作者机构：
[Zhao, Wei; Fu, Chao; Hu, Rong; Hu, R; Yin, Yuli; Yin, YL] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Tang, Ben Zhong] Chinese Univ Hong Kong, Shenzhen Inst Aggregate Sci & Technol, Sch Sci & Engn, Shenzhen CUHK Shenzhen, Shenzhen 518172, Guangdong, Peoples R China.;[Yan, Caihong] Univ South China, Affiliated Hosp 2, Hengyang Med Sch, Hengyang 421001, Hunan, Peoples R China.;[Zhou, Yizhao] Hunan Normal Univ, Hunan Prov Peoples Hosp, Affiliated Hosp 1, Dept Orthoped, Changsha 410005, Peoples R China.;[Gao, Hanyi] Univ South China, Affiliated Hosp 7, Hunan Prov Vet Adm Hosp, Hengyang Med Sch, Hengyang 421001, Hunan, Peoples R China.
通讯机构：
[Tang, BZ ] C;[Hu, R ; Yin, YL] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Chinese Univ Hong Kong, Shenzhen Inst Aggregate Sci & Technol, Sch Sci & Engn, Shenzhen CUHK Shenzhen, Shenzhen 518172, Guangdong, Peoples R China.
摘要：
Ultrasound-triggered sonodynamic therapy (SDT) presents growing promise in deep-seated or unresectable tumor inhibition because of the perfect tissue penetration ability. However, its therapeutic efficacy is always restricted by the limited reactive oxygen species (ROS) generation ability of sonosensitizers. In this work, based on molecular engineering, we have fabricated aggregation-induced emission (AIE)-active organic sonosensitizers bearing efficient ROS generation with US irradiation for tumor treatment. By enhancing the intramolecular charge transfer strength and intermolecular interaction, an organic sonosensitizer with reduced energy gap and AIE features was developed, presenting enhanced oxygen sensitization behavior to produce ROS upon an ultrasound trigger compared to Ce 6. Moreover, the excellent mitochondrial enrichment of the obtained sonosensitizer enables effective tumor cell eradication via apoptotic and ferroptosis pathways with ultrasound irradiation. The efficient in vivo tumor inhibition was also achieved based on the SDT approach. Therefore, this work provided a generalized and promising strategy for deep-seated or unresectable tumor treatment in the clinic. An organic sonosensitizer bearing a low-energy gap and aggregation-induced emission features was constructed for efficient tumor therapy based on ultrasound irradiation triggered-ROS generation.
摘要：
A branched core-shell nanosphere composed of an anatase TiO 2 (a-TiO 2 ) core and a TiO 2 nanobranch shell with gradient-doped N (a-TiO 2 @N-TiO 2 ) is synthesized by a simple in situ doping method, in which mixed crystal anatase-rutile TiO 2 (ar-TiO 2 ) nanosphere is first prepared by oxidizing Ti using H 2 O 2 , and then is etched by NH 3 middotH 2 O to form (NH 4 ) 2 TiO 3 nanobranches, which is converted into a-TiO 2 @N-TiO 2 following an ambient annealing process. The diameter of a-TiO 2 core is similar to 500 nm, and the thickness of NTiO 2 branched shell is similar to 100 nm with gradually increased N concentration from the bottom to the edge. Ultra-thin amorphous coating layers on the branches are also observed. The morphology of the composites could be further tuned by the amount of NH 3 middotH 2 O, and its effect on the photocatalytic performance is also investigated. The optimized a-TiO 2 @N-TiO 2 shows an outstanding hydrogen evolution rate of 308.1 mu mol g -1 h -1 under air mass (AM) 1.5 illumination, and also exhibits highly active in photocatalytic degradation of various refractory organic pollutants, including organic dyes, phenols, antibiotics, and personal care products, with removal ratios higher than 96% after 2 h operation. This can be due to the gradient-doped N-TiO 2 nanobranches, which not only provide bending band structure and defect level derived from the N impurities and O vacancies, resulting the formation of n-n + heterojunctions to improve the charge separation, but also enhance the charge transfer at the liquid-solid interface due to the numerous nanobranches and amorphous coating layers.(c) 2023 Published by Elsevier B.V. on behalf of Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
摘要：
The separation of thorium and uranium is an important guarantee for the fuel cycle of thorium-based molten salt reactors. Benzoxazole-based ligands have a wide range of applications and are also potential ligands for actinide separation. In this work, density functional theory (DFT) calculations were used to study the intrinsic properties of two ligands, 2,6-bis(benzo[d]oxazole-2-yl)pyridine (ligand a) and 1-(6-(4-acetylbenzo[d]oxazol-2-yl)pyridin2-yl)ethan-1-one (ligand b), revealing the structural characteristics and complexation behavior of their complexes with Th4+/UO5+. Quantum theory of atoms in molecules (QTAIM) and extended transition state - natural orbitals for chemical valence (ETS-NOCV) analyses show that the ligands form classical coordination bonds with Th4+/UO5+, with M- Noz bonds stronger than M- Npy bonds and partial electron acceptance by carbonyl O. The thermodynamic properties were used to evaluate the separation performance of these ligands for Th4+/UO5+ in four solvents (water, 1-hexanol, n-octanol and n-dodecane), with La more suitable for back extraction process and Lb having stronger binding with Th4+/UO5+. This work provides valuable theoretical insights into Th4+/UO5+ separation based on benzoxazole.
摘要：
A simple, practical and eco-friendly visible light-induced alkylation of N-sulfonyl ketamine under metal-,additive-, external photocatalyst-free conditions was developed. This photocatalytic method utilized low cost and abundant alkanes as the atom economy alkyl sources with H2O2 as the environmentally beneficial oxidant, allowing for the efficient construction of diverse valuable 4-alkylated sulfonyl ketamines.The N-sulfonyl ketamine played a dual role of reactant and photocatalyst, thus simplifying the reaction system.
摘要：
The first example of TBAI/H2O cooperative electrocatalytic coupling-annulation of quinoxalin-2(1H)-ones with N-arylglycines was developed. A broad range of tetrahydroimidazo[1,5-a]quinoxalin-4(5H)-ones were obtained in good to excellent yields with exclusive chemoselectivities and excellent regioselectivities. The H-hydrogen bond served as a key factor for the electrocatalytic production of aminomethyl radical at lower oxidative potential.
摘要：
The development of functional materials for tumor immunogenicity enhancement is desirable for overcoming the low therapeutic efficiency and easy metastasis during tumor treatments. Herein, the thermoresponsive nanoparticles composed of photothermal agent (PTA) and click reactive reagent are developed for enhanced immunotherapy application. A Ni-bis(dithiolene)-containing PTA with intense near-infrared absorption and efficient photothermal conversion is developed for thermoresponsive nanoparticles construction. The generated heat by encapsulated PTA further induces the phase transition of thermoresponsive nanoparticles with the release of chemotherapy reagent to react with the amino groups on functional proteins, realizing PTT and chemotherapy simultaneously. Moreover, the immunogenic cell death (ICD) of cancer cells evoked by PTT could be further enhanced by the released reactive reagent. As a result, the synergistic effect of photothermal treatment and reaction-mediated chemotherapy can suppress the growth of a primary tumor, and the evoked ICD could further activate the immune response with the suppression of a distant tumor. This synergistic treatment strategy provides a reliable and promising approach for cancer immunotherapy in clinic.
摘要：
Existing technologies used to detect monosodium urate (MSU) crystals for gout diagnosis are not ideal due to their low sensitivity and complexity of operation. The purpose of this study was to explore whether aggregation-induced emission luminogens (AIEgens) can be used for highly specific imaging of MSU crystals to assist in the diagnosis of gout. First, we developed a series of luminogens (i.e., tetraphenyl ethylene (TPE)-NH2, TPE-2NH2, TPE-4NH2, TPE-COOH, TPE-2COOH, TPE-4COOH, and TPE-Ketoalkyne), each of which was then evenly mixed with MSU crystals. Next, optimal fluorescence imaging of each of the luminogens was characterized by a confocal laser scanning microscope (CLSM). This approach was used for imaging standard samples of MSU, hydroxyapatite (HAP) crystals, and mixed samples with 1:1 mass ratio of MSU/HAP. We also imaged samples from mouse models of acute gouty arthritis, HAP deposition disease, and comorbidities of interest. Subsequently, CLSM imaging results were compared with those of compensated polarized light microscopy, and we assessed the biosafety of TPE-Ketoalkyne in the RAW264.7 cell line. Finally, CLSM time series and three-dimensional imaging were performed on MSU crystal samples from human gouty synovial fluid and tophi. As a promising candidate for MSU crystal labeling, TPE-Ketoalkyne was found to detect MSU crystals accurately and rapidly in standard samples, animal samples, and human samples, and could precisely distinguish gout from HAP deposition disease. This work demonstrates that TPE-Ketoalkyne is suitable for highly specific and timely imaging of MSU crystals in gouty arthritis and may facilitate future research on MSU crystal-related diseases.
期刊：
International Journal of Molecular Sciences,2023年24(3):2395- ISSN：1422-0067
通讯作者：
Jiakun Xu<&wdkj&>Osami Shoji
作者机构：
[Li, Yanqing] Shanghai Ocean Univ, Coll Food Sci & Technol, Shanghai 201306, Peoples R China.;[Li, Yanqing; Wang, Fang; Wang, Jinghan; Xu, Jiakun] Chinese Acad Fishery Sci, Yellow Sea Fisheries Res Inst, Key Lab Sustainable Dev Polar Fisheries, Lab Marine Drugs & Byprod,Minist Agr & Rural Affai, Qingdao 266071, Peoples R China.;[Lin, Yingwu] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Wang, Jinghan] Ocean Univ China, Coll Food Sci & Engn, Qingdao 266003, Peoples R China.;[Shoji, Osami] Nagoya Univ, Grad Sch Sci, Dept Chem, Furo Cho,Chikusa Ku, Nagoya 4648602, Japan.
通讯机构：
[Jiakun Xu; Osami Shoji] A;Authors to whom correspondence should be addressed.<&wdkj&>Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan<&wdkj&>Authors to whom correspondence should be addressed.<&wdkj&>Key Lab of Sustainable Development of Polar Fisheries, Ministry of Agriculture and Rural Affairs, Yellow Sea Fisheries Research Institute, Chinese Academy of Fishery Sciences, Lab for Marine Drugs and Byproducts of Pilot National Lab for Marine Science and Technology, Qingdao 266071, China
关键词：
cytochromes P450BM3;dual-functional small molecule co-catalysis;hydroxylated indole;indigo;directed evolution
摘要：
With the increasing demand for blue dyes, it is of vital importance to develop a green and efficient biocatalyst to produce indigo. This study constructed a hydrogen peroxide-dependent catalytic system for the direct conversion of indole to indigo using P450BM3 with the assistance of dual-functional small molecules (DFSM). The arrangements of amino acids at 78, 87, and 268 positions influenced the catalytic activity. F87G/T268V mutant gave the highest catalytic activity with k(cat) of 1402 min(-1) and with a yield of 73%. F87A/T268V mutant was found to produce the indigo product with chemoselectivity as high as 80%. Moreover, F87G/T268A mutant was found to efficiently catalyze indole oxidation with higher activity (k(cat)/K-m = 1388 mM(-1) min(-1)) than other enzymes, such as the NADPH-dependent P450BM3 (2.4-fold), the Ngb (32-fold) and the Mb (117-fold). Computer simulation results indicate that the arrangements of amino acid residues in the active site can significantly affect the catalytic activity of the protein. The DFSM-facilitated P450BM3 peroxygenase system provides an alternative, simple approach for a key step in the bioproduction of indigo.
通讯机构：
[Yunmei Liu] I;Institute of Pharmacy & Pharmacology, Hunan Province Cooperative Innovation Center for Molecular Target New Drug Study, University of South China, Hengyang City, Hunan Province 421001, PR China<&wdkj&>Hunan Provincial Key Laboratory of Tumor Microenvironment Responsive Drug Research, 28 Western Changshen Road, Hengyang City, Hunan Province 421001, PR China
摘要：
Photodynamic therapy is a promising novel tumor treatment method. In this study, novel porphyrin-chrysin photosensitizer derivatives were synthesized. Most of the compounds showed antitumor activity against human cervical cancer HeLa cells and human lung cancer A549 cells, among which compound 4c had the best photodynamic therapy effect on HeLa cells and A549 cells, with IC(50) values of 6.26μM and 23.37μM, respectively. Free-base porphyrin-chrysin derivatives bind to DNA through surface self-stacking, and zinc metalloporphyrin-chrysin derivatives bind to ct-DNA through intercalation. Notably, the tightness of compound binding to ct-DNA was positively correlated with its antitumor activity. What's more, three-dimensional quantitative conformation studies have shown that increasing the positive charge of the porphyrin ring and introducing a strong electron-withdrawing group at the meso position of the porphyrin ring at the para-position of the benzene ring or reducing the space volume of the compound can enhance the antitumor activity.
期刊：
JOURNAL OF ORGANIC CHEMISTRY,2023年88(21):15282-15287 ISSN：0022-3263
通讯作者：
Wang, Huamin;Lin, YW
作者机构：
[Wang, Huamin; Niu, Wenjing; He, Yongjun; Wei, Yibo; Li, Xianxian; Lin, Ying-Wu; Wang, HM] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Lin, Ying-Wu] Univ South China, Hengyang Med Coll, Hengyang 421001, Peoples R China.;[Lin, Ying-Wu] Univ South China, Med Sch, Lab Prot Struct & Funct, Hengyang 421001, Peoples R China.
通讯机构：
[Lin, YW ; Wang, HM] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Univ South China, Hengyang Med Coll, Hengyang 421001, Peoples R China.;Univ South China, Med Sch, Lab Prot Struct & Funct, Hengyang 421001, Peoples R China.
摘要：
We report herein a general and effective system achieving cyclization of β-trifluoromethyl enones with amidines in the presence of 1,3-diiodo-5,5-dimethylhydantoin (DIH), which affords a range of trifluoromethylated 2-imidazolines in synthetically useful yields with good diastereoselectivities (up to 95% yield, up to 98:2 dr) and good functional group tolerance. Furthermore, the one-pot synthesis of trifluoromethylated imidazoles via sequential cyclization and oxidation is demonstrated. More significantly, the reaction mechanism was verified by ESI-MS studies of possible intermediates, and a reasonable reaction mechanism was proposed.
通讯机构：
[Chuan-Wan Wei; Ying-Wu Lin] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China<&wdkj&>Key Lab of Protein Structure and Function of Universities in Hunan Province, University of South China, Hengyang 421001, China<&wdkj&>School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
摘要：
In this study, we have synthesized a facile tyrosine derivative based compound (2-QY), which can act both as a gelator and a reducing agent. 2-QY can assemble to form a functional metallohydrogel (2-QY-Au) in the presence of HAuCl4 under mild conditions (room temperature, aqueous solution, and simple sonication treatment). Au nanoparticles (Au NPs) can be in situ formed and dispersed uniformly in the gel system, which did not require an external reducing agent and a stabilizing agent. The obtained 2-QY-Au NP@metallohydrogel can be used as a catalyst to degrade a variety of dyes, such as methyl orange, methyl green, reactive black 5, reactive orange 16, and p-nitrophenol. In particular, it exhibits excellent catalytic activity towards degradation of methylene blue in the presence of NaBH4, with a k(app) value (13.23 +/- 0.21 s(-1)) higher than those of most of the reported catalysts in the literature. Moreover, 2-QY-Au NPs have good biocompatibility and exhibit antibacterial activity against E. coli and B. subtilis. Therefore, the 2-QY-Au NP@metallohydrogel could be used as an effective catalyst for the degradation of pollution containing organic dyes, as well as for potential applications in the biomedical field.
通讯机构：
[Wei-Min He] S;School of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
摘要：
A simple and practical electron donor–acceptor (EDA) strategy to synthesize various 3-alkylated coumarins from easily available coumarins and naturally abundant carboxylic acids under photocatalyst-, oxidant-, and additive-free and mild conditions is reported. Using Na2S as the catalytic electron donor, a series of primary, secondary, and tertiary carbon radicals can be efficiently generated, and the EDA complex can be regenerated without an alkaline additive.
摘要：
Here we report a strategy for the facile assembly of fused 3-trifluoromethyl-1,2,4-triazoles, which are difficult to synthesize using traditional strategies, in 50-96% yields through a triethylamine-promoted intermolecular [3 + 2] cycloaddition pathway. This protocol features high efficiency, good functional group tolerance, mild conditions, and easy operation. Furthermore, a gram-scale reaction and product derivatizations were carried out smoothly to illustrate the practicability of this method.
通讯机构：
[Wei, CW; Lin, YW ] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;Univ South China, Key Lab Prot Struct & Funct Univ Hunan Prov, Hengyang 421001, Peoples R China.
摘要：
The construction of smart materials, especially white light emitting (WLE) hydrogels with multi-stimuli responsive properties, has received widespread attention from researchers. In this study, a WLE hydrogel was obtained by the in situ doping of Eu3+ and Tb3+ into a blue emission low molecular weight gelator (MPF). Remarkably, the prepared WLE hydrogel possessed excellent stimuli responsiveness to pH, temperature and chemicals, and could be used as a soft thermometer and a selective sensor for Cu2+. The correlated color temperature of the WLE hydrogel was calculated to be 5063 K, suggesting a potential application in cool white light. Moreover, a series of metallohydrogels with different colors were obtained by modulating the ratio of MPF, Eu3+ and Tb3+ or changing the excitation wavelength, which was an excellent candidate to construct soft materials of a full-color system. Additionally, the WLE hydrogel could be used for constructing anti-counterfeiting materials. Therefore, this study provides a new approach for preparing smart WLE hydrogels with multiple functions.
期刊：
International Journal of Biological Macromolecules,2023年253(Pt 4):127016 ISSN：0141-8130
通讯作者：
Liu, Jing-Jing;Lin, YW
作者机构：
[Liu, Jing-Jing; Lin, Ying-Wu; Liu, JJ; Wang, Zhan-Yi; Jiang, Bin-Bin] Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.;[Gao, Shu-Qin; Lin, Ying-Wu] Univ South China, Lab Prot Struct & Funct, Hengyang 421001, Peoples R China.;[Liu, Jing-Jing] Hunan Normal Univ, Key Lab Chem Biol & Tradit Chinese Med Res, Minist Educ, Changsha 410081, Hunan, Peoples R China.
通讯机构：
[Lin, YW ; Liu, JJ] U;Univ South China, Sch Chem & Chem Engn, Hengyang 421001, Peoples R China.
关键词：
Glycation sites;Human myoglobin;Thymoquinone
摘要：
Nonenzymatic glycation and the subsequent accumulation of advanced glycation end-products (AGEs) in proteins are factors underlying long-term pathogenesis in diabetes. The study of protein glycation is crucial for elucidating their relationship with diabetes mellitus and related disorders. This study explores the interaction between d-ribose and human myoglobin (HMb), as well as the protective effect of thymoquinone (TQ) on glycation. A time-dependent in-vitro glycation study was performed to investigate the mechanism of d-ribose-induced structural interference of HMb in the absence and presence of TQ. Spectroscopic and proteomic analysis indicated that the presence of TQ significantly reduced the total amount of AGEs while maintaining structural characteristics of HMb. 14 glycated sites on HMb were further identified via liquid chromatography-tandem mass spectrometry (LC-MS/MS) after incubation with d-ribose for 12h, predominantly interacting with lysine residues. TQ was found to disrupt this interaction, reducing the glycated sites from 14 to 12 sites and the percentage of glycated peptides from 26.50% to 12.97%. Additionally, there was a significant decrease in the degree of glycation at the same sites. In summary, our findings suggest that TQ has the potential to act as an anti-glycation agent and provide a comprehensive understanding underlying the inhibition mechanism of glycation.
摘要：
The development of novel hydrogels with high biocompatibility is a vital and active topic of study. Here, we used a facile polycondensation approach to develop multifunctional poly (ether sulfone) (PES)-based hydrogels with diverse functional groups (−SO3Na, −COONa, −OH, and − NH2), as indicated by flourier transformed infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The chemical structure of the PES-based hydrogels could be modulated by monomer selection and post-treatment, resulting in a wide range of biomolecule-mimic structures and matching biological functions. In the current investigation, heparin-mimic PES-based hydrogels demonstrated good hemocompatibility, as evident by reduced platelet adhesion and activation, delayed clotting times, suppressed blood-related complement activations, and CD11b expression on leukocytes in the blood. Moreover, hyper-sulfonated PES-based hydrogels showed exceptional cytocompatibility with human umbilical vein endothelial cells (HUVECs) and considerable antiproliferative activity against human umbilical artery smooth muscle cells (HUASMCs), as revealed by cell proliferation and cytotoxicity assay findings. Finally, chitosan-mimic PES-based hydrogels had marked anti-microbial properties against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus), as shown by the number of colonies. The aforementioned bio-functions were attributed to the formation of various chemical structures on the surfaces of PES-based hydrogels. The distinctive PES-based hydrogels synthesized in this work would be of high utility not only in the synthesis of biomedical hydrogels but also in the rational design of various types of biocompatible materials.
通讯机构：
[Tao Gong; HongQing Wang] C;College of Chemistry and Chemical Engineering, University of South China, Hengyang 421001, China
关键词：
wearable electronics;MXene;adhesive hydrogels;conductive nanocomposites;pressure and strain sensors
摘要：
To address the shortcomings of traditional filler-based wearable hydrogels, a new type of nanochannel hydrogel sensor is fabricated in this work through a combination of the unique structure of electrospun fiber textile and the properties of a double network hydrogel. Unlike the traditional Ti3C2Tx MXene-based hydrogels, the continuously distributed Ti3C2Tx MXene in the nanochannels of the hydrogel forms a tightly interconnected structure similar to the neuron network. As a result, they have more free space to flip and perform micromovements, which allows one to significantly increase the electrical conductivity and sensitivity of the hydrogel. According to the findings, the Ti3C2Tx MXene nanochannel hydrogel has excellent mechanical properties as well as self-adhesion and antifreezing characteristics. The hydrogel sensor successfully detects different human motions and physiological signals (e.g., low pulse signals) with high stability and sensitivity. Therefore, the proposed Ti3C2Tx MXene-based hydrogel with a unique structure and properties is very promising in the field of flexible wearable devices.
摘要：
Additive strategy has been regarded as a promising approach for fabricating electronic copper patterns, since it has predominance over traditional lithography technology (subtractive strategy) in process simplicity, material economizing, and environmental protection. At present, the key challenge for additive strategy is how to precisely fabricate high-quality copper patterns adhering tightly to substrates, by facile and universally applicable process. Here a novel additive copper patterning process is explored by adopting a homogeneous Ag-based catalyst ink. The catalyst ink can be facilely patterned and tightly attached on various substrates by different patterning techniques, without any pre- and post-treatment procedures. In the catalyst ink formula, epoxy matrix contributes high adhesiveness and fixes ink form, valen Schiff base acts as a medium anchoring Ag catalyst, ethanol serves as both reductant and diluent, and polyethylene glycol improves hydrophility. The copper coating, forming on the catalyst layer by further electroless copper deposition process, exhibits compact structure and high electrical conductivity comparable to bulk copper. Moreover, the copper coating can be partially inserted into substrate body by porous surface design for substrates, thus achieving strong adhesion and high flexibility. This research contributes to the progress of next-generation copper patterning techniques.
