Amplified responses in materials using linear polymers that depolymerize from end‐to‐end when exposed to specific stimuli

This review describes new types of smart materials that have the dual capabilities of responding to selective signals and providing an amplified response. Amplification arises from a signal-induced depolymerization reaction, where a single signaling event causes an entire polymer to convert to small molecules. When incorporated into a material, depolymerization of these polymers causes a change in shape, internal structure, or surfaces properties of the material. Moreover, the small molecules arising from depolymerization can play a role in the amplified response, particularly when they provide a secondary function (e.g., production of color or fluorescence). A brief overview of the current examples of linear depolymerizable polymers is provided, as are representative proof-of-concept applications of these polymers in the context of diagnostics and materials that remodel themselves and/or their surroundings. Together, these examples highlight the potential of this new class of polymers to provide unique and dramatic function to stimuli-responsive materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40992.

[1]  Scott T. Phillips,et al.  Accessibility of Responsive End-Caps in Films Composed of Stimuli-Responsive, Depolymerizable Poly(phthalaldehydes) , 2013 .

[2]  D. Shabat,et al.  Modular theranostic prodrug based on a FRET-activated self-immolative linker. , 2012, Journal of controlled release : official journal of the Controlled Release Society.

[3]  Scott T. Phillips,et al.  Phase-Switching Depolymerizable Poly(carbamate) Oligomers for Signal Amplification in Quantitative Time-Based Assays , 2013 .

[4]  J. Sessler,et al.  Modern reaction-based indicator systems. , 2009, Chemical Society reviews.

[5]  Scott T. Phillips,et al.  End-Capped Poly(benzyl ethers): Acid and Base Stable Polymers That Depolymerize Rapidly from Head-to-Tail in Response to Specific Applied Signals , 2013 .

[6]  Elizabeth R Gillies,et al.  Amplified release through the stimulus triggered degradation of self-immolative oligomers, dendrimers, and linear polymers. , 2012, Advanced drug delivery reviews.

[7]  E. Gillies,et al.  Kinetics of Self-Immolative Degradation in a Linear Polymeric System: Demonstrating the Effect of Chain Length , 2013 .

[8]  M. C. Stuart,et al.  Emerging applications of stimuli-responsive polymer materials. , 2010, Nature materials.

[9]  C. Hawker,et al.  Triggered structural and property changes in polymeric nanomaterials , 2011 .

[10]  M. Grinstaff,et al.  Synthesis of atactic and isotactic poly(1,2-glycerol carbonate)s: degradable polymers for biomedical and pharmaceutical applications. , 2013, Journal of the American Chemical Society.

[11]  D. McGrath,et al.  Dendrimer disassembly by benzyl ether depolymerization. , 2003, Journal of the American Chemical Society.

[12]  D. McGrath,et al.  Vanillin and o-vanillin oligomers as models for dendrimer disassembly , 2012 .

[13]  D. Weitz,et al.  Stimuli-Responsive Core–Shell Microcapsules with Tunable Rates of Release by Using a Depolymerizable Poly(phthalaldehyde) Membrane , 2013 .

[14]  Scott T. Phillips,et al.  Continuous Head-to-Tail Depolymerization: An Emerging Concept for Imparting Amplified Responses to Stimuli-Responsive Materials. , 2014, ACS macro letters.

[15]  Roey J. Amir,et al.  Self-immolative dendrimer biodegradability by multi-enzymatic triggering. , 2004, Chemical communications.

[16]  W. Blaedel,et al.  Chemical amplification in analysis: a review , 1978 .

[17]  Adah Almutairi,et al.  Intramolecular cyclization assistance for fast degradation of ornithine‐based poly(ester amide)s , 2013 .

[18]  E. Gillies,et al.  Triggered degradation of poly(ester amide)s via cyclization of pendant functional groups of amino acid monomers , 2013 .

[19]  Roey J. Amir,et al.  Self-immolative dendrimers. , 2003, Angewandte Chemie.

[20]  Pavel Kratochvíl,et al.  Glossary of basic terms in polymer science (IUPAC Recommendations 1996) , 1996 .

[21]  E. Gillies,et al.  Self-Immolative Polymers Containing Rapidly Cyclizing Spacers: Toward Rapid Depolymerization Rates , 2012 .

[22]  Philippe Dubois,et al.  Probe‐Based 3‐D Nanolithography Using Self‐Amplified Depolymerization Polymers , 2010, Advanced materials.

[23]  Adah Almutairi,et al.  UV and near-IR triggered release from polymeric nanoparticles. , 2010, Journal of the American Chemical Society.

[24]  Andrew J. Boydston,et al.  Controlled Depolymerization: Stimuli-Responsive Self-Immolative Polymers , 2012 .

[25]  Kashan A. Shaikh,et al.  Gold Nanoparticle-Based Biodetection for Chip-Based Portable Diagnosis Systems , 2010 .

[26]  D. McGrath,et al.  Convergent synthesis of geometrically disassembling dendrimers using Cu(I)-catalyzed C-O bond formation. , 2010, Organic letters.

[27]  P. Dubois,et al.  Control over molar mass, dispersity, end-groups and kinetics in cyclopolymerization of ortho-phthalaldehyde: adapted choice of a phosphazene organocatalyst , 2014 .

[28]  Scott R White,et al.  Programmable microcapsules from self-immolative polymers. , 2010, Journal of the American Chemical Society.

[29]  E. W. Meijer,et al.  Depolymerizable, adaptive supramolecular polymer nanoparticles and networks , 2014 .

[30]  D. Darensbourg,et al.  An Efficient Method of Depolymerization of Poly(cyclopentene carbonate) to Its Comonomers: Cyclopent , 2013 .

[31]  Felix Holzner,et al.  Directed placement of gold nanorods using a removable template for guided assembly. , 2011, Nano letters.

[32]  E. Gillies,et al.  A reduction sensitive cascade biodegradable linear polymer , 2010 .

[33]  Ryan Pavlick,et al.  Intelligent, self-powered, drug delivery systems. , 2013, Nanoscale.

[34]  Richard C. Thompson,et al.  Accumulation and fragmentation of plastic debris in global environments , 2009, Philosophical Transactions of the Royal Society B: Biological Sciences.

[35]  Adah Almutairi,et al.  A Single UV or Near IR Triggering Event Leads to Polymer Degradation into Small Molecules. , 2012, ACS macro letters.

[36]  Hiroshi Ito,et al.  CHEMICAL AMPLIFICATION BASED ON ACID-CATALYZED DEPOLYMERIZATION , 1990 .

[37]  Gregory G. Lewis,et al.  Point-of-care assay platform for quantifying active enzymes to femtomolar levels using measurements of time as the readout. , 2013, Analytical chemistry.

[38]  Nancy R. Sottos,et al.  Triggered Release from Polymer Capsules , 2011 .

[39]  A. Knoll,et al.  Thermal probe maskless lithography for 27.5 nm half-pitch Si technology. , 2013, Nano letters.

[40]  Phil S Baran,et al.  Activity-linked labeling of enzymes by self-immolative polymers. , 2009, Bioconjugate chemistry.

[41]  Bernd Gotsmann,et al.  Probe-Based Nanolithography: Self-Amplified Depolymerization Media for Dry Lithography , 2010 .

[42]  F. Du,et al.  Chemical Synthesis of Functional Poly(4-hydroxybutyrate) with Controlled Degradation via Intramolecular Cyclization , 2013 .

[43]  S. T. Phillips,et al.  Self-powered microscale pumps based on analyte-initiated depolymerization reactions. , 2012, Angewandte Chemie.

[44]  Scott R White,et al.  Chemical treatment of poly(lactic acid) fibers to enhance the rate of thermal depolymerization. , 2012, ACS applied materials & interfaces.

[45]  D. Shabat,et al.  Self-immolative comb-polymers: multiple-release of side-reporters by a single stimulus event. , 2008, Chemistry.

[46]  Gregory G. Lewis,et al.  A prototype point-of-use assay for measuring heavy metal contamination in water using time as a quantitative readout. , 2014, Chemical communications.

[47]  T. Okano,et al.  Stimuli-Responsive Hydrogels and Their Application to Functional Materials , 2010 .

[48]  D. Shabat,et al.  Self-immolative dendrimers: A distinctive approach to molecular amplification , 2010 .

[49]  C. Barner‐Kowollik,et al.  Polyphthalaldehyde-block-polystyrene as a nanochannel template. , 2014, Journal of materials chemistry. B.

[50]  Brian B Haab,et al.  Applications of antibody array platforms. , 2006, Current opinion in biotechnology.

[51]  C. Willson,et al.  Chemical amplification in the design of dry developing resist materials , 1983 .

[52]  Wentao Duan,et al.  Depolymerization-powered autonomous motors using biocompatible fuel. , 2013, Journal of the American Chemical Society.

[53]  P. Scrimin,et al.  Sensing through signal amplification. , 2011, Chemical Society reviews.

[54]  Guoying Zhang,et al.  Self-immolative polymersomes for high-efficiency triggered release and programmed enzymatic reactions. , 2014, Journal of the American Chemical Society.

[55]  Elizabeth R Gillies,et al.  A cascade biodegradable polymer based on alternating cyclization and elimination reactions. , 2009, Journal of the American Chemical Society.

[56]  Joshua A. Kaitz,et al.  Functional Phthalaldehyde Polymers by Copolymerization with Substituted Benzaldehydes , 2013 .

[57]  S. T. Phillips,et al.  Effects of electronics, aromaticity, and solvent polarity on the rate of azaquinone-methide-mediated depolymerization of aromatic carbamate oligomers. , 2013, The Journal of organic chemistry.

[58]  Joseph Wang,et al.  Can man-made nanomachines compete with nature biomotors? , 2009, ACS nano.

[59]  Kinam Park,et al.  Biomedical Applications of Hydrogels Handbook , 2010 .

[60]  J. Katzenellenbogen,et al.  A novel connector linkage applicable in prodrug design. , 1981, Journal of medicinal chemistry.

[61]  Shota Hashimoto,et al.  Photoinduced depolymerization of poly(olefin sulfone)s possessing photobase generator side‐chains: Effect of spacer‐chain length , 2013 .

[62]  Scott T. Phillips,et al.  Reproducible and Scalable Synthesis of End-Cap-Functionalized Depolymerizable Poly(phthalaldehydes) , 2013 .

[63]  Adah Almutairi,et al.  Intramolecular Cyclization for Stimuli-Controlled Depolymerization of Polycaprolactone Particles Leading to Disassembly and Payload Release. , 2013, ACS macro letters.

[64]  D. McGrath,et al.  Geometric disassembly of dendrimers: dendritic amplification. , 2003, Journal of the American Chemical Society.

[65]  Joshua A. Kaitz,et al.  Dynamic Covalent Macrocyclic Poly(phthalaldehyde)s: Scrambling Cyclic Homopolymer Mixtures Produces Multi-Block and Random Cyclic Copolymers , 2013 .

[66]  H. W. Scheeren,et al.  "Cascade-release dendrimers" liberate all end groups upon a single triggering event in the dendritic core. , 2003, Angewandte Chemie.

[67]  Didier Raoult,et al.  Immuno-PCR: a promising ultrasensitive diagnostic method to detect antigens and antibodies. , 2011, Trends in microbiology.

[68]  Scott T. Phillips,et al.  Patterned plastics that change physical structure in response to applied chemical signals. , 2010, Journal of the American Chemical Society.

[69]  Joshua A. Kaitz,et al.  End group characterization of poly(phthalaldehyde): surprising discovery of a reversible, cationic macrocyclization mechanism. , 2013, Journal of the American Chemical Society.