conformational changes in aromatic side chains, switching between outward and inward orientations. Intriguingly, MSCs encapsulated within these chiral fibers displayed osteogenic differentiation that was predominantly influenced by higher-order supramolecular chirality rather than molecular chirality. Specifically, supM-nanofibrils significantly promoted the MSC commitment to the osteoblast lineage, whereas supP-nanofibrils lacked this osteoinductive potential. Additionally, we observed subtle positive and negative modulations of MSC osteogenic differentiation by l- and d-enantiomeric molecular chiralities, respectively. Our study presents a strategy for chiral hydrogel design and delineates how supramolecular chirality surpasses molecular chirality in directing MSC osteogenesis within 3D hydrogels, highlighting the potential of chiral biomaterials in bone tissue engineering.
研究领域:
生物材料学
·
再生医学
·
细胞生物学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2013
·
IF 3.172
Yangyang Xu,Jingguo Li,Wenlong Hu,Gang Zou,Qijin Zhang
Herein, a novel single-chain coumarin-substituted diacetylene monomer (CODA) was synthesized. CODA LB films exhibited obvious chirality although CODA monomer was achiral. Upon UV irradiation , CODA LB films could be polymerized into blue form and exhibit reversible thermochromism and chiroptical properties. Strong intermolecular interaction among the coumarin chromophores was assumed to be responsible for the complete reversibility of absorption and chiroptical changes for PCODA films upon thermal stimulus. And the helical packing of the coumarin chromophores seemed to play a dominating role in the subsequent formation of the helical PDA backbone. Moreover, the single-chain CODA monomer could be further photo-dimerized, and a novel gemini-type diacetylene monomer (DCODA) could be prepared. The effects of the photo-dimerization reaction of the coumarin moieties on the thermochromism and chiroptical properties of the resulting PDCODA films had been evaluated. The dimerization of head groups would enhance the thermal stability of PDCODA films but inhibit the chirality formation for PDA backbone.
研究领域:
材料化学
·
高分子科学
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产品关联
DOI
PubMed
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2020
·
IF 7.489
Gong Zhang,Liwei Zhang,Hengjun Rao,Yuefei Wang,Qing Li,Wei Qi,Xuejiao Yang,Rongxin Su,Zhimin He
We report the self-assembly of an ultra-pH-sensitive hydrogel from a simple dipeptide derivative, ferrocene-diphenylalanine (noted as Fc-FF). The pure Fc- L -Phe- L -Phe-OH (noted as (L)-Fc-FF) or Fc- D -Phe- D -Phe-OH (noted as (D)-Fc-FF) peptide could self-assemble into right- or left-handed nanohelices in a mixture of water and organic solvent leading to formation of stable chiral hydrogels at a very narrow pH range of 5.7–5.9. Intriguingly, if we used a racemic mixture (noted as (L,D)-Fc-FF) of (L)-Fc-FF and (D)-Fc-FF, stable hydrogels could only be formed at much lower pH values with a weak mechanical property. The results indicated that the molecular chirality has great influence on the gelation of the peptides. Moreover, we investigated the gelation behaviour of the peptides in various solvents. Here the water molecules are essential in directing the chiral self-assembly of Fc-FF into entangled chiral nanostructures, leading to the formation of stimuli-responsive hydrogels. And in the presence of water molecules, a small amount of organic co-solvents also has significant effect on the gelation of Fc-FF peptides. This work demonstrated that the gelation of such a bioorganometallic molecule is very sensitive to the molecular conformation of itself and the self-assembly environment (pH, solvents, etc.), which has potential applications in chemical sensing and biomedicine.
研究领域:
生物化学
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材料科学
·
纳米技术
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DOI
高影响因子
Polymer Chemistry
·
2015
·Vol. 6
·期 39
·7045-7052
·
IF 5.52
Lu Yin,Yin Zhao,Shunqin Jiang,Laibing Wang,Zhengbiao Zhang,Jian Zhu,Wei Zhang,Xiulin Zhu
A series of star-shaped azobenzene (Azo)-containing side chain polymers with 3, 4 and 6 arms were synthesized by the atom transfer radical polymerization technique initiated by multifunctional initiators. The intense bisignated circular dichroism (CD) signals in the UV–vis region were observed when these star polymers aggregated in a dichloroethane/limonene mixed solvent, indicating the successful chirality transfer from limonene molecules to these star Azo polymers. The chirality originates from the preferential supramolecular chirality of well-organized optically inactive side-chain Azo units. The supramolecular chirality is closely related to the volume fraction of cosolvents, the enantiopurity (ee) of limonene, molecular weight and arm numbers of star Azo polymers. Interestingly, the maximum values of CD and gCD of the polymer aggregates increase with molecular weight in the case of 3-armed Azo polymers, and increase simultaneously with arm numbers of the polymers having similar repeating units under each optimized experimental condition. Surprisingly, the first chiral amplification behaviours were observed in the 4- and 6-armed Azo polymers, but absent in linear and 3-armed counterparts. The supramolecular chirality can be destroyed by trans–cis photoisomerization and recovered by thermal cis–trans isomerization of Azo units. The current research will provide further insight into the mechanism study and production of effective chiroptical materials in chiral solvation induced supramolecular chirality of the achiral polymers.
研究领域:
高分子化学
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超分子化学
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材料科学
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产品关联
DOI
高影响因子
Journal of Physical Chemistry C
·
2021
·
IF 4.126
Yiran Xia,Hongdong Duan,Aiyou Hao,Pengyao Xing
Dynamic control of supramolecular chirality and chiroptical properties is a challenging task and has great significance in the preparation of responsive and intelligent functional materials. Here, we report the dynamic evolution of supramolecular chirality and the corresponding chiroptical properties via multicomponent coassembly driven by intermolecular hydrogen bonds. Stilbene conjugated with amino acids can self-assemble into chiral nanostructures with chiroptical activities including circular dichroism and circularly polarized luminescence (CPL). After coassembly with melamine (Mm), a macroscopic nanohelix was observed in assemblies. This evolution process is accompanied by variations in Cotton effects and CPL properties depending on the amino acid domains. The photoresponsiveness of the isomerization reaction was successfully achieved due to the existence of the stilbene structure, where the fluorescence changes can be applied to fluorescent carving. This work illustrates the dynamic chirality evolution and response, providing a simple method for the design and manufacture of smart chiroptical materials.
研究领域:
材料科学
·
化学
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产品关联
DOI
高影响因子
DRUG DELIVERY
·
2021
·
IF 6.419
Wei Xin,Yumei Wang,Yan Bian,Jiahui Lin,Wenhao Weng,Xinyi Zhao,Kaijun Gou,Xianmou Guo,Heran Li
The aim of this study was to build up a novel chiral mesoporous silica called PEIs@TA-CMS through a facile biomimetic strategy and to explore its potential to serve as a drug carrier for improving the delivery efficiency of poorly water-soluble drug. PEIs@TA-CMS was synthesized by using a chiral crystalline complex associated of tartaric acid and polyethyleneimine (PEIs) as templates, scaffolds and catalysts. The structural features including morphology, size, pore structure and texture properties were systematacially studied. The results showed that PEIs@TA-CMS was monodispersed spherical nanoparticles in a uniformed diameter of 120–130 nm with well-developed pore structure (SBET: 1009.94 m2/g, pore size <2.21 nm). Then PEIs@TA-CMS was employed as nimodipine (NMP) carrier and compared with the drug carry ability of MCM41. After drug loading, NMP was effectively transformed from the crystalline state to an amorphous state due to the space confinement in mesopores. As expected, PEIs@TA-CMS had superiority in both drug loading and drug release compared to MCM41. It could incorporate NMP with high efficiency, and the dissolution-promoting effect of PEIs@TA-CMS was more obvious because of the unique interconnected curved pore channels. Meanwhile, PEIs@TA-CMS could significantly improve the oral adsorption of NMP to a satisfactory level, which showed approximately 3.26-fold higher in bioavailability, and could effectively prolong the survival time of mice on cerebral anoxia from 10.98 to 17.33 min.
研究领域:
材料科学
·
药学
·
生物医学工程
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产品关联
DOI
PubMed
高影响因子
LANGMUIR
·
2018
·
IF 3.789
Fang Wang,Minggao Qin,Ting Peng,Xianhui Tang,Auphedeous Yinme Dang-i,Chuanliang Feng
Having control over the supramolecular chirality through multiexternal stimulators provides many possibilities in realizing functional chiral materials. Herein, the supramolecular chirality of nanotwists comprising PA centered with 1,4-phenyldicarboxamide bearing two l/d-helicogenic alanine motifs and achiral COOH at each terminus of the alanine arms is modulated by solvent, temperature, and ultrasound. The modulations are mainly due to the hydrogen bonds among gelators and solvent–gelator interactions, resulting in changes of the molecular arrangement and subsequent self-assembled nanostructures. Typically, the gel of PA in ethyl acetate prepared by ultrasonication method exhibits thixotropic property due to the participation of ethyl acetate in the self-assembly process, resulting in relatively flexible and tolerant networks. This study provides a simplistic way to control the handedness of chiral nanostructures and a rational design of the self-assembly system with multistimuli-responsive supramolecular chirality.
研究领域:
化学
·
材料科学
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DOI
PubMed
高影响因子
Materials Today Chemistry
·
2018
·
IF 0
A. Kousar,J. Liu,N. Mehwish,F. Wang,A.Y. Dang-i,C. Feng
To achieve desired physicochemical and biochemical activities of optically active molecules at targetted sites in biological systems, tuning of chiral sense by varying internal conditions (e.g., pH) is of utmost importance. However, it has been a challenge to gain the balance of non-covalent interactions required for chiral transformations merely by deviations in biochemical environment. Herein, pH-controlled chirality of supramolecular nanostructures obtained from coassembly of phenylalanine-derived gelator and achiral cationic polyacrylamide has successfully been achieved. Specifically, any changes in the pH remarkably influence the chirality of these nanostructures. For instance, coassembled hydrogels possessing l -enantiomer provide right-handed nanostructures at pH < 7; whereas at pH ≥ 7, handedness of nanostructures switches to the left-handed nanostructures. Moreover, viscoelastic properties and twist pitch were also regulated under the influence of pH change. This study may provide a methodology to control chirality by simply varying biochemical conditions, which points toward its potential to be used in biological systems as a key to gain preferential chiral sense in different sites of living systems.
研究领域:
材料科学
·
生物学
·
化学
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产品关联
DOI
Polymer Chemistry
·
2018
·Vol. 9
·期 6
·769-776
·
IF 4.927
Lu Yin,Meng Liu,Yin Zhao,Shuangshuang Zhang,Wei Zhang,Zhengbiao Zhang,Xiulin Zhu
Herein, a series of azobenzene (Azo)-containing side-chain cyclic polymers were successfully synthesized by combining atom transfer radical polymerization (ATRP) and Cu(I)-catalyzed azide/alkyne cycloaddition (CuAAc) “click” reaction. The aggregates of linear and cyclic Azo polymers in a dichloroethane/limonene mixed solvent were characterized by circular dichroism (CD) and UV-visible spectroscopy, demonstrating that the topological structural constraint and molecular mass of cyclic polymers have clear effects on the supramolecular chirality driven by a chiral solvent. The difference between linear and cyclic Azo aggregates in supramolecular chirality became less distinct with increasing molecular mass of Azo polymers. The chiroptical switch of cyclic Azo polymers was firstly constructed by trans–cis photoisomerization and cis–trans heating-assisted reorganization processes. These interesting findings suggest that the cyclic topology has a clear influence on the behavior of supramolecular chirality induced by chiral limonene.
研究领域:
高分子化学
·
超分子化学
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产品关联
DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
·
2016
·Vol. 40
·期 6
·5568-5576
·
IF 3.277
Yimeng Zhang,Shangyang Li,Mingfang Ma,Minmin Yang,Yajie Wang,Aiyou Hao,Pengyao Xing
Gel formation by an N-fluorenyl-9-methoxycarbonyl (Fmoc)-based molecule was investigated and the chirality amplification observed during the self-assembly process could be switched on and off by controlling the solvent environment. The molecules could form gel in mixed solvents of water and dimethyl sulfoxide (DMSO) at either a high water fraction to afford flat nanofibers or a low water fraction to generate nanofibers with supramolecular chirality. At a moderate fraction of water, the molecules self-assemble into a precipitate composed of nanosheets. Furthermore, the gels showed different mechanical properties and thermal stabilities. Mechanism studies showed that π–π stacking interactions between the aromatic Fmoc groups and hydrogen bondings between the amide groups played important roles in the self-assembly process of the different gels. This study strives to shed light on the tuning of chiral gels with various nanostructures via controlled self-assembly, which might have potential use in smart materials.
研究领域:
材料科学
·
化学
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产品关联
DOI
高影响因子
Journal of Materials Chemistry C
·
2023
·Vol. 11
·期 9
·3292-3299
·
IF 6.4
Yongjie Zhang,Yu-Ming Sun,Gonghui Li,Meiyan Du,Ning Sheng,Jinglin Shen
The photoluminescence properties of fluorescent hydrogels are strongly influenced by the supramolecular organization of the chromophores, which makes their modulation nontrivial. In this work, a series of fluorescent hydrogels with different emission colors were prepared by co-assembly of organic dyes with an amphiphilic peptide gelator. Depending on the two distinct gelation states of the peptide, the obtained fluorescent hydrogels exhibited different emission properties. The hydrogels prepared at lower alkalinity (Gel 1) could enhance the emission of the doped dyes that carry cationic groups (namely rhodamine B and sulforhodamine B), while those prepared at higher alkalinity (Gel 2) caused the emission quenching of the dyes. Based on the structural characterization of two types of hydrogels, it is speculated that nanowire aggregates in Gel 1 function as a template to direct the organization of co-assembled dye molecules through electrostatic interactions, and the emission is enhanced due to the restriction of molecular motion. In contrast, the less organized aggregates in Gel 2 allow the dye molecules to self-assemble through π–π stacking which leads to emission quenching. Due to the homochirality of the amino acid residues in peptide gelators, the aggregates of Gel 1 exhibit supramolecular chirality which is confirmed by CD spectroscopy. Consequently, optical activities including CD activity and CPL properties were also observed for the fluorescent hydrogels based on the Gel 1 matrix, and they originated from the chiral arrangement of dye molecules directed by the ordered anionic L-serine residues on the periphery of nanowires.
研究领域:
材料科学
·
光学
·
生物化学
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产品关联
DOI
高影响因子
Nanoscale
·
2024
·
IF 5.8
Mengjia Cen,Jiawei Wang,Ming Cheng,Ziyan Lei,Ye Li,Zhenming Wang,Xueqian Zhao,Zixuan Wu,Huanian Zhang,Yan Jun Liu
Manipulating circular dichroism in chiral metasurfaces has been increasingly important for a wide range of polarization-sensitive photonic applications. However, simple methods for presenting chiral nanostructures with tunable and considerable chiroptical responses in the near-infrared-I regime remains underexplored. Herein, two sheets of suspended symmetric bilayer metagratings fabricated via single-step electron beam lithography are stacked into a moiré metasurface with its circular dichroism value reaching up to 20.9°. The chirality of the moiré metasurface can be fully tuned in terms of both its sign and magnitude by adjusting the in-plane angle between the two twisted sheets of metagratings. The multilayered design is accessible to the coupling of hybridized plasmons for governing the chiroptical properties in the near-infrared-I regime. The ratio between the resonance wavelength and the grating period is about 1.65, which is much lower compared to that in most existing moiré metasurfaces with strong chiroptical responses. Furthermore, the superchiral fields in the inter-sheet region are further exploited for label-free enantiodiscrimination with ultrahigh sensitivity of 10.17 nm fmol−1 mm2. The proposed moiré metasurfaces with strong near-infrared-I chirality hold great potential for supporting polarization engineering and biomolecular detection, paving a way for advanced applications in medical diagnosis, biomedical imaging, and display technologies.
研究领域:
纳米光子学
·
生物医学检测
·
光学工程
✓ 已验证
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）