29 research outputs found
Molecular engineering of chiral colloidal liquid crystals using DNA origami
Establishing precise control over the shape and the interactions of the
microscopic building blocks is essential for design of macroscopic soft
materials with novel structural, optical and mechanical properties. Here, we
demonstrate robust assembly of DNA origami filaments into cholesteric liquid
crystals, 1D supramolecular twisted ribbons and 2D colloidal membranes. The
exquisite control afforded by the DNA origami technology establishes a
quantitative relationship between the microscopic filament structure and the
macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of
1D twisted ribbons, which behave as effective supramolecular polymers whose
structure and elastic properties can be precisely tuned by controlling the
geometry of the elemental building blocks. Our results demonstrate the
potential synergy between DNA origami technology and colloidal science, in
which the former allows for rapid and robust synthesis of complex particles,
and the latter can be used to assemble such particles into bulk materials
Achiral symmetry breaking and positive Gaussian modulus lead to scalloped colloidal membranes
In the presence of a non-adsorbing polymer, monodisperse rod-like particles
assemble into colloidal membranes, which are one rod-length thick liquid-like
monolayers of aligned rods. Unlike 3D edgeless bilayer vesicles, colloidal
monolayer membranes form open structures with an exposed edge, thus presenting
an opportunity to study physics of thin elastic sheets. Membranes assembled
from single-component chiral rods form flat disks with uniform edge twist. In
comparison, membranes comprised of mixture of rods with opposite chiralities
can have the edge twist of either handedness. In this limit disk-shaped
membranes become unstable, instead forming structures with scalloped edges,
where two adjacent lobes with opposite handedness are separated by a
cusp-shaped point defect. Such membranes adopt a 3D configuration, with cusp
defects alternatively located above and below the membrane plane. In the
achiral regime the cusp defects have repulsive interactions, but away from this
limit we measure effective long-ranged attractive binding. A phenomenological
model shows that the increase in the edge energy of scalloped membranes is
compensated by concomitant decrease in the deformation energy due to Gaussian
curvature associated with scalloped edges, demonstrating that colloidal
membranes have positive Gaussian modulus. A simple excluded volume argument
predicts the sign and magnitude of the Gaussian curvature modulus that is in
agreement with experimental measurements. Our results provide insight into how
the interplay between membrane elasticity, geometrical frustration and achiral
symmetry breaking can be used to fold colloidal membranes into 3D shapes.Comment: Main text: 25 pages, 6 figures. Supplementary information: 6 pages, 6
figure
TCT-342 Risk and Consequences of Periprocedural Myocardial Infarction Following Off-Label Use of Second Generation Drug-Eluting Stents: Two-Year Follow-up in the TWENTE Trial
Clinical Outcome Following Stringent Discontinuation of Dual Antiplatelet Therapy After 12 Months in Real-World Patients Treated With Second-Generation Zotarolimus-Eluting Resolute and Everolimus-Eluting Xience V Stents : 2-Year Follow-Up of the Randomized TWENTE Trial
Objectives
The aim of this study was to assess the safety and efficacy of the implantation of Resolute zotarolimus-eluting stents (ZES) (Medtronic Inc., Santa Rosa, California) and Xience V everolimus-eluting stents (EES) (Abbott Vascular, Santa Clara, California) following strict discontinuation of dual antiplatelet therapy (DAPT) after 12 months.
Background
Only limited long-term follow-up data are available from head-to-head comparisons of second-generation drug-eluting stents.
Methods
The randomized TWENTE (The Real-World Endeavor Resolute Versus Xience V Drug-Eluting Stent Study in Twente) trial is an investigator-initiated study performed in a population with many complex patients and lesions and only limited exclusion criteria. Patients were randomly assigned 1:1 to ZES (n = 697) or EES (n = 694).
Results
Two-year follow-up information was available on all patients. The rate of continuation of DAPT beyond 12 months was very low (5.4%). The primary endpoint of target vessel failure, a composite of cardiac death, target vessel–related myocardial infarction, and target vessel revascularization, did not differ between ZES and EES (10.8% vs. 11.6, p = 0.65), despite fewer target lesion revascularizations in patients with EES (2.6% vs. 4.9%, p = 0.03). The patient-oriented composite endpoint was similar (16.4% vs. 17.1%, p = 0.75). Two-year rates of definite or probable stent thrombosis were 1.2% and 1.4%, respectively (p = 0.63). Very late definite or probable stent thrombosis occurred only in 2 patients in each study arm (0.3% vs. 0.3%, p = 1.00).
Conclusions
After 2 years of follow-up and stringent discontinuation of DAPT beyond 12 months, Resolute ZES and Xience V EES showed similar results in terms of safety and efficacy for treating patients with a majority of complex lesions and off-label indications for drug-eluting stents. (The Real-World Endeavor Resolute Versus Xience V Drug-Eluting Stent Study in Twent
Reconfigurable self-assembly through chiral control of interfacial tension
Author Posting. © The Author(s), 2011. This is the author's version of the work. It is posted here by permission of Nature Publishing Group for personal use, not for redistribution. The definitive version was published in Nature 481 (2012): 348–351, doi:10.1038/nature10769.From determining optical properties of simple molecular crystals to establishing preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical, and optical properties of both synthetic and biological matter at macroscopic lengthscales1,2. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials3-6. An example of particular interest is smectic liquid crystals, where the 2D layered geometry cannot support twist, expelling chirality to the edges in a manner analogous to the expulsion of a magnetic field from superconductors7-10. Here, we demonstrate a previously unexplored consequence of this geometric frustration which leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes11, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This finding suggests an analogy between chiral twist which is expelled to the edge of 2D membranes, and amphiphilic surfactants which are expelled to oil-water interfaces12. Similar to surfactants, chiral control of interfacial tension drives the assembly of myriad polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ enables dynamical control of line tension that powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials which can easily be moved, stretched, attached to one another, and transformed between multiple conformational states, thus enabling precise assembly and nano-sculpting of highly dynamical and designable materials with complex topologies.This work was supported by the National Science Foundation (NSF-MRSEC-0820492, NSF-DMR-0955776, NSF-MRI 0923057) and Petroleum Research Fund (ACS-PRF 50558-DNI7).2012-07-0
Estimating Transit Dose for Nasobiliary High Dose Rate (HDR) Brachytherapy Using a Novel QA Device
Chiral edge fluctuations of colloidal membranes.
We study edge fluctuations of a flat colloidal membrane comprised of a monolayer of aligned filamentous viruses. Experiments reveal that a peak in the spectrum of the in-plane edge fluctuations arises for sufficiently strong virus chirality. Accounting for internal liquid crystalline degrees of freedom by the length, curvature, and geodesic torsion of the edge, we calculate the spectrum of the edge fluctuations. The theory quantitatively describes the experimental data, demonstrating that chirality couples in-plane and out-of-plane edge fluctuations to produce the peak
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Molecular engineering of chiral colloidal liquid crystals using DNA origami.
Establishing precise control over the shape and the interactions of the microscopic building blocks is essential for design of macroscopic soft materials with novel structural, optical and mechanical properties. Here, we demonstrate robust assembly of DNA origami filaments into cholesteric liquid crystals, one-dimensional supramolecular twisted ribbons and two-dimensional colloidal membranes. The exquisite control afforded by the DNA origami technology establishes a quantitative relationship between the microscopic filament structure and the macroscopic cholesteric pitch. Furthermore, it also enables robust assembly of one-dimensional twisted ribbons, which behave as effective supramolecular polymers whose structure and elastic properties can be precisely tuned by controlling the geometry of the elemental building blocks. Our results demonstrate the potential synergy between DNA origami technology and colloidal science, in which the former allows for rapid and robust synthesis of complex particles, and the latter can be used to assemble such particles into bulk materials
Equation of state of colloidal membranes
In the presence of a non-adsorbing polymer, monodisperse rod-like colloids assemble into one-rod-length thick liquid-like monolayers, called colloidal membranes. The density of the rods within a colloidal membrane is determined by a balance between the osmotic pressure exerted by the enveloping polymer suspension and the repulsion between the colloidal rods. We developed a microfluidic device for continuously observing an isolated membrane while dynamically controlling the osmotic pressure of the polymer suspension. Using this technology we measured the membrane rod density over a range of osmotic pressures than is wider that what is accessible in equilibrium samples. With increasing density we observed a first-order phase transition, in which the in-plane membrane order transforms from a 2D fluid into a 2D solid. In the limit of low osmotic pressures, we measured the rate at which individual rods evaporate from the membrane. The developed microfluidic technique could have wide applicability for in situ investigation of various soft materials and how their properties depend on the solvent composition