Hydrogen production through hydrogen evolution reaction(HER)offers a promising solution to combat climate change by replacing fossil fuels with clean energy sources.However,the widespread adoption of efficient electro...Hydrogen production through hydrogen evolution reaction(HER)offers a promising solution to combat climate change by replacing fossil fuels with clean energy sources.However,the widespread adoption of efficient electrocatalysts,such as platinum(Pt),has been hindered by their high cost.In this study,we developed an easy-to-implement method to create ultrathin Pt nanomembranes,which catalyze HER at a cost significantly lower than commercial Pt/C and comparable to non-noble metal electrocatalysts.These Pt nanomembranes consist of highly distorted Pt nanocrystals and exhibit a heterogeneous elastic strain field,a characteristic rarely seen in conventional crystals.This unique feature results in significantly higher electrocatalytic efficiency than various forms of Pt electrocatalysts,including Pt/C,Pt foils,and numerous Pt singleatom or single-cluster catalysts.Our research offers a promising approach to develop highly efficient and cost-effective low-dimensional electrocatalysts for sustainable hydrogen production,potentially addressing the challenges posed by the climate crisis.展开更多
Antibody-drug conjugates(ADCs)are a new type of targeting antibodies that conjugate with highly toxic anticancer drugs via chemical linkers to exert high specificity and efficient killing of tumor cells,thereby attrac...Antibody-drug conjugates(ADCs)are a new type of targeting antibodies that conjugate with highly toxic anticancer drugs via chemical linkers to exert high specificity and efficient killing of tumor cells,thereby attracting considerable attention in precise oncology therapy.Cetuximab(Cet)is a typical antibody that offers the benefits of good targeting and safety for individuals with advanced and inoperable cutaneous squamous cell carcinoma(cSCC);however,its anti-tumor activity is limited to a single use.Cisplatin(CisPt)shows good curative effects;however,its adverse effects and non-tumor-targeting ability are major drawbacks.In this study,we designed and developed a new ADC based on a new cytotoxic platinum(IV)prodrug(C8Pt(IV))and Cet.The so-called antibody-platinum(IV)prodrugs conjugates,named Cet-C8Pt(IV),showed excellent tumor targeting in cSCC.Specifically,it accurately delivered C8Pt(IV)into tumor cells to exert the combined anti-tumor effect of Cet and CisPt.Herein,metabolomic analysis showed that Cet-C8Pt(IV)promoted cellular apoptosis and increased DNA damage in cSCC cells by affecting the vitamin B6 metabolic pathway in tumor cells,thereby further enhancing the tumor-killing ability and providing a new strategy for clinical cancer treatment using antibody-platinum(IV)prodrugs conjugates.展开更多
Objective:The choice of chemotherapeutic regimen for triple-negative breast cancer(TNBC)remains controversial.Homologous recombination deficiency(HRD)has attracted increasing attention in informing chemotherapy treatm...Objective:The choice of chemotherapeutic regimen for triple-negative breast cancer(TNBC)remains controversial.Homologous recombination deficiency(HRD)has attracted increasing attention in informing chemotherapy treatment.This study was aimed at investigating the feasibility of HRD as a clinically actionable biomarker for platinum-containing and platinum-free therapy.Methods:Chinese patients with TNBC who received chemotherapy between May 1,2008 and March 31,2020 were retrospectively analyzed with a customized 3D-HRD panel.HRD positivity was defined by an HRD score≥30 or deleterious BRCA1/2 mutation.A total of 386 chemotherapy-treated patients with TNBC were screened from a surgical cohort(NCT01150513)and a metastatic cohort,and 189 patients with available clinical and tumor sequencing data were included.Results:In the entire cohort,49.2%(93/189)of patients were identified as HRD positive(40 with deleterious BRCA1/2 mutations and 53 with BRCA1/2 intact with an HRD score of≥30).In the first-line metastatic setting,platinum therapy was associated with longer median progression-free survival(mPFS)than platinum-free therapy[9.1 vs.3.0 months;hazard ratio(HR),0.43;95%confidence interval 0.22–0.84;P=0.01].Among HRD-positive patients,the mPFS was significantly longer in those treated with platinum rather than platinum-free therapy(13.6 vs.2.0 months;HR,0.11;P=0.001).Among patients administered a platinum-free regimen,HRD-negative patients showed a PFS significantly superior to that of HRD-positive patients(P=0.02;treatment-biomarker P-interaction=0.001).Similar results were observed in the BRCA1/2-intact subset.In the adjuvant setting,HRD-positive patients tended to benefit more from platinum chemotherapy than from platinum-free chemotherapy(P=0.05,P-interaction=0.02).Conclusions:HRD characterization may guide decision-making regarding the use of platinum treatment in patients with TNBC in both adjuvant and metastatic settings.展开更多
目的:鉴于脓毒症的高发病率和高病死率,早期识别高风险患者并及时干预至关重要,而现有死亡风险预测模型在操作、适用性和预测长期预后等方面均存在不足。本研究旨在探讨脓毒症患者死亡的危险因素,构建近期和远期死亡风险预测模型。方法...目的:鉴于脓毒症的高发病率和高病死率,早期识别高风险患者并及时干预至关重要,而现有死亡风险预测模型在操作、适用性和预测长期预后等方面均存在不足。本研究旨在探讨脓毒症患者死亡的危险因素,构建近期和远期死亡风险预测模型。方法:从美国重症监护医学信息数据库IV(Medical Information Mart for Intensive Care-IV,MIMIC-IV)中选取符合脓毒症3.0诊断标准的人群,按7?3的比例随机分为建模组和验证组,分析患者的基线资料。采用单因素Cox回归分析和全子集回归确定脓毒症患者死亡的危险因素并筛选出构建预测模型的变量。分别用时间依赖性曲线下面积(area under the curve,AUC)、校准曲线和决策曲线评估模型的区分度、校准度和临床实用性。结果:共纳入14240例脓毒症患者,28 d和1年病死率分别为21.45%(3054例)和36.50%(5198例)。高龄、女性、高感染相关器官衰竭评分(sepsis-related organ failure assessment,SOFA)、高简明急性生理学评分(simplified acute physiology score II,SAPS II)、心率快、呼吸频率快、脓毒症休克、充血性心力衰竭、慢性阻塞性肺疾病、肝脏疾病、肾脏疾病、糖尿病、恶性肿瘤、高白细胞计数(white blood cell count,WBC)、长凝血酶原时间(prothrombin time,PT)、高血肌酐(serum creatinine,SCr)水平均为脓毒症死亡的危险因素(均P<0.05)。由PT、呼吸频率、体温、合并恶性肿瘤、合并肝脏疾病、脓毒症休克、SAPS II及年龄8个变量构建的模型,其28 d和1年生存的AUC分别为0.717(95%CI 0.710~0.724)和0.716(95%CI 0.707~0.725)。校准曲线和决策曲线表明该模型具有良好的校准度及较好的临床应用价值。结论:基于MIMIC-IV建立的脓毒症患者近期和远期死亡风险预测模型有较好的识别能力,对患者预后风险评估及干预治疗具有一定的临床参考意义。展开更多
A three-dimensional graphene-based composite was prepared by a simple one-step in-site reduced-oxide method under atmospheric pressure. The obtained hydrogel was modified with 4-amino-benzenesulfonic acid and connecte...A three-dimensional graphene-based composite was prepared by a simple one-step in-site reduced-oxide method under atmospheric pressure. The obtained hydrogel was modified with 4-amino-benzenesulfonic acid and connected with ethylenediamine, and freeze-dried into an aerogel, which was characterized. Then the surface interaction with platinum (Pt, IV) was explored. The obtained aerogel showed good adsorption for Pt (IV) at acid conditions, giving a rising to the adsorption rate > 98% while pH ≥ 6. Using hexadecyl trimethyl ammonium bromide of 2% (m/V) as an eluent to desorb the Pt (IV) from the surface of the aerogel, a desorption rate of 81.1% was obtained in this process. Urea, buffer aquation and other surfactants were used in the desorption experiment to understand the adsorption mechanism between the aerogel and Pt (IV). In this work, hydrogen bond, van der Waals force and electronic interaction force mainly drove the adsorption process. For obtaining more purified Pt (IV), we used 0.5% CTAB to desorb Pd (II). A new three-dimensional graphene-based composite was prepared and the surface interaction between Pt (IV) and composite was experimented for understanding the adsorption mechanism and exploring its potential application in sample preparation in low concentration.展开更多
Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reactio...Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reaction(HOR).Herein,we describe the synthesis of a Pt single electrocatalyst inside single-walled carbon nanotubes(SWCNTs)via a redox reaction.Characterizations via electron microscopy,X-ray photoelectron microscopy,and X-ray absorption spectroscopy show the single-atom nature of the Pt.The electrochemical behavior of the sample to hydrogen and oxygen was investigated using the advanced floating electrode technique,which minimizes mass transport limitations and gives a thorough insight into the activity of the electrocatalyst.The single-atom samples showed higher HOR activity than state-of-the-art 30%Pt/C while almost no oxygen reduction reaction activity in the proton exchange membrane fuel cell operating range.The selective activity toward HOR arose as the main fingerprint of the catalyst confinement in the SWCNTs.展开更多
The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues fo...The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues for the commercial application of lithium-sulfur(Li-S) batteries.Rational design of cathode materials to catalyze Li_(2)S dissociation/nucleation processes is an appealing and valid strategy to develop high-energy practical Li-S batteries.Herein,considering the synergistic effect of bidirectional catalysis on LiPSs conversion and enhanced chemical immobilization for LiPSs by heteroatom doping,Pt nanoparticles loaded on nitrogen-doped carbon spheres(Pt/NCS composites) were constructed as cathode materials.According to the dynamic evolution of Pt catalysts and sulfur species,Pt~0 and Pt^(2+) species were identified as active species for the accelerated dissociation and nucleation of Li_(2)S,respectively.Meanwhile,in-situ Raman results demonstrated the expedited conversion of sulfur species resulted from bidirectional catalysis of active Pt species,corresponding to boosted redox kinetics.Consequently,Pt/NCS cathode exhibited improved long-term cyclability with high initial capacity,along with enhanced rate capability.This work provides a facile approach to construct cathode materials with bidirectional catalysis on Li_(2)S dissociation/nucleation,and sheds light on a more global understanding of the catalytic mechanism of metal catalysts during LiPSs conversion.展开更多
The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibite...The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibited similar phase compositions, specific surface areas, and Pt contents. High-resolution transmission electron microscopy coupled with pulsed CO adsorption revealed increased dispersity when photoreduction and the hydroxonitrate complex (Me _(4) N) _(2) [Pt _(2) (OH) _(2) (NO _(3) ) _(8) ] were used. The sample featured a high content of single-atom species and subnano-sized Pt clusters. The X-ray photoelectron spectroscopy results showed that the photoreduction method facilitated the appearance of a larger number of Pt ^(2+) states, which appeared owing to the strong metal-support interaction (SMSI) eff ect of the transfer of electron density from the electron-saturated defects on the TiO _(2) surface to Pt ^(4+) . In the hydrogen evolution reaction, samples with a significant fraction of the Pt ^(2+) ionic component, capable of generating short-lived Pt^(0) single-atom sites under irradiation due to the SMSI eff ect, exhibited the highest photocatalytic activity. The 0.5Pt(C)/TiO_(2) -Ph sample exhibited the highest hydrogen yield with a quantum efficiency of 0.53, retaining its activity even after 8 h of operation.展开更多
基金The research of YY is supported by the Research Grant Council(RGC)through the General Research Fund(GRF)with the grant number N_CityU 109/21,CityU11213118 and CityU11209317.
文摘Hydrogen production through hydrogen evolution reaction(HER)offers a promising solution to combat climate change by replacing fossil fuels with clean energy sources.However,the widespread adoption of efficient electrocatalysts,such as platinum(Pt),has been hindered by their high cost.In this study,we developed an easy-to-implement method to create ultrathin Pt nanomembranes,which catalyze HER at a cost significantly lower than commercial Pt/C and comparable to non-noble metal electrocatalysts.These Pt nanomembranes consist of highly distorted Pt nanocrystals and exhibit a heterogeneous elastic strain field,a characteristic rarely seen in conventional crystals.This unique feature results in significantly higher electrocatalytic efficiency than various forms of Pt electrocatalysts,including Pt/C,Pt foils,and numerous Pt singleatom or single-cluster catalysts.Our research offers a promising approach to develop highly efficient and cost-effective low-dimensional electrocatalysts for sustainable hydrogen production,potentially addressing the challenges posed by the climate crisis.
基金the National Natural Science Foundation of China(Grant No.:51803120).
文摘Antibody-drug conjugates(ADCs)are a new type of targeting antibodies that conjugate with highly toxic anticancer drugs via chemical linkers to exert high specificity and efficient killing of tumor cells,thereby attracting considerable attention in precise oncology therapy.Cetuximab(Cet)is a typical antibody that offers the benefits of good targeting and safety for individuals with advanced and inoperable cutaneous squamous cell carcinoma(cSCC);however,its anti-tumor activity is limited to a single use.Cisplatin(CisPt)shows good curative effects;however,its adverse effects and non-tumor-targeting ability are major drawbacks.In this study,we designed and developed a new ADC based on a new cytotoxic platinum(IV)prodrug(C8Pt(IV))and Cet.The so-called antibody-platinum(IV)prodrugs conjugates,named Cet-C8Pt(IV),showed excellent tumor targeting in cSCC.Specifically,it accurately delivered C8Pt(IV)into tumor cells to exert the combined anti-tumor effect of Cet and CisPt.Herein,metabolomic analysis showed that Cet-C8Pt(IV)promoted cellular apoptosis and increased DNA damage in cSCC cells by affecting the vitamin B6 metabolic pathway in tumor cells,thereby further enhancing the tumor-killing ability and providing a new strategy for clinical cancer treatment using antibody-platinum(IV)prodrugs conjugates.
基金granted by Capital’s Funds for Health Improvement and Research(Grant No.2018-2-4023)the National Natural Science Foundation of China(Grant No.82001559)。
文摘Objective:The choice of chemotherapeutic regimen for triple-negative breast cancer(TNBC)remains controversial.Homologous recombination deficiency(HRD)has attracted increasing attention in informing chemotherapy treatment.This study was aimed at investigating the feasibility of HRD as a clinically actionable biomarker for platinum-containing and platinum-free therapy.Methods:Chinese patients with TNBC who received chemotherapy between May 1,2008 and March 31,2020 were retrospectively analyzed with a customized 3D-HRD panel.HRD positivity was defined by an HRD score≥30 or deleterious BRCA1/2 mutation.A total of 386 chemotherapy-treated patients with TNBC were screened from a surgical cohort(NCT01150513)and a metastatic cohort,and 189 patients with available clinical and tumor sequencing data were included.Results:In the entire cohort,49.2%(93/189)of patients were identified as HRD positive(40 with deleterious BRCA1/2 mutations and 53 with BRCA1/2 intact with an HRD score of≥30).In the first-line metastatic setting,platinum therapy was associated with longer median progression-free survival(mPFS)than platinum-free therapy[9.1 vs.3.0 months;hazard ratio(HR),0.43;95%confidence interval 0.22–0.84;P=0.01].Among HRD-positive patients,the mPFS was significantly longer in those treated with platinum rather than platinum-free therapy(13.6 vs.2.0 months;HR,0.11;P=0.001).Among patients administered a platinum-free regimen,HRD-negative patients showed a PFS significantly superior to that of HRD-positive patients(P=0.02;treatment-biomarker P-interaction=0.001).Similar results were observed in the BRCA1/2-intact subset.In the adjuvant setting,HRD-positive patients tended to benefit more from platinum chemotherapy than from platinum-free chemotherapy(P=0.05,P-interaction=0.02).Conclusions:HRD characterization may guide decision-making regarding the use of platinum treatment in patients with TNBC in both adjuvant and metastatic settings.
文摘目的:鉴于脓毒症的高发病率和高病死率,早期识别高风险患者并及时干预至关重要,而现有死亡风险预测模型在操作、适用性和预测长期预后等方面均存在不足。本研究旨在探讨脓毒症患者死亡的危险因素,构建近期和远期死亡风险预测模型。方法:从美国重症监护医学信息数据库IV(Medical Information Mart for Intensive Care-IV,MIMIC-IV)中选取符合脓毒症3.0诊断标准的人群,按7?3的比例随机分为建模组和验证组,分析患者的基线资料。采用单因素Cox回归分析和全子集回归确定脓毒症患者死亡的危险因素并筛选出构建预测模型的变量。分别用时间依赖性曲线下面积(area under the curve,AUC)、校准曲线和决策曲线评估模型的区分度、校准度和临床实用性。结果:共纳入14240例脓毒症患者,28 d和1年病死率分别为21.45%(3054例)和36.50%(5198例)。高龄、女性、高感染相关器官衰竭评分(sepsis-related organ failure assessment,SOFA)、高简明急性生理学评分(simplified acute physiology score II,SAPS II)、心率快、呼吸频率快、脓毒症休克、充血性心力衰竭、慢性阻塞性肺疾病、肝脏疾病、肾脏疾病、糖尿病、恶性肿瘤、高白细胞计数(white blood cell count,WBC)、长凝血酶原时间(prothrombin time,PT)、高血肌酐(serum creatinine,SCr)水平均为脓毒症死亡的危险因素(均P<0.05)。由PT、呼吸频率、体温、合并恶性肿瘤、合并肝脏疾病、脓毒症休克、SAPS II及年龄8个变量构建的模型,其28 d和1年生存的AUC分别为0.717(95%CI 0.710~0.724)和0.716(95%CI 0.707~0.725)。校准曲线和决策曲线表明该模型具有良好的校准度及较好的临床应用价值。结论:基于MIMIC-IV建立的脓毒症患者近期和远期死亡风险预测模型有较好的识别能力,对患者预后风险评估及干预治疗具有一定的临床参考意义。
文摘A three-dimensional graphene-based composite was prepared by a simple one-step in-site reduced-oxide method under atmospheric pressure. The obtained hydrogel was modified with 4-amino-benzenesulfonic acid and connected with ethylenediamine, and freeze-dried into an aerogel, which was characterized. Then the surface interaction with platinum (Pt, IV) was explored. The obtained aerogel showed good adsorption for Pt (IV) at acid conditions, giving a rising to the adsorption rate > 98% while pH ≥ 6. Using hexadecyl trimethyl ammonium bromide of 2% (m/V) as an eluent to desorb the Pt (IV) from the surface of the aerogel, a desorption rate of 81.1% was obtained in this process. Urea, buffer aquation and other surfactants were used in the desorption experiment to understand the adsorption mechanism between the aerogel and Pt (IV). In this work, hydrogen bond, van der Waals force and electronic interaction force mainly drove the adsorption process. For obtaining more purified Pt (IV), we used 0.5% CTAB to desorb Pd (II). A new three-dimensional graphene-based composite was prepared and the surface interaction between Pt (IV) and composite was experimented for understanding the adsorption mechanism and exploring its potential application in sample preparation in low concentration.
基金support from Horizon 2020 program within the ITN FlowcampDZ acknowledges funding from the Wohl Foundation for research for the promotion of UK-Israel research cooperationDZ acknowledges funding from Israel Ministry of Energy(grant#220-11-047).
文摘Utilizing supported single atoms as catalysts presents an opportunity to reduce the usage of critical raw materials such as platinum,which are essential for electrochemical reactions such as hydrogen oxidation reaction(HOR).Herein,we describe the synthesis of a Pt single electrocatalyst inside single-walled carbon nanotubes(SWCNTs)via a redox reaction.Characterizations via electron microscopy,X-ray photoelectron microscopy,and X-ray absorption spectroscopy show the single-atom nature of the Pt.The electrochemical behavior of the sample to hydrogen and oxygen was investigated using the advanced floating electrode technique,which minimizes mass transport limitations and gives a thorough insight into the activity of the electrocatalyst.The single-atom samples showed higher HOR activity than state-of-the-art 30%Pt/C while almost no oxygen reduction reaction activity in the proton exchange membrane fuel cell operating range.The selective activity toward HOR arose as the main fingerprint of the catalyst confinement in the SWCNTs.
基金the financial support provided by the National Natural Science Foundation of China (51932005, 22072164)the Liaoning Revitalization Talents Program (XLYC1807175)+3 种基金the Research Fund of Shenyang National Laboratory for Materials Sciencethe IMR Innovation Fund (2023PY10)the Natural Science Foundation of Liaoning Province (2023-BS-013)the Science and Technology Research Project of Education Department of Jilin Province (JJKH20210453KJ)。
文摘The shuttle effect derived from diffusion of lithium polysulfides(LiPSs) and sluggish redox kinetic bring about poor cycling stability and low utilization of sulfur,which have always been the key challenging issues for the commercial application of lithium-sulfur(Li-S) batteries.Rational design of cathode materials to catalyze Li_(2)S dissociation/nucleation processes is an appealing and valid strategy to develop high-energy practical Li-S batteries.Herein,considering the synergistic effect of bidirectional catalysis on LiPSs conversion and enhanced chemical immobilization for LiPSs by heteroatom doping,Pt nanoparticles loaded on nitrogen-doped carbon spheres(Pt/NCS composites) were constructed as cathode materials.According to the dynamic evolution of Pt catalysts and sulfur species,Pt~0 and Pt^(2+) species were identified as active species for the accelerated dissociation and nucleation of Li_(2)S,respectively.Meanwhile,in-situ Raman results demonstrated the expedited conversion of sulfur species resulted from bidirectional catalysis of active Pt species,corresponding to boosted redox kinetics.Consequently,Pt/NCS cathode exhibited improved long-term cyclability with high initial capacity,along with enhanced rate capability.This work provides a facile approach to construct cathode materials with bidirectional catalysis on Li_(2)S dissociation/nucleation,and sheds light on a more global understanding of the catalytic mechanism of metal catalysts during LiPSs conversion.
文摘The study focused on the modification with platinum of dark defective titania obtained via pulsed laser ablation. Both the method of Pt introduction and the nature of the Pt precursor were varied. All samples exhibited similar phase compositions, specific surface areas, and Pt contents. High-resolution transmission electron microscopy coupled with pulsed CO adsorption revealed increased dispersity when photoreduction and the hydroxonitrate complex (Me _(4) N) _(2) [Pt _(2) (OH) _(2) (NO _(3) ) _(8) ] were used. The sample featured a high content of single-atom species and subnano-sized Pt clusters. The X-ray photoelectron spectroscopy results showed that the photoreduction method facilitated the appearance of a larger number of Pt ^(2+) states, which appeared owing to the strong metal-support interaction (SMSI) eff ect of the transfer of electron density from the electron-saturated defects on the TiO _(2) surface to Pt ^(4+) . In the hydrogen evolution reaction, samples with a significant fraction of the Pt ^(2+) ionic component, capable of generating short-lived Pt^(0) single-atom sites under irradiation due to the SMSI eff ect, exhibited the highest photocatalytic activity. The 0.5Pt(C)/TiO_(2) -Ph sample exhibited the highest hydrogen yield with a quantum efficiency of 0.53, retaining its activity even after 8 h of operation.