Structure and principles of self-assembly of giant“sea urchin”type sulfonatophenyl porphine aggregates  

作　　者：Marijus Pleckaitis Fayez Habach Lukas Kontenis Gábor Steinbach Greta Jarockyte Agne Kalnaityte IldikóDomonkos Parveen Akhtar Mehdi Alizadeh Saulius Bagdonas Vitalijus Karabanovas GyőzőGarab Ricardas Rotomskis Virginijus Barzda 

机构地区：[1]Laser Research Center,Faculty of Physics,Vilnius University,Sauletekio av.10,Vilnius LT-10223,Lithuania [2]Biomedical Physics Laboratory,National Cancer Institute,P.Baublio str.3b,Vilnius LT-08406,Lithuania [3]Department of Chemical and Physical Sciences,University of Toronto Mississauga,3359 Mississauga Rd,Mississauga L5L 1C6,Canada [4]Light Conversion,Keramiku str.2B,Vilnius LT-10233,Lithuania [5]Cellular Imaging Laboratory,Biological Research Centre,Eötvös Loránd Research Network,Temesvári körút 62,Szeged 6726,Hungary [6]Institute of Biophysics,Biological Research Centre,Eötvös Loránd Research Network,Temesvári körút 62,Szeged 6726,Hungary [7]Biofotonika Research and Development Ltd.,Dózsa u.7,Szeged 6720,Hungary [8]Institute of Plant Biology,Biological Research Centre,Eötvös Loránd Research Network,Temesvári körút 62,Szeged 6726,Hungary [9]Department of Chemistry and Bioengineering,Vilnius Gediminas Technical University,Sauletekio av.11,Vilnius LT-10223,Lithuania [10]Department of Physics,Faculty of Science,University of Ostrava,Chittussiho 10,Ostrava CZ-71000,Czech Republic [11]Department of Physics,University of Toronto,60 St.George St.Toronto,Toronto M5S 1A7,Canada

出　　处：《Nano Research》2022年第6期5527-5537,共11页纳米研究（英文版）

基　　金：supported by European Regional Development Fund(No.01.2.2.-LMT-K-718-02-0016)under grant agreement with the Research Council of Lithuania(LMTLT);Support was also provided by the Natural Sciences and Engineering Research Council of Canada(NSERC)(Nos.RGPIN-2017-06923 and DGDND-2017-00099);I.D.was supported by GINOP-2.3.2-15-2016-00058 and G.S.by GINOP-2.3.2-15-2016-00001;ELKH KÜ-37/2020 grants from the Hungarian Ministry for National Economy and the Eötvös Loránd Research Network,respectively。

摘　　要：Principles of molecular self-assembly into giant hierarchical structures of hundreds of micrometers in size are studied in aggregates of meso-tetra(4-sulfonatophenyl)porphine(TPPS_(4)).The aggregates form a central tubular core,which is covered with radially protruding filamentous non-branching aggregates.The filaments cluster and orient at varying angles from the core surface and some filaments form bundles.Due to shape resemblance,the structures are termed giant sea urchin(GSU)aggregates.Spectrally resolved fluorescence microscopy reveals J-and H-bands of TPPS_(4)aggregates in both the central core and the filaments.The fluorescence of the core is quenched while filaments exhibit strong fluorescence.Upon drying,the filament fluorescence gets quenched while the core is less affected,showing stronger relative fluorescence.Fluorescencedetected linear dichroism(FDLD)microscopy reveals that absorption dipoles corresponding to J-bands are oriented along the filament axis.The comparison of FDLD with scanning electron microscopy(SEM)reveals the structure of central core comprised of multilayer ribbons,which wind around the core axis forming a tube.Polarimetric second-harmonic generation(SHG)and thirdharmonic generation microscopy exhibits strong signal from the filaments with nonlinear dipoles oriented close to the filament axis,while central core displays very low SHG due to close to centrosymmetric organization.Large chiral nonlinear susceptibility points to helical arrangement of the filaments.The investigation shows that TPPS_(4)molecules form distinct aggregate types,including chiral nanotubes and nanogranular aggregates that associate into the hierarchical GSU structure,prototypical to complex biological structures.The chiral TPPS_(4)aggregates can serve as harmonophores for nonlinear microscopy.

关 键 词：meso-tetra(4-sulfonatophenyl)porphine(TPPS_(4))aggregates SELF-ASSEMBLY nanostructures harmonophores polarimetric second harmonic generation microscopy third harmonic generation microscopy 

分 类 号：O62[理学—有机化学] TB3[理学—化学]