期刊：
JOURNAL OF ORGANIC CHEMISTRY,2024年89(4):2505-2515 ISSN：0022-3263
通讯作者：
Wu, AX
作者机构：
[Wang, Can; Zhao, Peng] Taizhou Univ, Sch Pharmaceut Sci, Inst Adv Studies, Taizhou 318000, Zhejiang, Peoples R China.;[Wu, An-Xin; Zhou, You; Zhao, Peng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
通讯机构：
[Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
A novel iodine-promoted difunctionalization of alpha-C sites in enaminones was demonstrated as a means of synthesizing a variety of fully substituted thiazoles by constructing C-C(CO), C-S, and C-N bonds. This transformation allows the realization of enaminones as unusual aryl C2 synthons and simultaneously allows the thioylation and dicarbonylation of alpha-C sites. A preliminary mechanistic study was performed and indicated that the cleavage of C=C bonds in enaminones involves a bicyclization/ring-opening and oxidative coupling sequence.
摘要：
A mild strategy for the synthesis of boron‐handled pyrazoles through photocatalytic cascade radical cyclization of LBRs (Lewis base‐boryl radicals) with vinyldiazo reagents is described here. The reaction starts with the addition of LBRs at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Abstract Vinyldiazo compounds are one of the most important synthons in the construction of a cyclic ring. Most photochemical transformations of vinyldiazo compounds are mainly focusing on utilization of their C═C bond site, while reactions taking place at terminal nitrogen atom are largely unexplored. Herein, a photocatalytic cascade radical cyclization of LBRs with vinyldiazo reagents through sequential B─N/C─N bond formation is described. The reaction starts with the addition of LBRs (Lewis base–boryl radicals) at diazo site, followed by intramolecular radical cyclization to access a wide range of important boron‐handled pyrazoles in good to excellent yields. Control experiments, together with detailed mechanism studies well explain the observed reactivity. Further studies demonstrate the utility of this approach for applications in pharmaceutical and agrochemical research.
摘要：
Trichloroethylene (TCE) with trace concentrations is often detected in soils and groundwater, posing potential damages to public health. The elimination of TCE can be achieved through reductive dechlorination using zero-valent iron (ZVI). However, ZVI usually suffers from the presence of passive iron (hydro)oxides layer and low electron transfer rate, thus leading to the unsatisfactory reactivity. Herein, we fabricated oxalated ZVI (Ox-ZVI(bm)) by mechanical ball-milling of micro-scale ZVI and H2C2O4 center dot 2H(2)O to modify the ZVI surface composition. To be specific, the modification of the iron oxide shell by oxalic acid facilitated the generation of unsaturated coordination Fe(II), enhancing TCE adsorption. Furthermore, the formed FeC2O4 on the iron oxide shell improved electron transfer efficiency, contributing to the enhanced TCE reductive dechlorination. Impressively, the rate of TCE degradation by Ox-ZVI(bm) was 10-fold higher than that of ZVI(bm) without oxalate modification. Moreover, Ox-ZVI(bm) samples were filled in a laboratory Permeable Reactive Barriers (PRB) column to treat actual underground wastewater containing TCE pollutants. The effluent concentration of TCE maintained steadily below 0.21 mg/L for over 10 days, complying with the National Groundwater Class IV standard (GBT 14848-2017). This marks a significant step toward practical groundwater treatment.
作者机构：
[Yan, HY; Yan, Hongye; Zhou, Yu; Ding, Xilin; Liu, Jin; Lei, Mengdie; Chen, Hongxiang] Wuhan Univ Sci & Technol, Sch Chem & Chem Engn, Key Lab Hubei Prov Coal Convers & New Carbon Mat, Wuhan 430081, Peoples R China.;[Tang, Yinjun; Zhu, Chengzhou] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Zhu, Chengzhou] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.
通讯机构：
[Yan, HY ] W;Wuhan Univ Sci & Technol, Sch Chem & Chem Engn, Key Lab Hubei Prov Coal Convers & New Carbon Mat, Wuhan 430081, Peoples R China.
摘要：
The urgent need for sensitive and accurate assays to monitor acetylcholinesterase (AChE) activity and organophosphorus pesticides (OPs) arises from the imperative to safeguard human health and protect the ecosystem. Due to its cost-effectiveness, ease of operation, and rapid response, nanozyme-based colorimetry has been widely utilized in the determination of AChE activity and OPs. However, the rational design of nanozymes with high activity and specificity remains a great challenge. Herein, trace amount of Bi-doped core-shell Pd@Pt mesoporous nanospheres (Pd@PtBi(2)) have been successfully synthesized, exhibiting good peroxidase-like activity and specificity. With the incorporation of trace bismuth, there is a more than 4-fold enhancement in the peroxidase-like performance of Pd@PtBi(2) compared to that of Pd@Pt. Besides, no significant improvement of oxidase-like and catalase-like activities of Pd@PtBi(2) was found, which prevents interference from O(2) and undesirable consumption of substrate H(2)O(2). Based on the blocking impact of thiocholine, a colorimetric detection platform utilizing Pd@PtBi(2) was constructed to monitor AChE activity with sensitivity and selectivity. Given the inhibition of OPs on AChE activity, a biosensor was further developed by integrating Pd@PtBi(2) with AChE to detect OPs, capitalizing on the cascade amplification strategy. The OP biosensor achieved a detection limit as low as 0.06 ng mL(-1), exhibiting high sensitivity and anti-interference ability. This work is promising for the construction of nanozymes with high activity and specificity, as well as the development of nanozyme-based colorimetric biosensors.
期刊：
Highlights in Chemical Science,2024年15(14):5061-5081 ISSN：2041-580X
通讯作者：
Luo, Zhu;Guo, YB
作者机构：
[Guo, YB; Qiu, Xiaofeng; Luo, Zhu; Wu, Yan; Guo, Yanbing; Zhang, Shuhong; Zhu, Yuhua; Hao, Quanguo] Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430082, Hubei, Peoples R China.;[Guo, YB; Luo, Zhu; Guo, Yanbing] Wuhan Inst Photochem & Technol, 7 North Bingang Rd, Wuhan 430082, Hubei, Peoples R China.;[Zhu, Yuhua] Wuhan Univ, Sch Civil Engn, Wuhan 430072, Peoples R China.
通讯机构：
[Guo, YB ; Luo, Z] C;Cent China Normal Univ, Coll Chem, Engn Res Ctr Photoenergy Utilizat Pollut Control &, Minist Educ, Wuhan 430082, Hubei, Peoples R China.;Wuhan Inst Photochem & Technol, 7 North Bingang Rd, Wuhan 430082, Hubei, Peoples R China.
摘要：
Graphdiyne (GDY)-based materials, owing to their unique structure and tunable electronic properties, exhibit great potential in the fields of catalysis, energy, environmental science, and beyond. In particular, GDY/metal oxide hybrid materials (GDY/MOs) have attracted extensive attention in energy and environmental catalysis. The interaction between GDY and metal oxides can increase the number of intrinsic active sites, facilitate charge transfer, and regulate the adsorption and desorption of intermediate species. In this review, we summarize the structure, synthesis, advanced characterization, small molecule activation mechanism and applications of GDY/MOs in energy conversion and environmental remediation. The intrinsic structure-activity relationship and corresponding reaction mechanism are highlighted. In particular, the activation mechanisms of reactant molecules (H2O, O2, N2, etc.) on GDY/MOs are systemically discussed. Finally, we outline some new perspectives of opportunities and challenges in developing GDY/MOs for efficient energy and environmental catalysis. This review summarizes the structure, synthesis, advanced characterization, structure-activity relationship, and mechanisms of graphdiyne/metal oxide hybrid materials in efficient energy and environmental catalysis.
摘要：
In this study, PGM free metal oxide based nanorod array (nanoarray) forests have been conformally integrated onto the millimeter-sized channel walls and microscale pores of SiC diesel particulate filter (DPF) substrates using scalable microwave-assisted hydrothermal and dip-coating methods. High-efficiency and robust low temperature soot oxidation is successfully achieved using such a new type of cDPFs as a result of i) promoted tight soot-catalyst contact through spontaneous soot deposits in-between nanorods, ii) highly dispersed loading of LaSrCoO3 perovskite oxidation catalysts onto ZnO nanorod arrays, effectively mitigating active site blockage by soot deposition. The light-off temperature of soot oxidation was lowered to 250 degrees C in oxygen, a 250 degrees C decrease compared to that of the commercial Pt based catalyst, due to the abundant oxygen vacancies enabled by the LaSrCoO3/ZnO (LSCO/ZnO) nanorod array catalysts. The performance of the catalyst was further enhanced to initiate the soot oxidation at similar to 150 degrees C with co-fed gas of NO, due to the LSCO catalyzed NO2 formation and its favorable oxidation with soot at low temperature. Furthermore, the nanoarray supported perovskite catalyst shows excellent stability and activity after 120 h of hydrothermal aging at 650 degrees C. Soot oxidation Tmax is lowered from 542 degrees C to 510 degrees C under 6 % water steam condition due to the formation and promotion effect of oxidative-OH species. In situ DRIFTS study reveals that such-OH species form at various catalyst surfaces and interfaces, pointing to a potentially generic water promotion effect for solid/solid interfacial catalytic oxidation under humidity condition. Finally, the mechanistic soot oxidation pathways under O-2, NO2, and H2O feeds are pro-posed for understanding the low-temperature soot oxidation behaviors over the nanoarray supported perovskite catalysts.
作者机构：
[Zhou, Yan; Zhu, Chengzhou; Li, Jingshuai; Xi, Mengzhen; Zhu, CZ; Gu, Wenling] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Lu, Bingzhang] Xi An Jiao Tong Univ, Sch Chem Engn & Technol, Xian 710049, Shaanxi, Peoples R China.;[Zhu, Chengzhou; Zhu, CZ] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.
通讯机构：
[Lu, BZ ] X;[Zhu, CZ ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;Xi An Jiao Tong Univ, Sch Chem Engn & Technol, Xian 710049, Shaanxi, Peoples R China.;Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.
摘要：
For conventional potential-resolved ratiometric electrochemiluminescence (ECL) systems, the introduction of multiplex coreactants is imperative. However, the undesirable interactions between different coreactants inevitably affect analytical accuracy and sensitivity. Herein, through the coordination of aggregation-induced emission ligands with gadolinium cations, the self-luminescent metal-organic framework (Gd-MOF) is prepared and serves as a novel coreactant-free anodic ECL emitter. By the intercalation of [Ru(bpy)(2)dppz](2+) with light switch effect into DNA duplex, one high-efficiency cathodic ECL probe is obtained using K(2)S(2)O(8) as a coreactant. In the presence of acetamiprid, the strong affinity between the target and its aptamer induces the release of [Ru(bpy)(2)dppz](2+), resulting in a decreasing cathode signal and an increasing anode signal owing to the ECL resonance energy transfer from Gd-MOF to [Ru(bpy)(2)dppz](2+). In this way, an efficient dual-signal ECL aptasensor is constructed for the ratiometric analysis of acetamiprid, exhibiting a remarkably low detection limit of 0.033 pM. Strikingly, by using only one exogenous coreactant, the cross interference from multiple coreactants can be eliminated, thus improving the detection accuracy. The developed high-performance ECL sensing platform is successfully applied to monitor the residual level of acetamiprid in real samples, demonstrating its potential application in the field of food security.
作者：
Su, Rina;Wu, Yu;Xu, Weiqing;Tan, Rong;Qin, Ying;...
期刊：
Chemical Engineering Journal,2024年484 ISSN：1385-8947
通讯作者：
Zhu, CZ
作者机构：
[Xu, Weiqing; Qin, Ying; Zhu, Chengzhou; Wu, Yu; Xiao, Runshi; Tan, Rong; Su, Rina; Zhu, CZ; Gu, Wenling] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Xiao, Runshi; Hu, Liuyong] Wuhan Inst Technol, Hubei Engn Technol Res Ctr Optoelect & New Energy, Sch Mat Sci & Engn, Hubei Key Lab Plasma Chem & Adv Mat, Wuhan 430205, Peoples R China.;[Wang, Canglong] Chinese Acad Sci, Inst Modern Phys, Lanzhou 730000, Peoples R China.;[Sun, Hongcheng] Hangzhou Normal Univ, Coll Mat Chem & Chem Engn, Key Lab Organosilicon Chem & Mat Technol, Minist Educ, Hangzhou 311121, Peoples R China.
通讯机构：
[Zhu, CZ ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensing Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
Nanozymes have been widely reported to serve as promising alternatives to enzymes. However, insufficient activity is one prominent challenge that limits their further exploitation of applications. To address this issue, photoenzymes, that can borrow solar energy to boost catalysis, inspire the exploration of nanozyme catalysis upon illumination. Herein, a cyano-defective carbon nitride (CCN) nanozyme with photo -enhanced peroxidaselike (POD -like) activity was reported, where the photo -activation enables the 4.15 -fold activity enhancement. Based on in situ characterizations, a self -cascade mechanism was proposed, where CCN can catalyze H2O2 into hydroxyl radical (center dot OH) upon illumination and subsequently capture center dot OH to generate absorbed hydroxyl (*OH) for further catalysis in the dark. Taking advantage of the photo -enhanced activity, a sensing array was successfully constructed for alcohol discrimination. These findings not only set the foundation for photo -enhanced nanozymes but also highlight their potential for practical applications.
期刊：
POLYMER ENGINEERING AND SCIENCE,2024年 ISSN：0032-3888
通讯作者：
Wu, QX
作者机构：
[Liu, Yunguo; Wu, Qiangxian; Ren, Mingtian] Cent China Normal Univ, Coll Chem, Green Polymer Lab, Wuhan, Peoples R China.;[Liu, Yunguo; Wu, Qiangxian; Ren, Mingtian] Cent China Normal Univ, Coll Chem, Minist Educ, Key Lab Pesticide & Chem Biol, Wuhan, Peoples R China.;[Koranteng, Ernest] Univ Educ, Dept Chem Educ, Lab Sustainable Polymers & Synth, Winneba, Ghana.;[Weng, Fangqing] Hubei Univ Educ, Coll Chem & Life Sci, Hubei Key Lab Purificat & Applicat Plant Anticanc, Wuhan, Peoples R China.;[Wu, Qiangxian; Wu, QX] Cent China Normal Univ, Coll Chem, Wuhan 430205, Peoples R China.
通讯机构：
[Wu, QX ] C;Cent China Normal Univ, Coll Chem, Wuhan 430205, Peoples R China.
关键词：
biomaterials;composites;corn starch;PBAT;surfaces and interfaces
摘要：
Compatibility mechanise. Abstract Starch is an environmentally friendly, renewable, green resource and an ideal alternative to polymers from petroleum resources. The preparation of high‐performance poly (butylene adipate‐co‐terephthalate) (PBAT)/corn starch composite materials is of significant importance for saving production costs and expanding the application fields of PBAT plastics. This study employed novel processing techniques such as melt blending and injection molding to fabricate PBAT/corn starch composite materials with polyurethane prepolymer (PCLPU) as a compatibilizer. The impact of varying polyurethane prepolymer concentrations on the composite material's structure, mechanical properties, morphology, thermal behavior, and water absorption was scrutinized. Mechanical performance testing showed that compared to the composite material without PCLPU (P90CS10), adding 5% PCLPU can increase the material's elongation at break from 350.2% to 359.0% and the tensile strength from 12.9 to 19.8 MPa. Scanning electron microscopy, thermogravimetric analysis, and water absorption results indicate that the composite material with the addition of the PCLPU compatibilizer has better compatibility, thermal stability, and water resistance than P90CS10. Additionally, the prepared composite material could be successfully blown into a thin film, further enriching the application of the composite material. Highlights A special interface structure was prepared to increase the compatibility of the poly (butylene adipate‐co‐terephthalate)/corn starch composite. Both the strength and the flexibility of the composite were successfully improved. The processing method through which modification was conducted in the melt was convenient, green, and effective. The prepared composite material has potential application value, and the processing method of the composite material is easy to transfer to industrial production.
作者机构：
[Yonghui Xu; Yufei Liu; Wei Zhan; Dingle Zhang; Yiyun Liu; Yi Xu; Zhengshun Wu] Chemistry College, Central China of Normal University, Wuhan, 430079, China
通讯机构：
[Zhengshun Wu] C;Chemistry College, Central China of Normal University, Wuhan, 430079, China
摘要：
This study explores the transformation of peanut shells, an abundant agricultural waste, into high-efficiency activated carbon for CO2 capture using a two-step pyrolysis and K2CO3 activation method. Observations indicated that with an increasing impregnation ratio, the activated carbon demonstrates remarkable improvements in structural properties, achieving specific surface areas and pore volumes of 1150.02 m2/g and 0.46 cm3/g, respectively. Among the prepared samples, the activated carbon obtained with a peanut shell to K2CO3 impregnation mass ratio of 1:2 exhibits superior CO2 adsorption capacity at 1 bar, with values of 3.76 mmol/g at 25 °C and 5.70 mmol/g at 0 °C. The CO2 adsorption isotherms of the activated carbon conform to the Langmuir and Freundlich models. These results demonstrate the potential of this method in addressing environmental concerns, particularly in mitigating CO2 emissions, and highlight the broader application prospects of biomass-derived activated carbon in environmental management.
作者机构：
[Wang, Huai-Yu; Wu, Yan-Dong; Wu, An-Xin; Wu, Chun-Yan; Yu, Zhi-Cheng; Chen, Xiang-Long; Yang, Dong-Sheng] Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;[Tang, Bo-Cheng] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, State Key Lab Chem Biol & Drug Discovery, Kowloon, Hong Kong, Peoples R China.;[Li, Anling] Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;[Li, Anling] Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
通讯机构：
[Li, AL ] W;[Wu, YD; Wu, AX ] C;Cent China Normal Univ, Coll Chem, Int Joint Res Ctr Intelligent Biosensor Technol &, Natl Key Lab Green Pesticide, Wuhan 430079, Hubei, Peoples R China.;Wuhan Univ, Ctr Gene Diag, Dept Clin Lab, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.;Wuhan Univ, Program Clin Lab Med, Zhongnan Hosp, Wuhan 430062, Hubei, Peoples R China.
关键词：
Defluoroarylation;Transition metal free;gem-Difluoroalkenes;Rongalite;Single electron transfer;C-C coupling;Redox reactions;Cross-coupling
摘要：
A transition‐metal‐free allylic defluorination reductive cross‐coupling between CF3‐alkenes and diaryliodonium salts mediated by rongalite has been described for the first time. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates. The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs. Comprehensive Summary The conversion of CF3‐alkenes to gem‐difluoroalkenes using reductive cross‐coupling strategy has received much attention in recent years, however, the use of green and readily available reducing salt to mediate these reactions remains to be explored. In this work, a concise construction of gem‐difluoroalkenes, which requires neither a catalyst nor a metal reducing agent, was established. Rongalite, a safe and inexpensive industrial product, was employed as both a radical initiator and reductant. This procedure was compatible with both linear and cyclic diaryliodonium salts, enabling a wide variety of substrates (>70 examples). The utility of this approach was demonstrated through gram‐scale synthesis and efficient late‐stage functionalizations of anti‐inflammatory drugs.
摘要：
In an effort to make pesticide use safer, more efficient, and sustainable, micro-/nanocarriers are increasingly being utilized in agriculture to deliver pesticide-active agents, thereby reducing quantities and improving effectiveness. In the use of nanopesticides, the choice to further design and prepare pesticide stimulus-responsive nanocarriers based on changes in the plant growth environment (light, temperature, pH, enzymes, etc.) has received more and more attention from researchers. Based on this, this paper examines recent advancements in nanomaterials for the design of stimulus-responsive micro-/nanocarriers. It delves into the intricacies of preparation methods, material enhancements, in vivo/ex vivo controlled release, and application techniques for controlled release formulations. The aim is to provide a crucial reference for harnessing nanotechnology to pursue reduced pesticide use and increased efficiency.
作者机构：
[Wang, SW; Wang, Shaowei; Liu, Shuang] Chinese Acad Sci, Shanghai Inst Tech Phys, State Key Lab Infrared Phys, 420 Zhongshan Rd, Shanghai 200434, Peoples R China.;[Zhang, Qiuxin] Brandeis Univ, Dept Chem, 415 South St, Waltham, MA 02454 USA.;[Peng, Xingrao; Sun, Yao] Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.;[Hu, Cong] Guilin Univ Elect Technol, Guangxi Key Lab Automat Detecting Technol & Instru, Guilin 541004, Peoples R China.
通讯机构：
[Wang, SW ; Sun, Y ; Liu, S] C;Chinese Acad Sci, Shanghai Inst Tech Phys, State Key Lab Infrared Phys, 420 Zhongshan Rd, Shanghai 200434, Peoples R China.;Cent China Normal Univ, Coll Chem, Natl Key Lab Green Pesticide, Wuhan 430079, Peoples R China.
摘要：
Herein, we show a pair of leucine-rich l- and d-phosphopeptides which self-assemble into twisting nanofibers, whose secondary structures contain a strong beta-sheet component after being dephosphorylated by alkaline phosphatase (ALP). While being incubated with ALP overexpressing osteosarcoma cells, both of the peptides self-assemble in the nuclei and induce cell death. The cell death involves multiple cell death modalities and occurs along with the disruption of cell membranes. Enzyme-instructed self-assembly (EISA) inhibits osteosarcoma cells and shows no side effect to other cells. In addition, the cancer cells hardly gain drug resistance after repeated treatment. This work reports a pair of EISA-based nanofibers to target cell nuclei, and also provides a novel chemotherapeutic agent to inhibit osteosarcoma cells without side effects and drug resistance. Dephosphorylated by the highly expressed alkaline phosphatase, phosphopeptides self-assemble into twisted nanofibers in nuclei to selectively induce the death of osteosarcoma cells.
期刊：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY,2024年146(13):8991-9003 ISSN：0002-7863
作者机构：
[Tu, Le; Li, Meiqin; Li, Junrong; Sun, Yao; Li, Chonglu] National Key Laboratory of Green Pesticide, International Joint Research Center for Intelligent Biosensor Technology and Health, College of Chemistry, Central China Normal University, Wuhan 430079, China;[Li, Chonglu] State Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082, China;[Kim, Jong Seung; Ding, Qihang] Department of Chemistry, Korea University, Seoul 02841, Korea;[Sharma, Amit] Amity School of Chemical Sciences, Amity University Punjab, Sector 82A, Mohali, Punjab 140306, India
摘要：
Though immunogenic cell death (ICD) has garnered significant attention in the realm of anticancer therapies, effectively stimulating strong immune responses with minimal side effects in deep-seated tumors remains challenging. Herein, we introduce a novel self-assembled near-infrared-light-activated ruthenium(II) metallacycle, Ru1105 (λ(em) = 1105 nm), as a first example of a Ru(II) supramolecular ICD inducer. Ru1105 synergistically potentiates immunomodulatory responses and reduces adverse effects in deep-seated tumors through multiple regulated approaches, including NIR-light excitation, increased reactive oxygen species (ROS) generation, selective targeting of tumor cells, precision organelle localization, and improved tumor penetration/retention capabilities. Specifically, Ru1105 demonstrates excellent depth-activated ROS production (∼1 cm), strong resistance to diffusion, and anti-ROS quenching. Moreover, Ru1105 exhibits promising results in cellular uptake and ROS generation in cancer cells and multicellular tumor spheroids. Importantly, Ru1105 induces more efficient ICD in an ultralow dose (10 μM) compared to the conventional anticancer agent, oxaliplatin (300 μM). In vivo experiments further confirm Ru1105's potency as an ICD inducer, eliciting CD8(+) T cell responses and depleting Foxp3(+) T cells with minimal adverse effects. Our research lays the foundation for the design of secure and exceptionally potent metal-based ICD agents in immunotherapy.
期刊：
Proceedings of the National Academy of Sciences of the United States of America,2024年121(14):e2318391121 ISSN：0027-8424
作者机构：
[Ye, Yu-Yuan; Xiao, Ju; Wang, Xiao-Qiang; Li, Wen-Zhen; Wang, Zi-Xin] Interdisciplinary Institute of NMR and Molecular Sciences, Key Laboratory of Coal Conversion and New Carbon Materials of Hubei Province, School of Chemistry and Chemical Engineering, Wuhan University of Science and Technology, Wuhan 430081, China;[Liu, Ling-Ran; Sun, Yan] Key Laboratory for Special Functional Materials of Ministry of Education, School of Materials Science and Engineering, Collaborative Innovation Center of Nano Functional Materials and Applications, Henan University, Zhengzhou 450046, China;[Zhu, Mai-Yong; Liu, Ling-Ran] Research School of Polymeric Materials, School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, China;[Wang, Xin-Qiong] Department of Paediatrics, Ruijin Hospital, School of Medicine, Shanghai Jiao Tong University, Shanghai 200240, China;[Sun, Yao] Key Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, China
摘要：
The exploitation of novel wound healing methods with real-time infection sensing and high spatiotemporal precision is highly important for human health. Pt-based metal-organic cycles/cages (MOCs) have been employed as multifunctional antibacterial agents due to their superior Pt-related therapeutic efficiency, various functional subunits and specific geometries. However, how to rationally apply these nanoscale MOCs on the macroscale with controllable therapeutic output is still challenging. Here, a centimeter-scale Pt MOC film was constructed via multistage assembly and subsequently coated on a N,N'-dimethylated dipyridinium thiazolo[5,4-d]thiazole (MPT)-stained silk fabric to form a smart wound dressing for bacterial sensing and wound healing. The MPT on silk fabric could be used to monitor wound infection in real-time through the bacteria-mediated reduction of MPT to its radical form via a color change. The MPT radical also exhibited an excellent photothermal effect under 660 nm light irradiation, which could not only be applied for photothermal therapy but also induce the disassembly of the Pt MOC film suprastructure. The highly ordered Pt MOC film suprastructure exhibited high biosafety, while it also showed improved antibacterial efficiency after thermally induced disassembly. In vitro and in vivo studies revealed that the combination of the Pt MOC film and MPT-stained silk can provide real-time information on wound infection for timely treatment through noninvasive techniques. This study paves the way for bacterial sensing and wound healing with centimeter-scale metal-organic materials.
摘要：
Designing safer chemicals is an integral part of green chemistry that supports good health and well-being. The teaching of molecule design through relevant courses has important implications for the education of sustainable chemists. In these courses, training in toxicology and hazard assessment is essential for students to study benign chemical design that promotes social and environmental justices. However, toxicology training has been rarely included in the course of molecular design, and education of green molecular design at the postgraduate level has been less involved. In this study, we developed an online classroom for toxicology training as a new component of our chemical molecular design course. This class was designed to provide students with a toxicity perspective for viewing chemicals by integrating our three web-based tools. The average score of students' attitude evaluation toward the web-based class was 4.0/5.0, indicating that the toxicology class achieved the expected effects and provided a good experience for students to learn about designing safer chemicals. This work may facilitate the education of green molecular design and inspire students to seriously consider chemically toxic side effects.
摘要：
The role of AXL in various oncogenic processes has made it an attractive target for cancer therapy. Currently, kinase selectivity profiles, especially circumventing MET inhibition, remain a scientific issue of great interest in the discovery of selective type II AXL inhibitors. Starting from a dual MET/AXL-targeted lead structure from our previous work, we optimized a 1,6-naphthyridinone series using molecular modeling-assisted compound design to improve AXL potency and selectivity over MET, resulting in the potent and selective type II AXL-targeted compound 25c. This showed excellent AXL inhibitory activity (IC(50)=1.1nM) and 343-fold selectivity over the highly homologous kinase MET in biochemical assays. Moreover, compound 25c significantly inhibited AXL-driven cell proliferation, dose-dependently suppressed 4T1 cell migration and invasion, and induced apoptosis. Compound 25c also showed noticeable antitumor efficacy in a BaF3/TEL-AXL xenograft model at well-tolerated doses. Overall, this study presented a potent and selective type II AXL-targeted lead compound for further drug discovery.
摘要：
The development of efficient, bright, and stable narrowband light-emitting electrochemical cells (LECs) has remained a challenge. Here, intrinsically ionic multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters are reported as guest emitters for narrowband LECs, which are developed by attaching an imidazolium cation onto a typical MR-TADF emitter. In solution, the emitters show green-blue emission peaked at 486-497 nm with small full widths at half-maximum (FWHMs) at 24-26 nm. In doped films, they show narrowband green-blue emission with high luminescent efficiencies at approximate to 90%. LECs using an ionic exciplex host and the ionic MR-TADF guest emitters show green-blue emission peaked at 494-503 nm with small FWHMs at 31-34 nm, and afford high external quantum efficiencies (EQEs) up to 10% under constant-voltage driving. With ionic TADF small-molecule hosts, the narrowband LECs show high EQEs up to 13.0% under constant-voltage driving, which is the highest among all reported narrowband LECs, and afford peak brightness/EQE/half lifetime at 780 cd m-2/5.6%/62.2 h under constant-current driving. A long half-lifetime of approximate to 630 h has further been achieved at 136 cd m-2. The work demonstrates the great potential for the use of intrinsically ionic MR-TADF guest emitters and ionic TADF hosts to develop efficient, bright, and stable narrowband LECs. Narrowband light-emitting electrochemical cells (LECs) are fabricated with ionic multi-resonance thermally- activated delayed fluorescence (TADF) guest emitters, which show high external quantum efficiencies (EQEs) up to 13.0% under constant-voltage driving and peak brightness/EQE/half-lifetime at 780 cd m-2/5.6%/62.2 h under constant-current driving. A half-lifetime of approximate to 630 h is further achieved at 136 cd m-2. image
