About

Krzysztof Matyjaszewski is the J. C. Warner University Professor of Natural Sciences and the Director of the Center for Macromolecular Engineering at Carnegie Mellon University. His research focuses on the development of controlled/'living' radical polymerization techniques, including Atom Transfer Radical Polymerization (ATRP), which is a key method in the synthesis of well-defined macromolecules. His work encompasses the understanding of mechanistic parameters, catalyst development, and the application of ATRP in creating a variety of functional materials such as linear copolymers, block copolymers, graft copolymers, networks, gels, cyclic copolymers, and nanostructured materials. Matyjaszewski's contributions have significantly advanced the field of polymer chemistry, particularly in the synthesis of polymers with specific architectures and functionalities, and his research includes the development of new catalysts, understanding solvent effects, and exploring polymerization in different media.

Research topics

• Chemistry
• Organic chemistry
• Materials science
• Polymer chemistry
• Biochemistry
• Nanotechnology
• Composite material
• Biology
• Biophysics
• Photochemistry
• Chemical engineering
• Polymer science
• Combinatorial chemistry
• Engineering
• Architectural engineering
• Art
• Horticulture

Selected publications

• RNA-Polymer Hybrids via Direct and Site-Selective Acylation with the ATRP Initiator and Photoinduced Polymerization

  Journal of the American Chemical Society · 2023 · 30 citations

  Senior authorCorresponding
  • Chemistry
  • Polymer chemistry
  • Combinatorial chemistry

  -isopropylacrylamide monomers, resulting in RNA bottlebrushes, hydrogels, and stimuli-responsive materials. This approach, readily applicable to both post-synthetic and nature-derived RNA, can be used to engineer the properties of a variety of RNA-based macromolecular hybrids and assemblies providing access to a wide variety of RNA-polymer hybrids.

  PublisherOA PDFDOI

• Visible‐Light‐Mediated Controlled Radical Branching Polymerization in Water

  Angewandte Chemie International Edition · 2023 · 63 citations

  Senior authorCorresponding
  • Polymer chemistry
  • Chemistry
  • Materials science

  <170 000), tunable degree of branching, and low dispersity values (1.14≤Đ≤1.33). Moreover, the use of SBA inibramer enabled the synthesis of bioconjugates with a well-controlled branched architecture.

  DOI

• Highly Processable Ionogels with Mechanical Robustness

  Advanced Functional Materials · 2023 · 54 citations

  • Materials science
  • Nanotechnology
  • Composite material

  Abstract Currently, the increasing needs of conductive ionogels with intricate shapes and high processability by individual requirements of next‐generation flexible electronics constitute significant challenges. Here, the design of highly processable ionogels is reported with mechanical robustness by self‐assembly of a common triblock copolymer into a precursor in functional mixed ionic liquids (ILs) containing conductivity‐enhancing and polymerizable strength‐enhancing components. The subsequent in situ polymerization of the precursor forms physical‐co‐chemical cross‐linked networks, in which the entanglement between physical and chemical cross‐linked networks and microphase separation give rise to mechanical robustness of as‐fabricated ionogel. The viscosity of the self‐assembled precursor can be rationally tuned, which makes the fabrication process compatible with diverse technologies including inkjet printing, spray coating, and 3D printing. By virtue of highly processable capability of the designed ionogels, an auxetic‐structured ionogel can be easily generated using 3D printing, which exhibits greatly improved sensitivity and thus is able to monitor tiny deformations. This study that relies on designing functional mixed ILs as the dispersion phase rather than focusing on synthesizing new‐type polymers establishes a new route for versatile and programmable fabrication of high‐performance ionogels for broader applications.

  DOI

• Star Polymers with Designed Reactive Oxygen Species Scavenging and Agent Delivery Functionality Promote Plant Stress Tolerance

  ACS Nano · 2022 · 73 citations

  • Materials science
  • Nanotechnology
  • Chemical engineering

  assimilation, Rubisco carboxylation rate, and photosystem II quantum yield. Mg loaded RSP improved photosynthesis in Mg deficient plants, mainly by promoting Rubisco activity. These results indicate the potential of ROS scavenging nanocarriers like RSP to alleviate abiotic stress in crop plants, allowing crop plants to be more resilient to heat stress, and potentially other climate change induced abiotic stressors.

  PublisherDOI

• Open-air green-light-driven ATRP enabled by dual photoredox/copper catalysis

  Chemical Science · 2022 · 116 citations

  Senior authorCorresponding
  • Photochemistry
  • Chemistry
  • Combinatorial chemistry

  ≤ 1.22) under identical conditions.

  DOI

• Red-Light-Induced, Copper-Catalyzed Atom Transfer Radical Polymerization

  ACS Macro Letters · 2022 · 65 citations

  Senior authorCorresponding
  • Photochemistry
  • Chemistry
  • Polymer chemistry

  species under red-light irradiation. In addition, this system showed oxygen tolerance due to the consumption of oxygen in the photoredox reactions, yielding well-controlled polymerizations without the need for deoxygenation processes.

  PublisherDOI

• Rational Control of Protein–Protein Interactions with Protein-ATRP-Generated Protease-Sensitive Polymer Cages

  Biomacromolecules · 2022 · 17 citations

  • Chemistry
  • Biophysics
  • Biochemistry

  Protease-protease interactions lie at the heart of the biological cascades that provide rapid molecular responses to living systems. Blood clotting cascades, apoptosis signaling networks, bacterial infection, and virus trafficking have all evolved to be activated and sustained by protease-protease interactions. Biomimetic strategies designed to target drugs to specific locations have generated proprotein drugs that can be activated by proteolytic cleavage to release native protein. We have previously demonstrated that the modification of enzymes with a custom-designed comb-shaped polymer nanoarmor can shield the enzyme surface and eliminate almost all protein-protein interactions. We now describe the synthesis and characterization of protease-sensitive comb-shaped nanoarmor cages using poly(ethylene glycol) methacrylate macromonomers where the PEG tines of the comb are connected to the backbone of the growing polymer chain by peptide linkers. Protease-induced cleavage of the tines of the comb releases a polymer-modified protein that can once again participate in protein-protein interactions. Atom transfer radical polymerization (ATRP) was used to copolymerize the macromonomer and carboxybetaine methacrylate from initiator-labeled chymotrypsin and trypsin enzymes, yielding proprotease conjugates that retained activity toward small peptide substrates but prevented activity against proteins. Native proteases triggered the release of the PEG side chains from the polymer backbone within 20 min, thereby increasing the activity of the conjugate toward larger protein substrates by 100%. Biomimetic cascade initiation of nanoarmored protease-sensitive protein-polymer conjugates may open the door to a new class of responsive targeted therapies.

  PublisherDOI

• Making ATRP More Practical: Oxygen Tolerance

  Accounts of Chemical Research · 2021 · 229 citations

  Senior authorCorresponding
  • Chemistry
  • Organic chemistry

  -isopropylacrylamide, a challenging monomer, with a high degree of control.These contributions have substantially simplified the use of ATRP, making it more practical and accessible to everyone.

  DOI

• Star Polymer Size, Charge Content, and Hydrophobicity Affect their Leaf Uptake and Translocation in Plants

  Environmental Science & Technology · 2021 · 74 citations

  • Chemistry
  • Polymer chemistry
  • Organic chemistry

  star polymer solution. In spite of their property differences, ∼30% of the applied star polymers translocated to other plant organs, higher than uptake of conventional foliar applied agrochemicals (<5%). The property differences affected their distribution in the plant. The ∼6 nm star polymers exhibited 3 times higher transport to younger leaves than larger ones, while the ∼35 nm star polymer had over 2 times higher transport to roots than smaller ones, suggesting small star polymers favor symplastic unloading in young leaves, while larger polymers favor apoplastic unloading in roots. For the same sized star polymer, a smaller negative charge content (yielding ζ ∼ -12 mV) enhanced translocation to young leaves and roots, whereas a larger negative charge (ζ < -26 mV) had lower mobility. Hydrophobicity only affected leaf uptake pathways, but not translocation. This study can help design agrochemical nanocarriers for efficient foliar uptake and targeting to desired plant organs, which may decrease agrochemical use and environmental impacts of agriculture.

  PublisherDOI

• Cu-Catalyzed Atom Transfer Radical Polymerization in the Presence of Liquid Metal Micro/Nanodroplets

  Macromolecules · 2021 · 33 citations

  Senior authorCorresponding
  • Chemistry
  • Polymer chemistry
  • Chemical engineering

  Micro/nanodroplets of the liquid metal (LM) eutectic Ga–In alloy (EGaIn) were employed in atom transfer radical polymerization (ATRP) in organic solvents with low ppm (parts per million) loading of Cu catalysts. ATRP in the presence of EGaIn produced well-defined polymers (dispersity <1.1) that could be easily separated from EGaIn via centrifugation. Voltammetric analysis revealed that EGaIn micro/nanodroplets reduced CuII complexes to CuI complexes, which acted as ATRP activators. A key distinction from previously reported LM-mediated radical polymerizations is that this process did not require external forces, such as ultrasound sonication. EGaIn droplets also activated dormant alkyl bromide species. However, this reaction was ∼6 orders of magnitude slower than the corresponding activation by CuI complexes, resembling SARA (supplemental activators and reducing agents) ATRP.

  PublisherOA PDFDOI

Recent grants

• New Hybrid Materials by Controlled Polymerization of Monomers with Bulky Functional Substituents

  NSF · $1.2M · 2015–2022

• International Collaboration in Chemistry: Improving Livingness by Detailed Kinetic Studies into ATRP

  NSF · $502k · 2010–2013

• Development of More Active and More Selective Catalysts for ATRP

  NSF · $600k · 2020–2024

• Structure-Reactivity Correlation in Atom Transfer Radical Polymerization and Addition Processes

  NSF · $465k · 2004–2007

• Macromolecular Engineering by Controlled/Living Radical Polymerization

  NSF · $657k · 2005–2010

Frequent coauthors

• Sergei S. Sheiko

  180 shared

• Tomasz Kowalewski

  169 shared

• Rinaldo Poli

  Université de Toulouse

  137 shared

• Michael R. Bockstaller

  Materials Science & Engineering

  102 shared

• Joanna Pietrasik

  Lodz University of Technology

  97 shared

• Nicolay V. Tsarevsky

  Southern Methodist University

  88 shared

• Kathryn L. Beers

  National Institute of Standards and Technology

  84 shared

• Haifeng Gao

  81 shared

Labs

• Matyjaszewski Polymer GroupPI

Education

• Ph.D.

  Polish Academy of Sciences

  1976

Awards & honors

• Honorary Fellow, Polish Chemical Society, Poland (2024)
• Honorary Degree (Doctorate Honoris Causa) Rzeszow University…
• Honorary Degree (Doctorate Honoris Causa) University of Cret…
• National Academy of Sciences Award in Chemical Sciences (202…
• CNRS Fellow (France) (2023)

Similar researchers at Carnegie Mellon University

• Dr. Heather Millerh-158
• Christos Nick Faloutsosh-137
• Rongchao Jinh-128
• Ignacio Grossmannh-117
• Neil Donahueh-116