4 research outputs found
Physical Texturing for Superhydrophobic Polymeric Surfaces: A Design Perspective
Surface wetting on
the textured surface is classically explained
by the theories of Cassie–Baxter
or Wenzel. However, in recent years, an increasing number of complex
surface topographies with superhydrophobic properties have been achieved
without prediction or simulation using these theories. One example
is biomimetic surfaces. In many instances, theories were used to explain
surface properties found in nature but have not led to or predicted
the complex topographies. Although new wetting theories continue to
emerge, there is not yet a set of design rules to guide the selection
of surface topographies to achieve superhydrophobicity. By grouping
known surface topographies into common geometrical descriptions and
length scale, this paper suggests a set of surface topography classifications
to provide selection guidelines for engineering superhydrophobic surfaces.
Two key outcomes emerged from the design analysis: first, categorization
of frequently reported surface patterns shows that there exists a
set of commonly used descriptions among diverse designs; second, the
degree of hydrophobicity improvement within a class of topography
design can be used to predict the limit of improvement in superhydrophobicity
for a given material. The presentation of topography descriptors by
categories of design and performance may serve as a prologue to an
eventually complete set of design guidelines for superhydrophobic
performance
Thermoresponsive (Co)polymers through Postpolymerization Modification of Poly(2-vinyl-4,4-dimethylazlactone)
PolyÂ(2-vinyl-4,4-dimethylazlactone),
pVDMA, is emerging as a versatile
reactive platform in polymer chemistry. Herein, postpolymerization
modification of pVDMA leading to thermoresponsive homo- and copolymers
is investigated. VDMA was polymerized by reversible addition–fragmentation
chain transfer (RAFT) polymerization. The resulting reactive scaffolds
with molecular weights ranging from 3.0 to 12.5 kg/mol were converted
with a selection of alcohols and amines of varying polarity into functional
polyÂ(2-acrylamido isobutyrate)Âs and polyÂ(2-acrylamido isobutyramide)Âs
with molecular weights ranging from <i>M</i><sub>n</sub> = 4.2–65.1 kg/mol and low polydispersity indices <i>M</i><sub>w</sub>/<i>M</i><sub>n</sub> < 1.37.
Spectra obtained by <sup>1</sup>H NMR and infrared spectroscopic measurements
conformed to the expected structures. While alcohols and amines producing
water-soluble or water insoluble VDMA-derived homopolymers were identified,
seven homopolymers were found to show a lower critical solution temperature
in aqueous solution; those formed by reacting pVDMA with <i>N</i>-ethylamine, <i>N</i>-isopropylamine, <i>N</i>,<i>N</i>-dimethylamine, <i>N</i>,<i>N</i>-diethylamine, <i>N</i>,<i>N</i>-diethylaminoethylamine,
Jeffamine M-600, and tetrahydrofurfurylamine (THF amine). Cloud points
increased with decreasing molecular weight. With a cloud point of
31 °C, the phase separation of polyÂ(tetrahydrofurfuryl 2-acrylamido
isobutyramide) (pTAI) occurred close to body temperature, was highly
reproducible, and, above a concentration of 0.5 wt %, was largely
concentration independent. The transition temperature of pTAI-based
copolymers could easily be tuned by reacting pVDMA with a mixture
of THF amine and varying amounts of pentylamine or diÂ(ethylene glycol)
methyl ether amine
Block Copolymer Micelles with Pendant Bifunctional Chelator for Platinum Drugs: Effect of Spacer Length on the Viability of Tumor Cells
Three monomers with 1,3-dicarboxylate functional groups
but varying
spacer lengths were synthesized via carbon Michael addition using
malonate esters and ethylene- (MAETC), butylene- (MABTC), and hexylene
(MAHTC) glycol dimethacrylate, respectively. PolyÂ[oligo-(ethylene glycol)
methylether methacrylate] (POEGMEMA) was prepared in the presence
of a RAFT (reversible addition–fragmentation chain transfer)
agent, followed by chain extension with the prepared monomers to generate
three different block copolymers (BP-E80, BP-B82, and BP-H79) with
similar numbers of repeating units, but various spacer lengths as
distinguishing features. Conjugation with platinum drugs created macromolecular
platinum drugs resembling carboplatin. The amphiphilic natures of
these Pt-containing block copolymers led to the formation micelles
in solution. The rate of drug release of all micelles was similar,
but a noticeable difference was the increasing stability of the micelle
against dissociation with increasing spacer length. The platinum
conjugated polymer showed high activity against A549, OVCAR3, and
SKOV3 cancer cell lines exceeding the activity of carboplatin, but
only the micelle based on the longest spacer had IC<sub>50</sub> values
as low as cisplatin. Cellular uptake studies identified a better micelle
uptake with increasing micelle stability as a possible reason for
lower IC<sub>50</sub> values. The clonogenic assay revealed that
micelles loaded with platinum drugs, in contrast to low molecular
weight carboplatin, have not only better activity within the frame
of a 72 h cell viability study, but also display a longer lasting
effect by preventing the colony formation A549 for more than 10 days
RAFT Synthesis and Aqueous Solution Behavior of Novel pH- and Thermo-Responsive (Co)Polymers Derived from Reactive Poly(2-vinyl-4,4-dimethylazlactone) Scaffolds
Well-defined homopolymers of 2-vinyl-4,4-dimethylazlactone
(VDA)
and AB diblock copolymers of VDA with <i><i>N</i></i>,<i><i>N</i></i>-dimethylacrylamide (DMA) and <i>N</i>-isopropylÂacrylamide (NIPAM) prepared by reversible
addition–fragmentation
chain transfer (RAFT) radical polymerization are reported. VDA homopolymers
reacted with <i><i>N</i></i>,<i><i>N</i></i>-dimethylethylenediamine (DMEDA), <i><i>N</i></i>,<i><i>N</i>-</i>diethylethylenediamine
(DEEDA), and picoylamine (PA) give novel tertiary amine functional
polymers that exhibit inverse temperature aqueous solution characteristics
in the case of the DMEDA and DEEDA derivatives (provided they are
not protonated) and a pH-dependent solubility for the PA speciesî—¸it
is soluble at low solution pH but becomes hydrophobic at ca. pH 4.0.
VDA-DMA/NIPAM AB diblock copolymers are also readily modified with
DMEDA, DEEDA, and PA to give a novel series of stimulus responsive
block copolymers including tunably amphiphilic and schizophrenic species.
DMEDA-DMA and DEEDA-DMA/NIPAM block copolymer derivatives undergo
reversible temperature induced self-assembly in aqueous media by virtue
of the inverse temperature solubility characteristics associated with
these tertiary amino species. The aggregation behavior of these species
is characterized using a combination of dynamic light scattering (DLS), <sup>1</sup>H NMR spectroscopy and transmission electron microscopy (TEM).
For the PA derivatives, schizophrenic behavior is demonstrated in
AB block copolymers with NIPAM with normal and inverse micelles being
readily accessible simply by controlling the solution pH or temperature.
Self-assembled species derived from a DMEDA-DMA block copolymer, containing
tertiary amino functionality in the core, can be readily core cross-linked,
locking the self-assembled structure, using 1,10-dibromodecane as
evidenced by DLS. The ability of examples of the ‘smart’
block copolymers to sequester hydrophobic Nile Red upon application
of a pH or temperature stimulus from an aqueous environment is also
demonstrated. Finally, we show how, if desired, the DMEDA homopolymers
can be further modified via the facile reaction with 1,3-propanesultone
yielding the sulfopropylbetaine analogous materials