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FOOD CHEMISTRY · 2023 · IF 8.8

Small molecules interfacial assembly regulate the crystallization transition process for nobiletin stabilization

Xiaojuan Chen,Bojia Li,Sicheng Ji,Di Wu,Bing Cui,Xingling Ren,Bin Zhou,Bin Li,Hongshan Liang

Many bioactive nutraceuticals naturally occurring in food materials possess beneficial biological activities, while their use as functional supplements is subjected to hydrophobicity and crystallinity. Currently, inhibiting crystallization for such nutrients is of immense scientific interest. Here, we exploited diverse structural polyphenols as potential inhibitors for restraining Nobiletin crystallization. Specifically, the crystallization transition process could be influenced by the polyphenol gallol density, Nobiletin supersaturation (1, 1.5, 2, 2.5 mM), temperature (4, 10, 15, 25 and 37 ℃), and pH (3.5, 4, 4.5, 5), important factors for regulating the binding attachment and interactions. The optimized samples could be guided by NT100 lied in 4 ℃ at pH 4. Besides, the main assembly driving force was hydrogen-bonding cooperated with π-π stacking and electrostatic interaction, leading to a Nobiletin/TA combination ratio of ∼ 3:1. Our findings proposed an innovative synergistic strategy for inhibiting crystallization and broaden potential applications of polyphenol-based materials in advanced biological fields.

研究领域: 食品科学 · 分子生物学 · 材料科学
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CHEMICAL ENGINEERING JOURNAL · 2019 · IF 8.355

Semi-aromatic copolyesters with high strength and fire safety via hydrogen bonds and π-π stacking

Yan-Peng Ni,Qi-Tian Li,Lin Chen,Wan-Shou Wu,Zi-Hao Qin,Yi Zhang,Li Chen,Xiu-Li Wang,Yu-Zhong Wang

Currently, it is still a huge challenge to prepare flame-retardant polymeric materials with excellent fire safety, high strength, good durability and processability. We here propose a H-bonding cross-linking strategy that can simultaneously endow polymers with excellent flame retardancy, non-dripping behavior and enhanced strength. In this work, a novel benzimidazole monomer, 2-(4-methoxycarbonyl-phenyl)-1H-benzimidazole-5-carboxylic acid methyl ester (PBM) has been designed as a H-bonding cross-linking monomer to prepare poly(ethylene terephthalate)-based copolyesters (PET- co -PBMs). Interestingly, along with the hydrogen bonding, the π-π stacking interactions from the benzimidazole groups also exist. Due to the formation of physical crosslinking network via hydrogen bonding and π-π stacking, the melt strength of copolyesters are greatly improved. Combining with char forming ability of benzimidazole, PET- co -PBMs display excellent fire safety. Moreover, PET- co -PBMs also exhibit higher glass transition temperature, higher mechanical strength and good processability. This work provides a promising strategy to design polymers with high strength, good processability, excellent flame retardance and anti-dripping performance.

研究领域: 材料科学 · 高分子化学
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MACROMOLECULAR RAPID COMMUNICATIONS · 2010 ·Vol. 31 ·期 21 ·1886-1891 · IF 4.263

Fibrils Formed by Dendron-b-oligoaniline-b-dendron Block Co-oligomer

Wei Xiong,Hanfu Wang,Yanchun Han

Novel dendritic triblock co-oligomer (14G2A3) consisting of ester dendrons and aniline oligomer was synthesized and found to self-assemble into fibrils in THF. Studies reveal that the formation of the fibrils originates from both of the amphiphilic interactions between the ester dendrons and oligoaniline, as well as the intermolecular π-π stacking among oligoanilines. The shape effect of dendrons on molecular packing was comparatively analyzed with packing parameter against its linear analogous compound. At the same time, the driving forces that dominate the final aggregating state of the block oligomer were separately investigated using the bulky-group protecting method, which allows release of the intermolecular π-π stacking of oligoaniline in a controlled manner. Results show that both the introduction of dendrons and the intermolecular π-π stacking will increase the packing parameter of the block oligomer and, consequently, cause the self-assembly morphology to evolve step by step from micelles to vesicles and finally to fibrils. The fibrils can form complexes with SWNTs to increase solubility in THF. The effective fluorescence quenching accompanied also opens a gate for the block co-oligomer to have potential applications in organic electronic devices.

研究领域: 材料科学 · 化学
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CRYSTAL GROWTH & DESIGN · 2019 · IF 4.153

Structural Features of Sulfamethizole and Its Cocrystals: Beauty Within

Yue Yuan,Duanxiu Li,Chenguang Wang,Shaodong Chen,Minmin Kong,Zongwu Deng,Changquan Calvin Sun,Hailu Zhang

Sulfamethizole (SMZ) is an antibiotic drug with good solubility but short in vivo half-life. Thus, reducing the dissolution rate is expected to improve bioavailability and therapeutic activity through reducing the systemic elimination of SMZ. To this end, two novel pharmaceutical cocrystals, SMZ–sarcosine (SMZ–SAR) and SMZ–saccharin (SMZ–SAC), were designed and prepared according to the structural resemblance strategy. These cocrystals, along with a previously obtained SMZ–l-proline (SMZ–l-PRO) cocrystal, present an opportunity for detailed analysis of the crystal structure to identify key intermolecular interactions that guide their molecular assembly. 13C Solid state NMR data suggested more than one symmetry independent molecules in SMZ (Z′ > 1), which was confirmed by the SMZ crystal structure solved at 100 K (Z′ = 3). The amine–carboxylate synthon plays an important role in the intermolecular hydrogen bonding interactions of both SMZ–SAR and SMZ–l-PRO. In contrast, no strong intermolecular hydrogen bonding and π···π stacking interactions between SMZ and SAC were observed in SMZ–SAC, which features a shape-fit structure. Additionally, all cocrystals demonstrated lower equilibrium solubility and intrinsic dissolution rates compared to SMZ. Therefore, they are suitable crystal forms for the possible improvement in therapeutic performance of SMZ.

CAS / MDL: 160003-66-7 147-85-3
研究领域: 药学 · 晶体学 · 药物化学
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JOURNAL OF PHOTOCHEMISTRY AND PHOTOBIOLOGY A-CHEMISTRY · 2014 · IF 2.291

A new dinuclear terbium complex as a novel luminescence probe for detecting amines

Tianshu Chu,Huiping Liu,Yangyi Yang,Hongming Wang,Yunsong Hu,Yi Wang,Minghao Yu,Seik Weng Ng

A strong green-light-emitting Tb complex [Tb 2 (csal) 6 (H 2 O) 4 ]·4H 2 O ( 1 ) (Hcsal   =   4-chlorosalicylicacid) has been synthesized. The structure was determined by single crystal X-ray diffraction. 1 exhibits a discrete dinuclear structure which is further assembled into a 3D supramolecular network by hydrogen bonding and aromatic π−π stacking interactions. This complex was used to detect ethylenediamine (EDA), triethylamine (TEA) and ethanolamine (EOA), the relationship between luminescence intense of 1 and concentrate of EDA or TEA can be fitted in Stern–Volmer equation. The results indicate that 1 is a promising probe for detecting amines with high selectivity and sensitivity.

CAS / MDL: 7400-08-0
研究领域: 化学 · 材料科学
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Polymers · 2020 ·Vol. 12 ·期 1 ·72 · IF 3.426

Magnetic Template Anion Polyacrylamide–Polydopamine-Fe3O4 Combined with Ultraviolet/H2O2 for the Rapid Enrichment and Degradation of Diclofenac Sodium from Aqueous Environment

Qiang Sun,Huaili Zheng,Xuebin Hu,Jun Li,Rui Zhao,Chun Zhao,Wei Ding

In this study, a novel system was set up by preparing a magnetic flocculant combining with ultraviolet/H2O2to realize the rapid enrichment and degradation of diclofenac sodium (DCFS). For the magnetic flocculant, template anion polyacrylamide (TAPAM) with anion micro-block structure was prepared. Thereafter, polydopamine was used to modify TAPAM, Fe3O4nanoparticles was grafted to the modified TAPAM by chelation, named template anion polyacrylamide-polydopamine-Fe3O4(TAPAM-PDA-Fe3O4). Furthermore, the TAPAM-PDA-Fe3O4preparation protocol was optimized by the response surface method (RSM). In the DCFS enrichment section, the rapid separation of flocs from water was realized by an external magnetic field and it indicated that the π–π stacking effect was dominant in neutral/alkaline condition, whereas charge neutralization was favored in acidic conditions. Meanwhile, a DCFS enrichment kinetic curve was much fitted by the pseudo-second-order kinetic model and DCFS enrichment isothermal curve was close to the Freundlich isothermal model, indicating the dependence of DCFS quantity enriched by TAPAM-PDA-Fe3O4and a multilayer heterogeneous enrichment process. The degradation experiment confirmed that DCFS was effectively degraded by ultraviolet/H2O2/TAPAM-PDA-Fe3O4and the maximum value of DCFS degradation efficiency reached 98.1%. Furthermore, the regeneration experiment showed that the enrichment and degradation efficiency of DCFS could maintain a relatively high level in the initial three recycles.Keywords:diclofenac sodium;π–π stacking;charge neutralization;enrichment;degradation

CAS / MDL: 7727-54-0 62-31-7
研究领域: 环境科学 · 材料科学
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Journal of Materials Chemistry C · 2025 · IF 5.1

Enhanced intrinsic thermal conductivity of liquid crystalline polyester through monomer structure optimization in main chains

Panpan Yang,Yifei Wu,Kunxin Wang,Sheng Lu,Yuemiao Zhang,Junxi Wan,Kun Wu,Jun Shi

In order to investigate the influence of intermolecular interactions on polymer crystallization, a series of liquid crystal polyesters with high thermal conductivity (B-LCPs) were synthesized. These were synthesized using biphenyl diols and various dicarboxylic acids as raw materials, employing a “one pot” melt polycondensation method. The λ value of B-LCP4 reaches 0.462 W (m K)−1, marking an enhancement of 135.8% in comparison to that of B-LCP3, which is 2.3 times greater than that of traditional thermoplastics. The diffraction peak of B-LCP4 at 2θ = 27.4° indicates the formation of a π–π stacking structure and crystallinity around 58%. B-LCP4 exhibited significant melting peaks and weak cold crystallization during the second heating scan, which indicates the crystal phase becomes more integrated and regular. Furthermore, the T5%, Tmax and residual carbon at 800 °C of B-LCP4 were 387.7 °C, 422.2 °C and 15.4%, respectively. The augmented thermal stability of B-LCP4 is ascribed to the delocalization of π-electrons along the backbone, which facilitates a planar conformation. The findings indicate that the π–π stacking interaction can enhance the crystallinity of polymers, subsequently improving their thermal conductivity.

研究领域: 材料科学 · 高分子化学
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POLYMER · 2015 · IF 3.562

One-pot polymer conjugation on carbon nanotubes through simultaneous π–π stacking and the Biginelli reaction

Xu Ren,Bin Yang,Yuan Zhao,Xiaoyong Zhang,Xing Wang,Yen Wei,Lei Tao

The Biginelli reaction has been utilized as an effective click reaction to collaborate with π–π stacking to prepare carbon nanotube-polymer conjugates. The synthesized polymers are successfully anchored on carbon nanotube surface via ‘grafting to’ strategy, and the obtained carbon nanotube-polymer composites possessing characteristic properties of anchored polymer can be well dispersed in general solution to expand carbon nanotubes application realm.

研究领域: 材料科学 · 化学工程
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JOURNAL OF FLUORESCENCE · 2023 · IF 2.7

Facile Synthesis and Multiple Application of Ultralong-Afterglow Room Temperature Phosphorescence Aggregate Carbon Dots from Simple Raw Materials

Zhu Wenping,Wang Like,Yang Weijie,Chen Yahong,Liu Zengchen,Li Yanxia,Xue Yingying

Owing to the ultralong afterglow, room temperature decay phosphorescence nanomaterials have aroused enough attention. In the work, by simple one-pot solid-state thermal decomposition reaction, aggregate carbon dots (CDs) was prepared from trimesic and boric acid. Based on the intermolecular hydrogen bonds and intramolecular π-π stacking weak interaction from precursors, CDs was encapsulated in boron oxide matrix and formed aggregation. The aggregate state of CDs facilitated the triplet excited states (Tn), which could induce the room temperature decay phosphorescence properties. By careful investigation, under different excitation wavelengths at 254 and 365 nm, the aggregate CDs showed > 15 s and > 3 s room temperature phosphorescence emission in the naked eye, which was associated with 1516.12 ms and 718.62 ms lifetime respectively. And the aggregate CDs exhibited widespread application in encoding encryption, optical anti-counterfeiting and fingerprint identification etc. The interesting aggregate CDs revealed unexpected ultralong-afterglow room temperature decay phosphorescence properties and the work opened a window for constructing ultralong-afterglow room temperature decay phosphorescence aggregate CDs nanomaterials.

CAS / MDL: 10043-35-3 554-95-0
研究领域: 材料科学 · 化学
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DALTON TRANSACTIONS · 2017 ·Vol. 46 ·期 36 ·12209-12216 · IF 4.029

A crystalline AlPO4-5 intermediate: designed synthesis, structure, and phase transformation

Cong Lin,Jian Li,Fengjuan Pan,Yifang Zhao,Le Xu,Yanquan Yang,Xin Du,Xiaohuan Lin,Fuhui Liao,Jianhua Lin,Tao Yang,Junliang Sun

AlPO4-5 is the most extensively studied material in exploring the crystallization mechanism of aluminophosphate molecular sieves, and it can be synthesized using 4-dimethylaminopyridine (DMAP) as an organic structure-directing agent (OSDA). Achieving the AlPO4-5 intermediate in the crystalline form would be of great importance and significance for this purpose. In this study, we proposed a concept that by carefully regulating the synthesis conditions, crystalline alumimophosphate intermediates could be rationally prepared. A crystalline AlPO4-5 intermediate, (C7H11N2)2(H3O)(Al3P4O16)·(H2O)2.5 (1), was, therefore, synthesized by significantly increasing the amounts of orthophosphoric acid and DMAP. The intermediate 1 consists of alternating organic DMAP and inorganic [Al3P4O16]3− layers with abundant hydrogen bonds and can transform to the AlPO4-5 framework upon heating in air or through a steam-assisted conversion (SAC) method. To unravel the role of DMAP in the transformation, pure AlPO4-5 (2) was also synthesized by altering the synthesis conditions. The supramolecular assembly templating (SAT) effects of DMAP in 1 and 2 were verified via fluorescence spectra. Thus, the π–π stacking interactions between the DMAP molecules and the abundant hydrogen bonds between the adjacent layers are considered to be important for the phase transformation of 1. This crystalline intermediate would promote the understanding of the crystallization mechanism in the system of aluminophosphate molecular sieves.

研究领域: 材料科学 · 晶体化学
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Soft Matter · 2025 · IF 2.8

Ordered co-assembly based on chiral phenylalanine derivatives and achiral coumarin derivatives

Yun-song Zhou,Yang Sheng,Peng Zhang,Rong Zhang,Mark Bradley,Yi-xin Sun

The self-assembly of small molecules into supramolecular hydrogels is of great significance in mimicking biological systems. In this study, we investigated the formation and structure change of supramolecular hydrogels based on the self-assembly behavior of an achiral coumarin derivative (G1) and a chiral phenylalanine derivative (ALP). It was observed that G1 and ALP can self-assemble at various molar ratios, resulting in distinct nanostructured morphologies. Specifically, at a molar ratio of G1/ALP (4 : 1), the achiral G1 molecules initially bifurcate and diverge, ultimately forming a dendritic microstructure at the G1 termini. When the G1/ALP ratio was adjusted to 2 : 1, a chrysanthemum-like microstructure emerged. UV-light can destroy the self-assembled gel structure of different G1/ALP ratios, changing it from gel to sol. The emergence of these higher-order chiral structures during self-assembly was attributed to hydrogen bonding and π–π stacking interactions between the molecules. This research offers valuable insights into the understanding of biological self-assembly processes and the design of artificial biomedical materials.

研究领域: 材料科学 · 生物化学 · 纳米技术
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Advanced Optical Materials · 2025 · IF 7.2

Engineering Solid-State Fluorescent Carbon Dots with Aggregation-Induced Emission by Fatty Amine Chains-Regulated Charge Transfer and π-π Stacking

Canpu Yang,Jiusheng Hu,Wenjiang Tan,Jinhai Si,Xun Hou

Carbon dots (CDs) are an encouraging green luminescent material; however, the aggregation-caused quenching (ACQ) effect poses a significant limitation for their use in solid-state devices. By adjusting precursor fatty amine chains, this paper synthesized four solid-state emissive CDs with aggregation-induced emission (AIE) properties (Lx-CDs). When water is introduced, the generation of Lx-CDs aggregates creates the switching off of the carbon-core emission (blue) in acetic acid solution and the switching on of the surface-state emission (orange). Results demonstrate that the disulfide bond and fatty amine chain structures allow considerable inhibition in the distance of aromatic skeletons, causing the aggregation-state emission, and the multiple interactions in aggregates can reduce the non-radiative processes benefiting the AIE. Besides, the fast and slow fluorescence species can be confirmed to correspond to the emission paths of carbon-core and surface-state, respectively. The solid-state emission wavelength, photoluminescence quantum yield (PLQY), and AIE strength can be engineered by the fatty amine chain regulated charge transfer and π-π stacking. This study not only reveals the intrinsic mechanism of carbon-core and surface-state luminescence dynamics in AIE CDs but also provides a method for controlling fluorescence wavelength and enhancing the emission of aggregated particles using precursor fatty amine chain length.

CAS / MDL: 646-25-3 107-15-3
研究领域: 材料科学 · 光化学
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