End-Capped Poly(benzyl ethers): Acid and Base Stable Polymers That Depolymerize Rapidly from Head-to-Tail in Response to Specific Applied Signals

Olah, Michael G.; Robbins, Jessica S.; Baker, Matthew S.; Phillips, Scott T.

doi:10.1021/ma401169q

Cited by 74 publications

(88 citation statements)

References 37 publications

(65 reference statements)

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“…Three of the five current classes share related depolymerization mechanisms: that is, formation of quinone‐ or azaquinone‐methide intermediates. These polymers include poly(benzyl carbamates) [Figure (a)], poly(benzyl ethers) [Figure (b)], and polymers that depolymerize via alternating intramolecular cyclization/quinone methide elimination reactions [Figure (c)] . The two other classes offer unique mechanisms of depolymerization from one another as well as from the first three classes of polymers: they depolymerize via intramolecular cyclization reactions [Figure (d)] or acetal chemistry [Figure (e)] .…”

Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

“…Depolymerizable poly(benzyl ethers) [Figure (b)] are prepared via anionic polymerization of a stabilized quinone methide monomer, such as 2,6‐dimethyl‐7‐phenyl‐1,4‐benzoquinone methide . The polymerization procedure gives polymers with polydispersity index values (PDI) of 1.1–1.8.…”

Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

“…The polymers are depicted as they might exist after cleavage of the reaction‐based detection unit. These polymers are (a) a poly(benzyl carbamate), (b) a poly(benzyl ether), (c) a polymer that depolymerizes via alternating cyclization/quinone methide elimination reactions, (d) a polymer that depolymerizes entirely through cyclization reactions, and (e) poly(phthaladehyde) …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

Phillips

Robbins

DiLauro

et al. 2014

J of Applied Polymer Sci

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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.

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Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

Section: Current Classes Of Cdr Polymersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

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

Phillips

Robbins

DiLauro

et al. 2014

J of Applied Polymer Sci

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“…One class of SIPs is based on backbones that have low ceiling temperatures (T c ), but that can be stabilized by cyclization or endcapping. Examples include polyphthalaldehydes (PPAs), [57] polyglyoxylates (PGs), [58] poly(olefin sulfones) (POSs) [59] and poly(benzyl ether)s. [60] PPAs, PGs and POSs have been known since the 1960s to 1970s as PPAs and POSs were investigated as resists for lithography applications, [61][62] and PGs were studied as degradable detergent builders. [63] Recent advancements in their polymerization chemistry and end-capping have enabled their depolymerization to be triggered by specific stimuli such as light, acid, oxidizing and reducing species, and even combinations of these stimuli.…”

Section: Classes Of Smart Polymersmentioning

confidence: 99%

Reflections on the Evolution of Smart Polymers

Gillies

2019

Israel Journal of Chemistry

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Since Staudinger's recognition that polymers were long chain molecules with covalent bonds between repeating units, the field has evolved tremendously. In addition to their many structural roles, polymers have been developed to exhibit “smart” stimuli‐responsive behavior. This article will describe the evolution of selected classes of smart polymers including those responsive to changes in pH, temperature, light, and mechanical stimuli, as well as self‐immolative polymers and their application in drug delivery, sensors, and actuators. It will also highlight key advancements in polymer chemistry that enabled rapid progress over the past ∼20 years. Whether the key achievements were predictable will be discussed, and the extent to which polymer science remains an independent science versus a service tool will be addressed. Finally, some possibilities for the evolution of the field over the next 20–30 years will be described.

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“…38,39 New ideas based on other chemical reactions were cleverly developed 40 to achieve head-to-tail disassembly of polymers. 41,42 These concepts have resulted in polymer-based capsules, 43 polymeric nanoparticles, 44 and biodegradable polymers 45 with self-immolative disassembly patterns. 46 ■ DENDRITIC CHAIN REACTION The amplification effect achieved by self-immolative dendrimers or polymers is limited mainly by practical synthetic concerns.…”

Section: Accounts Of Chemical Researchmentioning

confidence: 99%

Quinone-Methide Species, A Gateway to Functional Molecular Systems: From Self-Immolative Dendrimers to Long-Wavelength Fluorescent Dyes

2014

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Over the last 30 years, the quinone-methide elimination has served as a valuable tool for achieving various important molecular functions. Molecular adaptors based on quinone-methide or aza-quinone-methide reactivity have been designed, synthesized, and used in diagnostic probes, molecular amplifiers, drug delivery systems, and self-immolative dendritic/polymeric molecular systems. These unique adaptors function as stable spacers between an enzyme- or reagent-responsive group and a reporter moiety and can undergo 1,4-, 1,6-, or 1,8-type elimination reactions upon cleavage of the triggering group. Such reactivity results in the release of the reporter group through formation of a quinone-methide species. This type of elimination was applied to design distinct molecular adaptors capable of multiple quinone-methide eliminations. Using this chemistry, we have developed unique molecular structures that are known today as self-immolative dendrimers. These dendrimers disassemble upon a single triggering event in a domino-like manner from the focal point to their periphery with the consequent release of multiple end-groups. Such molecular structures are used in self-immolative dendritic prodrugs and in diagnostic probes to obtain a significant amplification effect. To further enhance amplification, we have developed the dendritic chain reaction, which uses simple molecules to achieve functionality of high-generation virtual self-immolative dendrimers. In addition, we harnessed the quinone-methide elimination reactivity to design polymers that disassemble from head-to-tail initiated by an analyte-responsive event. Following this example, other chemical reactivities were demonstrated by scientists to design such polymeric molecules. In a manner analogous to the quinone-methide elimination, electron rearrangement can lead to formation of conjugated quinone-methide-type dyes with long-wavelength emission of fluorescence. We have recently applied an intramolecular charge transfer to form a unique kind of quinone-methide type derivative based on a donor-two-acceptors molecular structure. This intramolecular charge transfer produces a new fluorochrome with an extended conjugation of π-electron system that is used for the design of long-wavelength fluorogenic probes with a turn-ON option. The rapidly expanding use of quinone-methide species, reflected in the increased number of examples reported in the literature, indicates the importance of this tool in chemistry. These species provide a useful gateway to functional molecular structures with distinct reactivities and spectroscopic characteristics.

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End-Capped Poly(benzyl ethers): Acid and Base Stable Polymers That Depolymerize Rapidly from Head-to-Tail in Response to Specific Applied Signals

Cited by 74 publications

References 37 publications

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

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

Reflections on the Evolution of Smart Polymers

Quinone-Methide Species, A Gateway to Functional Molecular Systems: From Self-Immolative Dendrimers to Long-Wavelength Fluorescent Dyes

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