35 research outputs found
Reactive Sieving With M-Phenylene Ethynylene Foldamers: Effects of Structural Modification on Reactivity
114 p.Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 2008.In an attempt to further understand the nature of the host-guest interaction between mPE foldamers and the methylsulfonate esters used to study reactive sieving, a set of parameters for both the mPE foldamer and the methylsulfonate guests were developed for CHARMM-based molecular dynamics simulations. A total of 14 simulations were performed (500 ps each) and the dihedral angles of the guest alkyl chains were monitored. It was found that many of the dihedral angles could adopt and maintain a gauche conformation during the course of the simulation. Furthermore, a correlation between a number of gauche configurations in the alkyl chain and the relative rate of methylation was observed. Although the sample size and simulation time were too small to make any strong conclusions, these parameters provide a starting point for more sophisticated and lengthy simulations.U of I OnlyRestricted to the U of I community idenfinitely during batch ingest of legacy ETD
Biodegradable 3D Printed Polymer Microneedles for Transdermal Drug Delivery
Biodegradable polymer microneedle (MN) arrays are an
emerging class of transdermal drug delivery devices that promise a painless and
sanitary alternative to syringes; however, prototyping bespoke needle
architectures is expensive and requires production of new master templates.
Here, we present a new microfabrication technique for MNs using fused
deposition modeling (FDM) 3D printing using polylactic acid, an FDA approved,
renewable, biodegradable, thermoplastic material. We show how this natural
degradability can be exploited to overcome a key challenge of FDM 3D printing,
in particular the low resolution of these printers. We improved the feature
size of the printed parts significantly by developing a post fabrication
chemical etching protocol, which allowed us to access tip sizes as small as 1
ÎĽm. With 3D modeling software, various MN shapes were designed and printed
rapidly with custom needle density, length, and shape. Scanning electron
microscopy confirmed that our method resulted in needle tip sizes in the range of
1 – 55 µm, which could successfully penetrate and break off into porcine skin.
We have also shown that these MNs have comparable mechanical strengths to
currently fabricated MNs and we further demonstrated how the swellability of
PLA can be exploited to load small molecule drugs and how its degradability in
skin can release those small molecules over time
Biodegradable 3D Printed Polymer Microneedles for Transdermal Drug Delivery
Biodegradable polymer microneedle (MN) arrays are an
emerging class of transdermal drug delivery devices that promise a painless and
sanitary alternative to syringes; however, prototyping bespoke needle
architectures is expensive and requires production of new master templates.
Here, we present a new microfabrication technique for MNs using fused
deposition modeling (FDM) 3D printing using polylactic acid, an FDA approved,
renewable, biodegradable, thermoplastic material. We show how this natural
degradability can be exploited to overcome a key challenge of FDM 3D printing,
in particular the low resolution of these printers. We improved the feature
size of the printed parts significantly by developing a post fabrication
chemical etching protocol, which allowed us to access tip sizes as small as 1
ÎĽm. With 3D modeling software, various MN shapes were designed and printed
rapidly with custom needle density, length, and shape. Scanning electron
microscopy confirmed that our method resulted in needle tip sizes in the range of
1 – 55 µm, which could successfully penetrate and break off into porcine skin.
We have also shown that these MNs have comparable mechanical strengths to
currently fabricated MNs and we further demonstrated how the swellability of
PLA can be exploited to load small molecule drugs and how its degradability in
skin can release those small molecules over time
Design Paradigm Utilizing Reversible Diels–Alder Reactions to Enhance the Mechanical Properties of 3D Printed Materials
A design
paradigm is demonstrated that enables new functional 3D
printed materials made by fused filament fabrication (FFF) utilizing
a thermally reversible dynamic covalent Diels–Alder reaction
to dramatically improve both strength and toughness via self-healing
mechanisms. To achieve this, we used as a mending agent a partially
cross-linked terpolymer consisting of furan-maleimide Diels–Alder
(fmDA) adducts that exhibit reversibility at temperatures typically
used for FFF printing. When this mending agent is blended with commercially
available polylactic acid (PLA) and printed, the resulting materials
demonstrate an increase in the interfilament adhesion strength along
the <i>z</i>-axis of up to 130%, with ultimate tensile strength
increasing from 10 MPa in neat PLA to 24 MPa in fmDA-enhanced PLA.
Toughness in the <i>z</i>-axis aligned prints increases
by up to 460% from 0.05 MJ/m<sup>3</sup> for unmodified PLA to 0.28
MJ/m<sup>3</sup> for the remendable PLA. Importantly, it is demonstrated
that a thermally reversible cross-linking paradigm based on the furan-maleimide
Diels–Alder (fmDA) reaction can be more broadly applied to
engineer property enhancements and remending abilities to a host of
other 3D printable materials with superior mechanical properties