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ACS Nano · 2023 · IF 17.1

All-in-One Engineering Multifunctional Nanoplatforms for Sensitizing Tumor Low-Temperature Photothermal Therapy In Vivo

Ke Li,Kun Xu,Shaopeng Liu,Ye He,Meijun Tan,Yulan Mao,Yulu Yang,Jing Wu,Qian Feng,Zhong Luo,Kaiyong Cai

Low-temperature photothermal therapy (PTT) is a noninvasive method that harnesses the photothermal effect at low temperatures to selectively eliminate tumor cells, while safeguarding normal tissues, minimizing thermal damage, and enhancing treatment safety. First we evaluated the transcriptome of tumor cells at the gene level following low-temperature treatment and observed significant enrichment of genes involved in cell cycle and heat response-related signaling pathways. To address this challenge, we have developed an engineering multifunctional nanoplatform that offered an all-in-one strategy for efficient sensitization of low-temperature PTT. Specifically, we utilized MoS2 nanoparticles as the photothermal core to generate low temperature (40–48 °C). The nanoplatform was coated with DPA to load CPT-11 and Fe2+ and was further modified with PEG and iRGD to enhance tumor specificity (MoS2/Fe@CPT-11-PEG-iRGD). Laser- and acid-triggered release of CPT-11 can significantly increase intracellular H2O2 content, cooperate with Fe2+ ions to increase intracellular lipid ROS content, and activate ferroptosis. Furthermore, CPT-11 induced cell cycle arrest in the temperature-sensitive S-phase, and increased lipid ROS levels contributed to the degradation of HSPs protein expression. This synergistic approach could effectively induce tumor cell death by the sensitized low-temperature PTT and the combination of ferroptosis and chemotherapy. Our nanoplatform can also maximize tumor cell eradication and prolong the survival time of tumor-bearing mice in vivo. The multifunctional approach will provide more possibilities for clinical applications of low-temperature PTT and potential avenues for the development of multiple tumor treatments.

CAS / MDL: 62-31-7 7758-94-3
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CHEMICAL ENGINEERING JOURNAL · 2023 · IF 15.1

Activating and stabilizing Co sites in CoP for triggering oxygen electrocatalysis in zinc-air battery

Bin Liu,Xinyu Wang,Rongyue Wang,Guanyi Zhang,Xiaoqin Xu,Jin Liu,Zhiyao Sun,Mingyang Liu,Cheng Wang,Xin Meng,Jiahao Xie,Jinlong Zou

Catalysts with high activity and corrosion-resistance are desirable for oxygen reduction and evolution reactions (ORR/OER) in rechargeable zinc-air batteries (ZABs). Herein, via an etching-phosphating-annealing strategy, CoP is in situ formed in hollow carbon-nanobox, both of which are wrapped by a thin nitrogen-doped carbon layer (CoP/HNBs@NCL). Tannic acid etches ZIF-67 nanobox to release Co 2+ and 2-methylimidazole to generate hollow structure. As-marked CoP/HNBs@NCL-2 (271.9 m 2 g −1 ) exhibits robust activities towards ORR (half-wave potential of 0.88 V) and OER (overpotential of 0.36 V), which outperforms many non-precious metal catalysts due to the strong interactions between CoP and N-species and the smooth mass transfer via the porous hollow structure. Even at high potentials (OER), HNBs@NCL framework can still relieve the leaching of Co species (leaching ratio of 15.5 % after 6 h) to obtain high corrosion resistance and stability. Theoretical calculations reveal that N atoms enhance the electron delocalization degree of Co sites in CoP to lower energy barriers and balance adsorption free-energies of O-intermediates to enhance oxygen electrocatalysis. Notably, ZAB with CoP/HNBs@NCL-2 air-electrode exhibits high peak power density (139.8 mW cm −2 ) and charge–discharge cycling stability (132 h). This work presents a reliable protocol to design hollow electrocatalysts with desirable bifunctional activity and stability for ZABs.

CAS / MDL: 7782-42-5
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ANALYTICAL CHEMISTRY · 2023 · IF 7.4

In Situ Probing the Short-Lived Intermediates in Visible-Light Heterogeneous Photocatalysis by Mass Spectrometry

Qiu-Yue Cheng,Ting Wang,Jun Hu,Hong-Yuan Chen,Jing-Juan Xu

Visible-light-mediated heterogeneous photocatalysis has recently emerged as an environmentally friendly and energy-sustainable alternative for organic transformations. Despite the advancements in developing wide varieties of photocatalysts during the past decades, the accurate probing and identification of the photogenerated species, especially the short-lived radical intermediates, are still challenging. In this work, we reported a hybrid ion emitter that integrated with a pico-liter heterogeneous photocatalytic reactor, which was fabricated by depositing the photocatalyst (e.g., TiO2) into the front tip of a quartz micropipette. Benefited from the dual-function feature of the hybrid micropipette (i.e., a clog-free tip-confined pico-liter reactor for heterogeneous photocatalysis and an ion emitter for nanoelectrospray ionization), sensitized photoredox reactions at the catalyst–solution interface can be triggered upon visible-light irradiation using a cheap LED laser (453 nm), and the newly produced transient radical intermediates can be rapidly transformed into gaseous ions for mass spectrometric identification. Using this novel low-delay coupling device, photogenerated intermediates, including the cationic radicals produced during the photooxidation of anilines and the anionic radicals produced during the photoreduction of quinones, were successfully captured by mass spectrometry. We believe that our hybrid photochemical microreactor/ion emitter has provided a new and powerful tool for exploring the complicated heterogeneous photochemical processes, especially their ultrafast initial transformations.

CAS / MDL: 121-69-7 635-46-1
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Nature Communications · 2021 ·Vol. 12 ·期 1 ·1-13 · IF 14.919

Artificial dual solid-electrolyte interfaces based on in situ organothiol transformation in lithium sulfur battery

Guo Wei,Zhang Wanying,Si Yubing,Wang Donghai,Fu Yongzhu,Manthiram Arumugam

The interfacial instability of the lithium-metal anode and shuttling of lithium polysulfides in lithium-sulfur (Li-S) batteries hinder the commercial application. Herein, we report a bifunctional electrolyte additive, i.e., 1,3,5-benzenetrithiol (BTT), which is used to construct solid-electrolyte interfaces (SEIs) on both electrodes from in situ organothiol transformation. BTT reacts with lithium metal to form lithium 1,3,5-benzenetrithiolate depositing on the anode surface, enabling reversible lithium deposition/stripping. BTT also reacts with sulfur to form an oligomer/polymer SEI covering the cathode surface, reducing the dissolution and shuttling of lithium polysulfides. The Li–S cell with BTT delivers a specific discharge capacity of 1,239 mAh g −1 (based on sulfur), and high cycling stability of over 300 cycles at 1C rate. A Li–S pouch cell with BTT is also evaluated to prove the concept. This study constructs an ingenious interface reaction based on bond chemistry, aiming to solve the inherent problems of Li–S batteries.

CAS / MDL: 7704-34-9
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INORGANIC CHEMISTRY · 2021 · IF 5.165

Achievement of Excellent Thermoelectric Properties in Cu–Se–S Compounds via In Situ Phase Separation

Yi-Xin Zhang,Yun-Qiao Tang,Zheng Ma,Ming-Yu Hu,Jing Feng,Zhen-Hua Ge

In this study, Cu2Se1–xSx (x = 0.1, 0.3, and 0.5) alloy powders were prepared by the hydrothermal synthesis method. In the subsequent sintering process, the spontaneous in situ phase separation process of the sample forms a two-phase hybrid structure. The generated Cu2S precipitates in the Cu2Se matrix noticeably enhance phonon scattering, which is beneficial for low thermal conductivity without significantly affecting the electrical transport performance. Ultimately, an optimized thermoelectric performance was obtained in Cu2Se0.9S0.1, reaching a peak zT value of 1.43 at 773 K, the optimum value among the Cu–Se–S systems at this temperature.

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PLANT PHYSIOLOGY · 2021 ·Vol. 187 ·期 2 ·829-845 · IF 8.34

Regulation of carotenoid and chlorophyll pools in hesperidia, anatomically unique fruits found only in Citrus

Zhu Kaijie,Zheng Xiongjie,Ye Junli,Huang Yue,Chen Hongyan,Mei Xuehan,Xie Zongzhou,Cao Lixin,Zeng Yunliu,Larkin Robert M.,Xu Qiang,Perez-Roman Estela,Talón Manuel,Zumajo-Cardona Cecilia,Wurtzel Eleanore T.,Deng Xiuxin

Domesticated citrus varieties are woody perennials and interspecific hybrid crops of global economic and nutritional importance. The citrus fruit “hesperidium” is a unique morphological innovation not found in any other plant lineage. Efforts to improve the nutritional quality of the fruit are predicated on understanding the underlying regulatory mechanisms responsible for fruit development, including temporal control of chlorophyll degradation and carotenoid biosynthesis. Here, we investigated the molecular basis of the navel orange (Citrus sinensis) brown flavedo mutation, which conditions flavedo that is brown instead of orange. To overcome the limitations of using traditional genetic approaches in citrus and other woody perennials, we developed a strategy to elucidate the underlying genetic lesion. We used a multi-omics approach to collect data from several genetic sources and plant chimeras to successfully decipher this mutation. The multi-omics strategy applied here will be valuable in driving future gene discovery efforts in citrus as well as in other woody perennial plants. The comparison of transcriptomic and genomic data from multiple genotypes and plant sectors revealed an underlying lesion in the gene encoding STAY-GREEN (SGR) protein, which simultaneously regulates carotenoid biosynthesis and chlorophyll degradation. However, unlike SGR of other plant species, we found that the carotenoid and chlorophyll regulatory activities could be uncoupled in the case of certain SGR alleles in citrus and thus we propose a model for the molecular mechanism underlying the brown flavedo phenotype. The economic and nutritional value of citrus makes these findings of wide interest. The strategy implemented, and the results obtained, constitute an advance for agro-industry by driving opportunities for citrus crop improvement.

CAS / MDL: 631-61-8 10534-59-5
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SENSORS AND ACTUATORS B-CHEMICAL · 2020 · IF 7.1

Ratio fluorescent hybrid probe for visualized fluorescence detection of H2O2 in vitro and in vivo

Riyue Dong,Yuying Yao,Dongna Li,Haoran Zhang,Wei Li,Maxim Molokee,Yingliang Liu,Bingfu Lei

A silicon oxide quantum dots (Si-O QDs) and Ag nanoclusters hybrid nanosensing probe with dual-emission and small nanocrystals that acts as an “off-on” ratio fluorescent probe for hydrogen peroxide (H 2 O 2 ) detection was developed. The probe was used to measure the H 2 O 2 concentration generated by mitochondria in vitro via recording the I 455 /I 680 fluorescence ratio. Furthermore, this hybrid probe was applied to monitor the wound-induced H 2 O 2 in lettuce leaf, and realized the visualized fluorescence qualitative detection H 2 O 2 in vivo via laser scanning confocal microscope. The working mechanism of the probe is also investigated. Inner filter effect (IFE) estimation, Fourier transform infrared (FTIR) spectra and high-resolution transmission electron microscopy (HRTEM) images were applied to study the quenching mechanism and recovering reason of Si-O QDs fluorescence. The results show that the blue fluorescence of Si-O QDs can be quenched by Ag NCs via the IFE and fluorescent resonance energy transfer (FRET) effect. After adding H 2 O 2 , the surface groups of Ag NCs was changed and the IFE and FRET effects between the Si-O QDs and Ag NCs are disabled, thus the quenched Si-O QDs luminescence can be regularly recovered.

CAS / MDL: 7758-98-7
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DRUG DELIVERY · 2020 · IF 4.902

Increased antitumor efficacy of ginsenoside Rh2 via mixed micelles: in vivo and in vitro evaluation

Xiaojing Xia,Jin Tao,Zhuwa Ji,Chencheng Long,Ying Hu,Zhiying Zhao

The aim of this work is to apply Solutol® HS15 and TPGS to prepare self-assembled micelles loading with ginsenoside Rh2 to increase the solubility of ginsenoside Rh2, hence, improving the antitumor efficacy. Ginsenoside Rh2-mixed micelles (Rh2-M) were prepared by thin film dispersion method. The optimal Rh2-M was characterized by particle size, morphology, and drug encapsulation efficiency. The enhancement of in vivo anti-tumor efficacy of Rh2-M was evaluated by nude mice bearing tumor model. The solubility of Rh2 in self-assembled micelles was increased approximately 150-folds compared to free Rh2. In vitro results demonstrated that the particle size of Rh2-M is 74.72 ± 2.63 nm(PDI = 0.147 ± 0.15), and the morphology of Rh2-M is spherical or spheroid, and the EE% and LE% are 95.27 ± 1.26% and 7.68 ± 1.34%, respectively. The results of in vitro cell uptake and in vivo imaging showed that Rh2-M could not only increase the cell uptake of drugs, but also transport drug to tumor sites, prolonging the retention time. In vitro cytotoxicity and in vivo antitumor results showed that the anti-tumor effect of Rh2 can be effectively improved by Rh2-M. Therefore, Solutol® HS15 and TPGS could be used to entrapping Rh2 into micelles, enhancing solubility and antitumor efficacy.

CAS / MDL: 9002-96-4
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JOURNAL OF THE ELECTROCHEMICAL SOCIETY · 2020 ·Vol. 167 ·期 13 ·136506 · IF 3.721

Thermodynamics, Solubility and the Separation of Uranium from Cerium in Molten In/3LiCl-2KCl System

Minghui Xu,Valeri Smolenski,Qi Liu,Alena Novoselova,Kewei Jiang,Jing Yu,Jingyuan Liu,Rongrong Chen,Hongsen Zhang,Milin Zhang,Jun Wang

The purpose of this work is to study the electrochemical behavior of uranium and cerium in fused In/3LiCl-2KCl system in the temperature range of 723–823 K by open-circuit potentiometry. The apparent electrode potential of Ce3+/Ce (U4+/U) couples and apparent standard potential of Ce-In (U-In) alloys vs AgCl/Ag reference electrode were established. The principal thermodynamic properties, activity and solubility of cerium and uranium were determined. The separation factor of uranium/cerium couple on liquid indium electrode was calculated. The experimental results have been shown that a lower temperature should be more effective for the separation uranium from cerium.

CAS / MDL: 18618-55-8
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INSECT MOLECULAR BIOLOGY · 2020 ·Vol. 30 ·期 2 ·138-151 · IF 2.533

Chemosensory proteins participate in insecticide susceptibility in Rhopalosiphum padi, a serious pest on wheat crops

X. Peng,M. J. Qu,S. J. Wang,Y. X. Huang,C. Chen,M. H. Chen

Rhopalosiphum padi is a worldwide agricultural pest. Chemosensory proteins (CSPs) are considered to be a type of transporters which can bind chemicals from external environments. Previous research showed that the expression of some insect CSPs were significantly increased after exposure to insecticides, and CSPs were involved in insecticide resistance or susceptibility. However, the role of CSPs in the susceptibility and response of R. padi to insecticides is still unknown. In this study, we identified eight CSP ( RpCSP ) from R. padi by genome-wide investigation. Seven RpCSP genes had two exons, while RpCSP7 had three exons. qPCR analyses showed that the mRNA levels of the eight RpCSP genes were significantly affected by imidacloprid and beta-cypermethrin in different post-treatment periods. Molecular docking predicted that there were hydrogen bonding sites which played key roles in binding of RpCSP4 , RpCSP5 , RpCSP6 , RpCSP7 and RpCSP10 with imidacloprid and beta-cypermethrin. Knockdown of RpCSP4 , RpCSP5 , RpCSP6 and RpCSP10 by RNA interference significantly increased the aphid mortality under two sublethal concentrations of imidacloprid. Mortalities under two sublethal concentrations of beta-cypermethrin conditions were significantly higher after injection of R. padi with ds CSP4 and ds CSP6 . The results indicate that some RpCSP genes are involved in the insecticide susceptibility of R. padi .

CAS / MDL: 9002-93-1
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CHEMICAL RESEARCH IN TOXICOLOGY · 2020 · IF 3.184

Glutathione Conjugation and Protein Adduction by Environmental Pollutant 2,4-Dichlorophenol In Vitro and In Vivo

Qingmei Li,Wei Li,Jiaxing Zhao,Xiucai Guo,Qian Zou,Zixin Yang,Ruixue Tian,Ying Peng,Jiang Zheng

2,4-Dichlorophenol (2,4-DCP), an environmental pollutant, was reported to cause hepatotoxicity. The biochemical mechanisms of 2,4-DCP induced liver injury remain unknown. The present study showed that 2,4-DCP is chemically reactive and spontaneously reacts with GSH and bovine serum albumin to form GSH conjugates and BSA adducts. The observed conjugation/adduction apparently involved the addition of GSH and departure of chloride via the ipso substitution pathway. Two biliary GSH conjugates and one urinary N-acetyl cysteine conjugate were observed in rats given 2,4-DCP. The N-acetyl cysteine conjugate was chemically synthesized and characterized by mass spectrometry and NMR. As expected, 2,4-DCP was found to modify hepatic protein at cysteine residues in vivo by the same chemistry. The observed protein adduction reached its peak at 15 min and revealed dose dependency. The new findings allowed us to better understand the mechanisms of the toxic action of 2,4-DCP.

CAS / MDL: 120-83-2
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SCIENCE OF THE TOTAL ENVIRONMENT · 2020 · IF 6.551

Reducing phenanthrene uptake and translocation, and accumulation in the seeds by overexpressing OsNRT2.3b in rice

Xiaowen Wang,Ajay Jain,Xu Huang,Xiaoxia Lan,Li Xu,Gengmao Zhao,Xin Cong,Zhantian Zhang,Xiaorong Fan,Feng Hu

The uptake and accumulation of polycyclic aromatic hydrocarbons (PAHs) in crops have gained much attention due to their toxicity to humans. Nitrogen (N) is an essential element for plant growth and has also been implicated in the acquisition and acropetal translocation of PAHs. OsNRT2 . 3b encodes a nitrate (NO 3 − ) transporter that is involved in the acquisition and mobilization of N in rice. Here, we investigated whether overexpression of OsNRT2 . 3b would exert any mitigating influence on the uptake and translocation of phenanthrene (Phe, a model PAH) in transgenic rice ( Oryza sativa ). The wild-type seedlings exhibited a reduction in plant height, primary root length, and shoot biomass when grown hydroponically in a medium supplemented with Phe. Acquisition of Phe by the roots and its subsequent translocation to shoots increased concomitantly with an increase in Phe concentration in the medium and duration of the treatment. OsNRT2 . 3b -overexpressing lines (Ox-6 and Ox-8) were generated independently. Compared with the wild-type, the concentration of Phe in Ox-6 and Ox-8 were significantly lower in the roots (47%–54%) and shoots (22%–31%) grown hydroponically with Phe (1 mg/L). Further, the wild-type and Ox lines were grown to maturity in a pot soil under Phe conditions and the concentrations of Phe and total N were assayed in the culms and flag leaves. Compared with the wild-type, in Ox lines the concentration of total N significantly increased in the culms (288%–366%) and flag leaves (12%–25%), while that of Phe significantly reduced in the culms (25%–28%) and flag leaves (18%–21%). The results revealed an antagonistic correlation between the concentration of total N and Phe. The concentration of Phe was also significantly lower (29%–38%) in the seeds of Ox lines than the wild-type. The study highlighted the efficacy of overexpressing OsNRT2 . 3b in mitigating the Phe toxicity by attenuating its acquisition, mobilization, and allocation to the seeds.

CAS / MDL: 85-01-8
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