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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Growth mechanism of glucose-based hydrochar under the effects of acid and temperature regulation

Jian Peng,Xiheng Kang,Siyu Zhao,Peitao Zhao,Arthur J. Ragauskas,Chuanling Si,Ting Xu,Xueping Song

Improving the tailorability of hydrochar synthesis is an effective way to enhance its performance and utilization efficiency. In this study, the growth rate, morphology, and molecular structure of hydrochar were controlled by regulating the pH and temperature of the hydrothermal carbonization process. Growth process analysis indicates that hydrochar has three growth periods: induction, rapid, and stable growth periods. It is mainly controlled by 5-hydroxymethylfurfural (HMF), which is formed by converting glucose and its transformation products. The regulation of acid can significantly shorten the induction period of hydrochar, even under low-temperature conditions (<180   ℃), and increase the growth rate of hydrochar. However, the degree of hydrochar adhesion varies: the lower the temperature, the greater the degree of its adhesion. Molecular structural analysis demonstrates that hydrochar mainly consists of furan structural domains and aromatic clusters, and its surface is rich in oxygen-containing functional groups. The degree at which hydrochar was aromatized was improved by increasing the reaction temperature (160–220   ℃); whereas the regulation of acid reduced it and increased the content of oxygen-containing functional groups on the hydrochar surface. Based on these results, it is proposed that hydrochar formation has five stages and three growth periods with or without acid regulation.

研究领域: 化学工程 · 材料科学
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FOOD CHEMISTRY · 2021 · IF 7.514

Effects of processing parameters on furan formation in canned strawberry jam

Mingyue Shen,Lichun Liu,Fan Zhang,Yujie Jiang,Zhengbo Huang,Jianhua Xie,Yadong Zhong,Shaoping Nie,Mingyong Xie

The formation mechanism of furan has been studied extensively in model systems, however, furan formation in real foods are complex and far from being fully understood. In this study, the effects of acid-regulating agent (citric acid), sugar addition (glucose, fructose and sucrose) and thickening agents (xanthan gum, κ-carrageenan and pectin) on furan levels in strawberry jams were studied; meanwhile the formation pathway of furan in canned strawberry jam was proposed by carbon module labeling (CAMOLA) technique. Our results suggested low pH promoted furan formation in strawberry jam. Besides, fructose produces more furans than sucrose and glucose, and the addition of xanthan gum reduced furan levels significantly. The kinetic data showed that ascorbic and dehydroascorbic acid degradation followed first-order kinetics while rate of furan formation followed zero-order kinetics. This study presented the possibility of mitigating furan formation in canned strawberry jams by optimization of processing parameters and addition of xanthan gum.

研究领域: 食品科学 · 化学
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CHINESE JOURNAL OF CHEMICAL ENGINEERING · 2022 · IF 3.898

Defective NH2-UiO-66 (Zr) effectively converting CO2 into cyclic carbonate under ambient pressure, solvent-free and co-catalyst-free conditions

Xueting Liu,Chunhui Hu,Jingjing Wu,Peng Cui,Fengyu Wei

In this study, a series of metal–organic frameworks (MOFs) NH 2 -UiO-66- x HAc catalysts were synthesized by solvothermal method using acetic acid (HAc) as a modulator, and were applied to the cycloaddition of CO 2 and epichlorohydrin (EPIC) under ambient pressure. Influences of the modulation by HAc on morphologies and structures of the MOFs are demonstrated via PXRD, FESEM, FTIR, N 2 adsorption–desorption, XPS and 1 H NMR characterizations. The results show that the MOFs containing mesoporous pores can be prepared by adjusting the concentration of HAc. By optimizing the amount of HAc added, the specific surface area of NH 2 -UiO-66-8HAc is as high as 879.17 m 2 ·g −1 , which is 28.3% higher than that of the original MOFs. And the evaluation of catalytic performance showed that HAc modulation enhanced the activity of NH 2 -UiO-66- x HAc under mild conditions. The exposure of Lewis acid sites, increased specific surface area and porosity via the modulation of HAc defective ligand can be supposed the key factors to determine the enhanced catalytic activities. In addition, considering the influence of gas concentration on the reaction, the concept of TOP (Turnover of Pressure, defined as the mass of conversions of a unit mass catalyst under unit pressure and unit time) was first proposed in this article.

研究领域: 化学 · 材料科学
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RSC Advances · 2022 ·Vol. 12 ·期 10 ·6083-6092 · IF 4.036

An efficient modulated synthesis of zirconium metal–organic framework UiO-66

Xia Chen,Yongjie Li,Qiang Fu,Hongyun Qin,Junnan Lv,Kun Yang,Qicheng Zhang,Hui Zhang,Ming Wang

The use of large amounts of deleterious solvents in the synthesis of metal–organic frameworks (MOFs) is one of the important factors limiting their application in industry. Herein, we present a detailed study of the synthesis of UiO-66, which was conducted with hydrobromic (HBr) acid as a modulator for the first time, at a high concentration of precursor solution (ZrCl4 and H2BDC, both 0.2 mol L−1). Powder crystals with atypical cuboctahedron structure were obtained which indicated that the HBr acid modulator played roles by competitive coordination and deprotonation modulation, thereby controlling the processes of nucleation and crystal growth. The properties of the obtained materials were systematically characterized and compared with those of materials synthesized with hydrofluoric (HF) acid and hydrochloric (HCl) acid modulators. Despite the high concentration of defectivity, the UiO-66 material synthesized with the HBr acid additive has the characteristics of larger specific surface area, excellent thermal stability and higher porosity in the structure. Besides that, the present protocol has the advantages of high reaction mass efficiency (RME), and feasibility of scalable synthesis, providing a facile and sustainable route to diverse Zr-based MOFs.

研究领域: 材料科学 · 化学工程
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BIOCONJUGATE CHEMISTRY · 2025 · IF 3.9

Synthetic Redox-Responsive Nanocomplexes Facilitate Spatially Controlled mRNA Release and Tumor-Selective Expression

Sheng Lin,Xia Cheng,Xiyi Chen,Jinxuan He,Wenxiu An,Qiufang Bai,Qixian Chen,Lie Ma,Jianhua Hu,Yue Wang,Xiabin Lan

The refinement of dynamic molecular mechanisms regulating mRNA release kinetics represents a critical frontier in advancing the synthetic mRNA delivery systems. This study details the synthesis of an intriguing ROS-responsive cationic block copolymer (pM-pBD) via reversible addition−fragmentation chain transfer (RAFT) polymerization, employing biocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) and charge-reversible (2-acryloyl)ethyl(boronic acid benzyl)diethylammonium bromide (BD) as monomeric precursors. The synthesized copolymer facilitates electrostatic-driven self-assembly with anionic mRNA. Mechanistically, the pBD block exhibits ROS-mediated charge transition, enabling stimulus-dependent molecular decomposition and promoting mRNA payload liberation, thereby establishing spatial regulation of translational activity. Furthermore, intracellular ROS modulation experiments revealed that systemic ascorbic acid administration selectively enriches reactive oxygen species within tumor microenvironments. This redox microenvironment significantly amplifies pM-pBD nanocomplex-mediated mRNA expression by an order of magnitude across multiple carcinogenic cell lines, validating the ROS-responsive characteristics of our rationally designed delivery platform. In vivo studies demonstrated the highest mRNA expression levels in tumors when aided by ascorbic acid adjuvants, despite lower tumor accumulation of mRNA compared to renal and hepatic sequestration post intravenous administration of the pM-pBD nanocomplex. This spatial expression pattern correlates with ascorbic acid-mediated intratumoral ROS accumulation, which promotes cargo release and subsequent protein synthesis of approximately 6.4-fold enhancement. Our approach, integrating redox-responsive polymer design with organ-specific pharmacological modulation, signifies a transformative advancement in targeted nucleic acid delivery. By merging stimulus-responsive materials science with tumor microenvironment biology, this methodology provides a foundation for spatially controlled mRNA expression, presenting an innovative strategy for precision oncology applications.

CAS / MDL: 623-05-2
研究领域: 生物材料 · 肿瘤学 · 药剂学 · 分子生物学
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Nanoscale · 2022 ·Vol. 14 ·期 35 ·12762-12772 · IF 8.307

Acid-regulated boron–nitrogen codoped multicolor carbonized polymer dots and applications for pH sensing and trace water detection

Ge Lv,Ziwei Wang,Wenjing Li,Guannan Zhu,Beibei Liu,Bin Song,Min Wu,Xiao Gong

To obtain multicolor carbonized polymer dots (CPDs), acid-assisted hydrothermal/solvothermal reactions are an effective strategy. However, the long wavelength fluorescence of boron–nitrogen codoped CPDs (BN-CPDs) is rarely reported. In this work, we used concentrated hydrochloric acid to regulate the fluorescence (from green to orange) of BN-CPDs via a solvothermal reaction. Meanwhile, 3-formylphenylboronic acid with a benzene ring structure was employed as the boron source, which helped the formation of the internal conjugated structure of CPDs to obtain long wavelength fluorescent CPDs. The fluorescence properties of BN-CPDs were investigated, which indicated the concentration- and solvent-dependent properties of the BN-CPDs. Based on the experimental results, we assume that the multicolor emission of the BN-CPDs originates from the synergistic effects of the degree of graphitization and surface states. Due to the special fluorescence properties of the BN-CPDs, pH sensing and trace water detection in dichloromethane solution can be effectively achieved. The results of the study reveal the potential of BN-CPDs in sensing applications.

研究领域: 材料科学 · 分析化学
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CHEMISTRY OF MATERIALS · 2019 · IF 10.159

Nucleotide-Regulated Tough and Rapidly Self-Recoverable Hydrogels for Highly Sensitive and Durable Pressure and Strain Sensors

Qin Zhang,Xin Liu,Xiuyan Ren,Fei Jia,Lijie Duan,Guanghui Gao

Flexible and stretchable hydrogels have drawn much attention as wearable sensors; however, most hydrogel sensors usually suffer from poor mechanical toughness and self-recovery, causing great limitation in their application for repeated sensing. Here, highly stretchable, tough, and antifatigue hydrogels are fabricated by incorporating nucleotide (adenosine monophosphate, AMP) into hydrophobic association polyacrylamide (PAAm) networks. As a dynamic connected bridge, AMP significantly regulates mechanical performances of hydrogels, wherein the anionic phosphate groups from AMP form ionic bonds with cationic micelles and the nucleobases of AMP bind with PAAm chains through hydrogen bonds. The noncovalent synergistic interactions in the hydrogel networks contribute to achieving fast self-recoverable and antifatigue behaviors at room temperature without any external stimuli. More importantly, the nucleotide-regulated hydrogel presents durability and high sensitivity as pressure and strain sensors for the detection of various mechanical deformations. As a result, the hydrogels are successfully designed as wearable sensors for sensing various large and subtle human motions, including the bending of elbow, wrist, and finger and even the vibrations of the rib cage and larynx. It is envisioned that the nucleotide-regulated hydrogels would find broad applications in electric skins, medical monitoring, soft robotics, and flexible touch panels.

研究领域: 材料科学 · 生物医学工程 · 柔性电子
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Polymers · 2022 ·Vol. 14 ·期 18 ·3826 · IF 4.967

Effects of Acid Modulators on the Microwave-Assisted Synthesis of Cr/Sn Metal-Organic Frameworks

Wei Mao,Renting Huang,Hao Xu,Hao Wang,Yi Huang,Shurong Huang,Jinghong Zhou

Metal-organic frameworks (MOFs) have attracted remarkable attention for their distinguished structural designability. Precisely controlling the particle size and improving the structural stability of MOF nanoparticles influence their catalytic activity significantly. In this study, six acids (nitric, hydrochloric, formic, acetic, succinic, and citric acids) were used as modulators to prepare bimetallic MIL-101 (Cr, Sn) (MIL stands for Materials of Institut Lavoisier) via a microwave-assisted hydrothermal method. Changes in volumetric, structural, stability, and catalytic properties, size, and shape of MIL-101 (Cr, Sn) were examined using scanning electron microscopy, X-ray diffraction, thermogravimetric analysis, and N2adsorption–desorption measurements. All modulators altered the MOF properties. Compared with other samples, acetic acid as a modulator mildly altered the MOF morphology by narrowing their particle size distribution, enhancing the specific surface area, and significantly improving their water and thermal stabilities. The addition of acetic acid was suitable for the catalytic conversion of glucose to 5-hydroxymethylfurfural (5-HMF), achieving a 43.1% 5-HMF yield with 91.4% glucose conversion in a mixed solution of γ-valerolactone and saturated salt water at 150 °C after 30 min.Keywords:modulators;microwave synthesis;bimetallic MIL-101 (Cr, Sn)

研究领域: 材料科学 · 催化化学
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JOURNAL OF MATERIALS SCIENCE · 2021 ·Vol. 56 ·期 28 ·15782-15797 · IF 4.22

Acid-modulated porous AgI/D-MIL-53(Fe) composites for the removal of antibiotic contaminant

Jiang Danni,Zhou Yu,Wang Ping,Huang Chao,Zhu Jian,Liu Zhiming

In the MOFs-based composites, the co-catalyst nanoparticles loads tend to agglomerate. In the self-assembly process of MOFs-based composites, the use of acid modulators solved the accumulation of AgI nanoparticles cocatalyst. The active sites of carboxyl groups and mesoporous structure brought by acid modulator provide more loading sites for AgI nanoparticles. The novel AgI/D-MIL-53(Fe) showed good adsorption and photocatalytic performance in the process of removing tetracycline pollutants. Compared to the degradation efficiency of the MIL-53(Fe) with 50.8%, it of AgI/MIL-53(Fe) increased to 85.1% and which further increased to 96.2% by AgI/D-MIL-53(Fe) based on the HCl modulator. On the one hand, it is beneficial for the mesoporous D-MIL-53(Fe) modulated by HCl modulator to disperse the AgI nanoparticles co-catalyst. On the other hand, AgI nanoparticles, as a photosensitive agent, adsorb visible light to generate photogenerated electrons and holes, and electrons rapidly transferred to the heterojunction bridge Ag 0 and then captured by the holes from the D-MIL-53(Fe). The construction of AgI/D-MIL-53(Fe) Z-scheme heterojunction provided favorable conditions for the rapid separation and photogenerated electrons and holes. Finally, ·O 2 − , ·OH and h + as the main active free radicals were driving forces. This study provided more possibilities and opportunities for the construction of mesoporous MOFs-based composites.

CAS / MDL: 68-12-2 100-21-0
研究领域: 环境科学 · 材料科学
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Frontiers in Pharmacology · 2021 · IF 5.811

Bruceae Fructus Oil Inhibits Triple-Negative Breast Cancer by Restraining Autophagy: Dependence on the Gut Microbiota-Mediated Amino Acid Regulation

Su Jiyan,Chen Xiaohong,Xiao Yuanjie,Li Dan,Li Muxia,Li Hongfu,Huang Jiangjian,Lai Zhengquan,Su Ziren,Xie Yizhen,Zhu Dajiang,Chen Qianjun,Lu Hai,He Jingjin,Xia Chenglai

Triple-negative breast cancer (TNBC) has been acknowledged as an aggressive disease with worst prognosis, which requires endeavor to develop novel therapeutic agents. Bruceae fructus oil (BO), a vegetable oil derived from the fruit of Brucea javanica (L.) Merr., is an approved marketable drug for the treatment of cancer in China for several decades. Despite that the anti–breast cancer activity of several quassinoids derived from B. javanica has been found, it was the first time that the potential of BO against TNBC was revealed. Although BO had no cytotoxicity on TNBC cell lines in vitro, the oral administration of BO exhibited a gut microbiota–dependent tumor suppression without toxicity on the non-targeted organs in vivo. By metagenomics and untargeted metabolomics, it was found that BO not only altered the composition and amino acid metabolism function of gut microbiota but also regulated the host’s amino acid profile, which was in accordance with the metabolism alternation in gut microbiota. Moreover, the activity of mTOR in tumor was promoted by BO treatment as indicated by the phosphorylation of 4E-binding protein 1 (4E-BP1) and ribosomal protein S6, and hyper-autophagy was consequently restrained. By contrast, the failure of tumor suppression by BO under pseudo germ-free (PGF) condition came with indistinctive changes in autophagy and mTOR activity, implying the critical role of the gut microbiota in BO’s anticancer activity. The present study highlighted a promising application of BO against breast cancer with novel efficacy and safety.

研究领域: 肿瘤学 · 药理学 · 微生物学 · 代谢组学 · 癌症生物学
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JOURNAL OF CONTROLLED RELEASE · 2024 · IF 10.5

Biomimetic gold nanocages incorporating copper-human serum albumin for tumor immunotherapy via cuproptosis-lactate regulation

Hajra Zafar,Jun Zhang,Faisal Raza,Xiuhua Pan,Zongwei Hu,Hanxiao Feng,Qi Shen

Cancer immunotherapy remains a significant challenge due to insufficient proliferation of immune cells and the sturdy immunosuppressive tumor microenvironment. Herein, we proposed the hypothesis of cuproptosis-lactate regulation to provoke cuproptosis and enhance anti-tumor immunity. For this purpose, copper-human serum albumin nanocomplex loaded gold nanocages with bacterial membrane coating (BAu-CuNCs) were developed. The targeted delivery and disassembly of BAu-CuNCs in tumor cells initiated a cascade of reactions. Under near infrared (NIR) laser irradiation, the release of copper-human serum albumin (Cu-HSA) was enhanced that reacted with intratumoral glutathione (GSH) via a disulfide exchange reaction to liberate Cu 2+ ions and exert cuproptosis. Subsequently, the cuproptosis effect triggered immunogenic cell death (ICD) in tumor by the release of damage associated molecular patterns (DAMPs) to realize anti-tumor immunity via robust production of cytotoxic T cells (CD8 + ) and helper T cells (CD4 + ). Meanwhile, under NIR irradiation, gold nanocages (AuNCs) promoted excessive reactive oxygen species (ROS) generation that played a primary role in inhibiting glycolysis, reducing the lactate and ATP level. The combine action of lower lactate level, ATP reduction and GSH depletion further sensitized the tumor cells to cuproptosis. Also, the lower lactate production led to the significant blockage of immunosuppressive T regulatory cells (Tregs) and boosted the anti-tumor immunity. Additionally, the effective inhibition of breast cancer metastasis to the lungs enhanced the anti-tumor therapeutic impact of BAu-CuNCs + NIR treatment. Hence, BAu-CuNCs + NIR concurrently induced cuproptosis, ICD and hindered lactate production, leading to the inhibition of tumor growth, remodeling of the immunosuppressive tumor microenvironment and suppression of lung metastasis. Therefore, leveraging cuproptosis-lactate regulation, this approach presents a novel strategy for enhanced tumor immunotherapy.

CAS / MDL: 509-34-2
研究领域: 纳米技术 · 癌症免疫治疗 · 生物医学工程 · 分子生物学 · 诊疗学
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CHINESE JOURNAL OF POLYMER SCIENCE · 2022 ·Vol. 40 ·期 4 ·338-344 · IF 3.815

Morphology Engineering for Covalent Organic Frameworks (COFs) by Surfactant Mediation and Acid Adjustment

Yang Guang-Hui,Zhang Zhe,Yin Cong-Cong,Shi Xian-Song,Wang Yong

Two-dimensional covalent organic frameworks (COFs) with specific morphologies including nanofibers and nanoplates are highly desired in both nanoscience research and practical applications. Thus far, however, morphology engineering for COFs remains challenging because the mechanism underlying the morphology formation and evolution of COFs is not well understood. Herein, we propose a strategy of surfactant mediation coupled with acid adjustment to engineer the morphology of a β -ketoenamine-linked COF, TpPa, during solvothermal synthesis. The surfactants function as stabilizers that can encapsulate monomers and prepolymers to create micelles, enabling the formation of fiber-like and plate-like morphologies of TpPa rather than irregularly shaped aggregates. It is also found that acetic acid is important in regulating such morphologies, as the amino groups inside the prepolymers can be precisely protonated by acid adjustment, leading to an inhibited ripening process for the creation of specific morphologies. Benefitting from the synergistic enhancement of surfactant mediation and acid adjustment, TpPa nanofibers with a diameter down to ∼20 nm along with a length of up to a few microns and TpPa nanoplates with a thickness of ∼18 nm are created. Our work sheds light on the mechanism underlying the morphology formation and evolution of TpPa, providing some guidance for exquisite control over the growth of COFs, which is of great significance for their practical applications.

研究领域: 材料科学 · 纳米技术 · 化学工程
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