2013 – Present

(46) ACS Sustainable Chem. Eng., 2018, 6, 1650–1661

“Synthesis and thermorheological analysis of biobased lignin-graft-poly(lactide) copolymers and their blends”

Despite numerous accounts of biobased composite materials through blending and copolymerization of lignin and other polymers, there are no systematic studies connecting the synthetic methodology, molecular structure, and polymer topology with ….
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(45) Acc. Chem. Res. 2017, 50, 2861−2869
“Indium catalysts for ring opening polymerization: Exploring the importance of catalyst aggregation”

Inexorably, the environmental persistence and damage caused by polyolefins have become major drawbacks to their continued long-term use. Global shifts in thinking from fossil-fuel to renewable biobased resources have urged researchers to focus their attention  ….
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(44) J. Rheol. 2017, 61(6), 1137-1148
“Aromatic interactions in aryl-capped polylactides: A thermorheological investigation”

A series of aryl-capped poly(lactide)s (PLAs) were synthesized by living ring-opening polymerization with a chain transfer agent (also referred to as immortal polymerization, iROP) using a previously reported dinuclear indium catalyst, [(NNO)InCl]2(μ-Cl)(μ-OEt) (A) ….
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(43) ACS Catal. 2017 7, 6413–6418
“Air- and Moisture Stable Indium Salan Catalysts for Living Multiblock PLA Formation in Air”

We introduce an air- and moisture-stable hydroxy-bridged indium salan complex as a highly active and controlled catalyst for the ring- opening polymerization of cyclic esters in air. The reversible activation of this complex with linear and branched alcohols ….
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(42) Dalton Trans. 2017 46, 6723–6733
“Impact of Aryloxy Initiators on the Living and Immortal Polymerization of lactide”

This report describes two different methodologies for the synthesis of aryl end-functionalized poly (lactide)s (PLAs) catalyzed by indium complexes. In the first method, a series of para-functionalized phenoxy-bridged dinuclear indium complexes …
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(41) Macromolecules 2017 50 (6), 2535–2546
“Binary Blends of Entangled Star and Linear poly(hydroxybutyrate): Effect of Constraint Release and Dynamic Tube Dilation”

In order to further understand the relaxation behavior of binary blends of star and linear chains, new polymer blends consisting of linear poly(hydroxybutyrate) (PHB) matrix and PHB star molecules are designed, and their dynamics is investigated by varying the star concentrations  …
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(40) Inorg. Chem. 2017 56 (3), 1375–1385
“A Comparison of Gallium and Indium Alkoxide Complexes as Catalysts for Ring-Opening Polymerization of Lactide”

The impact of the metal size and Lewis acidity on the polymerization activity of group 13 metal complexes was studied, and it was shown that, within the same ligand family, indium complexes are far more reactive and selective than their gallium analogues. To this end …
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(39) Macromolecules 2016 49 (23), 8812–8824
“Highly Active Chiral Zinc Catalysts for Immortal Polymerization of β‐Butyrolactone Form Melt Processable Syndio-Rich Poly(hydroxybutyrate)”

Highly crystalline poly(hydroxybutyrate) suffers from high melting point and entanglement molecular weight. This leads to low melt strength, limits processing through regular techniques, and precludes many applications. In this work we report a series of racemic …
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(38) Inorg. Chem. 2016, 55(18), 9445–9453
“The role of nitrogen donors in zinc catalysts for lactide ring opening polymerization”

The electronic effects of nitrogen donors in zinc catalysts for ring opening polymerization of cyclic esters were investigated. Alkyl and benzyloxy zinc complexes supported by tridentate diamino- and aminoimino phenolate ligands were synthesized and their …
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(37) Inorg. Chem. 2016, 55(11), 5365–5374
“Dinucleating ligand platforms supporting indium and zinc catalysts for cyclic ester polymerization”

The synthesis of the first alkoxide-bridged indium complex supported by a chiral dinucleating ligand platform (1), along with its zinc analogue (2), is reported. Both complexes are synthesized in a one-pot reaction starting from a chiral dinucleating …
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(36) Macromolecules 2016, 49(3), 909–919
“A comparison of the rheological and mechanical properties of isotactic, syndiotactic, and heterotactic PLA”

A series of poly(lactide) (PLA) samples, exhibiting various levels of syndiotactic enrichment, were formed via the ring-opening polymerization of meso-lactide using two families of novel dinuclear indium catalysts…
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(35) Macromolecules 2015, 48 (18), 6672–6681
“Synthesis and Rheological Characterization of Star-Shaped and Linear Poly(hydroxybutyrate)”

Indium and zinc complexes, [(NNOtBu)InCl]2(μ-Cl)(μ-OTHMB) (2) and (NNiOtBu)Zn(CH2CH3) (3), were used to produce monodispersed three- and six-armed star-shaped PHBs using tris(hydroxymethyl)benzene (THMB) and…
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(34) Chem. Sci., 2015, 6, 5284–5292
“Overcoming aggregation in indium salen catalysts for isoselective lactide polymerization.”

A methodology for controlling aggregation in highly active and isoselective indium catalysts for the ring opening polymerization of racemic lactide is reported. A series of racemic and enantiopure dinuclear…
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(33) Dalton Trans. 2015, 44, 14248 – 14254
“Star-shaped PHB-PLA block copolymers: Immortal polymerization with dinuclear indium catalysts”

The first example of a one-component precursor to star-shaped polyesters, and its utilization in the syn- thesis of previously unknown star-shaped poly(hydroxybutyrate)–poly(lactic acid) block copolymers,…
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(32) Dalton Trans. 2015, 44, 6126 – 6139
“Effect of steric changes on the isoselectivity of dinuclear indium catalysts for lactide polymerization”

Functionalized diaminophenolates as ligands for dinuclear indium catalysts were investigated in the ring-opening polymerization of lactide. An increase in the steric bulk of the ligand…
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(31) Inorg. Chem. 2014, 53(18), 9897−9906
“Probing the role of secondary vs. tertiary amine donor ligands for indium catalysts in lactide polymerization”

The role of the central amine donor in a previously reported dinuclear indium catalyst, [NMe2NHO)InCl]2(m-Cl)(m-OEt) (1), for the polymerization of lactide was investigated through…
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(30) J. Am. Chem. Soc. 2014, 136(32), 11264–11267
“Redox Control of Group 4 Metal Ring-Opening Polymerization Activity toward l-Lactide and ε-Caprolactone”

The activity of several group 4 metal alkoxide complexes supported by ferrocene-based ligands was controlled using redox reagents during the ring-opening polymerization of l-lactide and…
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(29) Inorg. Chem. 2014, 53(13), 6828–6836
“The role of aggregation in the synthesis and polymerization activity of SalBinap indium alkoxide complexes”

The reaction of racemic SalBinap ligand, (±)-H2(ONN*OMe) with InCl3 and excess NaOEt generated a mixture of two dinuclear compounds [(µ-κ2-ONN*OMe)In(µ-OEt)]2 (1a) and [κ4-ONN*OMe)In(µ-OEt)]2…
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(28) Organometallics 2013, 32(23), 6950–6956
“Theoretical Investigation of Lactide Ring-Opening Polymerization Induced by a Dinuclear Indium Catalyst”

A DFT study of the ring-opening polymerization of lactide (LA) induced by a dinuclear indium catalyst supported by a chiral diamino phenoxy ligand, [(NNHO)InCl]2(μ-Cl)(μ-OEt) (1), is reported….
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(27) Macromolecules 2013, 46, 3965−3974
“PLA-PHB-PLA triblock copolymers: Synthesis by sequential addition and investigation of mechanical and rheological properties”

The dinuclear indium catalyst [(NNO)InCl]2(μ-OEt)(μ-Cl), previously reported to be highly active for the living ring-opening polymerization of cyclic esters lactide (LA) and…
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(26) Chem. Commun. 2013, 49, 4295-4297
“A highly active and site selective indium catalyst for lactide polymerization”
Invited article in the “Emerging Investigators” issue.

Chiral indium salen complexes are highly active, isoselective catalysts for the ring opening polymerization of racemic lactide. The polymerizations are well controlled…
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