通讯机构：
[Chen, W ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Organometall Mat, Coll Hunan Prov, Hengyang 421008, Peoples R China.
关键词：
G4s;ROS;Fluorescence imaging;Flow cytometry
摘要：
Endogenous G-quadruplexes (G4s) and reactive oxygen species (ROS) form a complex regulatory network in tumors, and their interaction is both a key link in tumor development and provides a breakthrough for the development of new diagnostic and therapeutic approaches. Although reports on the activation of G4s fluorescent probes are common, fluorescent probes suitable for studying the relationship between intracellular G4s and ROS are extremely rare. In this work, we successfully synthesized a series of novel neutral G4s-targeting molecules (PMT, PNB, PMI, and PMD). In vitro analysis experiments revealed that PMT, PNB, PMI, and PMD can be selectively activated by G4 structures, with their fluorescence intensities enhanced by 75-fold, 31-fold, 32-fold, and 3-fold, respectively. Molecular docking experiments have shown that small molecules are predominantly embedded within nucleic acids and stabilize the basis of binding through hydrogen bonding and Π-hydrogen interactions with nucleic acids. Moreover, confocal fluorescence imaging and flow cytometry (FC) analyses revealed the expression of intracellular G4s may be an increase under ROS conditions, further verifying that ROS may promote the formation of intracellular G4s by experiments in which the cells were made to generate endogenous reactive oxygen species through light exposure to the photosensitizer (BAMA). In the present work, a platform for simple and convenient accurate monitoring of G4s is provided, offering insights into the sensitivity and accuracy of detection and imaging of G4s in abnormal physiological processes and diseases.
Endogenous G-quadruplexes (G4s) and reactive oxygen species (ROS) form a complex regulatory network in tumors, and their interaction is both a key link in tumor development and provides a breakthrough for the development of new diagnostic and therapeutic approaches. Although reports on the activation of G4s fluorescent probes are common, fluorescent probes suitable for studying the relationship between intracellular G4s and ROS are extremely rare. In this work, we successfully synthesized a series of novel neutral G4s-targeting molecules (PMT, PNB, PMI, and PMD). In vitro analysis experiments revealed that PMT, PNB, PMI, and PMD can be selectively activated by G4 structures, with their fluorescence intensities enhanced by 75-fold, 31-fold, 32-fold, and 3-fold, respectively. Molecular docking experiments have shown that small molecules are predominantly embedded within nucleic acids and stabilize the basis of binding through hydrogen bonding and Π-hydrogen interactions with nucleic acids. Moreover, confocal fluorescence imaging and flow cytometry (FC) analyses revealed the expression of intracellular G4s may be an increase under ROS conditions, further verifying that ROS may promote the formation of intracellular G4s by experiments in which the cells were made to generate endogenous reactive oxygen species through light exposure to the photosensitizer (BAMA). In the present work, a platform for simple and convenient accurate monitoring of G4s is provided, offering insights into the sensitivity and accuracy of detection and imaging of G4s in abnormal physiological processes and diseases.
期刊：
Results in Engineering,2025年26:105171 ISSN：2590-1230
通讯作者：
Quanguo He
作者机构：
[Deng, Peihong] Hengyang Normal Univ, Dept Chem & Mat Sci, Key Lab Organometall New Mat, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[He, Quanguo; Chen, Aiting; Zhou, Chuanqin; Tang, Nana; Shi, Shuting; He, QG] Hunan Univ Technol, Coll Life Sci & Chem, Zhuzhou 412007, Peoples R China.
通讯机构：
[He, QG ] H;Hunan Univ Technol, Coll Life Sci & Chem, Zhuzhou 412007, Peoples R China.
关键词：
Co 9 S 8;reduced graphene oxide;electrochemical detection;tryptophan;uric acid;dopamine
摘要：
A cost-effective and simple electrochemical approach was developed for the simultaneous detection of tryptophan (Trp), uric acid (UA) and dopamine (DA). Through hydrothermal synthesis, Co 9 S 8 was combined with graphene oxide (GO) using physical ultrasound. Subsequently, the Co 9 S 8 -RGO/GCE was created by electrochemically reducing a Co 9 S 8 -GO dispersion after drop-coating it onto the GCE surface. The amalgamation of Co 9 S 8 with RGO conferred the sensor with remarkable sensitivity, outstanding selectivity, and robust catalytic prowess towards DA, UA and Trp. The ternary mixture exhibited notable peak separations of up to 160 mV, 278 mV, and 438 mV between DA–UA, UA–Trp, and DA–Trp, respectively. The linear calibration ranges spanned 0.1–2.0 μM and 2.0–10 μM for DA, 0.06–10 μM for UA, and 0.02–10 μM for Trp, with matching 0.04 µM for DA, 0.02 µM for UA, and 6.0 nM for Trp detection limits (S/N=3). Moreover, the sensor's effective use in the identification of DA, UA and Trp in authentic samples yielded satisfactory results.
A cost-effective and simple electrochemical approach was developed for the simultaneous detection of tryptophan (Trp), uric acid (UA) and dopamine (DA). Through hydrothermal synthesis, Co 9 S 8 was combined with graphene oxide (GO) using physical ultrasound. Subsequently, the Co 9 S 8 -RGO/GCE was created by electrochemically reducing a Co 9 S 8 -GO dispersion after drop-coating it onto the GCE surface. The amalgamation of Co 9 S 8 with RGO conferred the sensor with remarkable sensitivity, outstanding selectivity, and robust catalytic prowess towards DA, UA and Trp. The ternary mixture exhibited notable peak separations of up to 160 mV, 278 mV, and 438 mV between DA–UA, UA–Trp, and DA–Trp, respectively. The linear calibration ranges spanned 0.1–2.0 μM and 2.0–10 μM for DA, 0.06–10 μM for UA, and 0.02–10 μM for Trp, with matching 0.04 µM for DA, 0.02 µM for UA, and 6.0 nM for Trp detection limits (S/N=3). Moreover, the sensor's effective use in the identification of DA, UA and Trp in authentic samples yielded satisfactory results.
期刊：
Sensors and Actuators B-Chemical,2025年442:138164 ISSN：0925-4005
通讯作者：
Li, JH;Qian, D;Waterhouse, GIN
作者机构：
[Feng, Hao; Wang, Yu; Li, Junhua; Zhan, Huimin; Wang, Fan; Liao, Huiyang; Long, Ruiqing; Zhu, Jiacheng] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Liu, Jinlong; Qian, Dong] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Waterhouse, Geoffrey I. N.] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构：
[Li, JH ] H;[Qian, D ] C;[Waterhouse, GIN ] U;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.
关键词：
Prussian blue analogue;Bimetal/nitrogen-doped carbon composite;Multifunctional nanozyme;Dual-mode colorimetric-electrochemical;sensing
摘要：
Robust nanozymes with high activities and multifunctional catalytic properties are highly sought by the sensing community as replacements for delicate natural enzymes. Herein, we report the discovery of a multifunctional nanozyme comprising Mn 3 Fe 2.7 C nanoparticles encapsulated by nitrogen-doped carbon shells embedded with carbon nanotubes (Mn 3 Fe 2.7 C@C (700) ), prepared by pyrolysis of a Prussian blue analogue (specifically KMnFe(CN) 6 ·2 H 2 O) at 700 °C in N 2 . Due to synergy between the Mn 3 Fe 2.7 C nanoparticles and the distinctive nitrogen-doped carbon configuration, Mn 3 Fe 2.7 C@C (700) exhibits four exceptional catalytic activities including dual-enzyme oxidase-like and peroxidase-like activities along with bifunctional electrocatalytic activities for oxidation and reduction reactions. Leveraging these advantages, a dual-mode sensing strategy was proposed for dopamine (DA) and H 2 O 2 utilizing colorimetric and electrochemical signal readouts, enabling accurate real-time monitoring of both analytes. In colorimetric and electrochemical sensing modes, the linear ranges are 1.0–80.0 and 2.0–233.0 μM for DA, respectively, and 4.0–200.0 and 100.0–8650.0 μM for H 2 O 2 , respectively. Corresponding detection limits are 0.44 and 1.21 μM for DA, and 0.29 and 13.37 μM for H 2 O 2 . Furthermore, the Mn 3 Fe 2.7 C@C (700) nanozyme was successfully applied for the determination of DA and H 2 O 2 in milk, synthetic urine and sweat, and commercial detergents, achieving satisfactory recoveries ranging from 87.6 % to 112.9 % (with < 3 % deviation across the different detection modes). This work encourages the wide application of nanozymes for multi-modal sensing of target analytes.
Robust nanozymes with high activities and multifunctional catalytic properties are highly sought by the sensing community as replacements for delicate natural enzymes. Herein, we report the discovery of a multifunctional nanozyme comprising Mn 3 Fe 2.7 C nanoparticles encapsulated by nitrogen-doped carbon shells embedded with carbon nanotubes (Mn 3 Fe 2.7 C@C (700) ), prepared by pyrolysis of a Prussian blue analogue (specifically KMnFe(CN) 6 ·2 H 2 O) at 700 °C in N 2 . Due to synergy between the Mn 3 Fe 2.7 C nanoparticles and the distinctive nitrogen-doped carbon configuration, Mn 3 Fe 2.7 C@C (700) exhibits four exceptional catalytic activities including dual-enzyme oxidase-like and peroxidase-like activities along with bifunctional electrocatalytic activities for oxidation and reduction reactions. Leveraging these advantages, a dual-mode sensing strategy was proposed for dopamine (DA) and H 2 O 2 utilizing colorimetric and electrochemical signal readouts, enabling accurate real-time monitoring of both analytes. In colorimetric and electrochemical sensing modes, the linear ranges are 1.0–80.0 and 2.0–233.0 μM for DA, respectively, and 4.0–200.0 and 100.0–8650.0 μM for H 2 O 2 , respectively. Corresponding detection limits are 0.44 and 1.21 μM for DA, and 0.29 and 13.37 μM for H 2 O 2 . Furthermore, the Mn 3 Fe 2.7 C@C (700) nanozyme was successfully applied for the determination of DA and H 2 O 2 in milk, synthetic urine and sweat, and commercial detergents, achieving satisfactory recoveries ranging from 87.6 % to 112.9 % (with < 3 % deviation across the different detection modes). This work encourages the wide application of nanozymes for multi-modal sensing of target analytes.
作者机构：
[Liu, Wanxin; Li, Wen; Yin, Di; Li, Yi; Wu, Yijin] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.
通讯机构：
[Wu, YJ ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.
关键词：
5-hydroxymethylfurfural;heterogeneous catalyst;nickel-cobalt compounds;electrochemical performance;active species
摘要：
The electrochemical oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) coupled with water electrolysis for green hydrogen production is a promising strategy to address energy crises and environmental pollution. Despite the suitable adsorption energy for HMF due to their partially filled d-band electronic structures, Ni- or Co-based oxides/hydroxides still face challenges in insufficient activity and stability. In this study, a porous heterogeneous nickel cobalt oxide/hydroxide growth on nickel foam (NF), which is defined as NF@NiCo-H/O, was developed via immersion in concentrated alkali solution. Compared with the single-component NiCo oxides, the NF@NiCo-H/O catalyst exhibits a lower application potential of only 1.317 V, 1.395 V, and 1.443 V to achieve current densities of 20, 50, and 100 mA cm−2, respectively, in an alkaline solution containing HMF. Additionally, it demonstrates rapid reaction kinetics with a Tafel slope of 27.6 mV dec−1 and excellent cycling stability. Importantly, the presence of more high-valent Ni3+-O species on the catalyst surface contributes to its exceptional selectivity for 2,5-furandicarboxylic acid (86.7%), Faradaic efficiency (93.1%), and conversion rate (94.4%). This catalyst provides some theoretical guidance for the development of biomass electrooxidation catalysts for sustainable energy and chemical production.
期刊：
Journal of Electronic Materials,2025年54(1):712-717 ISSN：0361-5235
通讯作者：
Zhang, ZJ
作者机构：
[Zhang, Zhijian; Zhang, ZJ] Hengyang Normal Univ, Key Lab Funct Met Organ Cpds, Hengyang 421001, Peoples R China.;[Zhang, Zhijian; Zhang, ZJ] Hengyang Normal Univ, Key Lab Funct Organometall Mat Hunan Prov, Hengyang 421001, Peoples R China.;[Shi, Wei; Li, Xinghua] Collaborat Innovat Res Inst Hunan Prov, Hunan Prov Sci & Technol Affairs Ctr & Ind Technol, Changsha 410013, Hunan, Peoples R China.
通讯机构：
[Zhang, ZJ ] H;Hengyang Normal Univ, Key Lab Funct Met Organ Cpds, Hengyang 421001, Peoples R China.;Hengyang Normal Univ, Key Lab Funct Organometall Mat Hunan Prov, Hengyang 421001, Peoples R China.
关键词：
Ab initio calculation;magnetic properties;optical properties;two-dimensional gamma-GeSe;electronic properties
摘要：
Using ab initio calculations, the structural and photoelectric properties of gamma-GeSe with B, C, and N adsorption were systematically investigated. The atomic structure relaxations show that B, C, and N are preferentially located on the lower hexagonal hollow, upper hexagonal hollow, and on top of Se, respectively. The adsorption with B, C, and N can induce defective bands between the energy region n of the valence bands and the conduction bands, and all the systems with adatoms are magnetic, with 1 mu(B), 2 mu(B), and 1 mu(B) magnetic moments, respectively, which are mainly caused by the hybridization between adatoms and the adjacent Ge and Se atoms. Based on the spin-polarized band structure, we find that C-adsorbed gamma-GeSe is metallic, while gamma-GeSe with B and N adatoms is half-metallic, with 100% spin polarization at the Fermi level. Furthermore, owing to the electronic structural differences between spin-up and spin-down sections of B- and N-adsorbed gamma-GeSe, the light in the low-energy region (< 1.0 eV) can only cause electronic excitations in one spin channel, giving rise to interesting spin-polarized photoelectric properties. Our results suggest that gamma-GeSe with B, C, and N adsorption is a promising candidate for spintronic photoelectric device applications.
期刊：
Research on Chemical Intermediates,2025年:1-20 ISSN：0922-6168
通讯作者：
Ni, WJ
作者机构：
[Yang, Zhiyong; Yan, Jiaqi] Changde Coll, Coll Pharm, Changde 415000, Peoples R China.;[Yang, Qian; Li, Lu; Ni, Wenjin; Fu, Jinfeng] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Ni, Wenjin] Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Chen, Wenkai] China Coal Res Inst Corp Ltd, Beijing 100013, Peoples R China.
通讯机构：
[Ni, WJ ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.
关键词：
N -cyclohexylcyclohexanimine;Cyclohexanone oxime;Ti-based catalyst;Cyclohexylamine;Catalytic oxidation
摘要：
N-cyclohexylcyclohexanimine (N-CCA), a by-product of cyclohexylamine (CHA) oxidation to cyclohexanone oxime (CHO), was used as the starting reactant for the efficient conversion to CHO under an oxygen atmosphere, utilizing the constructed surface hydroxyl-rich Ti-based catalysts. Of these, the 20% TiO2/H beta catalyst exhibited unique catalytic activity and stability, achieving 45.9% N-CCA conversion and 82.1% CHO selectivity, with the content of high-boiling by-products not exceeding 1.0%. The superior catalytic performance, as evidenced by characterization results, stems primarily from: (i) the combination of TiO2 and H beta, which promotes the formation of a high specific surface area with fine TiO2 nanoparticles and high-density Ti delta+ active sites, which facilitate the adsorption and activation of N-CCA; (ii) the construction of rich hydroxyl groups, which enhances the Br & oslash;nsted acid sites, thereby improving the generation of active oxygen species; (iii) the intercrystalline embedding of TiO2 and H beta, which forms Ti-O-Si bonds, effectively inhibiting Ti leaching and ensuring excellent catalyst stability. The conversion of N-CCA, the main by-product of CHA oxidation, to the desired CHO using an efficient and robust 20% TiO2/H beta catalyst represents an attractive pathway.
摘要：
The accurate and sensitive quantification of hydroxyl radical (·OH) and glucose is necessary for disease diagnosis and health guidance, but still challenging owing to the low concentration of ·OH and poor water solubility of fluorescent probes. In addition, fluorescent probes may cause secondary pollution to the environment. Here an organic cage was reported as a sensitive fluorescent probe for ·OH and glucose in aqueous solution without serious secondary pollution. The prepared organic cage with good water solubility showed specific redox affinity to ·OH in acidic condition, resulting in two oxidation stages of mild oxidation and subsequent oxidative degradation. Fluorescence around 485 nm enhanced remarkably in the first stage, and benzene ring in organic cage was degraded in the second stage. Based on the significant fluorescence enhancement, a sensitive fluorescence turn-on sensing method for ·OH was established within 90 s with the limit of detection (3 s/k , where s and k are the standard deviation for 10 replicate detections of blank and the slope of calibration function) of 5 nM. The recoveries of spiked ·OH in human serum and water samples ranged from 95.2 % to 102.7 %. After the glucose oxidase enzyme-Fenton reaction was involved, the ·OH detection was also applied to sensitive sensing of glucose with the limit of detection (3 s/k ) of 6 nM. The recoveries of spiked glucose in sugary drinks ranged from 96.2 % to 102.6 %. Furthermore, the proposed method would also be suitable for other hazardous substances and biomarkers which can produce hydrogen peroxide and further form ·OH via Fenton reaction.
The accurate and sensitive quantification of hydroxyl radical (·OH) and glucose is necessary for disease diagnosis and health guidance, but still challenging owing to the low concentration of ·OH and poor water solubility of fluorescent probes. In addition, fluorescent probes may cause secondary pollution to the environment. Here an organic cage was reported as a sensitive fluorescent probe for ·OH and glucose in aqueous solution without serious secondary pollution. The prepared organic cage with good water solubility showed specific redox affinity to ·OH in acidic condition, resulting in two oxidation stages of mild oxidation and subsequent oxidative degradation. Fluorescence around 485 nm enhanced remarkably in the first stage, and benzene ring in organic cage was degraded in the second stage. Based on the significant fluorescence enhancement, a sensitive fluorescence turn-on sensing method for ·OH was established within 90 s with the limit of detection (3 s/k , where s and k are the standard deviation for 10 replicate detections of blank and the slope of calibration function) of 5 nM. The recoveries of spiked ·OH in human serum and water samples ranged from 95.2 % to 102.7 %. After the glucose oxidase enzyme-Fenton reaction was involved, the ·OH detection was also applied to sensitive sensing of glucose with the limit of detection (3 s/k ) of 6 nM. The recoveries of spiked glucose in sugary drinks ranged from 96.2 % to 102.6 %. Furthermore, the proposed method would also be suitable for other hazardous substances and biomarkers which can produce hydrogen peroxide and further form ·OH via Fenton reaction.
摘要：
A novel nickel foam supported NiFe 2 O 4 /NiO (NiFe 2 O 4 /NiO/NF) catalyst was prepared using one-step hydrothermal synthesis followed by calcination, and subsequently applied to the Catalytic Wet Peroxide Oxidation (CWPO) of Acid Orange 7 (AO7) in a continuous fixed bed system. The physicochemical properties of NiFe 2 O 4 /NiO/NF were characterized via XRD, XPS, SEM, and Raman, revealing that interconnected sheet-like NiFe 2 O 4 /NiO nanosheets with an ultra-thin structure and channel-opening characteristics were uniformly coated on the surface of NF. Remarkably, NiFe 2 O 4 /NiO/NF exhibited exceptional catalytic activity toward AO7 degradation under optimized conditions: urea/metal molar ratio of 5:1, hydrothermal reaction time of 6h, and Fe/Ni concentration of 20/20 mM. At the reaction temperature of 70 °C, pH 2.0, space velocity of 0.265 min −1 , and AO7 concentration of 50 mg/L, the AO7 conversion remained stable (>99.0 %) over 240 min, while COD removal ratios were 57.9 %, 66.4 %, 48.8 % and 47.9 % when the fixed bed system was continuously run for 60, 120, 180 and 240 min, respectively. After three consecutive cycles, AO7 conversion ratios at 240 min were 99.2 %, 98.8 %, and 98.4 %, with a total decrease of less than 1 %. DFT calculations indicated that the NiFe 2 O 4 /NiO catalyst, owing to the Fe/Ni bimetallic synergy, facilitated O-O bond cleavage in H 2 O 2 and HO· radical formation more effectively than Fe 2 O 3 or NiO alone.
A novel nickel foam supported NiFe 2 O 4 /NiO (NiFe 2 O 4 /NiO/NF) catalyst was prepared using one-step hydrothermal synthesis followed by calcination, and subsequently applied to the Catalytic Wet Peroxide Oxidation (CWPO) of Acid Orange 7 (AO7) in a continuous fixed bed system. The physicochemical properties of NiFe 2 O 4 /NiO/NF were characterized via XRD, XPS, SEM, and Raman, revealing that interconnected sheet-like NiFe 2 O 4 /NiO nanosheets with an ultra-thin structure and channel-opening characteristics were uniformly coated on the surface of NF. Remarkably, NiFe 2 O 4 /NiO/NF exhibited exceptional catalytic activity toward AO7 degradation under optimized conditions: urea/metal molar ratio of 5:1, hydrothermal reaction time of 6h, and Fe/Ni concentration of 20/20 mM. At the reaction temperature of 70 °C, pH 2.0, space velocity of 0.265 min −1 , and AO7 concentration of 50 mg/L, the AO7 conversion remained stable (>99.0 %) over 240 min, while COD removal ratios were 57.9 %, 66.4 %, 48.8 % and 47.9 % when the fixed bed system was continuously run for 60, 120, 180 and 240 min, respectively. After three consecutive cycles, AO7 conversion ratios at 240 min were 99.2 %, 98.8 %, and 98.4 %, with a total decrease of less than 1 %. DFT calculations indicated that the NiFe 2 O 4 /NiO catalyst, owing to the Fe/Ni bimetallic synergy, facilitated O-O bond cleavage in H 2 O 2 and HO· radical formation more effectively than Fe 2 O 3 or NiO alone.
期刊：
International Journal of Biological Macromolecules,2025年320(Pt 3):145752 ISSN：0141-8130
通讯作者：
Liu, Jing;Wang, LJ;Yuan, F
作者机构：
[Liu, Jing; Wang, Lijia; Li, Yang; Zheng, Zefeng; Liu, Yongjie] Zhejiang Univ, Childrens Hosp, Natl Clin Res Ctr Child Hlth, Natl Childrens Reg Med Ctr,Sch Med, Hangzhou 310052, Peoples R China.;[Liu, Jing; Wang, Lijia; Li, Yang; Zheng, Zefeng; Liu, Yongjie] Zhejiang Key Lab Neonatal Dis, Hangzhou 310052, Peoples R China.;[Cui, Ying] Hengyang Normal Univ, Coll Chem & Mat Sci, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421001, Peoples R China.;[Zhang, Boyou] Zhejiang Univ, Sir Run Run Shaw Hosp, Sch Med, Dept Thorac Surg, Hangzhou 310018, Peoples R China.;[Fan, Shanji] Univ South China, Affiliated Hosp 1, Hengyang Med Sch, Dept Breast & Thyroid Surg, Hengyang 421000, Peoples R China.
通讯机构：
[Liu, J; Wang, LJ ; Yuan, F ] Z;Zhejiang Univ, Childrens Hosp, Natl Clin Res Ctr Child Hlth, Natl Childrens Reg Med Ctr,Sch Med, Hangzhou 310052, Peoples R China.;Zhejiang Hosp, Dept Thorac Surg, Hangzhou 310013, Peoples R China.
关键词：
Deuterium;Macromolecules;Raman spectroscopy
摘要：
When macromolecules are exposed to deuterium-rich environments, hydrogen atoms on them undergo hydrogen‑deuterium exchange, which induces a characteristic Raman spectral redshift, providing a robust signature for probing intracellular microenvironments. This review is a comprehensively survey of the diverse applications of Raman spectroscopy of deuterium-labeled macromolecules in biomedicine over recent years. We summarize its utility in bacterial resistance and metabolism investigations, and discuss applications spanning cellular to whole-animal levels.
When macromolecules are exposed to deuterium-rich environments, hydrogen atoms on them undergo hydrogen‑deuterium exchange, which induces a characteristic Raman spectral redshift, providing a robust signature for probing intracellular microenvironments. This review is a comprehensively survey of the diverse applications of Raman spectroscopy of deuterium-labeled macromolecules in biomedicine over recent years. We summarize its utility in bacterial resistance and metabolism investigations, and discuss applications spanning cellular to whole-animal levels.
作者机构：
[Peihong Deng; Xue Nie; Wei Peng] College of Chemistry and Material Science, Hengyang Normal University, Hengyang 421008, China
通讯机构：
[Peihong Deng] C;College of Chemistry and Material Science, Hengyang Normal University, Hengyang 421008, China
摘要：
To synthetize a novel hollow nano-tubular Ni 3 S 4 /Co 3 S 4 , we employed a two-stage ion exchange process that included a precursor of cobalt chloride hexahydrate, sodium sulfide for anion exchange, and nickel chloride for cation exchange. The suspension of graphene oxide (GO) and Ni 3 S 4 /Co 3 S 4 was prepared by ultrasonic oscillation. After drying on a glassy carbon electrode (GCE) surface, the nanocomposites were subjected to potentiostatic reduction, effectively transforming GO into electrochemically reduced graphene oxide (ErGO). Characterization of the Ni 3 S 4 /Co 3 S 4 -ErGO nanocomposite by XRD, XPS, EDS and SEM has validated its effective synthesis. It was on this modified electrode (Ni 3 S 4 /Co 3 S 4 -ErGO/GCE) that the electrochemical detection of vanillin was investigated. Second derivative linear sweep voltammetry (SDLSV) was employed to determine the concentration of vanillin. Appropriate determination conditions have been optimized to improve sensitivity. The oxidation peak current of vanillin was approximately 88 times greater on the Ni 3 S 4 /Co 3 S 4 -ErGO/GCE compared to the bare GCE. Within the concentration range of 0.02–20 μM, a robust linear correlation was seen between the peak current and vanillin concentration. A limit of detection (LOD) of 0.8 nM was determined. Additional evaluations included stability, interference, repeatability and reproducibility. This sensor facilitated the detection of vanillin in various food samples.
To synthetize a novel hollow nano-tubular Ni 3 S 4 /Co 3 S 4 , we employed a two-stage ion exchange process that included a precursor of cobalt chloride hexahydrate, sodium sulfide for anion exchange, and nickel chloride for cation exchange. The suspension of graphene oxide (GO) and Ni 3 S 4 /Co 3 S 4 was prepared by ultrasonic oscillation. After drying on a glassy carbon electrode (GCE) surface, the nanocomposites were subjected to potentiostatic reduction, effectively transforming GO into electrochemically reduced graphene oxide (ErGO). Characterization of the Ni 3 S 4 /Co 3 S 4 -ErGO nanocomposite by XRD, XPS, EDS and SEM has validated its effective synthesis. It was on this modified electrode (Ni 3 S 4 /Co 3 S 4 -ErGO/GCE) that the electrochemical detection of vanillin was investigated. Second derivative linear sweep voltammetry (SDLSV) was employed to determine the concentration of vanillin. Appropriate determination conditions have been optimized to improve sensitivity. The oxidation peak current of vanillin was approximately 88 times greater on the Ni 3 S 4 /Co 3 S 4 -ErGO/GCE compared to the bare GCE. Within the concentration range of 0.02–20 μM, a robust linear correlation was seen between the peak current and vanillin concentration. A limit of detection (LOD) of 0.8 nM was determined. Additional evaluations included stability, interference, repeatability and reproducibility. This sensor facilitated the detection of vanillin in various food samples.
作者机构：
[Yan, Chuan; Xie, Xiaohui; Zhong, Qingmei; Zong, Huixiang; Rong, Xiaomei] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.
通讯机构：
[Yan, C ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.
关键词：
visual detection;ascorbic acid;radical TTM-DMODPA;non-catalytic;smartphone camera
摘要：
Ascorbic acid (AA) plays a multidimensional role in human physiological and pathological processes, and the detection of its urinary concentration facilitates the diagnosis of metabolic or kidney diseases. Visual detection exhibits minimal reliance on instrumentation and is suitable for on-site analysis in routine settings. Current visual colorimetric detection methods typically rely on enzymatic or nanozyme-based catalysis. Organic neutral radicals bearing unpaired electrons represent a class of materials exhibiting intrinsic responsiveness to redox stimuli. The tris (2,4,6-trichlorophenyl) methyl (TTM) radical has attracted widespread attention for its adjustable optical properties and sensitive response to external redox stimuli. We synthesized a novel radical TTM-DMODPA and applied it for non-catalytic colorimetric detection of AA. It not only enables quantitative AA measurement via UV-vis spectroscopy (linear range: 1.25-75 mu mol/L, LOD: 0.288 mu mol/L) but also facilitates instrument-free visual detection using smartphone cameras (linear range: 0-65 mu mol/L, LOD: 1.46 mu mol/L). This method demonstrated satisfactory performance in the measurement of AA in actual urine samples. Recovery rates ranged from 97.8% to 104.1%. Consequently, this work provides a portable and effective method for assessing AA levels in actual urine samples.
期刊：
FRONTIERS IN ONCOLOGY,2025年15:1509810 ISSN：2234-943X
通讯作者：
Tang, Si-Ping;Fu, D
作者机构：
[Tang, Si-Ping; Zhang, Shu-Ping; Fu, Da; Zhao, Jing-Jun; Gu, Biao; Zhai, Peng-Lei] Hengyang Normal Univ, Key Lab Funct Organometall Mat Coll Hunan Prov, Coll Chem & Mat Sci, Hengyang, Peoples R China.;[Tang, Xiao-Mei; Fu, Da; Lu, Cui-Ni; Chen, Meng-Min; Yang, Qin-Xin; Zhai, Peng-Lei; Liu, Jia] Shanghai Jiao Tong Univ, Sch Med, Ruijin Hosp, Dept Gen Surg,Pancreat Dis Ctr, Shanghai, Peoples R China.;[Chen, Meng-Min] Shanghai Jiao Tong Univ, Res Inst Pancreat Dis, Sch Med, Shanghai Key Lab Translat Res Pancreat Neoplasms, Shanghai, Peoples R China.;[Chen, Meng-Min] Shanghai Jiao Tong Univ, Inst Translat Med, State Key Lab Oncogenes & Related Genes, Shanghai, Peoples R China.;[Wang, Qi] Shanghai Jiao Tong Univ, Sch Med, Ruijin Hosp, Dept Urol, Shanghai, Peoples R China.
通讯机构：
[Tang, SP; Fu, D ] H;Hengyang Normal Univ, Key Lab Funct Organometall Mat Coll Hunan Prov, Coll Chem & Mat Sci, Hengyang, Peoples R China.;Shanghai Jiao Tong Univ, Sch Med, Ruijin Hosp, Dept Gen Surg,Pancreat Dis Ctr, Shanghai, Peoples R China.
关键词：
drug prediction;genomic alterations;immunotherapy;liquid-liquid phase separation;tumor immune microenvironment
摘要：
BACKGROUND: Growing evidence indicates that abnormal liquid-liquid phase separation (LLPS) can disrupt biomolecular condensates, contributing to cancer development and progression. However, the influence of LLPS on the prognosis of head and neck squamous cell carcinoma (HNSCC) patients and its effects on the tumor immune microenvironment (TIME) are not yet fully understood. Therefore, we aimed to categorize patients with HNSCC based on LLPS-related genes and explored their multidimensional heterogeneity. METHODS: We integrated the transcriptomic data of 3,541 LLPS-related genes to assess the LLPS patterns in 501 patients with HNSCC within The Cancer Genome Atlas cohort. Subsequently, we explored the differences among the three LLPS subtypes using multi-omics analysis. We also developed an LLPS-related prognostic risk signature (LPRS) to facilitate personalized and integrative assessments and then screened and validated potential therapeutic small molecule compounds targeting HNSCC via experimental analyses. RESULT: By analyzing the expression profiles of 85 scaffolds, 355 regulators, and 3,101 clients of LLPS in HNSCC, we identified three distinct LLPS subtypes: LS1, LS2, and LS3. We confirmed notable differences among these subtypes in terms of prognosis, functional enrichment, genomic alterations, TIME patterns, and responses to immunotherapy. Additionally, we developed the LPRS, a prognostic signature for personalized integrative assessments, which demonstrated strong predictive capability for HNSCC prognosis across multiple cohorts. The LPRS also showed significant correlations with the clinicopathological features and TIME patterns in HNSCC patients. Furthermore, the LPRS effectively predicted responses to immune checkpoint inhibitor therapy and facilitated the screening of potential small-molecule compounds for treating HNSCC patients. CONCLUSION: This study presents a new classification system for HNSCC patients grounded in LLPS. The LPRS developed in this research offers improved personalized prognosis and could optimize immunotherapy strategies for HNSCC.
作者机构：
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, People’s Republic of China;State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, People’s Republic of China;Advanced Ceramics Institute of Zibo New & High–Tech Industrial Development Zone, Zibo 255000, People’s Republic of China;[Xiaofang Liu] School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, People’s Republic of China;[Shibing Xiao] College of Chemistry and Material Science, Hengyang Normal University, Hengyang 421008, PR China
通讯机构：
[Huajun Sun] S;School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, People’s Republic of China<&wdkj&>State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, People’s Republic of China<&wdkj&>Advanced Ceramics Institute of Zibo New & High–Tech Industrial Development Zone, Zibo 255000, People’s Republic of China
摘要：
Owing to the inverse size effect and CMOS process compatibility of ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) films, they have emerged as one of the most promising candidates for next-generation non-volatile memory devices. However, the presence of excessive oxygen vacancies (V O ) within the film or at the film–electrode interface results in degraded ferroelectricity, elevated coercive fields, and poor fatigue endurance, thereby impeding the progress toward practical device applications. Currently, employing oxide materials as oxygen donors to supply additional oxygen atoms for compensating excessive V O within the film has emerged as a promising strategy. In this study, we systematically investigated sputtered tungsten oxide (WO x ) electrodes with optimized processing as oxygen donors for modulating oxygen atom injection into HZO thin films. This approach effectively suppresses the formation of V O at the HZO interface, facilitates the phase transition from the tetragonal phase to the ferroelectric orthorhombic phase, and enhances the remanent polarization (P r ) to 36.7 μC/cm 2 . Through first-order reversal curve analysis, it was revealed that WO x top electrodes exhibit superior performance as dynamic oxygen donors, enabling directional oxygen compensation under the synergistic effects of thermal treatment and electric field cycling, thereby reducing the coercive field (ΔE c ≈ 0.64 MV/cm) and achieving a low imprint field (E bias ≈ 0.15 MV/cm), and exhibits fatigue endurance over 10 11 cycles and excellent fatigue stability, providing insights into the design of low-field-driven, high-endurance memory devices. These findings indicate that using sputtered WO x as electrodes for HZO films holds great potential for future high-speed non-volatile memory applications, with excellent ferroelectric properties and stability.
Owing to the inverse size effect and CMOS process compatibility of ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) films, they have emerged as one of the most promising candidates for next-generation non-volatile memory devices. However, the presence of excessive oxygen vacancies (V O ) within the film or at the film–electrode interface results in degraded ferroelectricity, elevated coercive fields, and poor fatigue endurance, thereby impeding the progress toward practical device applications. Currently, employing oxide materials as oxygen donors to supply additional oxygen atoms for compensating excessive V O within the film has emerged as a promising strategy. In this study, we systematically investigated sputtered tungsten oxide (WO x ) electrodes with optimized processing as oxygen donors for modulating oxygen atom injection into HZO thin films. This approach effectively suppresses the formation of V O at the HZO interface, facilitates the phase transition from the tetragonal phase to the ferroelectric orthorhombic phase, and enhances the remanent polarization (P r ) to 36.7 μC/cm 2 . Through first-order reversal curve analysis, it was revealed that WO x top electrodes exhibit superior performance as dynamic oxygen donors, enabling directional oxygen compensation under the synergistic effects of thermal treatment and electric field cycling, thereby reducing the coercive field (ΔE c ≈ 0.64 MV/cm) and achieving a low imprint field (E bias ≈ 0.15 MV/cm), and exhibits fatigue endurance over 10 11 cycles and excellent fatigue stability, providing insights into the design of low-field-driven, high-endurance memory devices. These findings indicate that using sputtered WO x as electrodes for HZO films holds great potential for future high-speed non-volatile memory applications, with excellent ferroelectric properties and stability.
作者机构：
[Liu, Xingyue; Shen, Xing-Can; Jiang, Bang-Ping; Chen, Hua; Zhang, Shuping; Chen, H; Ji, Shi-Chen] Guangxi Normal Univ, Sch Chem & Pharmaceut Sci, Key Lab Chem & Mol Engn Med Resources, Guangxi Key Lab Chem & Mol Engn Med Resources,Mini, Guilin 541004, Peoples R China.;[Zhang, Shuping] Hengyang Normal Univ, Key Lab Funct Organometall Mat, Coll Chem & Mat Sci, Coll Hunan Prov, Hengyang 421008, Peoples R China.
通讯机构：
[Shen, XC ; Chen, H] G;Guangxi Normal Univ, Sch Chem & Pharmaceut Sci, Key Lab Chem & Mol Engn Med Resources, Guangxi Key Lab Chem & Mol Engn Med Resources,Mini, Guilin 541004, Peoples R China.
摘要：
Tracking the quantitative evaluation of therapeutic efficiency in tumors is essential for the precision management of cancer patients. Theranostic probes, which integrate diagnostic molecular imaging and therapeutic capabilities into a single entity, can be used to monitor the treatment process and reflect the therapeutic effect. However, current theranostic probes lack precise quantitative evaluations in vivo due to the use of single-wavelength imaging during tumor therapy. Here we present a portal library of dual ratiometric single-molecule theranostic probes for precise tumor therapy through photothermal therapy (PTT) and quantitative evaluation of tumor cell death in vivo via ratiometric near-infrared fluorescence (NIRF) and ratiometric photoacoustic (PA) imaging. One optimal single-molecule dye is further modified into an activatable probe (AF-1F-NO(2)), whose dual ratiometric NIRF/PA signal and photothermal activity are only activated in the presence of a tumor biomarker (nitroreductase). By eliciting a dual ratiometric response (NIRF/PA: NIRF(850)/NIRF(750); PA(770)/PA(670)) to tumor hypoxia, the new probe acts as a hypoxia-activated PTT theranostic agent, enabling real-time quantitative evaluation in vivo during PTT. Thus, this study not only presents the first dual ratiometric single-molecule theranostic probe for PTT and real-time quantitative evaluation of therapeutic efficacy in vivo, but also opens up a promising paradigm for engineering other single-molecule dual ratiometric theranostic probes in combination with more therapeutic modalities for precision medicine.
作者机构：
College of Chemistry and Materials Science, Hengyang Normal University, Hunan 421008, PR China;[Ye-Tang Pan; Rongjie Yang] National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, PR China;[Lubin Liu] Key Lab of Bio-based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, People’s Republic of China;Centre for Future Materials, University of Southern Queensland, Springfield 4300, Australia;School of Agriculture and Environmental Science, University of Southern Queensland, Springfield 4300, Australia
通讯机构：
[Ye-Tang Pan] N;[Lubin Liu] K;Key Lab of Bio-based Material Science and Technology, Ministry of Education, Northeast Forestry University, Harbin 150040, People’s Republic of China<&wdkj&>National Engineering Research Center of Flame Retardant Materials, School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, PR China
摘要：
Biomass resources are natural polymeric materials that are abundant, affordable, non-toxic and renewable. Although they find diverse applications in both everyday life and high-tech materials, their use is often constrained by the associated fire hazards. To address this issue, there is a growing interest in the development of flame-retardant biomass polymeric materials. Metal-organic frameworks (MOFs) consist of transition metal species, flame-retardant elements and potential carbon sources, allowing for easy adjustment of their structure and properties. This versatility makes MOFs and their derivatives and hybrids highly attractive for flame retardancy studies. Despite their distinctive properties, MOFs alone may not fully satisfy the demands of commercial flame-retardant applications. The combination of MOFs with biomass materials has been identified as a promising strategy for developing efficient flame-retardant biomass nanocomposites. This innovative approach aims to address the limitations of MOFs by capitalizing on synergistic effects. This review highlights recent advancements and strategies in MOF-based flame retardants incorporating biomass materials, and it elucidates the flame-retardant mechanisms of MOF/biomass nanocomposites to inform future design efforts in the field. Furthermore, the review discusses the current challenges and prospects in this field, aiming to provide a succinct yet comprehensive overview for researchers to quickly grasp the latest developments.
Biomass resources are natural polymeric materials that are abundant, affordable, non-toxic and renewable. Although they find diverse applications in both everyday life and high-tech materials, their use is often constrained by the associated fire hazards. To address this issue, there is a growing interest in the development of flame-retardant biomass polymeric materials. Metal-organic frameworks (MOFs) consist of transition metal species, flame-retardant elements and potential carbon sources, allowing for easy adjustment of their structure and properties. This versatility makes MOFs and their derivatives and hybrids highly attractive for flame retardancy studies. Despite their distinctive properties, MOFs alone may not fully satisfy the demands of commercial flame-retardant applications. The combination of MOFs with biomass materials has been identified as a promising strategy for developing efficient flame-retardant biomass nanocomposites. This innovative approach aims to address the limitations of MOFs by capitalizing on synergistic effects. This review highlights recent advancements and strategies in MOF-based flame retardants incorporating biomass materials, and it elucidates the flame-retardant mechanisms of MOF/biomass nanocomposites to inform future design efforts in the field. Furthermore, the review discusses the current challenges and prospects in this field, aiming to provide a succinct yet comprehensive overview for researchers to quickly grasp the latest developments.
作者机构：
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China;School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China;Advanced Ceramics Institute of Zibo New & High-Tech Industrial Development Zone, Zibo 255000, Shandong, China;[Xiaofang Liu] School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, China;College of Chemistry and Materials Science, Hengyang Normal University, Hengyang 421002, China
通讯机构：
[Huajun Sun] S;State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China<&wdkj&>School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, Hubei, China<&wdkj&>Advanced Ceramics Institute of Zibo New & High-Tech Industrial Development Zone, Zibo 255000, Shandong, China
摘要：
PbZrO 3 (PZO) demonstrates outstanding energy storage properties due to its characteristic electric field-induced antiferroelectric-to-ferroelectric (AFE-FE) phase transition. However, the high crystallization temperature of PZO thin films limits their practical applications in energy storage. In this study, we fabricated LaNiO 3 (LNO) electrodes and (Pb 0.94 La 0.06 ) ZrO 3 (PLZ) antiferroelectric thin films on Si(100) substrates through sol-gel method. By leveraging the lattice matching and interface modulation effects of LNO electrodes, we successfully stabilized the perovskite phase at low temperatures, providing a novel approach for phase composition control in antiferroelectric films. Through systematic investigation of annealing temperature effects on PLZ film microstructure, we demonstrate that 500 °C annealing enables crystallization into pure perovskite phase, significantly enhancing energy storage performance. The optimized PLZ films exhibit superior energy storage characteristics, delivering a recoverable energy density of 53.9 J/cm 3 with 78.4% efficiency, which represents a significant improvement over previously reported La-doped PZO films. Notably, the low-temperature processed PLZ films also exhibit excellent stability under frequency variations, temperature fluctuations, and electrical fatigue cycling, indicating promising potential for energy storage applications. This work demonstrates a low-temperature fabrication process for PLZ films on LNO electrodes, overcoming the limitations imposed by conventional high-temperature annealing on equipment and processing, thereby providing a feasible solution for practical energy storage device applications.
PbZrO 3 (PZO) demonstrates outstanding energy storage properties due to its characteristic electric field-induced antiferroelectric-to-ferroelectric (AFE-FE) phase transition. However, the high crystallization temperature of PZO thin films limits their practical applications in energy storage. In this study, we fabricated LaNiO 3 (LNO) electrodes and (Pb 0.94 La 0.06 ) ZrO 3 (PLZ) antiferroelectric thin films on Si(100) substrates through sol-gel method. By leveraging the lattice matching and interface modulation effects of LNO electrodes, we successfully stabilized the perovskite phase at low temperatures, providing a novel approach for phase composition control in antiferroelectric films. Through systematic investigation of annealing temperature effects on PLZ film microstructure, we demonstrate that 500 °C annealing enables crystallization into pure perovskite phase, significantly enhancing energy storage performance. The optimized PLZ films exhibit superior energy storage characteristics, delivering a recoverable energy density of 53.9 J/cm 3 with 78.4% efficiency, which represents a significant improvement over previously reported La-doped PZO films. Notably, the low-temperature processed PLZ films also exhibit excellent stability under frequency variations, temperature fluctuations, and electrical fatigue cycling, indicating promising potential for energy storage applications. This work demonstrates a low-temperature fabrication process for PLZ films on LNO electrodes, overcoming the limitations imposed by conventional high-temperature annealing on equipment and processing, thereby providing a feasible solution for practical energy storage device applications.
作者机构：
[Wu, Tingting; Yan, Chuan; Zhong, Qingmei; Rong, Xiaomei] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.
通讯机构：
[Zhong, QM ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.
关键词：
visual determination;hydrogen peroxide;radical TTM-DMODPA;non-catalytic;instrument-free;smartphone camera
摘要：
As a crucial reactive oxygen species, hydrogen peroxide (H(2)O(2)) serves as both a physiological regulator and a pathological indicator in human systems. Its urinary concentration has emerged as a valuable biomarker for assessing metabolic disorders and renal function. While conventional colorimetric determination methods predominantly employ enzymatic or nanozyme catalysts, we present an innovative non-catalytic approach utilizing the redox-responsive properties of organic neutral radicals. Specifically, we designed and synthesized a novel radical TTM-DMODPA based on the tris (2,4,6-trichlorophenyl) methyl (TTM) scaffold, which exhibits remarkable optical tunability and oxidative sensitivity. This system enables dual-mode H(2)O(2) quantification: (1) UV-vis spectrophotometry (linear range: 2.5-250 μmol/L, LOD: 1.275 μmol/L) and (2) smartphone-based visual analysis (linear range: 2.5-250 μmol/L, LOD: 3.633 μmol/L), the latter being particularly suitable for point-of-care testing. Validation studies using urine samples demonstrated excellent recovery rates (96-104%), confirming the method's reliability for real-sample applications. Our work establishes a portable, instrument-free platform for urinary H(2)O(2) determination, with significant potential in clinical diagnostics and environmental monitoring.
期刊：
Journal of Physical Chemistry Letters,2025年16(28):7249-7261 ISSN：1948-7185
通讯作者：
Li, JH;Qian, D;Waterhouse, GIN
作者机构：
[Li, Junhua; Wang, Fan] Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.;[Liu, Xing; Chen, Yang; Liao, Huiyang] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.;[Liu, Jinlong; Qian, Dong] Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.;[Waterhouse, Geoffrey I. N.; Waterhouse, GIN] Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand.
通讯机构：
[Li, JH ] H;[Qian, D ] C;[Waterhouse, GIN ] U;Hengyang Normal Univ, Coll Chem & Mat Sci, Hunan Engn Res Ctr Monitoring & Treatment Heavy Me, Hengyang 421008, Peoples R China.;Cent South Univ, Coll Chem & Chem Engn, Changsha 410083, Peoples R China.
摘要：
Metal dual-atom nanozymes (DAzymes) with two sites commonly offer more advantages over single-atom nanozymes (SAzymes) in terms of electronic structure modification and synergy. However, the design of DAzymes remains challenging. Herein, we present a novel ion-imprinting strategy for preparing an axially coordinated Fe-Fe DAzyme (CNBFe-3-800) with an unreported configuration of Fe(2)N(6)B(2) active sites on a N,B-doped carbon support. The active sites comprise coplanar Fe(2)N(4)B(2) units with two axial N atoms (one on each Fe atom). The exact configuration of CNBFe-3-800 was compellingly confirmed by robust characterizations including aberration-corrected transmission electron microscopy and X-ray absorption near-edge structure spectroscopy. SAzymes demonstrate peroxidase-like activity, catalyzing the oxidation of organic substrates using reactive oxygen species (ROS) generated by H(2)O(2) decomposition. Contrastingly, DAzymes often show oxidase-like activity, favorably generating ROS from O(2) without the need for toxic H(2)O(2). As a proof of concept, a three-channel colorimetric sensor array based on CNBFe-3-800 possessing excellent oxidase-like activity was developed for the discrimination and sensitive quantitation of tetracycline pollutants (tetracycline, oxytetracycline, and aureomycin). Principal component analysis enabled detection of these three tetracyclines at concentrations ranging from 8 to 2000 μM. Density functional theory calculations indicated that the Fe-Fe sites in CNBFe-3-800 exhibited a stronger adsorption energy for O(2) than the single Fe sites in iron phthalocyanine, with the enhanced oxidase-like activity of CNBFe-3-800 originating from an optimized bonding distance between the Fe-Fe dual-atom sites and the O intermediates, thus lowering the activation barrier of the rate-determining step (H(2)O desorption) on the binuclear iron sites. This work offers novel valuable insights for constructing dual-atom nanozymes.
作者机构：
[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin] Hengyang Normal Univ, Coll Hunan Prov, Key Lab Funct Met Organ Cpds Hunan Prov, Hengyang 421008, Peoples R China.;[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin] Hengyang Normal Univ, Coll Hunan Prov, Key Lab Organometall New Mat, Hengyang 421008, Peoples R China.;[Liu, Xing; Lai, Hua; Dai, Rui; Li, Junhua; Hu, Longxin; Liu, X] Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
通讯机构：
[Liu, X ] H;Hengyang Normal Univ, Coll Chem & Mat Sci, Hengyang 421008, Peoples R China.
关键词：
Cd 0.5 Zn 0.5 S;CoS;S2 adsorption;Photocatalytic H2 evolution
摘要：
Designing surface phase is an efficient strategy to facilitate charge separation and photocatalytic H 2 -evolution performance. In this work, CoS cocatalysts were intimately anchored on Cd 0.5 Zn 0.5 S (denoted as CZS) photocatalyst via in-situ precipitate transformation in S 2− /SO 3 2− solution with cobaltous phosphate (CoPi) as a precursor, meanwhile, S 2− ions were adsorbed on the CZS to form a sulfur-rich surface (denoted as CZS-S). The photocatalytic H 2 -evolution rate of CoS/CZS-S is 2.02 mmol·g −1 ·h −1 in 0.1 M Na 2 S/Na 2 SO 3 sacrificial agent system. In addition, CoS/CZS-S exhibits excellent stability in both Na 2 S/Na 2 SO 3 and lactic acid system. The theoretical calculations (DFT) and experimental results reveal that amorphous CoS can work as a highly effective cocatalyst for H 2 evolution reaction and the intimate contact between CZS and CoS facilitates the photoelectrons transfer from CZS to CoS. The adsorbed S 2− ions mainly work as effective hole acceptors. As a result of the synergism of CoS and adsorbed S 2− ions, the boosted separation and immigration of photoelectrons and photoholes and high photocatalytic H 2 -evolution performance of CoS/CZS-S are realized. The present work highlights simultaneous reinforcing reduction and oxidation half-reaction dynamics via a facile and economic surface strategy to achieve efficient solar H 2 -evolution from H 2 O splitting.
Designing surface phase is an efficient strategy to facilitate charge separation and photocatalytic H 2 -evolution performance. In this work, CoS cocatalysts were intimately anchored on Cd 0.5 Zn 0.5 S (denoted as CZS) photocatalyst via in-situ precipitate transformation in S 2− /SO 3 2− solution with cobaltous phosphate (CoPi) as a precursor, meanwhile, S 2− ions were adsorbed on the CZS to form a sulfur-rich surface (denoted as CZS-S). The photocatalytic H 2 -evolution rate of CoS/CZS-S is 2.02 mmol·g −1 ·h −1 in 0.1 M Na 2 S/Na 2 SO 3 sacrificial agent system. In addition, CoS/CZS-S exhibits excellent stability in both Na 2 S/Na 2 SO 3 and lactic acid system. The theoretical calculations (DFT) and experimental results reveal that amorphous CoS can work as a highly effective cocatalyst for H 2 evolution reaction and the intimate contact between CZS and CoS facilitates the photoelectrons transfer from CZS to CoS. The adsorbed S 2− ions mainly work as effective hole acceptors. As a result of the synergism of CoS and adsorbed S 2− ions, the boosted separation and immigration of photoelectrons and photoholes and high photocatalytic H 2 -evolution performance of CoS/CZS-S are realized. The present work highlights simultaneous reinforcing reduction and oxidation half-reaction dynamics via a facile and economic surface strategy to achieve efficient solar H 2 -evolution from H 2 O splitting.
摘要：
Diorganotin acylhydrazone complexes with mitochondrial targeting demonstrate significant potential as replacements for platinum-based complexes due to their potent anticancer properties. Twelve methylphenyltin arylformylhydrazone complexes have been synthesized by microwave “one-pot” reaction. The complexes have been characterized by FT-IR, multinuclear NMR (1H, 13C, and 119Sn), TGA, and HRMS. Crystal structures were determined for 10 out of the 12 complexes under study. Structures 1 through 8, 10 and 12 possessed a central symmetric structure of a di-nuclear Sn2O2 tetrahedral ring. All complexes were tested for their inhibitory activity against human cell lines NCI-H460, MCF-7, and HepG2. Complex 8 exhibited the most effective inhibitory effect on HepG2 cells, with an IC50 value of 1.34 ± 0.04 μM. Preliminary studies on the anticancer mechanism suggest that complex 8 induces apoptosis in HepG2 cells via the mitochondrial pathway, accompanied by G2/M phase cell cycle arrest.
Diorganotin acylhydrazone complexes with mitochondrial targeting demonstrate significant potential as replacements for platinum-based complexes due to their potent anticancer properties. Twelve methylphenyltin arylformylhydrazone complexes have been synthesized by microwave “one-pot” reaction. The complexes have been characterized by FT-IR, multinuclear NMR (1H, 13C, and 119Sn), TGA, and HRMS. Crystal structures were determined for 10 out of the 12 complexes under study. Structures 1 through 8, 10 and 12 possessed a central symmetric structure of a di-nuclear Sn2O2 tetrahedral ring. All complexes were tested for their inhibitory activity against human cell lines NCI-H460, MCF-7, and HepG2. Complex 8 exhibited the most effective inhibitory effect on HepG2 cells, with an IC50 value of 1.34 ± 0.04 μM. Preliminary studies on the anticancer mechanism suggest that complex 8 induces apoptosis in HepG2 cells via the mitochondrial pathway, accompanied by G2/M phase cell cycle arrest.
