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MICROCHEMICAL JOURNAL · 2025 · IF 5.1

Design of Mn-Car multivalent laccase mimics through self-assembled coordination and its application for ultrasensitive colorimetric detection of kanamycin in food

Siyu Wu,Xiaojuan Niu,Jiali Chen,Wangni Meng,Han Tao,Jianli Zhou,Yuangen Wu

Kanamycin (KAN) can generate a serious threat to human health due to its tendency to accumulate in food. Current colorimetric strategy for KAN detection still faces some challenges, and nanozyme-based colorimetry is an ideal alternative approach. Herein, a non‑copper-based multivalent laccase mimic named Mn-Car is first synthesized through a self-assembly of manganese ions and the endogenous biomolecule carnosine, which is further used to develop a novel colorimetric method for ultrasensitive and selective detection of KAN. The laccase-like catalytic center is formed through the multidentate chelation bonds between manganese ions and imidazolium groups of histidine as well as carboxyl groups of β-alanine in carnosine. The multivalent oxidation states of manganese dynamically regulate electron transfer pathways through synergistic coordination. The unique Mn-Car architecture drives the efficient generation of superoxide radicals (O 2 · − ) and semiquinone radicals (SQ· − ). Leveraging the excellent laccase-like activity of Mn-Car , a highly sensitive colorimetric method for KAN detection is developed. Mn-Car forms polydentate chelation with the amino and hydroxyl groups in KAN, which can trigger multi-step cascade oxidation reactions that disrupt the structural core of Mn-Car and lead to reduced colorimetric signals. The colorimetric method achieves a limit of detection (LOD) of 0.102 μM and is successfully applied for on-site detection of KAN in water samples and honey, providing a novel platform for antibiotic residue analysis.

研究领域: 分析化学 · 纳米技术 · 生物传感
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COLLOIDS AND SURFACES B-BIOINTERFACES · 2017 · IF 3.887

The study of angiogenesis stimulated by multivalent peptide ligand-modified alginate

Bicui Wang,Wei Wang,Yanyan Yu,Yingxue Zhang,Jingwei Zhang,Zhi Yuan

Enhancing the affinity of scaffolds for endothelial cell (EC) is a crucial procedure for promoting angiogenesis in tissue engineering. In this work, to achieve stronger binding affinity with ECs, the peptide sequence REDV was conjugated onto gold nanoparticles (AuNPs) to construct a multivalent ligand ( c REDV). Then, the EC adhesion and proliferation were studied to determine ligand affinity for ECs in vitro . The results show that the c REDV-modified alginate ( c REDV-ALG) surface exhibited a selective adhesion to human umbilical vein endothelial cells (HUVECs) compared with NIH 3T3 cells. The average area of individual HUVEC that adhered to c REDV-ALG was approximately 2.27-fold higher than that adhered to the monovalent REDV-modified alginate (REDV-ALG) surface. Additionally, a superior ability to promote the proliferation of HUVECs compared to the REDV-ALG surface was demonstrated. In vivo angiogenic assays were also carried out to assess the effect of multivalent strategy on the vascularization of scaffolds. The results illustrated that c REDV-ALG could stimulate new vessel formation in the scaffold, and the blood vessel density was at least 20% higher than that observed with monovalent REDV-ALG with a similar degree of ligand substitution. These results demonstrated that a multivalent ligand strategy was beneficial for the vascularization of engineered tissues.

研究领域: 组织工程 · 生物材料科学 · 分子生物学
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ChemistrySelect · 2024 ·Vol. 9 ·期 29 ·e202401592 · IF 1.9

Synergistic Effects of In-Situ-Formed Multivalent Titanium and Mg2Ni for Improving the Hydrogen-Storage Properties of MgH2

Yazhou Wang,Shunxiang Wang,Qingjie He,Weiqi Sun,Jiaao Wu,Yongpeng Xia,Cuili Xiang,Yongjin Zou,Fen Xu,Lixian Sun

Graphical We employ a hydrothermal method and high-temperature calcination to prepare well-dispersed NiTiO 3 nanoparticles with smaller than 20 nm. The NiTiO 3 nanoparticles show good catalytic effect on hydrogen storage of MgH 2 . The further structural analysis shows that the excellent hydrogen storage performance of MgH 2 -NiTiO 3 benefits from multivalent state of titanium and Mg 2 Ni/Mg 2 NiH 4 . Magnesium hydride (MgH 2 ) has gained significant consideration as a cost-effective solid-state hydrogen-storage material with a substantial hydrogen capacity. However, its practical applications are impeded by its poor kinetics and high thermal stability. In this study, we employed a hydrothermal method and high-temperature calcination to prepare well-dispersed NiTiO 3 nanoparticles smaller than 20 nm. Next, we investigated the effect of the NiTiO 3 nanoparticles for educating the hydrogen storage performance of MgH 2 . The synergistic catalytic effect of multivalent titanium and Mg 2 Ni/Mg 2 NiH 4 enhanced hydrogen storage performance of the MgH 2 system. The addition of 5 wt % NiTiO 3 lowered the initial hydrogen evolution temperature of MgH 2 to 194 °C. After 12 minutes at 275 °C, the 5 wt % NiTiO 3 -MgH 2 composites released 6.1 wt % of hydrogen. The dehydrogenation activation energy ( E a ) of the 5 wt % NiTiO 3 -MgH 2 composites decreased significantly to 38.78±2.1 kJ/mol. Furthermore, hydrogen uptake of 5 wt % NiTiO 3 -MgH 2 at 125 °C reaches 5.1 wt % in 300 s under hydrogen pressure of 20 bar. These findings introduce an innovative concept for preparing high active catalysts for improving the dehydrogenation/hydrogenation kinetics of MgH 2 .

CAS / MDL: 5593-70-4
研究领域: 材料科学 · 能源存储
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RSC Advances · 2017 ·Vol. 7 ·期 60 ·37596-37603 · IF 3.108

Notable in situ surface transformation of Cu2O nanomaterials leads to dramatic activity enhancement for CO oxidation

Dan Zhao,Chang-Man Tu,Xue-Jing Hu,Ning Zhang

Cu2O is an important compound for many promising applications; however, its real state under serious application conditions, such as redox atmosphere of catalysis reactions, has seldom been investigated. In this study, a dramatic and sustainable activity enhancement for CO oxidation on catalytically used Cu2O nanoporous sphere samples was discovered as compared to that on their fresh counterparts. To illustrate the phenomenon, comprehensive characterizations such as XRD, H2-TPR, TEM, XPS, and CO-TPD were performed on fresh and used Cu2O samples. It was found that after one or several catalytic runs, the main phase among the used samples retained the crystalline feature of Cu2O. However, the surface would transform into a stable multivalent composite interface with almost unchanged Cu(II) : Cu(I) ratio (around 4.0) and active oxygen distribution, even after only one catalytic run for CO oxidation; this indicated a notable reaction-induced or in situ surface restructuring effect of the Cu2O substrates. Compared to that of pure Cu2O, CuO, and reported CuxO samples, the active chemisorbed oxygen on these in situ restructured samples was observed in particularly higher surface composition (with the ratio of chemisorbed oxygen to lattice oxygen being around 5.5); this was further demonstrated to be highly efficient for the oxidization of CO in a relatively low temperature range even in the absence of O2 in the atmosphere and could be the main contributor to speed up CO oxidation in these samples. A similar enhancement in the activity on the used samples for CO oxidation as compared to that on the fresh samples was further testified in Cu2O nanomaterials with different morphologies such as cubic, octahedral, and 18-facet polyhedral nanoparticles; this implied that the surface restructuring effect under a redox reaction atmosphere was a common feature of the Cu2O-based materials, and the transformed surface could act as a superior and stable interface for heterogeneous catalysis. These findings might help in recognizing the real state of Cu2O-containing materials under serious application conditions or designing highly efficient Cu2O-based materials via convenient atmosphere-controlled manipulation for advanced applications.

CAS / MDL: 6046-93-1
研究领域: 催化化学 · 材料科学
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Membranes · 2022 ·Vol. 12 ·期 11 ·1151 · IF 4.562

Plant Polyphenol Pyrogallol and Polyamine-Based Co-Deposition for High-Efficiency Nanofiltration Membrane Preparation towards Inorganic Salt Removal

Jiawen Wu,Zhiwen Li,Qingfeng Zhou,Mercy Chigwidi,Yang Jiao,Yanchao Xu,Hongjun Lin

The co-deposition between polyphenols and amines has been demonstrated in order to prepare positively charged nanofiltration (NF) membranes for multivalent cation rejection in recent years; however, the low reactivities of the involved polyphenols usually cause a long co-deposition time and unsatisfactory rejection. Herein, a novel plant polyphenol (PG) was co-deposited with tetraethylenepentamine (TEPA) in a much shorter time period to prepare positively charged NF with high multivalent cation rejection membranes. The performance of the co-deposition membranes can be easily controlled by adjusting the mass ratio of PG and TEPA, reaction time, and pH value of the buffer solution. The optimal membrane, prepared under a polyphenol and polyamine mass ratio of 1:1, coating time of 2 h, and pH value of 8.0, shows a decent pure water permeability of 8.43 L m−2h−1bar−1while maintaining a superior 96.24% MgCl2rejection. More importantly, the universality of this method was corroborated by employing other amines with different molecular weights in the co-deposition. This work provides new insights for the preparation of high-performance positively charged NF membranes.

研究领域: 材料科学 · 环境工程 · 化学工程
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FUEL · 2020 · IF 5.578

MoSe2: a promising non-noble metal catalyst for direct ethanol synthesis from syngas

Hao Qu,Sihui He,Yue Su,Yulong Zhang,Haiquan Su

Direct synthesis of ethanol from syngas (a mixture of H 2 and CO) is considered as an eco-friendly and industrially important process to produce renewable fuels and chemicals. The current non-noble metal catalyst systems suffer from either low selectivity or multiple processes with high energy consumption. Here, we report a novel molybdenum diselenide-based catalyst system for high-selective conversion of syngas into ethanol. For a series of K-promoted MoSe 2 catalysts with different K/Mo ratios (K x -MoSe 2 , x = 0.25-1.00), K 1.00 -MoSe 2 surprisingly exhibits excellent ethanol selectivity up to 58.7 C mol % in total alcohols and 31.1 C mol % in the total product, which is higher than the highest selectivity value for the non-noble metal catalysts reported in the literature. The high ethanol selectivity is attributed to the formation of K-Mo-Se active phase and the synergistic effect of the Mo IV , Mo V and Mo VI multivalent species in the active phase. This study opens up a highly selective non-noble metal catalyst system for the direct synthesis of ethanol by syngas, which is of practical significance for the catalytic conversion of hydrogen-poor syngas.

研究领域: 化学工程 · 催化科学
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2022 · IF 9.965

Molten salt method synthesis of multivalent cobalt and oxygen vacancy modified Nitrogen-doped MXene as highly efficient hydrogen and oxygen Evolution reaction electrocatalysts

Xunxin Chen,Meishan Li,Juan Hou,Ke Lu,Xuanyu Yue,Yafei Li,Long Chen,Zhiyong Liu,Xiaodong Yang

Nitrogen-doped Ti 3 C 2 T y MXene with multivalent cobalt and oxygen vacancy (Vo) modification was obtained by using molten salt method and greatly improved electrocatalytic performance. The structural properties of MXene and the valence state of cobalt were adjusted by controlling the molten salt temperature. When the molten salt treatment temperature was 377 °C, the obtained 377-CoO x N 1-x -Ti 3 C 2 T y maintained the chemical structure of MXene well, and also has high Co 2+ content and Vo content. Electrochemical test results showed that 377-CoO x N 1-x -Ti 3 C 2 T y had the lowest Hydrogen Evolution Reaction (HER) overpotential of 87.73 mV and good electrocatalytic stability. X-ray Photoelectron Spectroscopy (XPS) results and Density Functional Theory (DFT) calculations showed that the introduction of polyvalent cobalt and Vo in the nitrogen-doped Ti 3 C 2 T y structure effectively reduced the energy barrier of the electrocatalytic reaction of MXene.

研究领域: 材料科学 · 电化学
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APPLIED SURFACE SCIENCE · 2024 · IF 6.3

Engineering the CuO/MnO2 interface with multivalent conversion for low-temperature and efficient CO oxidation

Siwen Gong,Gangqiang Zhu,Xiaoqian Xie,Fei Rao,Lujun Zhu,Yurong An,Xianjin Shi,Yu Huang,Peng Liu,Mirabbos Hojamberdiev

A novel interface of MnO 2 with CuO with multivalent conversion is fabricated by the deposition-precipitation method for low-temperature and efficient CO oxidation. It is found that the temperature for CO thermal-catalytic oxidation to reach a complete conversion significantly decreases to 105 °C for the CuO/MnO 2 . A combination of experimental and theoretical studies demonstrates the successful formation of the CuO/MnO 2 interface, inducing a pronounced effect that promotes CO oxidation. The CuO/MnO 2 interface leads to the formation of Cu-O-Mn, a superior redox system with multivalent conversion (Cu + + Mn 4+ ↔ Cu 2+ + Mn 3+ , Cu + + Mn 3+ ↔ Cu 2+ + Mn 2+ ), abundant active sites, excellent ability to activate O 2 , the rapid oxygen transfer, and more suitable adsorption energy for O 2 , CO, and CO 2 . These characteristics are advantageous to Cu x O-Mn x O y for achieving a 100 % removal of CO at a lower temperature. Furthermore, the computational study reveals that the CO oxidation process follows two mechanistic pathways (Eley-Rideal (E-R) and Mars-van Krevelen (M-K)), indicating that there is no competitive adsorption of CO and O 2 on the CuO/MnO 2 . This study shows that the interface created between suitable metal oxides can improve the catalytic performance and provides new perspective for catalyst design and performance enhancement mechanisms.

研究领域: 材料科学 · 催化化学
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2020 · IF 4.939

Superior catalysis of NbN nanoparticles with intrinsic multiple valence on reversible hydrogen storage properties of magnesium hydride

Meng Zhang,Xuezhang Xiao,Zhouming Hang,Man Chen,Xuancheng Wang,Nan Zhang,Lixin Chen

Magnesium hydride, as a potential solid state hydrogen carrier has attracted great attention around the world especially in the energy storage domain due to the high hydrogen storage capacity and the good cycling stability. But kinetic and thermodynamic barriers also impede the practical application and development of MgH 2 . Nanoscale catalysts are deemed to be the most effective measure to overcome the kinetic barrier and lower the temperature required for hydrogen release in MgH 2 . NbN nanoparticles (~20 nm) with intrinsic Nb 3+ -N and Nb 5+ -N were prepared using the molten salt method and used as catalysts in the MgH 2 system. It is found that the NbN nanoparticles exhibit a superior catalytic effect on de/rehydrogenation kinetics for the MgH 2 /Mg system. About 6.0 wt% hydrogen can be liberated for the MgH 2 +5NbN sample within 5 min at 300 °C, and it takes 12 min to desorb the same amount of hydrogen at 275 °C. Meanwhile, the MgH 2 +5NbN sample can absorb 6.0 wt% hydrogen within 16 min at 150 °C, and absorb 5.0 wt% hydrogen within 24 min even at 100 °C. Particularly, the catalyzed samples exhibit excellent hydrogen absorption/desorption kinetic stability. After multiple cycles, there is no kinetic attenuation and the hydrogen capacity remains at about 6.0 wt%. It is demonstrated that the NbN nanoparticles with intrinsic multiple valence can be the critical effect in improving the hydrogen storage kinetics of MgH 2 . The stability of Nb 4 N 3 phase and Nb 3+ -N and Nb 5+ -N valence states can ensure a stable catalytic effect in the system.

研究领域: 材料科学 · 能源存储
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JOURNAL OF MEMBRANE SCIENCE · 2016 · IF 5.557

A facile preparation of novel positively charged MOF/chitosan nanofiltration membranes

Xiao-Hua Ma,Zhe Yang,Zhi-Kan Yao,Zhen-Liang Xu,Chuyang Y. Tang

A novel positively charged nanofiltration (NF) membrane was fabricated by incorporating metal-organic frameworks (MOFs) into chitosan polymeric matrix for enhanced removal of multivalent cations. The synthesized MOFs, NH 2 -MIL-101(Al) and NH 2 -MIL-101(Cr), could be homogeneously dispersed in the chitosan polymeric matrix. The morphologies of MOFs had a significant influence on the permeability of NF membranes. NF membrane filled with NH 2 -MIL-101(Al) with rod-like structure attained two times higher flux but similar rejection compared with that filled with NH 2 -MIL-101(Cr) with grainy structure. The effect of MOF loadings (NH 2 -MIL-101(Al)) on the membrane performance were evaluated by XRD , FTIR and SEM. These positively charged MOF/chitosan NF membranes were able to reject up to 93.0% of MgCl 2 , and the salt rejection followed the order of MgCl 2 >CaCl 2 >NaCl>Na 2 SO 4 .

CAS / MDL: 9012-76-4
研究领域: 材料科学 · 环境工程
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SCIENCE OF THE TOTAL ENVIRONMENT · 2020 · IF 6.551

Sludge-derived biochar with multivalent iron as an efficient Fenton catalyst for degradation of 4-Chlorophenol

Quan Gan,Huijie Hou,Sha Liang,Jingjing Qiu,Shuangyi Tao,Liang Yang,Wenbo Yu,Keke Xiao,Bingchuan Liu,Jingping Hu,Yanfei Wang,Jiakuan Yang

Fe-rich biochar with multivalent iron compounds (Fe 0 , Fe 0.95 C 0.05 , Fe 3 O 4 , and FeAl 2 O 4 ) pyrolyzed from sludge cake conditioned with Fenton's reagent and red mud was utilized as an efficient Fenton catalyst for the degradation of 4-chlorophenol (4-CP). Effects of pyrolysis temperature and sludge conditioner composition on the transformation of iron compounds were studied. Both homogeneous Fenton reaction initiated by Fe 2+ leached from both low-valent Fe 0 and Fe 0.95 C 0.05 , and heterogeneous Fenton reaction initiated by solid iron phases of Fe 3 O 4 and FeAl 2 O 4 were revealed to contribute to the degradation of 4-CP. The removal efficiency of 4-CP remained 100% after five successive degradation rounds. The homogeneous Fenton reaction mainly works in the first degradation round, and the heterogeneous Fenton reaction dominates in subsequent degradation rounds. The findings of this study suggest that sewage sludge derived Fe-rich biochar could be utilized as an efficient Fenton catalyst for recalcitrant organics degradation .

CAS / MDL: 3317-61-1
研究领域: 环境科学 · 化学工程
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BIOMATERIALS · 2015 · IF 8.557

Pentacyclic triterpenes grafted on CD cores to interfere with influenza virus entry: A dramatic multivalent effect

Sulong Xiao,Longlong Si,Zhenyu Tian,Pingxuan Jiao,Zibo Fan,Kun Meng,Xiaoshu Zhou,Han Wang,Renyang Xu,Xu Han,Ge Fu,Yongmin Zhang,Lihe Zhang,Demin Zhou

Multivalent effect plays an important role in biological processes , particularly in the specific recognition of virus with its host cell during the first step of infection. Here we report the synthesis of multivalent pentacyclic triterpene grafted on cyclodextrin core and potency of against influenza entry activity. Nine star-shaped compounds containing six, seven and eight pentacyclic triterpene pharmacophore on cyclodextrin scaffold were prepared by way of copper-catalyzed azide-alkyl cycloaddition reaction under microwave activation. Some of the multimers exhibited much potent antiviral activity against H1N1 virus (A/WSN/33), even equivalent or superior to oseltamivir . The most active compound 31 , a heptavalent oleanolic acid- β -cyclodextrin conjugate , shows an up to 125-fold potency enhancement by its IC 50 value over the corresponding monovalent conjugate and oleanolic acid, disclosing a clear multivalent effect. Further studies show that three compounds 31 – 33 exhibited broad spectrum inhibitory activity against other two human influenza A/JX/312 (H3N2) and A/HN/1222 (H3N2) viruses with the IC 50 values at 2.47–14.90  μ M. Most importantly, we found that compound 31, one of the best representative conjugate, binds tightly to the viral envelope hemagglutinin with a dissociation constant of K D  = 2.08  μ M, disrupting the interaction of hemagglutinin with the sialic acid receptor and thus the attachment of viruses to host cells. Our study might establish a strategy for the design of new pharmaceutical agents based on multivalency so as to block influenza virus entry into host cells.

研究领域: 药理学 · 病毒学
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