Functionalization of covalent organic frameworks by metal modification: Construction, properties and applications
作者:
Huang, Jing;Liu, Xiaojuan;Zhang, Wei;Liu, Zhifeng* ;Zhong, Hua* ;...
期刊:
Chemical Engineering Journal ,2021年404:127136- ISSN:1385-8947
通讯作者:
Liu, Zhifeng;Zhong, Hua
作者机构:
[Shao, Binbin; Liang, Qinghua; Liu, Zhifeng; Liu, ZF; Zhong, Hua; Huang, Jing; Zhang, Wei; He, Qingyun; Liu, Yang] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Peoples R China.;[Shao, Binbin; Liang, Qinghua; Liu, Zhifeng; Liu, ZF; Zhong, Hua; Huang, Jing; Zhang, Wei; He, Qingyun; Liu, Yang] Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Peoples R China.;[Zhong, Hua] Wuhan Univ, State Key Lab Water Resources & Hydropower Engn S, Wuhan 430072, Hubei, Peoples R China.
通讯机构:
[Liu, ZF; Zhong, H] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Peoples R China.;Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Peoples R China.
关键词:
COFs;Metal modification strategy;Property;Gas adsorption;Catalysis
摘要:
As emerging crystalline porous materials, covalent organic frameworks (COFs) have drawn great interest due to their tunable porosity and modifiable skeletons. Multiple applications of COFs rely on the previous chemical functionality of organic building units or posterior modification of frameworks. The metal modification strategy utilizes metal–ligand coordination reactions to incorporate metal species into COF skeletons, providing the possibility for functionalization. In this review, we discuss the pristine properties (pore design, chemical stability and scalability) and characterization techniques of COFs to fully recognize these charming materials. Particular attentions are given to the construction (theoretical simulations and actual operation synthesis methods) and metallized properties (adsorption site, binding energy and structural effect) of metal-modified COFs in view of verifying the feasibility of modification. Moreover, the applications of hybrids in gas adsorption and catalysis are presented. Finally, we summarize the challenges and give outlook in the future perspectives of this modification strategy. © 2020 Elsevier B.V.
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In-situ self-assembly construction of hollow tubular g-C3N4 isotype heterojunction for enhanced visible-light photocatalysis: Experiments and theories
作者:
Liang, Qinghua;Liu, Xiaojuan;Wang, Jiajia;Liu, Yang;Liu, Zhifeng* ;...
期刊:
Journal of Hazardous Materials ,2021年401:123355- ISSN:0304-3894
通讯作者:
Liu, Zhifeng;Tang, Lin
作者机构:
[Shao, Binbin; Wang, Jiajia; Liu, Zhifeng; Tang, Lin; He, Qingyun; Liu, Yang; Cheng, Min; Liang, Qinghua; Liu, ZF; Tang, L; Feng, Chengyang] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;[Shao, Binbin; Wang, Jiajia; Liu, Zhifeng; Tang, Lin; He, Qingyun; Liu, Yang; Cheng, Min; Liang, Qinghua; Liu, ZF; Tang, L; Feng, Chengyang] Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Hunan, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Peoples R China.;[Gong, Shanxi] Guangxi Univ, Sch Chem & Chem Engn, Nanning 530004, Peoples R China.
通讯机构:
[Liu, ZF; Tang, L] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Hunan, Peoples R China.
关键词:
g-C3N4 isotype heterojunction;Self-assembly;Visible-light photocatalysis;Theoretical calculation;Degradation pathway
摘要:
A highly reactive hollow tubular g-C3N4 isotype heterojunction (SCN-CN) was designed to enhance visible light absorption and manipulate the directed transfer of electrons and holes. The results of UV-vis DRS, XPS valence band and DFT theoretical calculations indicated S doping increases the visible-light absorption capacity and changed the ba nd gap structure of g-C3N4 (CN), resulting in the transfer of electrons from the CN to the SCN and holes from the SCN to the CN under visible light. In addition, the tubular structure of the SCN-CN facilitated the transfer of electrons in the longitudinal direction, which reduced charge carrier recombination. Furthermore, the optical properties, electronic structure, and electron transfer of SCN-CN were also studied by experiments and theoretical calculations. The antibiotic tetracycline hydrochloride (TCH) and dye Rhodamine B (RHB) were subjected to evaluate the photocatalytic performance of SCN-CN. The scavenger tests and ESR data showed that the h(+), center dot O-2(-) and center dot OH worked together in the photocatalytic process. Moreover, the photocatalytic degradation pathway was analyzed by LC-MS. This study synthesized a hollow tubular CN isotype heterojunction with high visible-light photocatalytic performance and provided a theoretical basis for CN isotype heterojunction. Graphical abstract
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Application of QD-MOF composites for photocatalysis: Energy production and environmental remediation
作者:
Wu, Ting;Liu, Xiaojuan;Liu, Yang;Cheng, Min;Liu, Zhifeng* ;...
期刊:
Coordination Chemistry Reviews ,2020年403:213097- ISSN:0010-8545
通讯作者:
Liu, Zhifeng;Zeng, Guangming
作者机构:
[Shao, Binbin; Liang, Qinghua; Zeng, Guangming; Liu, Zhifeng; Zhang, Wei; He, Qingyun; Liu, ZF; Zeng, GM; Liu, Yang; Cheng, Min; Wu, Ting] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;[Shao, Binbin; Liang, Qinghua; Zeng, Guangming; Liu, Zhifeng; Zhang, Wei; He, Qingyun; Liu, ZF; Zeng, GM; Liu, Yang; Cheng, Min; Wu, Ting] Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Hunan, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Hunan, Peoples R China.
通讯机构:
[Liu, ZF; Zeng, GM] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Hunan, Peoples R China.
关键词:
Metal-organic frameworks;Quantum dots;Photocatalysis;Energy production;Environmental remediation
摘要:
Photocatalysis is an efficient technology for energy production and environmental remediation. The composites of metal organic frameworks (MOFs) combined with quantum dots (QDs) allow high photocatalytic ability. Recently, these composites have been applied increasingly in the fields of energy production and environmental remediation. Even so, QD-MOF composites still have some shortcomings in the field of photocatalysis. In this review, the synthesis methods and structures as well as the applications of QD-MOF composites in water splitting for hydrogen production, carbon dioxide (CO2) reduction to produce methane (CH4), organic dye degradation, Cr(VI) reduction, and nitric oxide (NO) oxidation are discussed. The mechanisms of these processes are also described in detail. Finally, new insights into the future development and challenges of the composite are proposed to advance further development of the research area. (C) 2019 Elsevier B.V. All rights reserved.
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Advances in photocatalysis based on fullerene C60 and its derivatives: Properties, mechanism, synthesis, and applications
作者:
Pan, Yuan;Liu, Xiaojuan;Zhang, Wei;Liu, Zhifeng* ;Zeng, Guangming* ;...
期刊:
Applied Catalysis B: Environmental ,2020年265:118579- ISSN:0926-3373
通讯作者:
Liu, Zhifeng;Zeng, Guangming
作者机构:
[Shao, Binbin; Huang, Danlian; Liang, Qinghua; Chen, Ming; Zeng, Guangming; Liu, Zhifeng; Yuan, Xingzhong; He, Qingyun; Liu, ZF; Pan, Yuan] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Peoples R China.;[Shao, Binbin; Huang, Danlian; Liang, Qinghua; Chen, Ming; Zeng, Guangming; Liu, Zhifeng; Yuan, Xingzhong; He, Qingyun; Liu, ZF; Pan, Yuan] Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Peoples R China.
通讯机构:
[Liu, ZF; Zeng, GM] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Peoples R China.;Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Peoples R China.
关键词:
Fullerenes;Semiconductor photocatalysis;Photocatalytic mechanism;Environmental remediation;Hydrogen production
摘要:
Fullerenes possess high chemical stability, large specific surface area, good electrical conductivity and unique three-dimensional structure. In this paper, we provide a general overview of the latest research results of fullerene-based photocatalysts. Firstly, the current status of semiconductor materials and fullerenes in photocatalytic applications are briefly introduced. Secondly, introduced action mechanisms of photocatalysts modified by fullerene C60 and its derivatives, including basic structure, exclusive properties and its effect in photocatalysis and material preparation process. Thirdly, factors affecting material effectiveness and the synthesis strategy of composite photocatalyst modified by fullerene are introduced. Meanwhile, the application advances of the photocatalysts are introduced, including in the degradation of pollutants, organic synthesis, hydrogen production, antibacterial and disinfection in water. Finally, the development trends of fullerenes and their derivatives in photocatalysis are also summarized, including theoretical calculations, the morphological structure control, stable derivatives and increase the selectivity, and new other types of fullerene materials. © 2019 Elsevier B.V.
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Advances in the application, toxicity and degradation of carbon nanomaterials in environment: A review
作者:
Peng, Zan;Liu, Xiaojuan;Zhang, Wei;Zeng, Zhuotong;Liu, Zhifeng* ;...
期刊:
Environment International ,2020年134:105298 ISSN:0160-4120
通讯作者:
Liu, Zhifeng;Zhang, Chang
作者机构:
[Peng, Zan; Shao, Binbin; Liang, Qinghua; Liu, Zhifeng; Yuan, Xingzhong; Zhang, Chang; Liu, Yang; Tang, Wangwang; Liu, ZF; Zhang, C] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;[Peng, Zan; Shao, Binbin; Liang, Qinghua; Liu, Zhifeng; Yuan, Xingzhong; Zhang, Chang; Liu, Yang; Tang, Wangwang; Liu, ZF; Zhang, C] Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Hunan, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Hunan, Peoples R China.;[Zeng, Zhuotong] Cent S Univ, Xiangya Hosp 2, Dept Dermatol, Changsha 410011, Hunan, Peoples R China.
通讯机构:
[Liu, ZF; Zhang, C] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;Hunan Univ, Minist Educ, Key Lab Environm Biol & Pollut Control, Changsha 410082, Hunan, Peoples R China.
关键词:
Application;Carbon nanomaterials;Degradation;Toxicity
摘要:
Carbon nanomaterials (CNMs) are novel nanomaterials with excellent physicochemical properties, which are widely used in biomedicine, energy and sensing. Besides, CNMs also play an important role in environmental pollution control, which can absorb heavy metals, antibiotics and harmful gases. However, CNMs are inevitably entering the environment while they are rapidly developing. They are harmful to living organisms in the environment and are difficult to degrade under natural conditions. Here, we systematically describe the toxicity of carbon nanotubes (CNTs), graphene (GRA) and C60 to cells, animals, humans, and microorganisms. According to the current research results, the toxicity mechanism is summarized, including oxidative stress response, mechanical damage and effects on biological enzymes. In addition, according to the latest research progress, we focus on the two major degradation methods of chemical degradation and biodegradation of CNTs, GRA and C60. Meanwhile, the reaction conditions and degradation mechanisms of degradation are respectively stated. Moreover, we have prospects for the limitations of CNM degradation under non-experimental conditions and their potential application. © 2019 The Authors
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英文
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A novel double Z-scheme photocatalyst Ag3PO4/Bi2S3/Bi2O3 with enhanced visible-light photocatalytic performance for antibiotic degradation
作者:
Shao, Binbin;Liu, Xiaojuan;Liu, Zhifeng* ;Zeng, Guangming* ;Liang, Qinghua;...
期刊:
Chemical Engineering Journal ,2019年368:730-745 ISSN:1385-8947
通讯作者:
Liu, Zhifeng;Zeng, Guangming
作者机构:
[Shao, Binbin; Liang, Qinghua; Zeng, Guangming; Liu, Zhifeng; Cheng, Ying; Liang, Chao; Liu, Yang; Liu, Z; Zeng, GM] Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;[Shao, Binbin; Liang, Qinghua; Zeng, Guangming; Liu, Zhifeng; Cheng, Ying; Liang, Chao; Liu, Yang; Liu, Z; Zeng, GM] Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Hunan, Peoples R China.;[Zhang, Wei; Liu, Xiaojuan] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha 410007, Hunan, Peoples R China.;[Gong, Shanxi] Guangxi Univ, Sch Chem & Chem Engn, Nanning 530004, Peoples R China.
通讯机构:
[Liu, Z; Zeng, GM] H;Hunan Univ, Coll Environm Sci & Engn, Changsha 410082, Hunan, Peoples R China.;Hunan Univ, Key Lab Environm Biol & Pollut Control, Minist Educ, Changsha 410082, Hunan, Peoples R China.
关键词:
Ag3PO4/Bi2S3/Bi2O3;Density functional theory;Photosensitization;Double Z-scheme photocatalytic system;Visible light;Antibiotics
摘要:
In this study, the novel visible light double Z-scheme photocatalysts (Ag3PO4/Bi2S3/Bi2O3) were synthesized by the facile means. The crystal texture, chemical states, morphology and optical characteristics of prepared photocatalysts were investigated by XRD, FTIR, XPS, SEM, TEM, N2 adsorption-desorption analysis, UV–vis DRS, and PL etc. techniques, respectively. Meanwhile, the band structures and the density of states of three single-phase semiconductor and Ag3PO4/Bi2S3/Bi2O3 (ABB) composite had been calculated by Materials Studio program based on density functional theory. For assessing the photocatalytic performance of these samples, the visible light photodegradation of antibiotics sulfamethazine (SAZ) and cloxacillin (CLX) were performed. The effects of initial antibiotic concentration, reaction pH, supporting electrolyte and surfactant on photocatalytic performance were all investigated. The results indicated that the ABB-3 composite exhibited higher photocatalytic performance than other comparison samples. Furthermore, four cycle experiments confirmed the ABB-3 composite also exhibited satisfactory photostability. The scavenger tests and ESR data demonstrated that the active species h+, [rad]O2−, and [rad]OH worked together in the photocatalytic process, and the h+ and [rad]O2− play a more important role than [rad]OH. All in all, the increased photocatalytic performance of ABB composite could owe to the photosensitization of Bi2S3 and the double Z-scheme photocatalytic system. This study could inspire some new idea for building the novel and efficient heterogeneous photocatalysts and benefiting their practical application. © 2019 Elsevier B.V.
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英文
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Lipid metabolism and carcinogenesis, cancer development
作者:
Long, Jia;Zhang, Chan-Juan;Zhu, Neng;Du, Ke;Yin, Yu-Fang;...
期刊:
American Journal of Cancer Research ,2018年8(5):778-791 ISSN:2156-6976
通讯作者:
Qin, Li
作者机构:
[Du, Ke; Zhang, Chan-Juan; Liao, Duan-Fang; Long, Jia; Qin, Li] Hunan Univ Chinese Med, Sch Pharm, 300 Xueshi Rd, Changsha 410208, Hunan, Peoples R China.;[Zhu, Neng] Hunan Univ Chinese Med, Affiliated Hosp 1, Changsha, Hunan, Peoples R China.;[Yin, Yu-Fang] Southern Illinois Univ, Sch Med, Dept Neurosci & Pharmacol, Springfield, IL USA.;[Tan, Xi] Univ Calgary, Dept Biochem & Mol Biol, Calgary, AB, Canada.;[Liao, Duan-Fang; Qin, Li] Hunan Univ Chinese Med, Div Stem Cell Regulat & Applicat, Key Lab Qual Evaluat Bulk Herbs Hunan Prov, Changsha, Hunan, Peoples R China.
通讯机构:
[Qin, Li] H;Hunan Univ Chinese Med, Sch Pharm, 300 Xueshi Rd, Changsha 410208, Hunan, Peoples R China.
关键词:
Lipid;cancer development;cancer treatment;carcinogenesis;lipid metabolism
摘要:
The disorder of lipid metabolism is pathologically linked to hyperlipidemia, lipid storage disease, obesity and other related diseases. Intriguingly, recent studies have revealed that lipid metabolism disorders play an important role in carcinogenesis and development as well, since they cause abnormal expression of various genes, proteins, and dysregulation of cytokines and signaling pathways. More importantly, lipid-lowering drugs and anti-lipid per-oxidation treatment have been showing their advantages in clinic, in comparison with other anti-cancer drugs with high toxicity. Thus, further elucidation of molecular mechanism between lipid metabolism and cancer is essential in developing novel diagnostic biomarkers and therapeutic targets of human cancers.
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英文
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Effect of electroacupuncture on urinary leakage among women with stress urinary incontinence: A randomized clinical trial
作者:
Liu, Zhishun;Liu, Yan;Xu, Huanfang;He, Liyun;Chen, Yuelai;...
期刊:
JAMA-JOURNAL OF THE AMERICAN MEDICAL ASSOCIATION ,2017年317(24):2493-2501 ISSN:0098-7484
通讯作者:
Liu, Baoyan
作者机构:
[Xu, Huanfang; Liu, Baoyan; Pang, Ran; Qin, Zongshi; Wang, Yang; Zhou, Jing; Liu, Zhishun; Wu, Jiani] China Acad Chinese Med Sci, Guangan Men Hosp, Beijing, Peoples R China.;[He, Liyun; Yan, Shiyan; Ai, Yanke; Li, Hongjiao; Luo, Lin; Liu, Yan] China Acad Chinese Med Sci, Inst Basic Res Clin Med, Beijing, Peoples R China.;[Xu, Huanfang] China Acad Chinese Med Sci, Inst Acupuncture & Moxibust, Beijing, Peoples R China.;[Chen, Yuelai] Shanghai Univ Tradit Chinese Med, Yueyang Hosp Integrated Tradit Chinese & Western, Shanghai, Peoples R China.;[Fu, Lixin] Tianjin Univ Tradit Chinese Med, Teaching Hosp 1, Tianjin, Peoples R China.
通讯机构:
[Liu, Baoyan] C;China Acad Chinese Med Sci, Dept Acupuncture & Moxibust, Guangan Men Hosp, 5 Beixiange St, Beijing 100053, Peoples R China.
关键词:
electroacupuncture;urinary incontinence, stress
摘要:
IMPORTANCE: Electroacupuncture involving the lumbosacral region may be effective for women with stress urinary incontinence (SUI), but evidence is limited. OBJECTIVE: To assess the effect of electroacupuncture vs sham electroacupuncture for women with SUI. DESIGN, SETTING, AND PARTICIPANTS: Multicenter, randomized clinical trial conducted at 12 hospitals in China and enrolling 504 women with SUI between October 2013 and May 2015, with data collection completed in December 2015. INTERVENTIONS: Participants were randomly assigned (1:1) to receive 18 sessions (over 6 weeks) of electroacupuncture involving the lumbosacral region (n = 252) or sham electroacupuncture (n = 252) with no skin penetration on sham acupoints. MAIN OUTCOMES AND MEASURES: The primary outcome was change from baseline to week 6 in the amount of urine leakage, measured by the 1-hour pad test. Secondary outcomes included mean 72-hour urinary incontinence episodes measured by a 72-hour bladder diary (72-hour incontinence episodes). RESULTS: Among the 504 randomized participants (mean [SD] age, 55.3 [8.4] years), 482 completed the study. Mean urine leakage at baseline was 18.4 g for the electroacupuncture group and 19.1 g for the sham electroacupuncture group. Mean 72-hour incontinence episodes were 7.9 for the electroacupuncture group and 7.7 for the sham electroacupuncture group. At week 6, the electroacupuncture group had greater decrease in mean urine leakage (-9.9 g) than the sham electroacupuncture group (-2.6 g) with a mean difference of 7.4 g (95% CI, 4.8 to 10.0; P < .001). During some time periods, the change in the mean 72-hour incontinence episodes from baseline was greater with electroacupuncture than sham electroacupuncture with between-group differences of 1.0 episode in weeks 1 to 6 (95% CI, 0.2-1.7; P = .01), 2.0 episodes in weeks 15 to 18 (95% CI, 1.3-2.7; P < .001), and 2.1 episodes in weeks 27 to 30 (95% CI, 1.3-2.8; P < .001). The incidence of treatment-related adverse events was 1.6% in the electroacupuncture group and 2.0% in the sham electroacupuncture group, and all events were classified as mild. CONCLUSIONS AND RELEVANCE: Among women with stress urinary incontinence, treatment with electroacupuncture involving the lumbosacral region, compared with sham electroacupuncture, resulted in less urine leakage after 6 weeks. Further research is needed to understand long-term efficacy and the mechanism of action of this intervention. TRIAL REGISTRATION: clinicaltrials.gov Identifier: NCT01784172. © 2017 American Medical Association. All rights reserved.
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Intratumoral CD3 and CD8 T-cell Densities Associated with Relapse-Free Survival in HCC
作者:
Gabrielson, Andrew;Wu, Yunan;Wang, Hongkun;Jiang, Jiji;Kallakury, Bhaskar;...
期刊:
Cancer Immunology Research ,2016年4(5):419-430 ISSN:2326-6066
通讯作者:
He, Aiwu Ruth
作者机构:
[Prins, Petra; Weiner, Louis; Jiang, Jiji; Atkins, Michael; Zhang, Tiger; Gabrielson, Andrew; Wang, Hongkun; Loffredo, Christopher; Kachhela, Jaydeep; Tesfaye, Anteneh; Feng, Perry; Marshall, John; He, Aiwu Ruth] Georgetown Lombardi Comprehens Canc Ctr, Div Hematol & Oncol, Washington, DC USA.;[Wu, Yunan] Hunan Univ Chinese Med, Hosp 1, Changsha, Hunan, Peoples R China.;[Kallakury, Bhaskar] Georgetown Univ Hosp, Dept Pathol, Washington, DC 20007 USA.;[Reddy, Sandeep; Gatalica, Zoran] Caris Life Sci, Irving, TX USA.;[Kleiner, David] NCI, Ctr Canc Res, Bethesda, MD 20892 USA.
通讯机构:
[He, Aiwu Ruth] L;[He, Aiwu Ruth] M;Lombardi Comprehens Canc Ctr, Dept Oncol, 3800 Reservoir Rd NW, Washington, DC 20007 USA.;MedStar Georgetown Univ Hosp, Div Hematol Oncol, 3800 Reservoir Rd NW, Washington, DC 20007 USA.
摘要:
Immune cells that infiltrate a tumor may be a prognostic factor for patients who have had surgically resected hepatocellular carcinoma (HCC). The density of intratumoral total (CD3+ ) and cytotoxic (CD8+ ) T lymphocytes was measured in the tumor interior and in the invasive margin of 65 stage I to IV HCC tissue specimens from a single cohort. Immune cell density in the interior and margin was converted to a binary score (0, low; 1, high), which was correlated with tumor recurrence and relapse-free survival (RFS). In addition, the expression of programmed death 1 (PD-1) and programmed death ligand 1 (PD-L1) was correlated with the density of CD3+and CD8+ cells and clinical outcome. High densities of both CD3+ and CD8+ T cells in both the interior and margin, along with corresponding Immunoscores, were significantly associated with a low rate of recurrence (P ? 0.007) and a prolonged RFS (P ? 0.002). In multivariate logistic regression models adjusted for vascular invasion and cellular differentiation, both CD3+and CD8+ cell densities predicted recurrence, with odds ratios of 5.8 [95% confidence interval (CI), 1.6-21.8] for CD3+ and 3.9 (95% CI, 1.1-14.1) for CD8+ . Positive PD-L1 staining was correlated with high CD3 and CD8 density (P ? 0.024 and 0.005, respectively) and predicted a lower rate of recurrence (P ? 0.034), as well as prolonged RFS (P ? 0.029). Immunoscore and PD-L1 expression, therefore, are useful prognostic markers in patients with HCC who have undergone primary tumor resection. © 2016 American Association for Cancer Research.
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