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Synthesis and characterization of iron clusters with an icosahedral [Fe@Fe12]16+ Core

National Science Review 2024年第4期11卷 123-129页

作者： Gan Xu yun-shu cui Xue-Lian Jiang Cong-Qiao Xu Jun Li Xu-Dong Chen Jiangsu Collaborative Innovation Center of Biomedical Functional Materials and Jiangsu Key Laboratory of New Power Batteries School of Chemistry and Materials Science Nanjing Normal University Department of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry Southern University of Science and Technology Department of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education Tsinghua University State Key Laboratory of Coordination Chemistry Nanjing University

Iron-metal clusters are crucial in a variety of critical biological and material systems,including metalloenzymes,catalysts,and magnetic storage devices.However,a synthetic high-nuclear iron cluster has been absent due to the extreme difficulty in stabilizing species with direct iron-iron bonding.In this work,we have synthesized,crystallized,and characterized a（Tp*）4W4S12(Fe@Fe12) cluster(Tp*=tris（3,5-dimethyl-1-pyrazolyl）borate（1-）),which features a rare trideca-nuclear,icosahedral[Fe@Fe12] cluster core with direct multicenter iron-iron bonding between the interstitial iron（Fei） and peripheral irons（Fep）,as well as Fep…Fepferromagnetic coupling.Quantum chemistry studies reveal that the stability of the cluster arises from the 18-electron shell-closing of the [Fe@Fe12]16+core,assisted by its bonding interactions with the peripheral tridentate [（Tp*）WS3]4-ligands which possess both S→Fe donation and spin-polarized Fe-Wσ bonds.The ground-state electron spin is theoretically predicted to be S=32/2 for the cluster.The existence of low oxidation-state（OS～+1.23） iron in this compound may find interesting applications in magnetic storage,spintronics,redox chemistry,and cluster catalysis.

关键词： Fe13 cluster iron-sulfur cluster low-valence iron iron−iron bond high spin complex

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Mechanistic Studies on Programmed C—O/C—H Activation with Valence-Adjusted Ti-Complexes

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Chinese Journal of Chemistry 2023年第9期41卷 1015-1022页

作者： Si-Jun Xie yun-shu cui Yi-Fei Huang Feng Liu Dan-Dan Zhai Zhang-Jie Shi Department of Chemistry Fudan UniversityShanghai 200433ChinaDepartment of ChemistryFudan UniversityShanghai 200433China State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic ChemistryChinese Academy of SciencesShanghai 200032China

Two-electron reduction of[N_(2)NBn]Ti^(Ⅳ)Cl2(3)gave a highly reactive[N_(2)N]Ti^(Ⅱ)species,which underwent C—O bond activation of THF(tetrahydrofuran)to generate[N2NBn]Ti^(Ⅳ)[O(CH2)4](4)through oxidative addition.The resulted Ti^(Ⅳ)-Csp^(3)bond in oxametallacyclo-hexane was tantamount to the elaborately-designed Ti-alkyl complexes,competent to activate intramolecular Csp^(2)-H bond,forming ortho-cyclometalated complex[N_(2)NCH_(2)C_(6)H_(4)]Ti^(Ⅳ)(O^(n)Bu)(5).Key intermediates were isolated and fully characterized by X-ray crystal-lography.Mechanistic studies revealed that the oxidative addition of C-O bond took place at Ti^(Ⅱ)-center via a radical intermediate,while a Csp^(2)-H bond activation proceeded byσ-bond metathesis with a kitelike four-centered Ti^(Ⅳ)-transition state.

关键词： Reaction mechanisms Valence-adjusted Ti-complexes C—O oxidative addition C—H activation Metathesis

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High-resolution remote thermometry based on Bi3+-doped 0D zinc halide hybrids

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Science China Chemistry 2024年第8期67卷 2599-2605页

作者： cui-Mi Shi shu-Hua Xue Jin-yun Wang Liang-Jin Xu Zhong-Ning Chen State Key Laboratory of Structural Chemistry Fujian Institute of Research on the Structure of Matter Chinese Academy of Sciences Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China University of Chinese Academy of Sciences

Developing highly sensitive optical thermometers is of great significance due to their capability to enable remote and non-contact temperature measurements, rendering them highly applicable in diverse and harsh environments. Herein we report a temperature-dependent phosphor of 0D metal halide hybrid by incorporating Bi3+into the（MePPh3）2ZnCl4matrix. Through Bi3+doping,the initially non-luminescent（MePPh3）2ZnCl4matrix exhibits a deep-blue emission centered at 453 nm, with a photoluminescence quantum yield（PLQY） of 5.71% and a Stokes shift of 75 nm at room temperature. Experimental characterization demonstrates that exciton-like luminescence of Bi3+is mainly responsible for the blue emission. Single crystals of Bi3+-doped（MePPh3）2ZnCl4show an unusual correlation between photoluminescence（PL） lifetime and temperature. Particularly, the dependence of luminescence lifetime on temperature is most remarkable in the temperature range of 80 to 100 K with an exceptional sensitivity up to 0.09 K-1, representing one of the best levels for thermometry based on PL decay lifetime. Our work not only provides a viable strategy for designing a novel, environmentally friendly, and stable blue emitter, but also paves the way for precise thermometric application at low temperature.

关键词： Bi3+ doping blue emission lead-free hybrids temperature sensing

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Granulomatous mastitis in a 50-year-old male:A case report and review of literature

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World Journal of Clinical Cases 2024年第2期12卷 451-459页

作者： Le-Yin cui Chen-Ping Sun yun-Yuan Li Sheng Liu Department of Breast Surgery Longhua Hospital Shanghai University of Traditional Chinese MedicineShanghai 200032China Department of Pathology Longhua Hospital Shanghai University of Traditional Chinese MedicineShanghai 200032China Graduate School Shanghai University of Traditional Chinese MedicineShanghai 201203China

BACKGROUND Granulomatous mastitis(GM)an inflammatory disease of the breast that usually affects women of childbearing age,occurs very rarely in males.CASE SUMMARY We present a case study of a 50-year-old male patient with GM.The patient developed a breast lump following the cleaning of a previously embedded dirtfilled nipple.While an initial improvement was noted with antibiotic therapy,a recurrence occurred a year later,showing resistance to the previously effective antibiotics.Subsequently,the lesion was excised.The histopathological examination confirmed the diagnosis of GM.CONCLUSION GM should be considered a possible diagnosis of male breast masses.

关键词： Granulomatous mastitis Male Pathology Differential diagnosis Case report

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High-resolution remote thermometry based on Bi-doped 0D zinc halide hybrids

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Science China Chemistry 2024年

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Accurate diagnosis of severe coronary stenosis based on resting magnetocardiography: a prospective, single-center, cross-sectional analysis

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Journal of Geriatric Cardiology 2024年第4期21卷 407-420页

作者： Jian-Guo cui Feng TIAN Yu-Hao MIAO Qin-Hua JIN Ya-Jun SHI Li LI Meng-Jun SHEN Xiao-Ming XIE shu-Lin ZHANG yun-Dai CHEN School of Medicine Nankai UniversityTianjinChina Senior Department of Cardiology the Sixth Medical CenterChinese PLA General HospitalBeijingChina Joint Laboratory of Bioimaging Technology and Applications SAS-SIM-IT&MEDIShanghaiChina Shanghai Institute of Microsystem and Information Technology Chinese Academy of SciencesShanghaiChina

OBJECTIVE To evalu ate the role of resting magnetocardiography in identifying seve re coronary artery stenosis in patients with suspected coronary artery disease.METHODS A total of 513 patients with angina symptoms were included and divided into two groups based on the extent of coronary artery disease determined by angiography:the non-severe coronary stenusis group(<70% stenosis) and the severe coronary stenosis group(≥70% stenosis).The diagnostic model was constructed using magnetic field map(MFM) parameters,either individually or in combination with clinical indicators.The performance of the models was evaluated using receiver operating characteristic curves,accuracy,sensitivity,specificity,positive predictive value(PPV) and ne gative predictive value(NPV).Calibration plots and decision curve analysis were performed to investigate the clinical utility and performance of the models,respectively.RESULTS In the severe coronary stenosis group,QR_MCTDd,S_MDp,and TT_(MA)C_(50) were significantly higher than those in the non-severe coronary stenosis group(10,46±10.66 vs,5.11±6.07,P <0.001;7.2±8.64 vs.4.68±6.95,P=0.003;0.32±57.29 vs.0.26±57.29,P <0.001).While,QR_MV_(amp),R_(MA),and T_(MA) in the severe coronary stenosis group were lower(0.23±0.16 vs.0.28±0.16,P<0.001;55.06±48.68 vs.59.24±53.01,P<0.001;51.67±39.32 vs. 60.45±51.33,P <0.001).Seven MFM parameters were integrated into the model,resulting in an area under the curve of 0.810(95% CI:0.765-0.855).The sensitivity,specificity,PPV,NPV,and accurecy were 71.7%,80.4%,93.3%,42.8 %,and 73.5%;respectevely.The combined model exhibited an area under the curve of 0.845(95% CI:0.798-0.892).The sensitivity,specificity,PPV,NPV,and accuracy were 84.3%,73.8%,92.6%,54.6%,and 82.1%;respectively.Calibration curves demonstrate d excellent agreement between the nomogram prediction and actual observation.The decision curve analysis showed that the c ombine d model provided greater net benefit compared to the magnetocardingraphy model.CONCLUSIONS The novel quantitative MFM parameters

关键词： coronary stenosis specificity

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Chromosome-level genome assembly of the Asian citrus psyllid,Diaphorina citri

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Insect Science 2024年第1期31卷 13-27页

作者： shuang Lei Shi-Jiang Yu Qi Pan Li-Li Ding Si-Chen Li Lu-Yan Cheng shu-Qi Wang Bing-Hai Lou Jun He cui-yun Lei Lin Cong Hao-Qiang Liu Xue-Feng Wang Chun Ran Citrus Research Institute Southwest University/Chinese Academy of Agricultural SciencesNational Engineering Research Center for CitrusChongqingChina

Diaphorina citri is a global citrus pest.As a vector insect,it can transmit the causative agents of citrus huanglongbing,causing irreversible losses to the citrus industry.The acquisition of genomic information can provide a molecular genetic basis for effective control of D.citri.Here,the DNBSEQ™,Oxford Nanopore Technologies,and Hi-C technologies are applied to generate a high-quality chromosome-level genome of D.citri.The genome size of D.citri was 523.78 Mb with a scaffold N50 of 47.05 Mb distributed on 13 chromosomes.A total of 250.64 Mb(47.85%)repeat sequences and 24048 protein-coding genes were predicted.Genome resequencing of female and male individuals indicated that the sex chromosome system of D.citri is XO.Phylogenetic analysis demonstrated that D.citri and Pachypsylla venusta,which separated from their most recent common ancestor about 336.62 million years ago,were the most closely related.Additionally,we identified genes potentially involved in detoxification metabolism,pathogen transmission,and honeydew secretion for further investigation.The high-quality genome provides an important reference for developing effective management strategies of D.citri.

关键词： Asian citrus psyllid chromosome-level genome comparative genomics cytochrome P450 detoxification Huanglongbing

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Ketogenic diet therapy in children with epilepsy caused by SLC2A1 mutations:a single-center single-arm retrospective study

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World Journal of Pediatrics 2024年第5期20卷 517-524页

作者： Ying-Yan Wang yun-Qing Zhou Li-Juan Luo cui-Jin Wang Nan Shen Hao Li Ji-Wen Wang Department of Neurology Shanghai Children’s Medical CenterSchool of MedicineShanghai Jiao Tong UniversityShanghaiChina Department of Infectious Diseases Shanghai Children’s Medical CenterSchool of MedicineShanghai Jiao Tong UniversityShanghaiChina Clinical Research Ward Clinical Research CenterShanghai Children’s Medical CenterSchool of MedicineShanghai Jiao Tong UniversityShanghaiChina

Background This retrospective study assessed the efficacy and safety of ketogenic diet therapies in children with epilepsy caused by SLC2A1 genetic mutations and glucose transporter type 1 deficiency syndrome.Methods Pediatric patients with epilepsy symptoms admitted to our medical center between January 2017 and October 2021 were included if they presented with an SLC2A1 genetic mutation on whole-exome sequencing.We analyzed the patients’convulsions and treatment with antiepileptic drugs.The patients were followed up at different time periods after ketogenic diet therapies.Results Six patients with SLC2A1 mutations were included in this study.The patients had seizures of different types and frequencies,and they took antiepileptic drugs to relieve their symptoms.They were then treated with a ketogenic diet for at least four months.We analyzed epilepsy control rates at 1,2,3,6,and 12 months after ketogenic diet treatment.All patients were seizure-free within a month of receiving the diet therapy.All patients were followed up for six months,three were followed up for 12 months after the treatment,and there was no recurrence of epilepsy during this period.After antiepileptic drug withdrawal,none of the patients experienced seizure relapse when receiving ketogenic diet treatment alone.No severe adverse events occurred during the therapy.Conclusions Ketogenic diet therapy is very effective and safe for the treatment of epilepsy caused by SLC2A1 mutations.Therefore,patients with glucose transporter type 1 deficiency syndrome caused by SLC2A1 mutations should begin ketogenic diet treatment as soon as possible.

关键词： Epilepsy Glucose transporter type 1 Ketogenic diet SLC2A1

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The chemical characteristics of different sodium iron ethylenediaminetetraacetate sources and their relative bioavailabilities for broilers fed with a conventional corn‑soybean meal diet

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Journal of Animal Science and Biotechnology 2024年第2期15卷 826-843页

作者： Shengchen Wang Bingxin Wu Ling Zhu Weiyun Zhang Liyang Zhang We Wu Jiaqi Wu yun Hu Tingting Li Xiaoyan cui Xugang Luo College of Animal Science and Technology Yangzhou UniversityYangzhou 225000People’s Republic of China Mineral Nutrition Research Division State Key Laboratory of Animal NutritionInstitute of Animal ScienceChinese Academy of Agricultural SciencesBeijing 100193China

Background Our previous studies demonstrated that divalent organic iron(Fe)proteinate sources with higher complexation or chelation strengths as expressed by the greater quotient of formation(Qf)values displayed higher Fe bioavailabilities for broilers.Sodium iron ethylenediaminetetraacetate(NaFeEDTA)is a trivalent organic Fe source with the strongest chelating ligand EDTA.However,the bioavailability of Fe when administered as NaFeEDTA in broilers and other agricultural animals remains untested.Herein,the chemical characteristics of 12 NaFeEDTA products were determined.Of these,one feed grade NaFeEDTA(Qf=2.07×10^(8)),one food grade NaFeEDTA(Qf=3.31×10^(8)),and one Fe proteinate with an extremely strong chelation strength(Fe-Prot ES,Qf value=8,590)were selected.Their bioavailabilities relative to Fe sulfate(FeSO_(4)·7H_(2)O)for broilers fed with a conventional corn-soybean meal diet were evaluated during d 1 to 21 by investigating the effects of the above Fe sources and added Fe levels on the growth performance,hematological indices,Fe contents,activities and gene expressions of Fe-containing enzymes in various tissues of broilers.Results NaFeEDTA sources varied greatly in their chemical characteristics.Plasma Fe concentration(PI),transferrin saturation(TS),liver Fe content,succinate dehydrogenase(SDH)activities in liver,heart,and kidney,catalase(CAT)activity in liver,and SDH mRNA expressions in liver and kidney increased linearly(P<0.05)with increasing levels of Fe supplementation.However,differences among Fe sources were detected(P<0.05)only for PI,liver Fe content,CAT activity in liver,SDH activities in heart and kidney,and SDH mRNA expressions in liver and kidney.Based on slope ratios from multiple linear regressions of the above indices on daily dietary analyzed Fe intake,the average bioavailabilities of Fe-Prot ES,feed grade NaFeEDTA,and food grade NaFeEDTA relative to the inorganic FeSO_(4)·7H_(2)O(100%)for broilers were 139%,155%,and 166%,respectively.Conclusions The bioavailabilities of organic Fe sources

关键词： Broilers Chelation strengths Fe-containing enzymes NaFeEDTA Relative bioavailabilities

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Efficient and bright broadband electroluminescence based on environmentfriendly metal halide nanoclusters

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Light(Science & Applications) 2024年第4期13卷 727-737页

作者： Dingshuo Zhang Meiyi Zhu Yifan He Qingli Cao yun Gao Hongjin Li Guochao Lu Qiaopeng cui Yongmiao Shen Haiping He Xingliang Dai Zhizhen Ye School of Materials Science and Engineering State Key Laboratory of Silicon and Advanced Semiconductor MaterialsZhejiang University310027 HangzhouChina. Wenzhou Key Laboratory of Novel Optoelectronic and Nano Materials and Engineering Research Centre of Zhejiang Province Institute of WenzhouZhejiang University325006 WenzhouChina. Wenzhou XINXINTAIJING Tech.Co.Ltd. 325006 WenzhouChina. Department of Chemistry Zhejiang Sci-Tech University310018 HangzhouChina

Broadband electroluminescence based on environment-friendly emitters is promising for healthy lighting yet remains an unprecedented challenge to progress.The copper halide-based emitters are competitive candidates for broadband emission,but their high-performance electroluminescence shows inadequate broad emission bandwidth of less than 90 nm.Here,we demonstrate efficient ultra-broadband electroluminescence from a copper halide(cui)nanocluster single emitter prepared by a one-step solution synthesis-deposition process,through dedicated design of ligands and subtle selection of solvents.The cui nanocluster exhibits high rigidity in the excitation state as well as dual-emissive modes of phosphorescence and temperature-activated delayed fluorescence,enabling the uniform cluster-composed film to show excellent stability and high photoluminescent efficiency.In consequence,ultra-broadband light-emitting diodes(LEDs)present nearly identical performance in an inert or air atmosphere without encapsulation and outstanding high-temperature operation performance,reaching an emission full width at half maximum(FWHM)of~120 nm,a peak external quantum efficiency of 13%,a record maximum luminance of~50,000 cd m^(−2),and an operating half-lifetime of 137 h at 100 cd m^(−2).The results highlight the potential of copper halide nanoclusters for next-generation healthy lighting.

关键词： halide cluster rigidity

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