Andrew Magenau

Andrew Magenau
Drexel University | DU · Department of Materials Science and Engineering

About

38
Publications
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2,500
Citations

Publications

Publications (38)
Article
Two-dimensional (2D) materials offer advantages that their 3D counterparts do not. The conventional method for the bulk synthesis of 2D materials has predominantly been through etching layered solids. Herein, we convert – through a bottom-up approach – 10 binary and ternary titanium carbides, nitrides, borides, phosphides, and silicides into 2D fla...
Article
Despite the excellent mechanical and electrical performance of MXene-polymer nanocomposites, methods for producing these materials on a larger scale are limited by low-yielding, delaminated, MXene suspensions that are typically employed for their synthesis. Moreover, the hydrophilicity of MXenes restricts the production of well-dispersed nanocompos...
Article
Thiol-ene nanocomposites were synthesized for the first time using an alkylborane-ligand initiator complex under bulk and ambient conditions without external light or thermal stimuli. Initiation was triggered by the in situ decomplexation of an air-stable trialkylborane-amine complex to liberate trialkylborane, which rapidly autoxidizes with atmosp...
Article
Reaction-induced phase transitions (RIPTs) encompass a broad range of synthetic strategies that use chemical reactions to drive the organization of macromolecules into complex, nanoscale morphologies. A diverse set of chemical reactions are now available which can alter a polymer's composition and can provide access to a rich landscape of tailorabl...
Article
An alkylborane initiated reversible addition‐fragmentation chain transfer (AI‐RAFT) process was developed for the synthesis of star‐polymers using a one‐pot approach at room‐temperature in the presence of oxygen. Linear poly(tert‐butyl acrylate) arms were first polymerized using a latent trialkylborane‐amine initiator, which generated trialkylboran...
Article
Polymer micelles were formed using thiol-epoxide “click” chemistry to trigger functionalization-induced self-assembly (FISA) of block copolymers by modifying a reactive glycidyl methacrylate block with solvophobes. Ambient conditions, polymer concentrations up to 10 wt%, and an array of functional thiols were found effective for nanoparticle synthe...
Article
Nanoparticle synthesis was demonstrated via functionalization-induced self-assembly (FISA) of block copolymers using Suzuki-Miyaura cross-coupling. In situ self-assembly was triggered in organic media by the progressive installation of solvophobic pendant groups onto an initially soluble diblock copolymer, rendering the reactive block insoluble and...
Article
For electrochemically mediated atom transfer radical polymerization (eATRP), novel mechanistic insights are formulated based on a two-compartment kinetic Monte Carlo model in which catalyst concentration gradients between a large "bulk" compartment away from the electrode and a very small compartment around the electrode are accounted for to reflec...
Article
A new type of chemically-crosslinked polymeric network was synthesized by grafting-through ring-opening metathesis polymerization (gt-ROMP) using well-defined norbornene functionalized macrocrosslinkers. These macromolecular grafted-through networks uniquely possessed two molecular-level dials for tuning network microstructure and mechanical proper...
Article
For electrochemically mediated atom transfer radical polymerization (eATRP), novel mechanistic insights are formulated based on a two-compartment kinetic Monte Carlo model in which catalyst concentration gradients between a large “bulk” compartment away from the electrode and a very small compartment around the electrode are accounted for to reflec...
Article
A reversible addition–fragmentation chain transfer (RAFT) process was developed capable of being performed at room temperature and in the presence of oxygen by initiating polymerization through an alkylborane–amine complex. This air-stable alkylborane–amine complex was chemically deblocked with carboxylic acid or isocyanate functionalities to liber...
Article
Palladium-catalyzed Suzuki–Miyaura cross-coupling was demonstrated to be a versatile reaction platform to install functional groups onto well-defined polymers derived from reversible addition–fragmentation chain-transfer (RAFT) polymerization. Cross-coupled products were achieved utilizing a range of functional boronic acids including, but not limi...
Article
This review covers both fundamental aspects and applications of electrochemically mediated atom transfer radical polymerization (eATRP). eATRP setup is discussed in detail, together with the advantages and limitations of this technique. All relevant parameters that can influence eATRP outcome are evaluated (e.g. applied current and potential, stirr...
Article
Predicting polymer hydrophobicity based on monomer structure is an ill-posed problem. Generally, the hydrophobicity of a polymer or a series of polymers has been determined through indirect methods (i.e., contact angle) after polymerization. This sequence presents a problem for the systematic design and rapid evaluation of specialty polymers synthe...
Article
The alteration of cellular functions by anchoring macromolecules to specified organelles may reveal a new area of therapeutic potential and clinical treatment. In this work, a unique phenotype was evoked by influencing cellular behavior through the modification of subcellular structures with genetically targetable macromolecules. These fluorogen-fu...
Chapter
This chapter provides an overview of controlled/living polymerization systems of vinyl monomers. It discusses the attributes of living polymerizations, and provides an overview of anionic, cationic, coordination-insertion, and controlled radical polymerization (CRP) methods. The discussion of CRP focuses on atom transfer radical polymerization (ATR...
Article
Electrochemically mediated atom transfer radical polymerization (eATRP) was investigated for synthesis of star polymers using macroinitiators (MIs), achieving high star yield with low Cu catalyst loading (100 ppm, w/w). The arm first method, using MIs, is one of the most robust procedures for star polymer synthesis. During the polymerization, MIs c...
Article
Electrochemically mediated atom transfer radical polymerization (eATRP) of n-butyl acrylate was systematically investigated using diminished catalyst concentrations (<= 300 parts per million) under a variety of formulations and electrochemical conditions. Critical polymerization parameters, including the applied potential, catalyst concentration, a...
Article
The principle of halogen conservation (PHC) which can be used as a tool to quantify the degree of termination in atom transfer radical polymerization (ATRP) systems and should lead to the development of more efficient ATRP procedures, was studied. The principle of halogen (denoted as X) conservation dictates that the quantity of X must remain const...
Article
Cationic nanogels with site-selected functionality were designed for the delivery of nucleic acid payloads targeting numerous therapeutic applications. Functional cationic nanogels containing quaternized 2-(dimethylamino)ethyl methacrylate and a cross-linker with reducible disulfide moieties (qNG) were prepared by activators generated by electron t...
Article
The synthesis and application of a very active catalyst for copper-catalyzed atom transfer radical polymerizations (ATRP) with tris([(4-methoxy-2,5-dimethyl)-2-pyridyl] methyl)amine (TPMA*) ligand is reported. Catalysts with TPMA* ligands are approximately 3 orders of magnitude more active than those with tris(2-pyridylmethyl)amine (TPMA). Catalyst...
Article
Initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) with ppm amount of Cu catalyst was successfully developed in water. For the first time, Cu catalyst concentrations of 100 ppm and lower were used in aqueous media to prepare well-defined macromolecules. Polymers of oligo(ethylene oxide) methyl ether ac...
Article
A series of 2,2′-bipyridines with 4,4′-substituents (R-bpy) were investigated for atom transfer radical polymerization (ATRP) of methyl acrylate (MA) and methyl methacrylate (MMA). Ligand substituents with a large range of Hammett parameters (R = Cl, H, Me, dinonyl (dN), MeO, and (Me)2N) were studied with cyclic voltammetry (CV), revealing that inc...
Patent
Electrochemical reduction of an exemplary ATRP catalyst, C.sup.11Br.sub.2/Me.sub.6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu.sup.1Br.sub.2/Me.sub.6TREN, within the reaction medium. Unprecedente...
Article
Enhanced control: Electrochemically mediated atom transfer radical polymerization (ATRP) allows easy modulation of the overall rate and control of polymerization through the variation of an external applied potential, E app (see picture). This method has been successfully applied to aqueous ATRP of oligo(ethylene glycol) methyl ether methacrylate (...
Article
Atom transfer radical polymerization (ATRP) methods were developed in water-based media, to grow polymers from proteins under biologically relevant conditions. These conditions gave good control over the resulting polymers, while still preserving the protein’s native structure. Several reaction parameters, such as ligand structure, halide species,...
Article
Using a genetically engineered protein, containing a non-natural amino acid bearing an atom transfer radical polymerization (ATRP) initiator, protein–nanogel hybrids (PNHs) were synthesized by activator generated by electron transfer (AGET) ATRP in an inverse miniemulsion. The route presented is an appropriate synthetic strategy to covalently and s...
Article
Atom transfer radical polymerization is a versatile technique for exerting precise control over polymer molecular weights, molecular weight distributions, and complex architectures. Here, we show that an externally applied electrochemical potential can reversibly activate the copper catalyst for this process by a one-electron reduction of an initia...
Article
A simple and versatile polymerization technique via activators regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) of methyl acrylate (MA) with inexpensive commercially available ligands, including diethylenetriamine (DETA), N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA), and tris(2-aminoethyl)amine (TREN), is...
Article
Thiol-terminated polyisobutylene (α,ω-PIB-SH) was synthesized from thiourea and α,ω-bromine-terminated PIB in a three-step, one-pot procedure, using a cosolvent system of 1:1 (v:v) heptane:dimethylformamide. The initial alkylisothiouronium salt was produced at 90 °C. Aqueous base hydrolysis at 110 °C resulted in thiolate chain ends, which were re-a...
Article
Methacrylate monomers were successfully polymerized by ATRP utilizing copper wire as an in situ reducing agent at near-ambient temperatures (35 °C). Well-controlled polymerizations were demonstrated with both PMDETA and dNbpy ligands. Polymerization rates, when conducted with PMDETA, were dependent on the surface area of Cu0. Upon reduction of the...
Article
Thiol–ene click chemistry was adapted to easily and rapidly modify exo-olefin polyisobutylene with an array of thiol compounds bearing useful functionalities, including primary halogen, primary amine, primary hydroxyl, and carboxylic acid.
Article
1-(ω-Azidoalkyl)pyrrolyl-terminated polyisobutylene (PIB) was successfully synthesized both by substitution of the terminal halide of 1-(ω-haloalkyl)pyrrolyl-terminated PIB with sodium azide and by in situ quenching of quasiliving PIB with a 1-(ω-azidoalkyl)pyrrole. Azide substitution of the terminal halide was carried out in 50/50 heptane/DMF at 9...
Article
The primary objectives of this research were twofold: (1) development of synthetic procedures for combining quasiliving carbocationic polymerization (QLCCP) of isobutylene (IB) and reversible addition fragmentation chain transfer (RAFT) polymerization for block copolymer synthesis; (2) utilization of efficient, robust, and modular chemistries for f...
Article
A novel block copolymer, composed of polyisobutylene (PIB) and poly(N-isopropylacrylamide) (PNIPAM) segments, was synthesized. The PIB block was prepared via quasiliving cationic polymerization and end-functionalized by in-situ quenching to yield telechelic halogen-terminated PIB. Azido functionality was obtained by displacement of the terminal hal...
Conference Paper
A novel block copolymer, composed of polyisobutylene (PIB) and poly(N-isopropylacrylamide) (PNIPAM) segments, was synthesized. The PIB block was prepared via quasiliving cationic polymerization and end functionalized by in-situ quenching to yield telechelic halogen-terminated PIB. Azido functionality was obtained by displacement of the terminal hal...
Article
Block copolymers consisting of polyisobutylene (PIB) and either poly(methyl methacrylate) (PMMA) or polystyrene (PS) block segments were synthesized by a site transformation approach combining living cationic and reversible addition−fragmentation transfer (RAFT) polymerizations. The initial PIB block was synthesized via quasi-living cationic polyme...

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