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Soft Matter · 2020 ·Vol. 16 ·期 22 ·5203-5209 · IF 3.14

Impact of a chiral supramolecular nanostructure on the mechanical and electrical performances of triphenylene-based discotic physical gels

Hongli Zhang,Junjie Cheng,Qiang Zhou,Qijin Zhang,Gang Zou

Discotic π-conjugated supramolecular assemblies, especially with chiral supramolecular nanostructures, have been attracting growing research interest due to their significant optoelectronic properties and the possibilities of their applications in the new generation of organic semiconductors. However, the impact of supramolecular chirality on their mechanical and electrical performances remains poorly understood. Herein, a series of optically active supramolecular gels were formed from achiral triphenylene derivatives by introducing limonene as the chiral source. Owing to the well-ordered supramolecular packing, the homochiral supramolecular gels exhibited greater mechanical strength and higher conductivity, compared to heterochiral architectures. The impact of supramolecular packing in homochiral or heterochiral assemblies on their resulting mechanical and electrical performances was investigated in detail, which might be of great fundamental value for the rational design of chiral π-conjugated supramolecular nanostructures for applications in chiral optoelectronics.

CAS / MDL: 106-96-7
研究领域: 材料科学 · 有机化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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MOLECULES · 2021 ·Vol. 26 ·期 8 ·2191 · IF 4.412

A Stretchable Pillararene-Containing Supramolecular Polymeric Material with Self-Healing Property

Meng Zhao,Changjun Li,Xiaotao Shan,Huijing Han,Qiuhua Zhao,Meiran Xie,Jianzhuang Chen,Xiaojuan Liao

Constructing polymeric materials with stretchable and self-healing properties arise increasing interest in the field of tissue engineering, wearable electronics and soft actuators. Herein, a new type of supramolecular cross-linker was constructed through host-guest interaction between pillar[5]arene functionalized acrylate and pyridinium functionalized acrylate, which could form supramolecular polymeric material via photo-polymerization of n-butyl acrylate (BA). Such material exhibited excellent tensile properties, with maximum tensile strength of 3.4 MPa and strain of 3000%, respectively. Moreover, this material can effectively dissipate energy with the energy absorption efficiency of 93%, which could be applied in the field of energy absorbing materials. In addition, the material showed self-healing property after cut and responded to competitive guest.Keywords:pillararene;host-guest chemistry;supramolecular chemistry;supramolecular polymer

CAS / MDL: 150-78-7
研究领域: 材料科学 · 生物医学工程 · 高分子化学
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ACS Nano · 2023 · IF 17.1

“Reaction”-Like Shaping of Self-Delivery Supramolecular Nanodrugs in the Nanoprecipitation Process

Wenzhe Xu,Yang Chen,Ruixu Yang,Yiying Fu,Wanxin Zhuang,Yonggang Wang,Yi Liu,Hao Zhang

Nanoprecipitation, which is achieved through the diffusion and precipitation of drug molecules in blended solvent and antisolvent phases, is a classic route for constructing nanodrugs (NDs) and previously directed by diffusion-controlled theory. However, the diffusion-controlled mechanism is out of date in the recent preparation of self-delivery supramolecular NDs (SDSNDs), characterized by the construction of drug nanoparticles through supramolecular interactions in the absence of carriers and surfactants. Herein, a “reaction”-like complement, contributed from supramolecular interactions, is proposed for the preparation of naphthoquinone SDSNDs. Different from the diffusion-controlled process, the formation rate of SDSNDs via the “reaction”-like process is almost constant and highly dependent on the supramolecular interaction-determined Gibbs free energy of molecular binding. Thus, the formation rate and drug availability of SDSNDs are greatly improved by engineering the supramolecular interactions, which facilitates the preparation of SDSNDs with expected sizes, components, and therapeutic functions. As a deep understanding of supramolecular-interaction-involved nanoprecipitation, the current “reaction”-like protocol not only provides a theoretical supplement for classic nanoprecipitation but also highlights the potential of nanoprecipitation in shaping self-assembled, coassembled, and metal-ion-associated SDSNDs.

研究领域: 药剂学 · 纳米医学 · 生物化学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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REACTIVE & FUNCTIONAL POLYMERS · 2017 · IF 3.151

Design of folic acid based supramolecular hybrid gel with improved mechanical properties in NMP/H2O for dye adsorption

Chaoyue Hao,Jianping Gao,Yongli Wu,Xiaoxue Wang,Ruiru Zhao,Shunkang Mei,Jiangbing Yang,Xiangang Zhai,Haixia Qiu

Folic acid (FA) supramolecular gel was prepared in a mixture solvent of N -methylpyrrolidone (NMP)/H 2 O at a 1/1 volume ratio by using FA as gelator with a concentration of 0.4% (w/v). In the mixture solvent, NMP was first of time used as a good solvent to tune the solvent properties in order to be able to induce formation of FA supramolecular gel. The folic acid-gelatin (FA-GA) hybrid gels were synthesized by adding different amount of gelatin (GA) into FA gelator. The gelation temperature (T Gel ) of the FA-GA hybrid gel is 30   °C which is much higher than that of FA gel (10   °C). The gel to sol transition temperature (T GS ) is about 58   °C, which demonstrates that the hybrid gel has good stability at room temperature . The FT-IR and UV–vis spectra of FA-GA hybrid gel indicate that GA involves in the self-assembly process of FA via hydrogen bonding and π-π interactions with FA molecules. Owing to the π-π interaction happened between FA and GA molecules the fluorescence intensity of FA-GA gel is four times as high as that of FA gel. SEM images shows that the hybrid gel has a helical-fiber network structure which would enhance the gel strength to a great extent. Good stability, large specific surface and porosity in three-dimensional network structure of the FA-GA hybrid gel make it a highly promising adsorbent for dye adsorption. The FA-GA hybrid gel is able to absorb 63.5% of Congo red (CR), 68% of methyl blue (MB) and 44% of methyl orange (MO) respectively from their solutions.

研究领域: 材料科学 · 化学工程
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Polymer Chemistry · 2022 ·Vol. 13 ·期 20 ·2964-2970 · IF 5.364

Supramolecular polymeric prodrug micelles for efficient anticancer drug delivery

Ying Wang,Peng Chen,Qiaojie Luo,Xiaodong Li,Weipu Zhu

Polymeric prodrugs have attracted great interest in the field of anticancer drug delivery owing to their integrated advantages of prodrugs and nanoparticles. However, the ambiguous chemical composition of polymeric prodrugs is still a major obstacle to their clinical applications. In this study, an amphiphilic poly(ethylene glycol) derivative with multiple thiols was first synthesized on a large scale through the melt co-polycondensation of oligo(ethylene glycol), 1,4-butanediol and mercaptosuccinic acid. Then an adamantane modified doxorubicin (DOX) with a pH-sensitive hydrazone bond and a β-cyclodextrin derivative with multiple acryloyls were precisely synthesized. Finally, novel supramolecular polymeric prodrug (SPP) micelles with a precise drug molecular structure and drug loading content were facilely prepared using the above three components via simultaneous self-assembly, a thiol–ene “click” reaction and a host–guest supramolecular interaction in water. The resultant pH-sensitive SPP micelles with a stable core-crosslinked structure and strong drug “bonding” show long blood circulation time, effective cellular uptake and fast DOX release in tumor cells, which significantly improved the antitumor efficacy and security compared with free DOX. This work established a promising drug delivery platform for cancer chemotherapy.

研究领域: 药剂学 · 化学 · 肿瘤学
✓ 已验证 DOI 高影响因子
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Catalysts · 2018 ·Vol. 8 ·期 2 ·53 · IF 3.465

Carbon-Supported Copper-Based Nitrogen-Containing Supramolecule as an Efficient Oxygen Reduction Reaction Catalyst in Neutral Medium

Yuanyuan Zhao,Ya Chu,Xiuping Ju,Jinsheng Zhao,Lingqian Kong,Yan Zhang

In this work, a nitrogen-containing bidentate ligand named 5,5′-(9-octyl-9H-carbazole-2,7-diyl)bis(1,10-phenanthroline) (OCBP) was synthesized as a nitrogen precursor for making an oxygen reduction catalyst. The 1,10-phenanthroline unit provides a coordination site for copper ions, and the resulting Cu-Nxunit may be responsible for the catalytic activities of the catalyst. Carbon black was selected as a support to improve the electroconductibility of the resulting catalyst. The metallo-supramolecule (Cu-SOCBP) was dispersed on the surface of Vulcan XC-72 carbon and was used as a catalyst (designated as Cu-SOCBP/C) for the oxygen reduction reaction (ORR). The microscope structure and surface components of the catalyst were acquired via scanning electron microscopy and X-ray photoelectron spectroscopy, as well as X-ray powder diffraction. The electrochemical property and ORR mechanism of Cu-SOCBP/C were analyzed using a variety of electroanalytical methods including cyclic voltammetry, electrochemical impedance spectroscopy, and linear sweep voltammetry. These results show that Cu-SOCBP/C was successfully synthesized and that ORR was achieved mainly via a four-electron transfer process to water. Thus, Cu-SOCBP/C was an effective catalyst and might have potential application as a cathodic catalyst in microbial fuel cells, which operate in an aqueous medium.Keywords:supramolecule;ORR activity;kinetics study

研究领域: 电化学 · 材料科学
✓ 已验证 DOI 高影响因子
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JOURNAL OF MOLECULAR STRUCTURE · 2023 · IF 3.8

Molecular structures of eight hydrogen bond-mediated minoxidil adducts from different aryl acids

Xiaodan Ma,Xinlei Chen,Yaoqi Zhen,Xunjie Zheng,Chengzhe Shi,Shouwen Jin,Bin Liu,Bin Chen,Daqi Wang

Cocrystallization experiments between the widely popular active pharmaceutical ingredient (API) minoxidil and an array of aryl acids coformers were carried out, successfully yielding 8 multi-component samples consisting of 3 co-crystals and 5 salts. Most of them are hydrates. The nature of the samples have been featured by XRD, IR and EA, the melting points were also gauged. The structural and supramolecular aspects are investigated in detail. In all adducts the N-oxide shows various nonbonding contacts. The Hmnd dimer was established at both 1 and 4 by a pair of symmetric N H···O H-bonds. In all cases the minoxidil and coformers were connected by the N H···O/O H···O synthon which is proved to be the highest extensive associates (appearing in 8/8 structures), even in the coexistence of other potentially disruptive non-covalent bonding moieties. Interestingly, the piperidine moieties as effective H-bond acceptor never participated in accepting the H-bonds. The pyrimidine amino also only acts as the H-bond donors. The outcomes unveil that the crystal packing is relied on the strong N H⋯O/O H···O H-bonds. Deep insight into the crystal packing uncovered that a different set of extra O N/O O, CH···C, N H···C, CH···O/CH 2 O, CH CH/CH 2 CH/CH 2 CH 2 , CH 2 Cl, CH 3 -π/CH 2 -π, NH-π, O-π, and π-π contacts contribute to the stabilization and expansion of the total structures. For the synergism of the various nonbonding forces there had the homo/hetero supramolecular synthons. Some classical graph set notations of R 2 2 (9) and R 4 2 (8) were present in the relative high frequency.

研究领域: 药物化学 · 晶体学
✓ 已验证 DOI 高影响因子
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EUROPEAN POLYMER JOURNAL · 2019 · IF 3.621

Supramolecularly toughened and elastic epoxy resins by grafting 2-ureido-4[1H]-pyrimidone moieties on the side chain

Peng Zhang,Lei Kan,Xinyue Zhang,Rui Li,Chuanqi Qiu,Ning Ma,Hao Wei

Multiple hydrogen bonds have been widely used to form a supramolecular network and endow materials with enhanced mechanical strength, good elasticity, and/or self-healing properties. In this study, 2-ureido-4[1H]-pyrimidone (UPy) compounds were synthesized and chemically grafted onto the side chain of epoxy resins. The UPy-modified epoxy resin demonstrated substantial improvements in toughness and elasticity compared with unmodified epoxy resin as proven by a tensile test and distortion test. The breaking elongation of the UPy-modified epoxy resin was 5 times higher than that of unmodified epoxy resin under a tensile test. In addition, the fracture mechanism of the modified epoxy resin matched with the ductile fracture rather than the brittle fracture of unmodified epoxy resins. The introduction of quadruple hydrogen bonds by chemical modification may provide a simple and effective way to design and prepare highly flexible thermosetting resin materials.

CAS / MDL: 111-36-4 9046-10-0
研究领域: 材料科学 · 化学工程
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JOURNAL OF MATERIALS SCIENCE · 2018 ·Vol. 54 ·期 6 ·5136-5148 · IF 2.993

Development of supramolecular shape-memory polyurethanes based on Cu(II)–pyridine coordination interactions

Zou Faxing,Chen Heng,Chen Shaojun,Zhuo Haitao

Shape-memory polymers with supramolecular switch have received increasing attention. This study reports the synthesis and characterization of supramolecular shape-memory polyurethane based on Cu(II)–pyridine coordination, obtained by mixing pyridine containing polyurethane with CuCl 2 . The results show that there are strong metal–ligand coordination interactions formed between Cu(II) and the pyridine ring in a series of CuCl 2 -doped polyurethane samples. The Cu(II)–pyridine coordination plays a crucial role in the enhanced physical netpoints for outstanding shape-memory properties. Indeed, the so-synthesized CuCl 2 -doped polyurethane exhibits not only a rapid tensile shape recovery but also excellent crimp shape recovery. The CuCl 2 -doped polyurethane containing suitable metal–ligand coordination interactions shows more than 99% shape fixation and more than 95% shape recovery. Our findings promote further applications of shape-memory polymers in multiple engineering fields.

研究领域: 材料科学 · 高分子化学
✓ 已验证 产品关联 DOI 高影响因子
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Materials Today Nano · 2021 · IF 8.109

Supramolecular PEGylation of camptothecin for cancer therapy

R. Sun,Q. Luo,X. Li,X. Huang,L. Teng,Z. Shen,W. Zhu

PEGylated drugs and their self-assembled nanoparticles have been used as a first-line technology in nanomedicines . However, premature disassembly before reaching the lesions under dilute conditions limits their bioavailability. This challenge can be overcome by covalent crosslinking. However, undefined molecular structures of the prodrugs are introduced, which hinder large-scale production and clinical translation. Herein, a supramolecular PEGylated camptothecin nanodrug with a crosslinked architecture and defined molecular drug structure was developed. PEGylated mono-tetraethylenepentamine β-cyclodextrin (mPEG-TEPA-CD) and adamantane modified camptothecin (AD-SS-CPT) were first synthesized. The host-guest coupling of β-cyclodextrin (β-CD) and adamantine (AD) moieties between mPEG-TEPA-CD and AD-SS-CPT induced the formation of supramolecular PEGylated camptothecin, which could self-assemble into micelles in the aqueous medium. They were further stabilized by the addition of a diacrylate crosslinker for reaction with the amine groups on mPEG-TEPA-CD, maintaining the unaltered AD-SS-CPT. The nanodrugs can internalize into tumor cells quickly and release free camptothecin in response to glutathione . They also have prolonged blood circulation time and can accumulate efficiently at tumor sites, thus showing effective antitumor activity . This supramolecular drug delivery system provides a new strategy for the design of nanodrugs.

研究领域: 药学 · 纳米医学 · 肿瘤学
✓ 已验证 DOI 高影响因子
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2019 · IF 6.361

Efficient removal of uranium using a melamine/trimesic acid-modified hydrothermal carbon-based supramolecular organic framework

Hualun Li,Ye Li,Yuzhi Zhou,Bolin Li,Dongbin Liu,Hanyang Liao

In this study, we prepared a hydrothermal carbon-based supramolecular organic framework (HTC-MA-TMA) by grafting melamine and trimesic acid on hydrothermal carbon (HTC) for efficient removal of U (VI) from aqueous solutions. The nano-sized supramolecular organic framework (SOF) particles consisted of N-donor-containing melamine and O-donor-containing trimesic acid self-assembled through hydrogen bonds . Their large number of specific active sites acted as the immobilization center for capturing U (VI). Chemical modification facilitated the dispersion of the SOF particles on HTC, which was synthesized using a novel covalent/non-covalent bond strategy. The HTC-MA-TMA adsorbent exhibited exceptional U (VI) adsorption capacity (271.83 mg/g) because of the coordination interaction between UO 2 2+ and its ligands (amino, carboxyl and amide groups). The adsorption equilibrium was achieved within 30 min and followed a pseudo-second-order equation, suggesting the occurrence of a chemical adsorption process . Furthermore, the U (VI) ions adsorbed onto the HTC-MA-TMA adsorbent could be easily desorbed using 0.1 M HNO 3 solution. This regeneration caused no significant decrease in the sorption capacity of the adsorbent. These results suggest that advanced HTC-MA-TMA adsorbent can be applied in the nuclear-fuel industry for extracting U (VI) from radioactive wastewater .

CAS / MDL: 538-75-0 554-95-0
研究领域: 环境科学 · 材料科学
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Materials Science & Engineering C-Materials for Biological Applications · 2017 · IF 4.164

Fabrication of thermal sensitive folic acid based supramolecular hybrid gels for injectable drug release gels

Yahui Song,Jianping Gao,Xiaoyang Xu,Huilin Zhao,Ruinan Xue,Jingkuo Zhou,Wei Hong,Haixia Qiu

Thermal sensitive supramolecular hybrid gels for injectable drug release were prepared by adding different amounts of agar into folic acid (FA) gelator. The gelation temperature was modulated in order to form injectable gel with body temperature (37   °C). Such kind of folic acid-agar (FAG) hybrid gel makes it possible to use supramolecular gel as injectable drug loaded gels for drug release. FT-IR and UV–vis spectra indicate that agar macromolecules involve in the self-assembly process through intermolecular H-bonding and π-π stacking interactions with FA molecules. The SEM and TEM images demonstrate that the fiber diameter of FAG hybrid gel is about 20   nm, much smaller than that of FA gel (40   nm). However, FAG hybrid has a denser nano-fibrous network structure than FA gels. Moreover, FAG hybrid gel is endowed with a more ordered network structure and a little better crystallization capability by adding agar. FAG hybrid gel also shows a shear-thinning behavior but the shear viscosity is about 2 times higher than that of FA gel. Compared with FA gel, the storage (G′) and loss (G″) moduli of the FAG gel are higher, which implies an enhanced gel strength. At the same time, both FA and FAG gels are facilely affected by some external factors such as acid, base and salts. In acidic or basic conditions, the strength became weak and the gelation temperature (Tg) decreased. While, within certain concentrations, the salt (NaCl) increased the gel strength and Tg. FAG gel suffered lower mass loss and owned better stability in different pH solutions compared with pure FA gel. The release behavior of the FA and injectable FAG gels was investigated by using Rhodamine B as a mimic model drug. FAG hybrid gel shows a long release profile and the release time is 3 times longer than that of FA gel, up to 30   h, and the accumulative release amount reaches about 86%. So it is a potential injectable gel for sustained release drug delivery system.

CAS / MDL: 9002-18-0 59-30-3
研究领域: 材料科学 · 药学
✓ 已验证 产品关联 DOI PubMed 高影响因子
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