化学材料(功能分子固体教育部重点实验室)

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代表性研究成果简介

作者:fms 编辑:fms 时间:2018-12-10


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 代表性研究成果的主要内容、实验室人员在其中的主要创新贡献以及成果的国内外学术影响:

稀土金属配合物的成键、结构及反应性能研究是稀土金属有机化学领域的重要研究领域。围绕我国丰富资源稀土的开发与利用,课题组一直从事稀土金属功能配合物的合成、结构、成键性能和应用研究,已取得了一系列创新性的研究成果。

1)利用稀土金属离子半径大,配位数多的特点,发展了稀土与吡咯、吲哚及卡宾与稀土金属胺基配合物或稀土金属烃基配合物的反应。发现了多种成键形式的取代吲哚稀土金属配合物,并发现了首例稀土金属胺基配合物引发的二级胺脱氢反应,同时发现了含吲哚稀土金属胺基配合物引发的C-H键活化反应合成得到了稀土金属与吲哚环体系多种新的成键形式。

2)根据稀土金属配合物在异戊二烯的控制聚合方面具有较好的调控性,设计合成了系列稀土金属有机配合物,研究其催化聚异戊二烯聚合反应,筛选高顺式-1,4选择性的异戊二烯聚合催化剂。开发了系列含有取代吲哚基稀土金属配合物作为异戊二烯聚合催化剂,通过调节配体的电子效应和立体效应,实现了异戊二烯的高选择性顺式-1,4聚合,该成果为高选择性合成顺式1,4-聚异戊二烯橡胶提供了具有重要理论意义和应用价值的方法,对发展合成天然橡胶产业具有潜在应用价值。

3)利用三氟磺酸稀土作为Lewis酸催化成环反应构筑四氢异喹啉衍生物、四氢咔啉衍生物、咔唑和取代萘等具有重要生理活性的含氮杂环化合物。

另:每项代表性成果的成果佐证材料:

1. Xiancui Zhu, Yang Li, Yun Wei, Shaowu Wang*, Shuangliu Zhou, and Lijun Zhang, Reactivity of Imino-Functionalized Indoles with Rare-Earth-Metal Amides: Unexpected Substituent Effects on C?H Activation Pathways and Assembly of Rare-Earth-Metal Complexes. Organometallics, 2016, 35, 1838?1846.

2. Xiaoxia Gu, Xiancui Zhu,* Yun Wei, Shaowu Wang*,  Shuangliu Zhou, Guangchao Zhang, and Xiaolong Mu, “CNC-Pincer Rare-Earth Metal Amido Complexes with a Diarylamido Linked Biscarbene Ligand: Synthesis, Characterization and Catalytic Activity, Organometallics, 2014, 33 (9), 2372–2379.

3. Guangchao Zhang, Yun Wei, Liping Guo, Xiancui Zhu, Shaowu Wang*,  Shuangliu Zhou, and Xiaolong Mu, Dinuclear Rare-Earth Metal Alkyl Complexes Supported by Indolyl Ligands in m-h2:h1:h1 Hapticities and their High Catalytic Activity for Isoprene 1,4-cis-Polymerization. Chem. Eur. J. 2015, 21(6), 2519-2526.

4. Liping Guo, Xiancui Zhu, Guangchao Zhang, Yun Wei, Lixin Ning, Shuangliu Zhou,* Zhijun, Feng, Shaowu Wang*, Xiaolong Mu, Jun Chen, and Yuzhe Jiang, “Synthesis, Characterization of Organo Rare-Earth Metal Monoalkyl Complexes Supported by Carbon σ-Bonded Indolyl Ligands: High Specific Isoprene 1,4-cis Polymerization Catalysts,” Inorg. Chem. 2015, 54(12), 5725-5731.

5. Shaoyin Wang, Zhuo Chai, Yun Wei, Xiancui Zhu, Shuangliu Zhou, and Shaowu Wang*, Lewis Acid Catalyzed Cascade Reaction to Carbazoles and Naphthalenes via Dehydrative [3 + 3]-Annulation.  Org. Lett. 2014, 16, 3592-3595.

6. Qingbing Yuan, Shuangliu Zhou*, Xiancui Zhu, Yun Wei, Shaowu Wang, Xiaolong Mu, Fangshi Yao, Guangchao Zhang and Zheng Chen, Heterometallic rare-earth metal complexes with imino-functionalized 8-hydroxyquinolyl ligands: synthesis, characterization and catalytic activity towards hydrophosphinylation of trans-β-nitroalkene. New J. Chem., 2015, 39, 7626-7632.

7. Shuangliu Zhou,* Zhiyong Yang, Xu Chen, Yimei Li, Lijun Zhang, Hong Fang, Wei Wang, Xiancui Zhu, and Shaowu Wang*, “Copper-Catalyzed Electrophilic Amination of Organoaluminum Nucleophiles with O-Benzoyl Hydroxylamines” J. Org. Chem. 2015, 80, 6323-6328.

8. Liping Guo, Xiancui Zhu, Shuangliu Zhou,* Xiaolong Mu, Yun Wei, Shaowu Wang*,Zhijun Feng, Guangchao Zhang, and Baojia Deng, Rare-Earth Alkyl Complexes Supported by Formamidinate Ligands: Synthesis, Structure, and Catalytic Activity for Isoprene Polymerization. Dalton Trans. 2014, 43 (18), 6842 – 6847.

9. N-磺酰基取代四氢异喹啉衍生物的制备方法,王绍武、王少印、周双六、柴卓,国家发明专利,201310019604.6.

10. N-磺酰基取代-β-四氢咔啉衍生物的制备方法,王绍武、王少印、周双六、柴卓,国家发明专利,201310019601.2.

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 围绕功能纳米材料的可控合成、性能及应用,在能源催化(例如锂离子电池,光电催化)及生物科学(例如光热催化治疗和抗氧化)等领域取得创新性结果:

1)以减少燃料电池中贵金属催化剂使用量为目标,致力于发展新的氧化物及其与贵金属复合催化剂,合成几类新型的电催化纳米材料。这类催化剂在电催化水分解和氧还原性能方面呈现了较低的过电位和较好的持久性,为开发和实现低成本燃料电池催化剂提供了新的选择。相关研究成果发表于Angew. Chem. Int. Ed. 2017, 56, 14977; Angew. Chem. Int. Ed. 2014, 53, 7547; Nano Energy, 2017, 43, 81; Chem. Eur. J. 2016, 22; 14480. Chem. Eur. J. 2016, 22, 9909; Chem. Eur. J., 2015, 21, 13291; ChemSusChem2015, 8, 659. 获专利授权5件。

2)以氧化物、硫化物和第四主族元素等高容量负极材料为对象,设计合成了一系列新颖结构的材料,通过精确调控材料的形态、组分并采用材料复合的方法有效抑制了高容量负极材料在电化学循环过程中的容量衰减,提高了高容量负极材料的循环寿命和倍率性能,进一步推动了锂离子电池的基础理论研究和应用。相关研究成果发表于Angew. Chem. Int. Ed. 2017, 56, 12649; Chem. Eur. J. 2017. 40, 9517; Chem. Commun., 2017, 53, 13125; J. Mater. Chem. A, 2016, 4, 17000. 获专利授权6件。

3)设计了一些可见光响应的铋基纳米异质结构光催化剂,通过有效的带隙结构设计和纳米结构物理性能调控,异质结构光催化剂在可见光范围内表现出优良的量子效率和优越的抗腐蚀性能,在光降解有机污染物和光解水等方面具有优异光学表现。相关研究成果发表于Appl Catal B-Environ, 2017, 203, 946; J. Phys. Chem. C, 2015, 119, 13032; ACS Appl. Mater. Interfaces, 2014, 6, 5061. J. Mater. Chem. A, 2014, 2, 8517. 获专利授权3件。

 佐证材料:

1.  Wenhai Wang, Long Kuai, Wei Cao, Marko Huttula, Sami Ollikkala, Taru Ahopelto, Ari-Pekka Honkanen, Simo Huotari, Mengkang Yu, and Baoyou Geng*, Mass-Production of Mesoporous MnCo2O4 Spinels with Manganese(IV)- and Cobalt(II)-Rich Surfaces for Superior Bifunctional Oxygen Electrocatalysis. Angew. Chem. Int. Ed. 2017, 56, 14977-14981.  

2. Li, Min, Du, Haoran, Kuai, Long, Huang, Kuangfu, Xia, Yuanyuan, Geng, Baoyou*, Scalable Dry Production Process of a Superior 3D Net-Like Carbon-Based Iron Oxide Anode Material for Lithium-Ion Batteries. Angew. Chem. Int. Ed. 2017,56,41, 1249-12653. 

3. Kuai, Long, Geng, Jing, Chen Changyu, Kan Erjie, Liu Yadong, Wang Qing and Baoyou Geng*,  A Reliable Aerosol-Spray-Assisted Approach to Produce and Optimize Amorphous Metal Oxide Catalysts for Electrochemical Water Splitting, Angew. Chem. Int. Ed. 2014, 53, 7547 –7551.

4.  Yadong Liu, Zhen Fang, Long Kuai and Baoyou Geng*,  One-pot facile synthesis of reusable tremella-like M1@M2@M1(OH)2 (M1 = Co, Ni, M2 = Pt/Pd, Pt, Pd and Au) three layers core–shell nanostructures as highly efficient catalysts, Nanoscale2014,6, 9791-9797.

5.  Zhao Yanyan, Kuai Long, Liu Yanguo, Wang Pengpeng, Arandiyan Hamidreza, Cao Sufeng, Zhang Jie, Li Fengyun, Wang Qing, Geng Baoyou &Hongyu Sun, Well-Constructed Single-Layer Molybdenum Disulfide Nanorose Cross-Linked by Three Dimensional-Reduced Graphene Oxide Network for Superior Water Splitting and Lithium Storage Property, Sci. Rep. 2015,5.

6. Kan Erjie, Kuai Long, Wang Wenhai, Geng Baoyou, Delivery of Highly Active Noble-Metal Nanoparticles into Microspherical Supports by an Aerosol-Spray Method. Chem. Eur. J., 2015, 21, 13291-13296.

7. Wenzheng Li, Long Kuai, Qing Qin and Baoyou Geng*. Ag–Au bimetallic nanostructures: co-reduction synthesis and their component-dependent performance for enzyme-free H2O2 sensing. J. Mater. Chem. A, 2013, 1, 7111–7117.

8. Wang, Qing, Geng, Jing, Yuan, Chao, Kuai, Long and Geng, Baoyou*, Mesoporous spherical Li4Ti5O12/TiO2 composites as an excellent anode material for lithium-ion batteries. Electrochim. Acta, 2016,212, 41-46.  

9. ZnO nanorods/ZnSe heteronanostructure arrays with a tunable microstructure of ZnSe shell for visible light photocatalysis. J. Mater. Chem. A, 2014, 2, 17502-17510.

10. 耿保友,王文海,蒯龙,一种Mn2O3及其制备方法以及在ORR中的应用,发明专利,专利号:ZL201510779849.8.

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    亲核试剂对吖丙啶的不对称开环反应是制备重要功能性手性有机含氮化合物的高效方法之一。目前,这一领域的研究主要集中在内消旋吖丙啶的去对称化反应上,而对于外消旋吖丙啶的不对称开环反应,不仅要解决对映选择性的问题,同时还有区域选择性的问题,成功的例子很少。围绕这一科学问题,团队致力于亲核试剂对吖丙啶的不对称开环反应体系的研究,取得了一些创新性的研究成果。

(1) 利用简单的一价铜盐和手性双膦配体组成的催化体系,实现了首例不对称的N-对甲苯磺酰基吖丙啶和吲哚衍生物的[3+2]环化反应,构建具有重要生物活性和药理活性的四氢吡咯并吲哚啉类化合物。该工作也是首例通过简单手性路易酸络合物的催化体系来实现外消旋2-芳基吖丙啶的不对称动力学拆分。该反应体系具有反应条件温和、原子经济性好的优点,可放大至克级规模。相关研究成果发表于J. Am. Chem. Soc., 2015, 137, 10088–10091,申报发明专利1项,应邀在南京大学主办的第十三届江淮有机化学论坛作青年学者报告。

(2) 发展了由一价银和手性双膦配体成的催化体系催化有机胺对吖丙啶的不对称亲核开环反应构建手性邻二胺类化合物,该类化合物在不对称催化和药物化学等研究领域中具有广泛而重要的应用。该催化体系不仅适用于对内消旋吖丙啶的去对称化反应,也适用于对外消旋吖丙啶的动力学拆分,且两类体系均可放大至克级规模。相关研究成果发表于Angew. Chem. Int. Ed., 2017, ?2017,?56, 650–654.,申报发明专利1项。

?佐证材料:

1.?Zhuo Chai,* You-Min Zhu, Pei-Jun Yang, Shaoyin Wang, Shaowu Wang,* Zhen Liu, Gaosheng Yang, “Copper(I)-Catalyzed Kinetic Resolution of N-Sulfonylaziridines with Indoles: Efficient Construction of Pyrroloindolines”,?J. Am. Chem. Soc.?2015,?137, 1008810091.

2.?Zhuo Chai,* Pei-Jun Yang, Hu Zhang, Shaowu Wang, Gaosheng Yang, “Synthesis of Chiral Vicinal Diamines by Silver(I)-Catalyzed Enantioselective Aminolysis of N-Tosylaziridines”,?Angew. Chem. Int. Ed.?2017,?56, 650654.

3.?Zhuo Chai,* Jia-Nan Chen, Zhen Liu, Xue-Fei Li, Pei-Jun Yang, Ji-Ping Hu, Gaosheng Yang, “[3+2]-Annulations of N-alkyl-3-substituted indoles with quinone monoketals catalysed by Br?nsted acids”,?Org. Biomol. Chem.?2016,?14, 10241030.

4.?Zhuo Chai, Dezhi Hua, Kui Li, Jiang Chu, Gaosheng Yang,*?“A novel chiral yttrium complex with a tridentate linked amido-indenyl ligand for intramolecular hydroamination”,?Chem. Commun.?2014,?50, 177179.

5.?Zhuo Chai,* Biao Wang, Jia-Nan Chen, Gaosheng Yang, “Arylation of Azlactones using Diaryliodonium Bromides and Silver Carbonate: Facile Access to alpha-Tetrasubstituted Amino Acid Derivatives”,?Adv. Synth. Catal.?2014,356, 27142718.

6.?Shaoyin Wang, Xiancui Zhu,?Zhuo Chai,* and Shaowu Wang,* “Synthesis of polysubstituted pyrroles via [3+2]-annulation of aziridines and beta-nitroalkenes under aerobic conditions”,?Org. Biomol. Chem.?2014,?12, 13511356.?

7.?Gaosheng Yang,*?Yongxian Sun, Yue Shen,?Zhuo Chai,* Shuangliu Zhou, Jiang Chu, Jun Chai, “cis-2,3-Disubstituted Cyclopropane 1,1-Diesters in [3+2] Annulations with Aldehydes: Highly Diastereoselective Construction of Densely Substituted Tetrahydrofurans”,?J. Org. Chem.?2013,?78, 5393–5400.

8.?柴卓,朱佑民,王绍武,杨培俊,杨高升,一种手性六氢吡咯并吲哚类化合物的制备方法,中国发明专利,?专利号:ZL 2015 1 0262771.2.

9.?柴卓,杨培俊,王绍武,杨高升,一种手性邻二胺类化合物及其制备方法,中国发明专利,?专利号:ZL 2016 1 0234895.4.?


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     课题组从新型染料母体结构设计开发、染料高效选择性修饰衍生、染料激发态调控三个方面出发,揭示了染料光学性能调控的理论规律,在含硼功能有机染料的设计开发、光电性质研究及其在生命科学和材料化学上的应用等领域取得了系列创新性成果。

(1) 围绕氟硼二吡咯功能染料的设计开发,发展了一组高效区域选择性修饰衍生氟硼二吡咯母核的新反应和新方法(醛基化、卤化、芳基化、烯丙基化、烷基化等),构建了系列重要平台分子及功能染料;发展了一组高效调控多吡咯类荧光染料光谱性能的新策略,构建了系列近红外功能染料和光敏剂。这些新反应、新方法和新平台分子为构建新型近红外有机染料、调控其光电性质、开发新型功能染料提供了基础。

(2) 发展了几种简洁高效构建共轭三吡咯/四吡咯染料的新方法,构建了系列天然产物灵菌红素衍生及类似物。

(3) 围绕高固态和大斯托克斯位移荧光染料的设计开发,发展了几类新型含硼有机染料的母核及其简洁高效构建策略,构建了系列吸收发射/波长可调的固态荧光染料。

这些相关工作发表论文四十余篇,成果被国内外学者多次专文报道和评述,主要论文被SCI他引次数600余次。焦莉娟教授获得了2015年度安徽省杰出青年基金项目资助和2016年度国际卟啉和酞菁学会(Society of Porphyrins and Phthalocyanines)的青年科学家奖 (SPP/JPP Young Investigator Awards)

佐证材料:

1. Sheng, W.; Zheng, Y.; Wu, Q.; Wu, Y.; Yu, C.; Jiao, L.* Hao, E.; Wang, J.-Y.* Pei, J. Synthesis, Properties, and Semiconducting Characteristics of BF2 Complexes of beta,beta-Bisphenanthrene-Fused Azadipyrromethenes. Org. Let.,  201719, 2893-2896.

2. Chen, N.; Zhang, W.; Chen, S.; Wu, Q.; Yu, C.; Wei, Y.; Xu, Y.; Hao, E.; Jiao, L.* Sterically Protected N2O-Type Benzopyrromethene Boron Complexes from Boronic Acids with Intense Red/Near-Infrared Fluorescence. Org. Let.,  201719, 2026-2029.

3. Zhang, W.; Sheng, W.; Yu, C.; Wei, Y.; Wang, H.; Hao, E.;* Jiao, L.* One-pot synthesis and properties of well-defined butadiynylene-BODIPY oligomers. Chem. Commun., 2017, 5318-5321.

4. Li, J.; Zhang, Q.; Yin, J.; Yu, C.; Hao, E.; Wei, Y.; Mu, X.; Jiao, L.* Metal-Free and Versatile Synthetic Routes to Natural and Synthetic Prodiginines from Boron Dipyrrin. Org. Let., 201618, 5696-5699.

5.Feng, Z.; Jiao, L.*;Feng, Y.; Yu, C.; Chen, N.; Wei, Y.; Mu, X.; Hao, E.* Regioselective and Stepwise Syntheses of Functionalized BODIPY Dyes through Palladium-Catalyzed Cross-Coupling Reactions and Direct C-H Arylations. J. Org. Chem.,201681, 6281-6291.

6.  Zhou, X.;Wu, Q.; Yu, Y.; Yu, C.; Hao, E.; Wei, Y.; Mu, X.; Jiao, L.* Metal-Free Direct alpha-Selective Arylation of Boron Dipyrromethenes via Base-Mediated C-H Functionalization. Org. Let., 2016, 18, 736-739.

7. Zhou, X.; Yu, C.; Feng, Z.; Yu, Y.; Wang, J.; Hao, E.; Wei, Y.; Mu, X.; Jiao, L.* Highly Regioselective α-Chlorination of the BODIPY Chromophore with Copper(II) Chloride. Org. Let.,  201517, 4632-4635.

8. Yu, C.; Jiao, L.*; Li, T.; Wu, Q.; Miao, W.; Wang, J.; Wei, Y.; Mu, X.; Hao, E.* Fusion and Planarization of bisBODIPY: a New Family of Photostable Near Infrared Dyes. Chem. Commun.,  201551, 16852-16855.

9.Wu, Y.; Cheng, C.; Jiao, L.*; Yu, C.; Wang, S.;* Wei, Y.; Mu, X.; Hao, E.* β-Thiophene-Fused BF2-Azadipyrromethenes as Near-Infrared Dyes. Org. Let., 201416, 748-751. 

10.学术带头人焦莉娟教授获2016年酞菁学会(Society of Porphyrins and Phthalocyanines)的青年科学家奖 (SPP/JPP Young Investigator Awards)

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      瞄准环境污染物、生物分子及疾病标志物等物种的精准甄别与检测等关键科学问题,课题组设计合成功能分子传感材料,藉光学、电学、色谱以及成像等技术手段,着力开展生化物质的检测新原理、新方法及新技术研究。特别是在分子光谱与成像分析、生物电分析化学方向取得了一批高质量的研究成果。

    利用聚多巴胺膜的强吸附性与纳米材料复合共筑免疫传感界面,开创高稳定、电子传递快、信号增敏的聚多巴胺基传感器对肿瘤标志物检测的新时期。创建三维网状表面分子印迹聚合物界面,实现对多巴胺的特异性快速识别和高灵敏检测。首次利用聚多巴胺复合物开发新型酶直接电子传递界面,开启聚多巴胺基复合材料在构筑酶直接电子转移界面的新局面。创建新型电子媒介体纳米复合传感界面,显示出独特的电催化及信号放大能力,对生物分子检测具有显著的灵敏性和选择性。创建基于DNA构象变化的复合纳米信号放大界面,开创了电化学传感界面的构建新途径。获得教育部高校科学研究自然科学奖二等奖和安徽省自然科学二等奖各1项。

    将纳米材料引入到传感器中以提高灵敏度与选择性。碳纳米管、石墨烯、金纳米粒子通过层层组装或静电吸引组装传感界面。通过各种谱学技术对组装过程进行表征。导电聚合物与纳米材料组装传感界面;研究了纳米材料的信号放大作用,获得的传感器具有高的灵敏度及选择性。应用于实际样品中特殊序列的靶DNA检测,实现了单碱基错配序列的识别。采用了多种电化学技术获得传感信号,将电化学的原理与实际紧密联系一起,拓宽了方法的应用领域。获得安徽省自然科学二等奖1项。佐证材料

1. Yan Zhao, Yucheng Huang (cofirst author), Hui Zhu, Qingqing Zhu, Yunsheng Xia*, Three-in-one: Sensing, self-assembly and cascade catalysis of cyclodextrin modified gold nanoparticles, J.Am.Chem.Soc., 2016, 138, 16645-16654.

2. Junyong Sun, Han Mei, Sufan Wang, and Feng Gao*.Two-Photon Semiconducting Polymer Dots with Dual-Emission for Ratiometric Fluorescent Sensing and Bioimaging of Tyrosinase Activity. Anal. Chem., 2016, 88, 7372-7377.

3. Mei Zhao, Yue Gao, Junyong Sun, and Feng Gao*.Mediatorless Glucose Biosensor and Direct Electron Transfer Type Glucose/Air Biofuel Cell Enabled with Carbon Nanodots. Anal. Chem., 2015, 87, 2615-2622.

4. Huide Chen,Yunsheng Xia*, Compact hybrid (gold nanodendrite-quantum dots) assembly: Plasmon enhanced fluorescence-based platform for small molecule sensing in solution, Analytical Chemistry, 2014, 86, 11062-11069.

5. Linlin Lu,Yunsheng Xia*, Enzymatic reaction modulated gold nanorod end-to-end self-assembly for ultrahigh sensitively colorimetric sensing of cholinesterase and organophosphate pesticides in human blood, Analytical Chemistry, 2015, 87, 8584-8591.

6.  Wang, Guangfeng*, Xu, Gang, Zhu, Yanhong, Zhang, Xiaojun*, A "turn-on'' carbon nanotube-Ag nanoclusters fluorescent sensor for sensitive and selective detection of Hg2+ with cyclic amplification of exonuclease III activity, Chem. Commun., 2014, 50(6): 747-750.

7. Yongxin Li,* Qingqing Wu, Shoufeng Jiao, Chaodi Xu, and Lun Wang,Single Pt Nanowire Electrode: Preparation, Electrochemistry, and Electrocatalysis,Anal. Chem. 2013, 85, 4135?4140.

8. Yaoyao Zhang, Shen Xu, Xiaoqing Xiao, Yong Liu, Yuanyuan Qian and Yongxin Li*,Single gold nanowire electrodes and single Pt@Au nanowire electrodes: electrochemistry and applications,Chem. Commun., 2017, 53, 2850—2853.

9. 王广凤,电化学生物传感界面的构建、性能研究及应用,教育部高校科学研究自然科学奖二等奖。

10. 张玉忠,DNA传感器的设计、制备及应用,安徽省自然科学二等奖。