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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2015 · IF 2.495

Photo-induced secondary assembly of bis(terpyridyl)dibenzo-24-crown-8/Zn2+ supramolecular polymer

Chao Xu,Yong Chen,Heng-Yi Zhang,Yu Liu

A crown ether-based supramolecular gel with a three-dimensional network structure was successfully constructed via a hierarchical induced assembly strategy and characterized by UV/vis NMR, viscometry and DLS. Therein, the coordination linkage of bis(terpyridyl)dibenzo-24-crown-8 1 with Zn 2+ produces the 1 /Zn 2+ supramolecular polymer as the primary assembly. Then, the anthryl-dibenzylammonium guest 2 was grafted to the 1 /Zn 2+ supramolecular polymer via the non-covalent association of dibenzylammonium moieties on guests with the dibenzo-24-crown-8 rings on supramolecular polymer. Furthermore, the supramolecular polymer with anthryl grafts underwent a photo-induced secondary assembly to produce the supramolecular gel, which could be reversibly disassembled by a thermo-induced dissociation of anthracene dimers. These photo/thermo-induced hierarchical assembly/disassembly behaviors will provide a potential way to construct degradable hierarchical supramolecular assemblies employing environment-friendly external stimuli, such as light and heat, as controlling method.

研究领域: 化学 · 材料科学
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Polymer Chemistry · 2019 ·Vol. 10 ·期 9 ·1150-1157 · IF 4.76

Synthesis of block copolymer nano-assemblies via ICAR ATRP and RAFT dispersion polymerization: how ATRP and RAFT lead to differences

Shuwen Qu,Ke Wang,Habib Khan,Weifeng Xiong,Wangqing Zhang

Block copolymer nano-assemblies were synthesized via initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) dispersion polymerization employing the CuBr2/tris(2-pyridylmethyl)amine catalyst in an alcoholic solvent at a relatively low temperature of 45 °C. The typical poly(ethylene glycol)-block-polystyrene (PEG-b-PS) nano-assemblies synthesized via ICAR ATRP dispersion polymerization are compared with those synthesized via RAFT dispersion polymerization under other similar conditions. It is found that the PEG45-b-PS nano-assemblies, e.g., including lamellas, vesicles and vesicular clusters, synthesized via ICAR ATRP dispersion polymerization have very complicated morphologies, which are different from those synthesized via RAFT dispersion polymerization. The reasons leading to the differences are investigated, and it is conclusively supposed that the high Đ of the synthesized BCPs and the salt of the copper catalyst used in ICAR ATRP dispersion polymerization should be involved. This low temperature initiated ICAR ATRP dispersion polymerization is believed to be a valid method to prepare block copolymer nano-assemblies through polymerization-induced self-assembly.

CAS / MDL: 7447-39-4
研究领域: 材料科学 · 高分子化学
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ADVANCED FUNCTIONAL MATERIALS · 2022 ·Vol. 32 ·期 18 ·2111184 · IF 19.924

Sequential Assembly Tailored Interior of Porous Carbon Spheres for Boosted Water Decontamination through Peroxymonosulfate Activation

Shu-Chuan Mei,Gui-Xiang Huang,Xian-Hong Rui,Liang Li,Ming-Kun Ke,Xiao-Qiang Pan,Zhao-Hua Wang,Xu-Dan Yang,Han-Qing Yu,Yan Yu

Self-assembly is an appealing strategy for preparing nanospheres with different interiors, which are essential for their applications. Although many assembly strategies have been proposed, controlling the assembly processes from kinetic aspects is a big challenge. Here, by employing the different reaction kinetics of the assembly precursors, a sequential assembly strategy is proposed to tailor the interior structure of porous carbon spheres. Through changing the feeding interval of resin and silica precursors from 0 to 60 min, their nucleation order can be controlled in the assembly process to prepare porous carbon spheres (≈450 nm in size) with tunable type (i.e., hollow or solid) and size (from less than 100 nm to around 230 nm) of interiors. The hollow spheres exhibit over three times the catalytic activity of the core–shell counterparts for activating peroxymonosulfate to remove organic water contaminants, and the activity can be further improved by decreasing the cavity size. These results show the great significance of the sequential assembly strategy for interior engineering of nanospheres. This work opens up a new approach for rational design and synthesis of interior-structured nanospheres.

CAS / MDL: 57-68-1
研究领域: 材料科学 · 环境科学
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Polymers · 2021 ·Vol. 13 ·期 19 ·3270 · IF 4.329

Layer-by-Layer Assembly of Polystyrene/Ag for a Highly Reproducible SERS Substrate and Its Use for the Detection of Food Contaminants

Sihan Zhang,Zhihua Xu,Jiaqi Guo,Haiying Wang,Yibo Ma,Xianming Kong,Hongtao Fan,Qian Yu

Polystyrene (PS) spheres were prepared through an emulsifier-free emulsion polymerization method, in which the reaction time, ionic strength, concentrations of copolymer were studied in detail. The resulting PS microspheres and Ag nanoparticles were used to construct a surface enhanced Raman scattering (SERS) substrate by a layer-by-layer assembly method. A relatively uniform distribution of PS/Ag in the films was obtained, and the multilayer substrate presented excellent SERS reproducibility and a tunable enhancement effect. The SERS substrate was used for detecting harmful pesticides (malachite green and dimetridazole) in food samples, with a limit of detection as low as 3.5 ppb. The obtained plasmonic composite has a promising future in the field of SERS sensing.Keywords:polystyrene;self-assembly;Ag nanoparticle;layer by layer;SERS;reproducibility

CAS / MDL: 1074-36-8 26062-79-3
研究领域: 材料科学 · 分析化学
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ACS Omega · 2022 · IF 4.132

Fluorescent Imaging Probe Targeting Mitochondria Based on Supramolecular Host–Guest Assembly and Disassembly

Ning Chu,Lili Cong,Jing Yue,Weiqing Xu,Shuping Xu

Fluorescent dyes and probes play an indispensable role in bioimaging. The mitochondrion is one of the crucial organelles which takes charge of energy production and is the primary site of aerobic respiration in the cell. To illuminate mitochondria, a series of supramolecular fluorescent imaging probes were developed based on the host–guest assembly of 1,4-bis[2-(4-pyridyl)ethenyl]-benzene (BPEB) derivatives and cucurbituril[6] (CB[6]). These host–guest conjugates can be efficiently internalized into cells due to their water solubility and target mitochondria according to their positive charges. In response to the intracellular microenvironments, these conjugates start dynamic disassembly. The released BPEBs show a highly hydrophobic feature, which can crystallize to form fluorescent solids that illuminate the mitochondria. The intracellular disassembly of the host–guest probes was evidenced by fluorescence lifetime imaging in situ. These smart mitochondrion-targeting fluorescent imaging probes can be available to investigate the structures and functions of mitochondria, which are of great significance in the intracellular dynamic transformation of supramolecular assemblies.

研究领域: 生物化学 · 细胞生物学 · 分析化学
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ACS Applied Materials & Interfaces · 2017 · IF 7.504

pH-Sensitive Reversible Programmed Targeting Strategy by the Self-Assembly/Disassembly of Gold Nanoparticles

Jinlong Ma,Zhenpeng Hu,Wei Wang,Xinyu Wang,Qiang Wu,Zhi Yuan

A reversible programmed targeting strategy could achieve high tumor accumulation due to its long blood circulation time and high cellular internalization. Here, targeting ligand-modified poly(ethylene glycol) (PEG-ligand), dibutylamines (Bu), and pyrrolidinamines (Py) were introduced on the surface of gold nanoparticles (Au NPs) for reversible shielding/deshielding of the targeting ligands by pH-responsive self-assembly. Hydrophobic interaction and steric repulsion are the main driving forces for the self-assembly/disassembly of Au NPs. The precise self-assembly (pH ≥ 7.2) and disassembly (pH ≤ 6.8) of Au NPs with different ligands could be achieved by fine-tuning the modifying molar ratio of Bu and Py (Rm), which followed the formula Rm = 1/(−0.0013X2 + 0.0323X + 1), in which X is the logarithm of the partition coefficient of the targeting ligand. The assembled/disassembled behavior of Au NPs at pH 7.2 and 6.8 was confirmed by transmission electron microscopy and dynamic light scattering. Enzyme-linked immunosorbent assays and cellular uptake studies showed that the ligands could be buried inside the assembly and exposed when disassembled. More importantly, this process was reversible, which provides the possibility of prolonging blood circulation by shielding ligands associated with the NPs that were effused from tumor tissue.

研究领域: 纳米医学 · 生物材料 · 肿瘤学
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ACS Nano · 2021 · IF 15.881

Self-Templated, Enantioselective Assembly of an Amyloid-like Dipeptide into Multifunctional Hierarchical Helical Arrays

Yuefei Wang,Qing Li,Jiaxing Zhang,Wei Qi,Shengping You,Rongxin Su,Zhimin He

Chiral self-assembly of peptides has attracted great interest owing to their promising applications in biomedicine, chemistry, and materials science. However, compared with the rich knowledge about their chiral self-assembly at the molecular or nanoscale, the formation of long-range-ordered hierarchical helical arrays (HHAs) from simple peptides remains a formidable challenge. Herein, we report the self-templated assembly of an amyloid-like dipeptide into long-range-ordered HHAs by their spontaneous fibrillization and hierarchical helical assembly within a confined film. The chiral interactions between the peptide and diamines result in geometry frustration and the phase transition of self-assembling peptide films from achiral spherulite structures into chiral HHAs. By changing the chirality and enantioselective interactions, we can control the phase behavior, handedness, and chiroptics of the self-assembled HHAs precisely. Moreover, the redox activity of the HHAs allows the in situ decoration of nanoparticles with high catalytic activity. These results provide insights into the chiral self-assembly of peptides and the fabrication of highly ordered materials with complex architectures and promising applications in chiroptics and catalysis.

CAS / MDL: 920-66-1
研究领域: 生物化学 · 材料科学 · 纳米技术
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Small · 2015 ·Vol. 11 ·期 24 ·2893-2902 · IF 8.368

Capillary Force-Driven, Hierarchical Co-Assembly of Dandelion-Like Peptide Microstructures

Yuefei Wang,Renliang Huang,Wei Qi,Yanyan Xie,Mengfan Wang,Rongxin Su,Zhimin He

The wetting and drying of drops on flexible fibers occurs ubiquitously in nature, and the capillary force underlying this phenomenon has motivated our great interest in learning how to direct supramolecular self-assembly. Here, the hierarchical co-assembly of two aromatic peptides, diphenylalanine (FF) and ferrocene-diphenylalanine (Fc-FF), is reported via sequential, combinatorial assembly. The resulting dandelion-like microstructures have highly complex architectures, where FF microtube arrays serve as the scapes and the Fc-FF nanofibers serve as the flower heads. Homogeneous FF microtubes with diameters tailored between 1 and 9 μm and wall thickness ranging from 70 to 950 nm are initially formed by controlling the degree of supersaturation of the FF and the water content. Once the FF microtubes are formed, the growth of the dandelion-like microstructures is then driven by the capillary force, derived from the wetting and drying of the Fc-FF solution on the FF microtubes. This simple and ingenious strategy offers many opportunities to develop new and creative methods for controlling the hierarchical self-assembly of peptides and thus building highly complex nano and microstructures.

CAS / MDL: 920-66-1
研究领域: 材料科学 · 生物化学
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Gels · 2022 ·Vol. 8 ·期 8 ·459 · IF 4.432

Aerogel Assembled by Two Types of Carbon Nanoparticles for Efficient Removal of Heavy Metal Ions

Xue-Chun Yang,Song Gao,Sha-Qi Fu,Xuan Yao,Zheng Jiao,Jing-Tai Zhao,Zhi-Jun Zhang,Ling-Li Cheng

Both sodium alginate and polyethyleneimine (PEI) have a good ability to adsorb heavy metal ions. PEI and sodium alginate were used as important precursors to synthesize positively charged carbon nanoparticles (p-CNDs) with hydroxyl and carboxyl, and negatively charged carbon nanoparticles (n-CNDs) with amino, respectively. The carbon nanoparticles (CNDs) aerogel with a large specific surface area and rich functional groups were constructed by self-assembled p-CNDs and n-CNDs via electrostatic attraction for adsorption of heavy metal ions in water. The results show that CNDs aerogel has good adsorption properties for Pb2+(96%), Cu2+(91%), Co2+(86%), Ni2+(82%), and Cd2+(78%). Furthermore, the fluorescence emission intensity of CNDs aerogel will gradually decrease with the increase in the adsorption rate, indicating that it can detect the adsorption process synchronously. In addition, the cytotoxicity test reveals that CNDs have good biocompatibility and will not cause secondary damage to biological cells.Keywords:self-assembled;Pb2+;Cu2+;adsorption

研究领域: 环境科学 · 材料科学
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ADVANCED FUNCTIONAL MATERIALS · 2024 ·Vol. 34 ·期 52 ·2410997 · IF 18.5

Precision Self-Assembly of Supramolecules with Heterogeneous Derivatives

Jiawen Zhang,Li Xiang,Binglin Zhou,Yuhao Zhang,Weijie Zhang,Jinyang Jiang,Hongbo Zeng

Supramolecular self-assembly with well-defined building blocks like lipids, deoxyribonucleic acid, or ligands relies on accessible molecular structures and predictable interactions. However, assembling heterogeneous, undefined blocks, such as disordered proteins, amorphous solids, and catecholic derivatives, remains challenging due to their unpredictable assembly, leading to irreversible aggregation, severe precipitation, and unreliable performance. Here, the first programmable, sustainable, and durable self-assembly strategy of supramolecules with heterogenous is presented, derived blocks via harmonizing multiple molecular interactions. This approach achieves reversible assembly/disassembly, ≈73.7% reduced precipitation, and salt- and alkaline-durability under freeze-thaw cycles in model catecholic derivatives, functioning effectively as robust adhesive primers and hydrogel interfacial strengtheners. Moreover, through molecular force measurements and computational simulations, the first general criterion and benchmark for high precision supramolecular self-assembly is proposed, applicable to complex derivatives and interactions: with blocks bearing multiple binding sites existing, the co-assembling blocks should bear at least two binding sites with minimum binding strength (≈17 to ≈37 kJ mol −1 ) to prevent disassembly. This study paves the way and provides benchmarks for precision self-assembly of diverse supramolecules using heterogeneous derivatives for adhesion technology, nanomaterial synthesis and bio-inspired applications.

研究领域: 材料科学 · 化学 · 生物化学
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Polymer Chemistry · 2020 ·Vol. 11 ·期 19 ·3296-3304 · IF 5.342

A general method to greatly enhance ultrasound-responsiveness for common polymeric assemblies

Jinkang Dou,Ruiqi Yang,Kun Du,Li Jiang,Xiayun Huang,Daoyong Chen

Ultrasound-controlled drug release is a very promising technique for controlled drug delivery due to the unique advantages of ultrasound as the stimulus. For this technique, the polymer assemblies that are sufficiently stable in the suspensions but dissociable under a gentle ultrasound treatment are very desirable. In most cases, such polymer assemblies were constructed by few specific polymers. Few examples of the polymer assemblies that are formed by common linear polymers while able to respond strongly to a gentle ultrasound treatment have been reported, because the chain entanglements within the assemblies resist efficiently the ultrasound-induced shearing force; notably, the ultrasound treatment should be gentle enough and incapable of breaking the polymer chains, otherwise it will damage biological tissues. In this study, we report that through intermediate intrachain-crosslinking of one block of a common diblock copolymer, and then self-assembly of the crosslinked polymer in the selective solvent for the uncrosslinked block, vesicles, worm-like micelles and spherical micelles that are highly regular and stable in the suspensions but dissociable under a gentle ultrasound treatment were prepared. The intermediate crosslinking restricts the chain entanglements within the assemblies remarkably, and thus enhances greatly ultrasound-responsiveness for the polymer assemblies. In addition, during the self-assembly, the as-crosslinked block chains are still flexible and less entangled and thus more dynamic, making the crosslinked polymer much more capable than its precursor in forming regular assemblies with various morphologies. Since most of common polymers either are crosslinkable or can be modified to be crosslinkable, this approach is a general method for preparing the strongly ultrasound-responsive polymer assemblies with different compositions, morphologies and structures.

CAS / MDL: 100-66-3
研究领域: 材料科学 · 生物医学工程
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Theranostics · 2021 · IF 11.556

Probing the fluorination effect on the self-assembly characteristics, in vivo fate and antitumor efficacy of paclitaxel prodrug nanoassemblies

Xin Wang,Bin Yang,Lingxiao Li,Tian Liu,Shiyi Zuo,Dongxu Chi,Zhonggui He,Bingjun Sun,Jin Sun

Rationale: Small-molecule prodrug nanoassembly is emerging as an efficient platform for chemotherapy. The self-assembly stability plays a vital role on the drug delivery efficiency of prodrug nanoassembly. It is reported that fluoroalkylation could improve the self-assembly stability of amphiphilic polymers by utilizing the unique fluorination effect. But the application of fluoroalkylation on small-molecule prodrug nanoassembly has never been reported. Methods: Here, fluoro-modified prodrug was developed by conjugating paclitaxel with perfluorooctanol (F 8 -SS-PTX), and the paclitaxel-octanol prodrug (C 8 -SS-PTX) was used as control. The fluoro-mediated self-assembly mechanisms were illustrated using molecular dynamics simulation. In addition, the impacts of fluoroalkylation on the pharmacy characters, in vivo fate and antitumor effect of small-molecule prodrug nanoassembly were investigated in details. Results: Fluoroalkylation significantly improved the self-assembly stability of F 8 -SS-PTX NPs both in vitro and in vivo , which could be attributed to the fluoro-mediated hydrophobic force and halogen bonds. The AUC 0-24h and tumor accumulation of F 8 -SS-PTX NPs was 6-fold and 2-fold higher than that of C 8 -SS-PTX NPs, respectively. As a result, F 8 -SS-PTX NPs exhibited much better antitumor effect than C 8 -SS-PTX NPs and Abraxane. Conclusion: Fluoroalkylation could improve the self-assembly stability, in vivo fate, and antitumor efficacy of small-molecule prodrug nanoassemblies, which could be an effective strategy for the rational design of advanced nanomedicines.

研究领域: 药学 · 纳米技术 · 肿瘤学 · 药物递送系统
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