Malonitrile‐Functionalized Tetraphenylpyrazine: Aggregation‐Induced Emission, Ratiometric Detection of Hydrogen Sulfide, and Mechanochromism

Development of new aggregation-induced emission (AIE) luminogens has been a hot research topic because they thoroughly solve the notorious aggregation-caused quenching effect confronted in conventional fluorogens and their promising applications in, for example, organic light-emitting diodes, chemoand biosensors and bioimaging. Many AIE luminogens (AIEgens) have been prepared but most of them are silole, tetraphenylethene, distyrylanthracene, and their derivatives. In this work, based on the skeleton of tetraphenylpyrazine (TPP), a new AIEgen, named TPP-PDCV, is generated by functionalizing TPP with malonitrile group. TPP-PDCV can serve as a sensitive ratiometric fluorescent probe for detecting hydrogen sulfide with high speciality and low detection limit of down to 0.5 × 10−6 m. The mechanism for such detection is fully investigated and deciphered. Unlike most reported mechanochromic AIEgens, which undergo turn-off or -on emission or emission bathochromic shift in the presence of external stimuli, TPP-PDCV exhibits an abnormal and reversible mechanochromism with hypsochromic effect. These indicate that TPP-PDCV possesses a huge potential for high-tech applications through rational modification of TPP core.

[1]  B. Tang,et al.  N-type pyrazine and triazole-based luminogens with aggregation-enhanced emission characteristics. , 2015, Chemical communications.

[2]  D. Lefer,et al.  A fluorescent probe for fast and quantitative detection of hydrogen sulfide in blood. , 2011, Angewandte Chemie.

[3]  B. Halliwell,et al.  The novel neuromodulator hydrogen sulfide: an endogenous peroxynitrite ‘scavenger’? , 2004, Journal of neurochemistry.

[4]  J. Parneix,et al.  Nanostructuration of phenylenevinylenediimide-bridged silsesquioxane: from electroluminescent molecular J-aggregates to photoresponsive polymeric H-aggregates. , 2006, Journal of the American Chemical Society.

[5]  B. Tang,et al.  Triphenylamine-functionalized tetraphenylpyrazine: facile preparation and multifaceted functionalities , 2016 .

[6]  Kai Li,et al.  Bright and Photostable Organic Fluorescent Dots with Aggregation‐Induced Emission Characteristics for Noninvasive Long‐Term Cell Imaging , 2014 .

[7]  Christopher J. Chang,et al.  A reaction-based fluorescent probe for selective imaging of carbon monoxide in living cells using a palladium-mediated carbonylation. , 2012, Journal of the American Chemical Society.

[8]  M. Oba,et al.  Aerobic oxidation of thiols to disulfides catalyzed by diaryl tellurides under photosensitized conditions. , 2011, The Journal of organic chemistry.

[9]  Dong Ryeol Whang,et al.  High-contrast red-green-blue tricolor fluorescence switching in bicomponent molecular film. , 2015, Angewandte Chemie.

[10]  Xiao Feng,et al.  A malonitrile-functionalized metal-organic framework for hydrogen sulfide detection and selective amino acid molecular recognition , 2014, Scientific Reports.

[11]  C. Niu,et al.  Solvatochromism, Reversible Chromism and Self-Assembly Effects of Heteroatom-Assisted Aggregation-Induced Enhanced Emission (AIEE) Compounds. , 2015, Chemistry.

[12]  B. Tang,et al.  Defect-sensitive crystals based on diaminomaleonitrile-functionalized Schiff base with aggregation-enhanced emission , 2013 .

[13]  Ben Zhong Tang,et al.  Biocompatible Nanoparticles with Aggregation‐Induced Emission Characteristics as Far‐Red/Near‐Infrared Fluorescent Bioprobes for In Vitro and In Vivo Imaging Applications , 2012 .

[14]  Oksana Ostroverkhova,et al.  Organic Optoelectronic Materials: Mechanisms and Applications. , 2016, Chemical reviews.

[15]  D. Ding,et al.  Bioprobes based on AIE fluorogens. , 2013, Accounts of chemical research.

[16]  Khai Leok Chan,et al.  Synthesis of light-emitting conjugated polymers for applications in electroluminescent devices. , 2009, Chemical reviews.

[17]  B. Tang,et al.  Aggregation-enhanced emission active tetraphenylbenzene-cored efficient blue light emitter. , 2017, Faraday discussions.

[18]  T. Chatterjee,et al.  Aerobic oxidation of thiols to disulfides under ball-milling in the absence of any catalyst, solvent, or base , 2013 .

[19]  P. Eaton.  Protein thiol oxidation in health and disease: techniques for measuring disulfides and related modifications in complex protein mixtures. , 2006, Free radical biology & medicine.

[20]  B. Tang,et al.  A Selective Glutathione Probe based on AIE Fluorogen and its Application in Enzymatic Activity Assay , 2014, Scientific Reports.

[21]  B. Tang,et al.  A sensitivity tuneable tetraphenylethene-based fluorescent probe for directly indicating the concentration of hydrogen sulfide. , 2014, Chemical communications.

[22]  W. Tan,et al.  Design of a simultaneous target and location-activatable fluorescent probe for visualizing hydrogen sulfide in lysosomes. , 2014, Analytical chemistry.

[23]  Ryan T. K. Kwok,et al.  Aggregation-Induced Emission: Together We Shine, United We Soar! , 2015, Chemical reviews.

[24]  Liang Yan,et al.  Recent Advances in Design and Fabrication of Upconversion Nanoparticles and Their Safe Theranostic Applications , 2013, Advanced materials.

[25]  Fangjun Huo,et al.  A coumarin-based “off-on” sensor for fluorescence selectivily discriminating GSH from Cys/Hcy and its bioimaging in living cells , 2017 .

[26]  Wei Chen,et al.  Chemical probes for molecular imaging and detection of hydrogen sulfide and reactive sulfur species in biological systems. , 2015, Chemical Society reviews.

[27]  Zhiqiang Gao,et al.  Silver/gold core-shell nanoprism-based plasmonic nanoprobes for highly sensitive and selective detection of hydrogen sulfide. , 2015, Chemistry.

[28]  Ben Zhong Tang,et al.  Aggregation-induced emission: phenomenon, mechanism and applications. , 2009, Chemical communications.

[29]  K. Hanaoka,et al.  Development of a highly selective fluorescence probe for hydrogen sulfide. , 2011, Journal of the American Chemical Society.

[30]  Dong Wang,et al.  Aggregation induced blue-shifted emission--the molecular picture from a QM/MM study. , 2014, Physical chemistry chemical physics : PCCP.

[31]  Hongbin Wu,et al.  White Polymer Light‐Emitting Devices for Solid‐State Lighting: Materials, Devices, and Recent Progress , 2014, Advanced materials.

[32]  D. Gould,et al.  Determination of sulfide in brain tissue and rumen fluid by ion-interaction reversed-phase high-performance liquid chromatography. , 1990, Journal of chromatography.

[33]  D. D. Di Monte,et al.  Menadione-induced cytotoxicity is associated with protein thiol oxidation and alteration in intracellular Ca2+ homeostasis. , 1984, Archives of biochemistry and biophysics.

[34]  T. Asada,et al.  Brain hydrogen sulfide is severely decreased in Alzheimer's disease. , 2002, Biochemical and biophysical research communications.

[35]  Daoben Zhu,et al.  Efficient blue emission from siloles , 2001 .

[36]  Q. Tu,et al.  Aggregation-induced bathochromic fluorescent enhancement for fluorenone dyes , 2015 .

[37]  Soo Young Park,et al.  Unique Piezochromic Fluorescence Behavior of Dicyanodistyrylbenzene Based Donor–Acceptor–Donor Triad: Mechanically Controlled Photo‐Induced Electron Transfer (eT) in Molecular Assemblies , 2012, Advanced materials.

[38]  Yuchuan Liu,et al.  Multifunctional Zinc Metal–Organic Framework Based on Designed H4TCPP Ligand with Aggregation-Induced Emission Effect: CO2 Adsorption, Luminescence, and Sensing Property , 2017 .

[39]  Jia-rui Xu,et al.  Recent advances in mechanochromic luminescent metal complexes , 2013 .

[40]  H. Dai,et al.  Carbon Nanomaterials for Biological Imaging and Nanomedicinal Therapy. , 2015, Chemical reviews.

[41]  Yongqiang Dong,et al.  Reversible Switching of the Emission of Diphenyldibenzofulvenes by Thermal and Mechanical Stimuli , 2011, Advanced materials.

[42]  S. Fukuzumi,et al.  Ordered assembly of protonated porphyrin driven by single-wall carbon nanotubes. J- and H-aggregates to nanorods. , 2005, Journal of the American Chemical Society.

[43]  Xiao‐Qi Yu,et al.  A real-time colorimetric and ratiometric fluorescent probe for sulfite. , 2013, The Analyst.

[44]  H S Kwok,et al.  Aggregation-induced emission of 1-methyl-1,2,3,4,5-pentaphenylsilole. , 2001, Chemical communications.

[45]  R. Cohen,et al.  Thiol oxidation in signaling and response to stress: detection and quantification of physiological and pathophysiological thiol modifications. , 2007, Free radical biology & medicine.

[46]  N. Maiti,et al.  J- and H-aggregates of porphyrin-surfactant complexes: time-resolved fluorescence and other spectroscopic studies , 1998 .

[47]  Wei Huang,et al.  Exceptional blueshifted and enhanced aggregation-induced emission of conjugated asymmetric triazines and their applications in superamplified detection of explosives. , 2012, Chemistry.

[48]  Jia-rui Xu,et al.  Recent advances in organic mechanofluorochromic materials. , 2012, Chemical Society reviews.

[49]  K. Hanaoka,et al.  A Water‐Soluble Mechanochromic Luminescent Pyrene Derivative Exhibiting Recovery of the Initial Photoluminescence Color in a High‐Humidity Environment , 2013 .

[50]  Lin Qiu,et al.  A ratiometric fluorescent probe for rapid detection of hydrogen sulfide in mitochondria. , 2013, Angewandte Chemie.

[51]  Zhen Li,et al.  The Strong Light‐Emission Materials in the Aggregated State: What Happens from a Single Molecule to the Collective Group , 2017, Advanced science.

[52]  Yuping Dong,et al.  Hexaphenylbenzene-Based, π-Conjugated Snowflake-Shaped Luminophores: Tunable Aggregation-Induced Emission Effect and Piezofluorochromism. , 2015, Chemistry.

[53]  M. Montalti,et al.  Nanodiamonds and silicon quantum dots: ultrastable and biocompatible luminescent nanoprobes for long-term bioimaging. , 2015, Chemical Society reviews.

[54]  Zejun Xu,et al.  Fluorescent Sensor for Rapid Detection of Nucleophile and Convenient Comparison of Nucleophilicity. , 2017, Analytical chemistry.

[55]  B. Tang,et al.  A 1,3-indandione-functionalized tetraphenylethene: aggregation-induced emission, solvatochromism, mechanochromism, and potential application as a multiresponsive fluorescent probe. , 2014, Chemistry.

[56]  Desuo Yang,et al.  Selective Host-Guest Co-crystallization of Pyridine-Functionalized Tetraphenylethylenes with Phthalic Acids and Multicolor Emission of the Co-crystals. , 2017, Chemistry.

[57]  Ben Zhong Tang,et al.  Aggregation-induced emission. , 2011, Chemical Society reviews.

[58]  Ryan S. Balok,et al.  Aggregation Induced Enhancement of Linear and Nonlinear Optical Emission from a Hexaphenylene Derivative , 2016 .

[59]  Michael D. Pluth,et al.  Development of selective colorimetric probes for hydrogen sulfide based on nucleophilic aromatic substitution. , 2013, The Journal of organic chemistry.

[60]  Yu Zhao,et al.  Capture and visualization of hydrogen sulfide by a fluorescent probe. , 2011, Angewandte Chemie.

[61]  S. Roth,et al.  Toxicology of hydrogen sulfide. , 1992 .

[62]  Ian D. Williams,et al.  A mechanistic study of AIE processes of TPE luminogens: intramolecular rotation vs. configurational isomerization , 2016 .

[63]  Guoqing Zhang,et al.  Polymorphism and reversible mechanochromic luminescence for solid-state difluoroboron avobenzone. , 2010, Journal of the American Chemical Society.

[64]  Li-juan Wang,et al.  Remarkable Turn‐On and Color‐Tuned Piezochromic Luminescence: Mechanically Switching Intramolecular Charge Transfer in Molecular Crystals , 2015 .

[65]  F. Spano.  The spectral signatures of Frenkel polarons in H- and J-aggregates. , 2010, Accounts of chemical research.

[66]  Ben Zhong Tang,et al.  Aggregation‐Induced Emission: The Whole Is More Brilliant than the Parts , 2014, Advanced materials.

[67]  B. Tang,et al.  Aggregation-induced emission of siloles , 2015, Chemical science.

[68]  S. Inagaki,et al.  Isothermally Reversible Fluorescence Switching of a Mechanochromic Perylene Bisimide Dye , 2012, Advanced materials.

[69]  J. Anzai,et al.  pH-induced interconversion between J-aggregates and H-aggregates of 5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin in polyelectrolyte multilayer films. , 2007, Langmuir : the ACS journal of surfaces and colloids.

[70]  K. Abe,et al.  The possible role of hydrogen sulfide as an endogenous neuromodulator , 1996, The Journal of neuroscience : the official journal of the Society for Neuroscience.

[71]  P. Moore,et al.  Streptozotocin-induced diabetes in the rat is associated with enhanced tissue hydrogen sulfide biosynthesis. , 2005, Biochemical and biophysical research communications.

[72]  Ian D. Williams,et al.  Aggregation-induced and crystallization-enhanced emissions of 1,2-diphenyl-3,4-bis(diphenylmethylene)-1-cyclobutene. , 2007, Chemical communications.

[73]  J. Bocchini,et al.  Low levels of hydrogen sulfide in the blood of diabetes patients and streptozotocin-treated rats causes vascular inflammation? , 2010, Antioxidants & redox signaling.

[74]  B. Tang,et al.  Comparative study of the dicyanovinyl-functionalized 1,1-dimethyl-2,3,4,5-tetraphenylsilole derivatives on their structures, properties, and applications in thiol detection , 2017 .

[75]  Yongqiang Dong,et al.  Mechanochromic Luminescence of Aggregation-Induced Emission Luminogens. , 2015, The journal of physical chemistry letters.