Enabling technologies in polymer synthesis: accessing a new design space for advanced polymer materials

Knox, Stephen T.; Warren, Nicholas J.

doi:10.1039/c9re00474b

Cited by 31 publications

(25 citation statements)

References 241 publications

(447 reference statements)

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“…Of the available HT technologies applied to the synthesis of polymeric biomaterials,,, , the continuous-flow (CF) reactor has emerged as a main technology, offering low-cost, precise, and scalable polymer synthesis.…”

Section: High Throughput Synthesis: Turning Monomers Into Biofunction...mentioning

confidence: 99%

High-Throughput Routes to Biomaterials Discovery

2021

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Many existing clinical treatments are limited in their ability to completely restore decreased or lost tissue and organ function, an unenviable situation only further exacerbated by a globally aging population. As a result, the demand for new medical interventions has increased substantially over the past 20 years, with the burgeoning fields of gene therapy, tissue engineering, and regenerative medicine showing promise to offer solutions for full repair or replacement of damaged or aging tissues. Success in these fields, however, inherently relies on biomaterials that are engendered with the ability to provide the necessary biological cues mimicking native extracellular matrixes that support cell fate. Accelerating the development of such “directive” biomaterials requires a shift in current design practices toward those that enable rapid synthesis and characterization of polymeric materials and the coupling of these processes with techniques that enable similarly rapid quantification and optimization of the interactions between these new material systems and target cells and tissues. This manuscript reviews recent advances in combinatorial and high-throughput (HT) technologies applied to polymeric biomaterial synthesis, fabrication, and chemical, physical, and biological screening with targeted end-point applications in the fields of gene therapy, tissue engineering, and regenerative medicine. Limitations of, and future opportunities for, the further application of these research tools and methodologies are also discussed.

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Section: High Throughput Synthesis: Turning Monomers Into Biofunction...mentioning

confidence: 99%

High-Throughput Routes to Biomaterials Discovery

2021

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“…8 Moving from thermal initiation to photoinitiation enables to employ the light only for the sensitive step of chain initiation, saving energy, avoiding heating and cooling delays, and in the very end puts less thermal stress on a potentially sensitive reaction system. 9 Baris Kumru and Paolo Giusto contributed equally to this article. Dedicated to Professor Klaus Müllen on the occasion of his 75 th birthday.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, it is also important to facilitate straightforward reaction conditions, such as polymerization with oxygen tolerance, 5–7 which would allow more benign strategy for automated synthesis 8 . Moving from thermal initiation to photoinitiation enables to employ the light only for the sensitive step of chain initiation, saving energy, avoiding heating and cooling delays, and in the very end puts less thermal stress on a potentially sensitive reaction system 9 . In addition to direct radical formation by using light as a stimuli (i.e., Irgacure materials), photoredox‐based initiation has been popularized recently in which Lalevee and colleagues summarized the mechanism and available molecules for photoredox‐based initiation in polymer chemistry 10 .…”

Section: Introductionmentioning

confidence: 99%

Carbon nitride‐coated transparent glass vials as photoinitiators for radical polymerization

Kumru

Giusto

Antonietti

2021

Journal of Polymer Science

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Benign polymerization routes offer new perspectives in current polymer technology. Especially for automated or continuous flow synthesis of polymers, new devices and principles have to be considered by the means of minimizing addition or separation sequences as well as the type of a polymer initiation. Near‐UV and visible light‐induced polymerization utilizing metal‐free semiconductor polymeric carbon nitride (pCN) as heterogeneous photocatalyst was a first step into this direction. Moving from heterogeneous powder catalysis (which still requests catalyst separation) to surface photocatalysis via coating glass tubes or vials with pCN thin films is presented. Performance and effectivity of those photoactive reactors are proven by free radical photopolymerization of variety of monomers. Reusability of vials is demonstrated via reversible addition‐fragmentation chain‐transfer polymerization‐assisted block copolymer synthesis. This strategy eliminates the necessity of adding or removing initiators, works at room temperature, and offers a platform for cheap and effective polymer synthesis at the age of automated synthesis.

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“…Concurrently, with the exploration of diverse polymeric architectures, polymer chemists have sought more efficient routes for macromolecular production to increase the commercial appeal of these interesting materials. In particular, flow-mediated approaches have shown great promise for streamlining multistep macromolecular syntheses; the ability to temporally control the addition of specific reagents through multiple injection points has enabled the development of many one-pass procedures for synthesizing structurally diverse copolymers. − For example, (multi)block, , star, and brush copolymers; copolymer mixtures with tailored molecular weight distributions; , and postfunctionalized polymers , have been synthesized via readily up-scalable one-pass flow approaches. , In addition, flow-mediated chemistries provide access to polymer libraries through slug or droplet flow approaches; in these systems, many segregated droplets are injected into the flow reactor, which allows a high-throughput synthetic approach. − Such approaches reduce synthetic burdens and facilitate the more rapid and efficient discovery of value-added polymer materials.…”

Section: Introductionmentioning

confidence: 99%

Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors

Corrigan

Trujillo

et al. 2021

Macromolecules

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In this work, we demonstrate the controlled synthesis of graft and branched copolymers using one-pot (batch) or one-pass (flow) processes without intermediate purification. The formation of poly(methacrylate) copolymers with pendent reversible addition–fragmentation chain transfer (RAFT) agent functionalities was performed using a selective photoactivation approach in the first step, specifically via green light-mediated direct photoRAFT polymerization. A nonselective photoinduced chain extension using red light-triggered photoinduced energy/electron transfer (PET)-RAFT polymerization was then performed to provide tailored graft copolymers. Notably, the application of this protocol to a flow process with two spatially segregated unit operations provides a route to independent control of the backbone-forming step (unit operation one) and the subsequent chain extensions (unit operation two). By alternating the light sources in both unit operations between the On and Off states, a range of macromolecular architectures could be prepared from the same starting materials. To demonstrate the power of this divergent approach, a series of graft copolymers with tailored backbone lengths and number and molecular weight characteristics of side chains were synthesized using the same starting materials by a single pass process. Additionally, the polymer architecture was switched between graft and hyperbranched architectures via external manipulation of light sources.

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Enabling technologies in polymer synthesis: accessing a new design space for advanced polymer materials

Abstract: This review discusses how developments in laboratory technologies can push the boundaries of what is achievable using existing polymer synthesis techniques.

Cited by 31 publications

References 241 publications

High-Throughput Routes to Biomaterials Discovery

High-Throughput Routes to Biomaterials Discovery

Carbon nitride‐coated transparent glass vials as photoinitiators for radical polymerization

Divergent Synthesis of Graft and Branched Copolymers through Spatially Controlled Photopolymerization in Flow Reactors

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