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FOOD CHEMISTRY · 2019 · IF 5.399

Bioaccessibility and variation of arsenic species in polished rice grains by an in vitro physiologically based extraction test method

Fan Du,Zhaoguang Yang,Peng Liu,Lin Wang

The bioaccessibility and speciation of arsenic (As) in rice grains have been investigated by the physiologically based extraction test (PBET) method. A total of 42 rice samples were collected from Hunan Province, a typical mine-impacted province in China. The bioaccessibility in the gastrointestinal tract was 71.7 ± 13.5% for the collected rice grains. Arsenite [As(III)] was the predominant As species in the simulated gastric and gastrointestinal solutions, followed by dimethylarsinic acid (DMA), arsenate [As(V)] and monomethylarsonic acid (MMA). The bioaccessible As(V) was irrelevant to As(V) in the rice grains, suggesting that interconversion between As(V) and other species was occurred in the simulated gastrointestinal tract. Monte-Carlo simulation was introduced to assess the health risk from exposure to inorganic As. The average values for target hazard quotient (THQ) and bioaccessible THQ were 2.704 and 1.637, respectively. The inclusion of bioaccessibility reduced the probability of non-carcinogenic health risk from 97.32% to 76.86%.

研究领域: 环境科学 · 毒理学 · 食品安全 · 公共卫生
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Journal of Materials Chemistry C · 2019 ·Vol. 8 ·期 4 ·1319-1325 · IF 6.641

Mixed-ligand engineering of quasi-2D perovskites for efficient sky-blue light-emitting diodes

Siyuan Zeng,Shasha Shi,Shirong Wang,Yin Xiao

Achieving efficient blue emission with spectrum stability in perovskite light-emitting diodes (PeLEDs) is a great challenge, although the external quantum efficiency (EQE) of PeLEDs for red and green emission has exceeded 20%. Here, we report efficient sky-blue PeLEDs with high brightness based on mixed-ligand confined quasi-2D perovskites. By detailed characterization of the optical and physicochemical properties of n-butylammonium (BA) or 2-phenylethylammonium (PEA)-based perovskites with various alkyl ammonium bromides as co-ligands, it is found that the molecular size and charge on the amino-groups of the co-ligand hold the key to constructing effective mixed-ligand systems. Accordingly, dimethylammonium (DMA) is an ideal co-ligand in both BA- and PEA-based quasi-2D perovskites. Thanks to its appropriate molecular size, DMA could help to confine the diameter of perovskite nanocrystals (NCs) and improve their dispersity in organic ligands. Besides, DMA is prone to disperse among PEA or BA molecules to cap the perovskite synergistically, and the phase of n = 1 caused by excess co-ligands could be effectively avoided benefiting from the relatively weak coordination ability of DMA due to the relatively small positive charge on amino-groups. The optimized PeLEDs based on BA2DMA1.6Cs2Pb3Br11.6 and PEA2DMA1.2Cs2Pb3Br11.2 exhibit color-stable sky-blue (490 nm) and bluish green (499 nm) emission with a record maximum luminance of 2825 and 7760 cd m−2 respectively. The applicability of this approach in the red emission region is also demonstrated, which provides a versatile strategy for full spectrum modulation.

研究领域: 材料科学 · 光电子学 · 纳米技术 · 光子学
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ADVANCED FUNCTIONAL MATERIALS · 2023 · IF 19

Dopamine-Based High-Transparent Hydrogel as Bioadhesive for Sutureless Ocular Tissue Repair

Yuna Qian,Kejia Xu,Liangliang Shen,Mali Dai,Zelin Zhao,Yujing Zheng,Haiou Wang,Hailin Xie,Xuan Wu,Decheng Xiao,Qinxiang Zheng,Jinyi Zhang,Yang Song,Jianliang Shen,Wei Chen

Ocular injuries and their complications represent the most common causes of visual impairment. For ocular surgery, there is an unmet need for highly transparent bioadhesives with superior adhesion, biocompatibility, and regenerative properties. Herein, a novel high-transparent bioadhesive hydrogel composed of gelatin methacryloyl (GelMA) and dopamine methacrylamide (DMA) is developed by in situ oxidative free-radical polymerization. This bioadhesive hydrogel overcomes the fundamental weakness of mussel-inspired adhesive copolymers in clinical practice by combining multiple favorable properties, including high light transmission, mechanical strength, adhesive strength, and biocompatibility. DMA significantly enhances corneal epithelial cells adhesion, proliferation, and migration on GelMA, and prevents the accumulation of reactive oxygen species (ROS) in corneal epithelial cells. In rabbit models of corneal and conjunctiva transplantation, the bioadhesive is able to decrease the inflammatory response and fibrosis formation induced by suture surgical trauma. In addition, the rabbit corneal stromal defect model reveals that the Gel/DMA bioadhesive could effectively seal corneal defects, accelerates corneal re-epithelialization, and promotes wound healing. Thus, given the advantages of high bioactivity and simple preparation, the Gel/DMA bioadhesive represents a promising strategy for suture-free ocular repair.

CAS / MDL: 38862-25-8
研究领域: 材料科学 · 生物医学工程 · 眼科学 · 组织工程
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ACS Applied Polymer Materials · 2024 · IF 4.4

Degradable Underwater Adhesive Utilizing Free Radical Ring-Opening Polymerization

Jiaqiang Ding,Yiming Han,Jinqiu Wu,Dongliang Chen,Chengdong Xiong,Dongling Huang,Zuochun Xiong

Inspired by the amino acid residues in mussel adhesion proteins, vinyl polymer underwater adhesives containing dopamine structures have gradually become a research hot spot. Researchers have done a lot of work on how to improve the bonding properties, mechanical properties, and rapid response properties of dopamine-based adhesives. However, vinyl polymers are not degradable, which limit their application in the biomedical field. It is considered to be the most promising method to achieve the degradation of vinyl polymers by free radical ring-opening polymerization of vinyl monomers and cyclic ketene acetals. In this study, we used N-(3,4-dihydroxyphenethyl) methacrylamide (DMA) and 2-methyl-1,3-dioxane (MDO) as raw materials to synthesize biodegradable copolymers P(MDO–DMA) with different compositions by free radical ring-opening polymerization. We carried out adhesion strength and in vitro degradation experiments on polymer adhesives under different conditions. The results showed that the prepared copolymers had good adhesion and biodegradability. This is the result of the synergistic effect of the two functional monomers in the system. DMA achieves adhesion performance and MDO gives effective degradability. We believe that this will expand the current limited application scenarios and provide exciting prospects for applications in areas such as drug delivery and tissue engineering.

CAS / MDL: 497-19-8 1303-96-4
研究领域: 材料科学 · 高分子化学 · 生物医学工程
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INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH · 2023 · IF 4.2

Enhanced Compatibility, Morphology, and Low-Temperature Toughness of Polyamide 6/Poly(dimethylsiloxane)/Epoxidized Silicone Rubber Composites

Weizhen Zhang,Zhilong Yang,Yuan Li,Qi Zhang,Shijun Zhang,Liqun Zhang

Epoxidized silicone rubber with an epoxy content of 5% (ESR-5) was introduced to improve the compatibility of the polyamide 6 (PA6)/poly(dimethylsiloxane) (PDMS) composite. The effects of the ESR-5 on the molecular structure, interfacial morphology, and toughness and thermal properties of the PA6/PDMS composite were investigated using nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared (FT-IR) spectroscopy, differential scanning calorimetry (DSC), scanning electron microscopy (SEM), atomic force microscopy (AFM), and dynamic thermomechanical analysis (DMA). The FT-IR spectra and torque rheological testing confirmed the reaction between the epoxy group of ESR-5 and the carboxyl group at the end of PA6. The AFM and SEM images confirmed that the ESR-5 altered the interfacial thickness and remarkably decreased the average size of the dispersed rubber particles, which enhanced the interfacial compatibility. At a rubber content of 20% by weight in PA6/PDMS composites, the optimum impact strength at −60 °C, which is 469% higher than pure PA6, was obtained with an ESR-5 content of 50% in rubber phase.

CAS / MDL: 2370-88-9 556-67-2
研究领域: 材料科学 · 高分子科学 · 复合材料
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Polymer Chemistry · 2020 ·Vol. 11 ·期 31 ·4995-5004 · IF 5.342

Bioinspired by both mussel foot protein and bone sialoprotein: universal adhesive coatings for the promotion of mineralization and osteogenic differentiation

Xiaoling Long,Huilin Xu,Dongyue Zhang,Jianshu Li

Generally, the poor osteointegration between bone implant materials and host tissue can lead to severe implant failure, accompanied by a series of postoperative complications. One of the reliable and valid solutions for eliminating these concerns is to improve the biointerface performance of implants via various modification methods. Although some progress has been achieved in recent decades, it still remains a great challenge and requirement to develop a facile and universal method for the implant modification of various materials. In this work, bioinspired by the physiological functions in osteoanagenesis of bone sialoprotein (glutamic acid-rich protein), a series of bi-functional polymers were elaborately designed and synthesized through the reversible addition–fragmentation chain transfer (RAFT) polymerization of methacryloylamido glutamic acid (MGlu) and dopamine methacrylamide (DMA ). Due to the abundant catechol pendants of the polymer chains, these functional polymers are able to form stable coatings on the surfaces of various substrates via only an environmentally friendly and mild spin-coating process. Furthermore, the results of mineralization experiments in vitro clearly indicated that these functional polymeric coatings on titanium plates have the capability to effectively promote mineral deposition. In particular, polymeric coatings composed with a nearly equal monomer composition (1.0/1.2) could induce the formation of calcium phosphate (CaP) with a Ca/P ratio of 1.7/1, which is close to the ratio of calcium to phosphorus in natural hydroxyapatite. Moreover, all of the polymeric coatings facilitated the adhesion, spreading, proliferation, and osteogenic differentiation of MC3T3-E1 cells. These effects were directly affected by the composition of the polymer chains, especially the content of glutamic units.

研究领域: 生物材料 · 生物医学工程 · 材料科学 · 组织工程 · 骨再生
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CONSTRUCTION AND BUILDING MATERIALS · 2024 · IF 7.4

Synthesis of polyurethane with asymmetric hard segments and its effect on room-temperature self-healing property of bitumen

Shiyun Zhou,Tian Xia,Shuo Wu,Wanting Zhang,Jianhui Xu,Yi Yang,Youbing Li,Guangxian Li

Self-healing bitumen can significantly enhance the durability and service life of bituminous pavement, thereby reducing the need for frequent maintenance and repairs. In this study, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and isophorone diamine (IPDA) were utilized to design asymmetric dynamic hard segments, imparting self-healing properties to polyurethane even at room temperature. Particular emphasis was placed on hydrogen bonding, as its reversible formation serves as a primary mechanism for the self-healing characteristics of the material. During the synthesis of polyurethane (PU), two different composition ratios were employed to produce two types of PU with distinct chemical structures, molecular weights, and dynamic crosslink densities, which were characterized using NMR, FTIR, GPC, and DMA, respectively. Furthermore, these two PU types exhibited varying mechanical properties and glass transition temperatures, leading to differences in the rheological properties of the corresponding PU-modified bitumen. Dynamic frequency sweep test results indicated that bitumen modified with PU exhibiting higher molecular weight and narrower molecular weight distribution had superior rutting resistance and enhanced room-temperature self-healing capabilities. The underlying reasons for this improvement can be attributed to the hydrogen bonding present in the PU as well as the phase separation structure between the PU and bitumen.

研究领域: 材料科学 · 高分子化学 · 土木工程
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Chemical Science · 2024 ·Vol. 15 ·期 10 ·3721-3729 · IF 7.6

Regulating luminescence thermal enhancement in negative thermal expansion metal–organic frameworks

Liang Chen,Yili Cao,Rui Ma,Hongmei Cao,Xin Chen,Kun Lin,Qiang Li,Jinxia Deng,Chunyu Liu,Yilin Wang,Ling Huang,Xianran Xing

Overcoming thermal quenching is generally essential for the practical application of luminescent materials. It has been recently found that frameworks with negative thermal expansion (NTE) could be a promising candidate to engineer unconventional luminescence thermal enhancement. However, the mechanism through which luminescence thermal enhancement can be well tuned remains an open issue. In this work, enabled by altering ligands in a series of UiO-66 derived Eu-based metal–organic frameworks, it was revealed that the changes in the thermal expansion are closely related to luminescence thermal enhancement. The NTE of the aromatic ring part favors luminescence thermal enhancement, while contraction of the carboxylic acid part plays the opposite role. Modulation of functional groups in ligands can change the thermal vibration of aromatic rings and then achieve luminescence thermal enhancement in a wide temperature window. Our findings pave the way to manipulate the NTE and luminescence thermal enhancement based on ligand engineering.

CAS / MDL: 188860-26-6
研究领域: 材料科学 · 光学
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FOOD CHEMISTRY · 2024 · IF 8.5

Rational selection of 4,4′,4″-(1,3,5-triazine-2,4,6-triyl) trianiline-based covalent organic framework as adsorbent for effective co-extraction of aflatoxins, zearalenone and its metabolites from food and biological samples

Dan Wei,Jianliang Li,Ming Guo,Jingjing Xu,Qiao Deng,Xu Wang

Aflatoxins, zearalenone and its metabolites, as representative hazard mycotoxins cause adverse effects on food safety and human health. Developing a sensitive and reliable extraction and detection method is of great importance for monitoring their residue and exposure levels. In contrast to traditional trial-and-error selection steps, 4,4′,4″-(1,3,5-triazine-2,4,6-triyl) trianiline covalent-bonding with 2,5-dihydroxyterephthalaldehyde, namely TAPT-OH-COF was screened as a potential adsorbent utilizing density functional theory calculations prior to the synthesis procedure. After experimental verification, magnetic TAPT-OH-COFs were prepared, characterized and applied for the extraction of aflatoxins, zearalenone and its metabolites from food and biological samples, coupled with high-performance liquid chromatography tandem mass spectrophy detection. Under the optimal conditions, the developed method exhibited low limits of quantification (0.05–0.50 μg/kg), satisfactory recoveries (75.8 %–110.9 %) and good precision with intraday and interday relative standard deviations (RSDs) not exceeding 12.2 %. This study may provide great potential for the selection of candidate adsorbents for multi-mycotoxins extraction from complex samples.

研究领域: 食品安全 · 分析化学 · 毒理学
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Small · 2024 ·Vol. 20 ·期 38 ·2400605 · IF 13

Supramolecular Complexation Reinforced Polymer Frustrated Packing: Controllable Dual Porosity for Improved Permselectivity of Coordination Nanocage Mixed Matrix Membranes

Yuan Liu,Binghui Xue,Jiadong Chen,Yuyan Lai,Linkun Cai,Panchao Yin

The developments of mixed matrix membranes (MMMs) are severely hindered by the complex inter-phase interaction and the resulting poor utilization of inorganics’ microporosity. Herein, a dual porosity framework is constructed in MMMs to enhance the accessibility of inorganics’ microporosity to external gas molecules for the effective application of microporosity for gas separation. Nanocomposite organogels are first prepared from the supramolecular complexation of rigid polymers and 2 nm microporous coordination nanocages (CNCs). The network structures can be maintained with microporous features after solvent removal originated from the rigid nature of polymers, and the strong coordination and hydrogen bond between the two components. Moreover, the strong supramolecular attraction reinforces the frustrated packing of the rigid polymers on CNC surface, leading to polymer networks’ extrinsic pores and the interconnection of CNCs’ micro-cavities for the fast gas transportation. The gas permeabilities of the MMMs are 869 times for H 2 and 1099 times for CO 2 higher than those of pure polymers. The open metal sites from nanocage also contribute to the enhanced gas selectivity and the overall performance surpasses 2008 H 2 /CO 2 Robeson upper bound. The supramolecular complexation reinforced packing frustration strategy offers a simple and practical solution to achieve improved gas permselectivity in MMMs.

研究领域: 材料科学 · 化学工程
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BIOMACROMOLECULES · 2024 · IF 5.5

Amphiphilic Block Copolymers Containing Benzenesulfonyl Azide Groups as Visible Light-Responsive Drug Carriers for Image-Guided Delivery

Lei Luo,Fei Liu,Zhiying Li,Siyuan Yue,Liang Wang,Shiling Zhang,Shanmeng Lin,Jinyan Luo,Meng Wang,Yichuan Zhang,Mohamed Abdelrahim,Qi Xing,Jin Geng

Nanoparticles (NPs) containing light-responsive polymers and imaging agents show great promise for controlled drug delivery. However, most light-responsive NPs rely on short-wavelength excitation, resulting in poor tissue penetration and potential cytotoxicity. Moreover, excessively sensitive NPs may prematurely release drugs during storage and circulation, diminishing their efficacy and causing off-target toxicity. Herein, we report visible-light-responsive NPs composed of an amphiphilic block copolymer containing responsive 4-acrylamide benzenesulfonyl azide (ABSA) and hydrophilic N,N′-dimethylacrylamide (DMA) units. The polymer pDMA-ABSA was loaded with the chemotherapy drug dasatinib and zinc tetraphenylporphyrin (ZnTPP). ZnTPP acted as an imaging reagent and a photosensitizer to reduce ABSA upon visible light irradiation, converting hydrophobic units to hydrophilic units and disrupting NPs to trigger drug release. These NPs enabled real-time fluorescence imaging in cells and exhibited synergistic chemophotodynamic therapy against multiple cancer cell lines. Our light-responsive NP platform holds great promise for controlled drug delivery and cancer theranostics, circumventing the limitations of traditional photosensitive nanosystems.

研究领域: 材料科学 · 药学 · 生物医学工程 · 纳米技术 · 癌症研究
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Catalysis Science & Technology · 2024 · IF 4.4

Ambient conversion of CO2 and epoxides to cyclic carbonates using 3D amide-functionalized MOFs

Zafar A. K. Khattak,Nazir Ahmad,Hussein A. Younus,Habib Ullah,Baoyi Yu,Khurram S. Munawar,Muhammad Ashfaq,Muhammad Yaseen,Muhammad Danish,Mohammed Al-Abri,Rashid AlHajri,Francis Verpoort

Metal(II)-carboxylate frameworks are an important class of MOF materials finding applications in gas storage, separation, sensing, catalysis, etc. Recently, their design, synthesis and characterization have been established at a very fast pace. Here two novel MOFs based on 5,5′-(([1,1′-biphenyl]-4,4′-dicarbonyl)bis(azanediyl))diisophthalic acid (H4L, an amide containing ligand) and transition metals (copper and zinc) are reported. Several characterization tools e.g., FT-IR, XRD, SEM, TGA, and XPS are used to characterize these MOFs. Single-crystal X-ray diffraction and Hirshfeld surface analyses are used to characterize the 3D structural framework. The void and cavity analysis revealed the strength of the crystal packing. Both MOFs followed multistage thermogravimetric disintegration profiles. The solvent molecules escaped around 200 °C and the structural changes due to decompositions in the frameworks continued till 500 °C. The morphological analysis for Zn-MOF and Cu-MOF showed uniform wedge-shaped rectangular blocks and spherical balls with dimensions around 100 and 50 μm, respectively. The amide functionalized Zn(II)-carboxylate framework exhibited high catalytic activity (85–>99%) towards the solvent-free cycloaddition of CO2 to different epoxides e.g., epichlorohydrin, propylene oxide, allyl glycidyl ether and glycidyl isopropyl ether with 100% selectivity under ambient conditions (i.e., 1 bar at 40 °C for 24 h) at very low catalyst loading. By adjusting the reaction conditions (T, P, and co-catalyst), the catalytic conversion reached 100% within only 2 hours. The results showed Zn-MOF as a superior and efficient catalyst compared to other reported MOFs. Additionally, the catalyst can be easily recovered and regenerated for repeated use without performance loss.

研究领域: 材料科学 · 催化化学 · 环境科学
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