\”Shanghai Science and Technology hero\” Tian Academy of the team Recent research highlights

“上海市科技功臣”田禾院士团队近期研究成果集锦 \”to carry out from the international first dye-sensitized solar cell research, international first signal indicative of a fluorescent molecule motion machine, emitting (VIE) induction of new concepts and mechanisms made from the original vibration, and then create a dynamic covalent Construction of basic and applied research supramolecular polymers intelligent new strategies …… Chinese Academy of Sciences, East China University Professor Tian contained more than 30 deep organic functional molecular materials bonds, non-covalent bond and photo-responsive groups in the field of chemical the international level make a significant contribution to achieve the transition from heel and went running. \”- CNR network reported that the above report highly summarized the important contribution Tian Academy of Sciences in the field of organic functional molecular materials. Of course, its achievements more than that. 2014 and 2015 annual Tian Academy of Sciences in the field of chemistry are cited high international scholars \”Highly Cited Researchers\”. In addition, in 2000 the project of \”5-inch CD production technology, materials research and development and mastering CD recorded\” National Science and Technology Progress Award. In 2007 the \”organic fluorescent functional materials,\” the State Natural Science Award. 2020 May 19, was named Tian Academy of Sciences\’ 2019 annual Shanghai Science and Technology hero \”despite nearly sixty years of age, but Tian Academy of Sciences is also active in the field of chemistry research, important results frequently reported. The following classification will sort Tian Academy recent research results, divided into five directions, namely, a solar cell, a fluorescent material, a phosphorescent material, an antibacterial material and a supramolecular polymer. Wherein, the fluorescent material for emitting a thermometer and quantification of biomolecules made significant progress. Furthermore, Tian Academy team innovation developed a fluorescence-activated microspheres and photodynamic antimicrobial peptides with antibacterial photothermal dual mode for antibacterial material. In terms of the supramolecular polymer, they enhance iron carboxylate complex by introducing the fastener and the molecular ion cluster, resolve contradiction strength and toughness of the polymer. .

First, the solar cell

1 \”Angew\”: phenanthrene fused quinoxaline for a dye-sensitized solar cell sensitizer

In Cu (II / I) bipyridine or phenanthroline the redox agent is a dye-sensitized solar cell (the DSSCs) have a high open-circuit voltage (VOC,> 1v). However, their short-circuit photocurrent density (JSC) is still not high. Tian Academy of Sciences, Professor Zhu macro and Lausanne Institute of Technology Michael Grätzel reported two new D-A-π-A wherein the sensitizer (HY63 and HY64), they are benzothiadiazole (BT) or phenanthrene fused quinoxaline (PFQ) withdrawing as an auxiliary electron acceptor moiety. Although initial absorption and energy level are very similar, but the HY64 DSSCs largely superior to similar products HY63, to achieve 12.5 percent of high power conversion efficiency (the PCE), has excellent stability and is based. Kinetics of in-depth study of the sub-interface indicates that the charge carriers, BT PFQ superior in inhibiting charge recombination, thereby achieving near-quantitative collection of photogenerated carriers. “上海市科技功臣”田禾院士团队近期研究成果集锦 Link: http://dx.doi.org/10.1002/anie.202000892

2 \”Chemical Science\”:. Thione electron-rich high quality of perovskite CsPbI3 mine film

lead cesium iodide (CsPbI3) is a perovskite having good thermal stability and band gap photovoltaic material. However, it involves complex phase transition, black and phase CsPbI3 most stable form at high temperatures (200-360 deg.] C), which makes it challenging to practical application. Tian and Professor Wu Yong Academy proved true for the first time under mild conditions, using 4 (1H) – pyridine feasible way parathion (4-PT) to grow high quality neutral molecular additive phase CsPbI3 black film. CsPbI3 prepared film having a uniform morphology, phase stability characteristics at ambient conditions, by the accumulation micron grains and crystal orientation is made. They found that 4-PT thione group of the electron-rich Pb-S form a strong interaction not only affects the crystalline pathway, and by the crystal phase of the black surface functionalization CsPbI3 stable. In the device structure of a pin structure based on CsPbI3 4-PT achieved 13.88% power conversion efficiency, packaged device memory 20 days to maintain the initial efficiency of 85% or more in the environment, which is totally cold treatment CsPbI3 photovoltaic cell the best results. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://pubs.rsc.org/en/content/articlelanding/2020/sc/c9sc06574! A # divAbstract

3 \”JACS\”:. On two complementary components of the synergistic dye solar cell efficiency

To achieve efficient dye-sensitized solar cell (the DSSCs) panchromatic absorption, developed two complementary co-sensitizer dye uptake method. However, this method usually requires the distribution and proportional control of two co-TiO2 film in a dye adsorption, optimized time-consuming. Professor Tian Academy reconciliation a class permanent tree design with two complementary \”synergistic dye\” dye component covalently attached. The newly synthesized double-stranded organic dye Z2 connected porphyrin dyes XW51 recently reported by a flexible chain of different length, to afford XW60-XW63. These dyes exhibit good absorption and efficiency in the range of 8.8% -11.7%. After the co-adsorbed with chenodeoxycholic acid (CDCA), XW61 provides 12.4% efficiency (iodine-based electrolyte DSSC). Furthermore, these dyes also exhibit the advantages of the battery is easy to manufacture, simple to optimize and excellent light stability. “上海市科技功臣”田禾院士团队近期研究成果集锦 Link:. https://pubs.acs.org/doi/10.1021/jacs.9b12675

Second, the fluorescent material

1 \”Nature Communications\”: Anti- reliable ratio Kasha / Kasha fluorophore achieve biomolecule quantization

phosphor technology in vivo monitoring of biological molecules has undergone revolutionary changes. However, probes and chemical complex cellular environments major technical obstacles restrict the quantitative accuracy of these biomolecules. Professor Zhu macro, Tian Academy of Sciences, and Professor Guo Zhiqian Professor Liu Xiaogang Singapore University of Technology and Design reported a dual anti-emitting fluorophore Kasha activity, which binds integrated fluorescein and chromium-ene (IFC) and the donor building blocks -π- receptor structural modification. These fluorophores exhibit constant state S1 from the near-infrared emission Kasha, while the state S2 from about fine adjustment of the emission can be obtained by trans Kasha spironolactone on / off of 520nm. They biometric portion is introduced into the IFC structure, as emitted by S1 and reliable internal reference signal, with the ratio (S2 / S1) and viable cells was quantified animal cysteineAcid and glutathione. This adjustment Kasha new strategy for anti-active properties extends the in vivo ratio quantification kit for high-precision analysis of life science research and clinical applications. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://doi.org/10.1038/s41467-020-14615-3

2 \”Materials Horizons\”:. Intelligent Molecular butterfly

Tian Academy of Sciences, Zhang Zhiyun researchers and Associate Professor Meiju dihydro using phenazine derivative (dibenzo [a, c] phenazine-diyl -9,14- bis (4,1-phenylene)) bis (methylene) bis (isocyanate) (the DPC)) of the excited state of transform configuration, to achieve high sensitivity in a single molecule systems, adjustable color temperature response range. Conveniently controlled by DPC disaggregation and aggregation, it can be configured to control transitions excited state, thereby providing a temperature change in response to the ratio. By changing the composition of the mixture of ethanol glycerol / fine tuned in response to the temperature region, the entire wide linear range 49.18 degrees C (Celsius 11.4-37.78). Addition to the relatively high sensitivity of about 2000% per ° C outside and good reproducibility (stability) due to the establishment of a precise functional relationship between temperature and CIE coordinates fluorescent colors, so this test (maximum emission at all reported in the thermometer) temperature program can be accurately read even from the fluorescent color temperature, which greatly expand the application range of the light emitting thermometer. The strategy to solve the contradiction between the high sensitivity and wide range of temperature response. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://pubs.rsc.org/en/content/articlelanding/2020/mh/c9mh01167f#!divAbstract

3 \”Chemical Science\”:. Envelope protein to improve small-molecule fluorescence probe performance

Tian Academy of Sciences, Professor He Xiaopeng, University of Bath Tony D. James, University of Texas at Austin Jonathan L. Sessler and the Shanghai Institute of Materia Medica Chinese Academy of Sciences researcher Li Jia, a report based on protein hybrid strategy, LeeWith human serum albumin (HSA) was dissolved to a host-guest chemistry fluorescent probe Pinkment-OAc other cell impermeable. SAXS analysis confirmed the solution state, and the hybrid formed HSA / Pinkment-OAc supramolecular. In vitro experiments confirmed HSA / Pinkment-OAc hybrid of ONOO (-) response fluorescence enhancement. HSA / Pinkment-OAc hybrid also the original 264.7 macrophages and HeLa cancer cell lines were evaluated, showing cell permeability, ONOO- SIN-1 can be detected and generated and acute LPS LPS treated mice in vivo imaging of inflammation. And in vivo at the cellular level, compared with separate Pinkment-OAc, which was significantly increased by 5.6-fold (RAW 264.7), 8.7 times (of HeLa) and 2.7-fold response. “上海市科技功臣”田禾院士团队近期研究成果集锦 Link:. https://pubs.rsc.org/en/Content/ArticleLanding/2020/SC/C9SC03961A#!divAbstract

4 \”Nature Communications\”: having assembled the transmitted encoded tunable single fluorophore supramolecular systems

Several strategies have been developed, although controllable to dynamically adjust the fluorescence properties of small organic molecules, but molecules emit multicolor single fluorophore remains a challenge. Tian Academy and Hui Professor Qu reported a large light emitting system and pyrene fluorophores bound acylhydrazone unit, which may be generated in different multicolor switchable assembled state fluorescence emission. Using amphiphilic assembly from the guest to identify and γ- cyclodextrin mediated supramolecular two tools, control of molecular packing distance aromatic compound to produce a tunable blue to yellow emitting phosphor, comprising a white light emission. In addition, the introduction of an external chemical signals amylase, on the time scale of the control system of the assembled state, to generate a unique dynamic light emitting system. Dynamic characteristics of such multicolor system may also be implemented in the hydrogel network, it indicates the potential intelligent fluorescent material. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://doi.org/10.1038/s41467-019-13994-6

Third, the phosphorescent material

1 \”Chemical Science\”: cucurbituril making water becomes bright Gold Clusters

Gold Clusters having precise atomic structure ( AuNCs) has good biocompatibility and optical properties. However, most of the light emission efficiency is relatively low AuNCs solution. Tian Ma Xiang by Professor Academy between cucurbituril (CBs for) and FGGC (Phe-Gly-Gly-Cys peptide) to change the self-assembled primary object excited state transition rates. In aqueous solution, CB / FGGC-AuNCs exhibits a strong red phosphorescent emission, CB [7] and CB [8] the quantum yield (QY) of 51% and 39%, respectively, while only the simple FGGC -AuNCs exhibit weak emission, QY 7.5%. In addition, CB [7] / FGGC-AuNCs showed good results in vivo luminescence imaging cancer cells A549. Studies have shown that the main object of the macrocyclic secondary self-assembly is a simple and effective non-covalent modification and adjustment means nanostructure optical properties. “上海市科技功臣”田禾院士团队近期研究成果集锦 Link: https://pubs.rsc.org/en/content/articlelanding/2020/sc/d0sc00473a#!divAbstract

2 \”Chemical Science\”:. Preparation of dye-based Bodipy near-infrared room-temperature phosphorescence flexible material

Study pure organic room temperature phosphorescence (RTP) materials has made great progress, but the near infrared (NIR) Study RTP luminescent material still rare. Fellow Professor Tian Ma Xiang and the iodine-substituted pyrrole boron difluoride (Bodipy) new preparation of an amorphous copolymer of acrylamide, as compared with the conventional Bodipy dyes have a strong absorption in the visible region, moderate in the near infrared region RTP, Stokes displacement is much greater. Urea pyrimidone (UPy) and N, N\’- methylene-bisacrylamide (of MBAA) as raw materials, the gel having a near-infrared emission RTP prepared. Due to the quadruple hydrogen bonds between molecules UPy, the gel has a fast self-healing. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: . Https://pubs.rsc.org/en/content/articlelanding/2019/sc/c9sc05502a#!divAbstract

3 \”Angew\”: Cucurbit [8] urea supramolecular assembly under visible in water exciting phosphorescence at room temperature

the solid state material having high room-temperature phosphorescence (RTP) emitted been widely used in materials science, and purely organic liquid or liquid RTP transmission system due to non-radiative decay, and liquid quenching medium and fresh It reported. Professor Ma Xiang and Tian Academy of Sciences presents the first example of a host-guest supramolecular assembly strategy to stimulate pure organic RTP in aqueous solution. Unique cucurbit [8] urea mediated quaternary structure allows the bulk tunable photoluminescence excitation and visible light, and that the preparation of hydrogel cells multicolor imaging possible. The current \”assembly-induced emission\” method as a proof of concept, help build RTP system having a novel metal-free tunable photoluminescence in aqueous solution, provides a further application in the field of biological imaging, detection, optical sensors, etc. vast opportunities. “上海市科技功臣”田禾院士团队近期研究成果集锦 Link: http://dx.doi.org/10.1002/anie.201914513

Fourth, the antimicrobial material

on clinical multidrug resistant (super bacteria) refractory infection has become one of the primary threats to life and safety of hospital ICU patients, but traditional antibiotics development process is greatly lags behind the resistant bacteria, so how to develop efficient, innovative type of non-antibiotic antimicrobial strategy to become a global bio Chinese medicine practitioners are facing major challenges of the problem. .

1 \”JACS\”: cyclodextrin-based self-assembling peptides to enhance peptide-based fluorescence imaging and antibacterial effects

Tian Academy of Sciences, Professor He Xiaopeng, Shanghai Institute of Materia Medica Chinese Academy of Sciences researcher Li Jia, France Cachan Ecole Normale Superieure Juan an additional beta] Professor xie, professor at University of Texas at Austin Jonathan Sessler prepared cyclodextrin hept – two cyanomethyl -4H- pyran (DCM7-β-CD), as 1-bromonaphthalene modified peptides to enhance delivery \”host.\” Fluorescent peptide P1-P3 with each other DCM7-β-CDEffect, form a unique supramolecular structures, called Supramolecular peptide point (Spds). Each Spd (Spd-1, Spd-2, Spd-3) can promote consisting of fluorescent probe (P1-P3) transmitted within the cell, enabling biomarkers of apoptosis (caspase-3), and mitosis spatiotemporal imaging. Peptide P4 binding of Spd-4 alone as compared to P4, of Gram-positive and Gram-negative bacteria have a greater therapeutic effect. In addition, they are also a fluorescent Spd-4, as compared to individual peptides (P4-FITC), the fluorescence Spd-4 shows more in Escherichia coli (ATCC 25922) and Staphylococcus aureus (ATCC 25923) was prepared large bacterial cell uptake. Spd platform to facilitate delivery of therapeutic peptides, and provides an easy to implement strategies to enhance the antibacterial effect of the known therapeutic peptides. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://pubs.acs.org/doi/10.1021/jacs.9b11207 Related: Rick He Xiaopeng team: In the non-antibiotic antimicrobial materials, micro antimicrobial peptides ball fields has made significant progress

2 \”Angew\”:. supramolecular has broad-spectrum antimicrobial activity of the two-wavelength light therapy agent

Tian Academy of Sciences, Professor He Xiaopeng, Professor Juyoung Yoon Korea Ewha Womans University, Shanghai Jiaotong University Professor Michael Valiant and Professor Chen Daijie reported controllable structure of graphene nanoribbons (GNRs) with cationic porphyrins (Pp4N) simple supramolecular self-assembly, in order to obtain coated with a unique one-dimensional linear GNR superstructure Pp4N nanoparticles . Such Pp4N / GNR nanocomposite at 660 and 808nm light respectively exhibit good dual-mode characteristics, have significant reactive oxygen species (ROS) generation (photodynamic therapy) and temperature (photothermal therapy ). This method combines the synergy demonstrated in vitro and in vivo annihilated a broad spectrum of gram-positive and gram-negative resistant bacteria. The study also reveals GNRs prospects overcome antibiotic resistance as the development of dual-mode antibacterial agent. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: http://dx.doi.org/10.1002/anie.201913506

V. supramolecular polymer

refers to an array of supramolecular polymer repeating unit is non-directional and reversible covalent interactions connected to. Due to the presence of reversible non-covalent interaction, the supramolecular polymer generally has a good self-healing ability, but at the same time, due to non-covalent interactions are weak interaction, the mechanical properties of the supramolecular polymer often poor. .

1 \”AM\”: Effect of the fastener elements of the elastic polymer

Tian Academy and Hui Professor Qu large supramolecular strategy proposed mechanism similar to the slide fastener is introduced into the hydrogen bonding network crosslinked polyurethane. A very small amount (0.5 mol%) of the external additive (Pseudo [2] rotaxane crosslinking agents) can significantly increase the mechanical strength of the polyurethane network and elongation nearly an order of magnitude. This enhancement is due to the unique loop fastener similar sliding motion on the molecular level, the mechanical power dissipated effectively solventless network. The present study not only provides a clear overall strategy for preparing a high-performance elastomer, and paved the way for the practical application of artificial molecular machines without a solvent in the polyurethane network. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: https://onlinelibrary.wiley.com/doi/10.1002/adma.202000345 Related: East China University Professor Qu Hui big team \”AM\”: the elastic polymer molecular effects fastener body

2 \”Angew\”: ion clustering and iron carboxylate complex, a self-healing supramolecular polymer toughening

University of Groningen Ben L. Feringa, Tian Fellow Professor Qu Wo and large brightness enhanced by introducing a carboxylate ion cluster iron complexes to toughening supramolecular network. The resulting dry supramolecular network also has a strong mechanical strength, high stretchability, the self-healing property and workability at room temperature. This is due to the presence of four types of dynamic combination of high density of the dry network, including dynamic covalent disulfide bond, non-covalent hydrogen bonds, iron carboxylate complex and ionic clusters of hydration. The preparation of such polymers healing extremely simple, high-performance, low-cost device and wear resistant coating materials offer the prospect. “上海市科技功臣”田禾院士团队近期研究成果集锦 The full text link: http://dx.doi.org/10.1002/anie.201913893 Related: East China University of Qu Tai-fai \”Germany should\”: A self-healing polymers research work in the field of supramolecular made progress

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