Fluorescence microscopy as an alternative to electron microscopy for microscale dispersion evaluation of organic–inorganic composites

Inorganic dispersion is of great importance for actual implementation of advanced properties of organic–inorganic composites. Currently, electron microscopy is the most conventional approach for observing dispersion of inorganic fillers from ultrathin sections of organic–inorganic composites at the nanoscale by professional technicians. However, direct visualization of macrodispersion of inorganic fillers in organic–inorganic composites using high-contrast fluorescent imaging method is hampered. Here we design and synthesize a unique fluorescent surfactant, which combines the properties of the aggregation-induced emission (AIE) and amphiphilicity, to image macrodispersion of montmorillonite and layered double hydroxide fillers in polymer matrix. The proposed fluorescence imaging provides a number of important advantages over electron microscope imaging, and opens a new avenue in the development of direct three-dimensional observation of inorganic filler macrodispersion in organic–inorganic composites.

[1]  J. Götze.  Application of Cathodoluminescence Microscopy and Spectroscopy in Geosciences , 2012, Microscopy and Microanalysis.

[2]  Chao Lu,et al.  Chemiluminescence as a Novel Indicator for Interactions of Surfactant–Polymer Mixtures at the Surface of Layered Double Hydroxides , 2014 .

[3]  Emmanuel P. Giannelis,et al.  Polymer Layered Silicate Nanocomposites , 1996 .

[4]  B. Weckhuysen.  Chemical imaging of spatial heterogeneities in catalytic solids at different length and time scales. , 2009, Angewandte Chemie.

[5]  T. Lunkenbein,et al.  UV‐Cured, Flexible, and Transparent Nanocomposite Coating with Remarkable Oxygen Barrier , 2012, Advanced materials.

[6]  S. G. Krivoshlykov,et al.  Rational design of a Nile Red/polymer composite film for fluorescence sensing of organophosphonate vapors using hydrogen bond acidic polymers. , 2001, Analytical chemistry.

[7]  Johan Hofkens,et al.  Three-Dimensional Visualization of Defects Formed during the Synthesis of Metal–Organic Frameworks: A Fluorescence Microscopy Study , 2012, Angewandte Chemie.

[8]  E. Chen,et al.  Stereochemically controlled PMMA-exfoliated silicate nanocomposites using intergallery-anchored metallocenium cations. , 2003, Journal of the American Chemical Society.

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

[10]  M. J. Rosen,et al.  Surfactants and Interfacial Phenomena: Rosen/Surfactants 4E , 2012 .

[11]  Michiya Fujiki,et al.  Visualizing spontaneous physisorption of non-charged π-conjugated polymers onto neutral surfaces of spherical silica in nonpolar solvents , 2015 .

[12]  Rodney D. Priestley,et al.  Model polymer nanocomposites provide an understanding of confinement effects in real nanocomposites. , 2007, Nature materials.

[13]  Quan-hong Yang,et al.  Functionalization of graphene by tetraphenylethylene using nitrene chemistry , 2012 .

[14]  Fang Zeng,et al.  Hyperbranched polyester-based fluorescent probe for histone deacetylase via aggregation-induced emission. , 2013, Biomacromolecules.

[15]  Chao Lu,et al.  Organo-Modified Montmorillonite Enhanced Chemiluminescence via Inactivation of Halide Counterions in a Micellar Solution , 2014 .

[16]  V. Mehrotra,et al.  Matrix-Mediated Synthesis of Nanocrystalline γ-Fe2O3: A New Optically Transparent Magnetic Material , 1992, Science.

[17]  B. Tang,et al.  AIE macromolecules: syntheses, structures and functionalities. , 2014, Chemical Society reviews.

[18]  Daphne Benderly,et al.  Material properties of nanoclay PVC composites , 2009 .

[19]  Ben Zhong Tang,et al.  Synthesis and Design of Aggregation-Induced Emission Surfactants: Direct Observation of Micelle Transitions and Microemulsion Droplets. , 2015, Angewandte Chemie.

[20]  B. Song,et al.  Water-soluble nano-fluorogens fabricated by self-assembly of bolaamphiphiles bearing AIE moieties: towards application in cell imaging. , 2015, Journal of materials chemistry. B.

[21]  M. Lerner,et al.  Synthesis and characterization of low-generation polyamidoamine (PAMAM) dendrimer-sodium montmorillonite (Na-MMT) clay nanocomposites. , 2013, Inorganic chemistry.

[22]  Motoyuki Iijima,et al.  Anionic surfactant with hydrophobic and hydrophilic chains for nanoparticle dispersion and shape memory polymer nanocomposites. , 2009, Journal of the American Chemical Society.

[23]  E. Giannelis,et al.  Silicate Dispersion and Mechanical Reinforcement in Polysiloxane/Layered Silicate Nanocomposites , 2010 .

[24]  Xiaohu Gao,et al.  An aggregation-induced-emission platform for direct visualization of interfacial dynamic self-assembly. , 2014, Angewandte Chemie.

[25]  Ben Zhong Tang,et al.  Protein detection and quantitation by tetraphenylethene-based fluorescent probes with aggregation-induced emission characteristics. , 2007, The journal of physical chemistry. B.

[26]  Y. Liu,et al.  Photomodulated fluorescence of supramolecular assemblies of sulfonatocalixarenes and tetraphenylethene. , 2014, ACS nano.

[27]  Ryan T. K. Kwok,et al.  Biosensing by luminogens with aggregation-induced emission characteristics. , 2015, Chemical Society reviews.

[28]  J. E. Mark.  Some novel polymeric nanocomposites. , 2006, Accounts of chemical research.

[29]  Mark Bates,et al.  Three-Dimensional Super-Resolution Imaging by Stochastic Optical Reconstruction Microscopy , 2008, Science.

[30]  Jian Wang,et al.  Click synthesis, aggregation-induced emission, E/Z isomerization, self-organization, and multiple chromisms of pure stereoisomers of a tetraphenylethene-cored luminogen. , 2012, Journal of the American Chemical Society.

[31]  L. Archer,et al.  Phase stability and dynamics of entangled polymer–nanoparticle composites , 2015, Nature Communications.

[32]  F. Bates,et al.  Layer structure preservation during swelling, pillaring, and exfoliation of a zeolite precursor. , 2008, Journal of the American Chemical Society.

[33]  Suprakas Sinha Ray,et al.  Recent Trends and Future Outlooks in the Field of Clay-Containing Polymer Nanocomposites , 2014 .

[34]  D. Tyler,et al.  Stimuli-Responsive Polymer Nanocomposites Inspired by the Sea Cucumber Dermis , 2008, Science.

[35]  Deqing Zhang,et al.  Polymorphism‐Dependent Emission for Di(p‐methoxylphenyl)dibenzofulvene and Analogues: Optical Waveguide/Amplified Spontaneous Emission Behaviors , 2012 .

[36]  J. Basu,et al.  Confinement enhances dispersion in nanoparticle–polymer blend films , 2014, Nature Communications.

[37]  A. Waas,et al.  Ultrastrong and Stiff Layered Polymer Nanocomposites , 2007, Science.

[38]  Anna C. Balazs,et al.  Nanoparticle Polymer Composites: Where Two Small Worlds Meet , 2006, Science.

[39]  M. Strano,et al.  Molecular insights into the surface morphology, layering structure, and aggregation kinetics of surfactant-stabilized graphene dispersions. , 2011, Journal of the American Chemical Society.

[40]  B. Jönsson.  Surfactants and Polymers in Aqueous Solution , 1998 .

[41]  Chao Lu,et al.  Aggregation-induced emission molecules in layered matrices for two-color luminescence films. , 2014, Chemical communications.

[42]  Chang Ming Li,et al.  Fabrication of Strongly Fluorescent Quantum Dot−Polymer Composite in Aqueous Solution , 2007 .

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

[44]  Derek Groen,et al.  Chemically Specific Multiscale Modeling of Clay–Polymer Nanocomposites Reveals Intercalation Dynamics, Tactoid Self-Assembly and Emergent Materials Properties , 2014, Advanced materials.

[45]  M. Avena,et al.  Geometrical and Electronic Properties of Hydrated Sodium Montmorillonite and Tetracycline Montmorillonite from DFT Calculations , 2015 .

[46]  Jiping Yang,et al.  Preparation and characterization of poly(vinyl chloride)/layered double hydroxide nanocomposites with enhanced thermal stability , 2008 .

[47]  E. Manias.  Nanocomposites: stiffer by design. , 2007, Nature materials.

[48]  David M. Kaz,et al.  Cathodoluminescence-activated nanoimaging: noninvasive near-field optical microscopy in an electron microscope. , 2015, Nano letters.

[49]  Yihe Zhang,et al.  Interfacial Modification of Magnetic Montmorillonite (MMT) Using Covalently Assembled LbL Multilayers , 2014 .

[50]  R. Oreffo,et al.  Clay: New Opportunities for Tissue Regeneration and Biomaterial Design , 2013, Advanced materials.

[51]  T. Jackson,et al.  Flexible high-temperature dielectric materials from polymer nanocomposites , 2015, Nature.

[52]  S. Ray,et al.  Nano-biocomposites based on synthetic aliphatic polyesters and nanoclay , 2014 .

[53]  E. Giannelis,et al.  On The Origins of Silicate Dispersion in Polysiloxane/Layered‐Silicate Nanocomposites , 2006 .

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

[55]  Sarah Kuester,et al.  Surfactants And Interfacial Phenomena , 2016 .

[56]  S. Hell.  Nanoscopy with Focused Light (Nobel Lecture). , 2015, Angewandte Chemie.

[57]  Ling Lin,et al.  A strong bio-inspired layered PNIPAM-clay nanocomposite hydrogel. , 2012, Angewandte Chemie.

[58]  Zheng Gu,et al.  Montmorillonite Functionalized with Zwitterionic Surfactant as a Highly Efficient Adsorbent for Herbicides , 2015 .

[59]  J. Lakowicz.  Principles of fluorescence spectroscopy , 1983 .

[60]  D. Musaev,et al.  [12]Annulene gemini surfactants: structure and self-assembly. , 2007, Angewandte Chemie.

[61]  Richard H. Harris,et al.  Polymer/Layered Silicate Nanocomposites from Thermally Stable Trialkylimidazolium-Treated Montmorillonite , 2002 .

[62]  J. Coleman,et al.  Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions , 2008, 0809.2690.