Functional composites by programming entropy-driven nanosheet growth.

Nanomaterials must be systematically designed to be technologically viable1-5. Driven by optimizing intermolecular interactions, current designs are too rigid to plug in new chemical functionalities and cannot mitigate condition differences during integration6,7. Despite extensive optimization of building blocks and treatments, accessing nanostructures with the required feature sizes and chemistries is difficult. Programming their growth across the nano-to-macro hierarchy also remains challenging, if not impossible8-13. To address these limitations, we should shift to entropy-driven assemblies to gain design flexibility, as seen in high-entropy alloys, and program nanomaterial growth to kinetically match target feature sizes to the mobility of the system during processing14-17. Here, following a micro-then-nano growth sequence in ternary composite blends composed of block-copolymer-based supramolecules, small molecules and nanoparticles, we successfully fabricate high-performance barrier materials composed of more than 200 stacked nanosheets (125 nm sheet thickness) with a defect density less than 0.056 µm-2 and about 98% efficiency in controlling the defect type. Contrary to common perception, polymer-chain entanglements are advantageous to realize long-range order, accelerate the fabrication process (<30 min) and satisfy specific requirements to advance multilayered film technology3,4,18. This study showcases the feasibility, necessity and unlimited opportunities to transform laboratory nanoscience into nanotechnology through systems engineering of self-assembly.

The Projectile Perforation Resistance of Materials: Scaling the Impact Resistance of Thin Films to Macroscale Materials.

From drug delivery to ballistic impact, the ability to control or mitigate the puncture of a fast-moving projectile through a material is critical. While puncture is a common occurrence, which can span many orders of magnitude in the size, speed, and energy of the projectile, there remains a need to connect our understanding of the perforation resistance of materials at the nano- and microscale to the actual behavior at the macroscale that is relevant for engineering applications. In this article, we address this challenge by combining a new dimensional analysis scheme with experimental data from micro- and macroscale impact tests to develop a relationship that connects the size-scale effects and materials properties during high-speed puncture events. By relating the minimum perforation velocity to fundamental material properties and geometric test conditions, we provide new insights and establish an alternative methodology for evaluating the performance of materials that is independent of the impact energy or the specific projectile puncture experiment type. Finally, we demonstrate the utility of this approach by assessing the relevance of novel materials, such as nanocomposites and graphene for real-world impact applications.

Studying the high-rate deformation of soft materials via laser-induced membrane expansion.

Cavitation is a phenomenon that occurs when the internal pressure of a material exceeds the resistance to deformation provided by the surrounding medium. Several measurements, such as the blister test, bubble inflation, and cavitation rheology, take advantage of this phenomenon to measure the local mechanical properties of soft materials at relatively low deformation rates. Here, we introduce a new measurement called laser-induced membrane expansion (LIME) that measures the shear modulus of a thin membrane at high strain rates (≈106 s-1 to 108 s-1) by using laser ablation to rapidly expand a thin (tens of microns) elastomeric membrane. To demonstrate the capabilities of this measurement, we use LIME to study the mechanical properties of poly(dimethylsiloxane) (PDMS) membranes at several thicknesses (from 10 µm to 60 µm) and crosslink densities. We find that the shear modulus of the PDMS measured by LIME was weakly dependent on the crosslink density, but was strongly strain rate dependent with values ranging from 106 Pa to 108 Pa. This measurement platform presents a new approach to studying the mechanical properties of soft but thin materials over a range of deformation rates.

Relative effects of polymer composition and sample preparation on glass dynamics.

Modern design of common adhesives, composites and polymeric parts makes use of polymer glasses that are stiff enough to maintain their shape under a high stress while still having a ductile behavior after the yield point. Typically, material compositions are tuned with co-monomers, polymer blends, plasticizers, or other additives to arrive at a tradeoff between the elastic modulus and toughness. In contrast, strong changes to the mechanics of a glass are possible by changing only the molecular packing during vitrification or even deep in the glassy state. For example, physical aging or processing techniques such as physical vapor deposition increase the density, embrittle the material, and increase elastic modulus. Here, we use molecular simulations, validated by positron annihilation lifetime spectroscopy (PALS) and quasi-elastic neutron scattering, to understand the free volume distribution and the resulting dynamics of glassy co-polymers where the composition is systemically varied between polar 5-norbornene-2-methanol (NBOH) and non-polar ethylidene norbornene (ENB) monomers. In these polymer glasses, we analyze the structural features of the unoccupied volume using clustering analysis, where the clustering is parameterized to reproduce experimental measurements of the same features from PALS. Further, we analyze the dynamics, quantified by the Debye-Waller factor, and compare the results with softer, lower density states. Our findings indicate that faster structural relaxations and potentially improved ductility are possible through changes to the geometric structure and fraction of the free volume, and that the resulting changes to the glass dynamics are comparable to large changes in the monomer composition.

Using Machine Learning to Predict and Understand Complex Self-Assembly Behaviors of a Multicomponent Nanocomposite.

Blends of nanoparticles, polymers, and small molecules can self-assemble into optical, magnetic, and electronic devices with structure-dependent properties. However, the relationship between a multicomponent nanocomposite's formulation and its assembled structure is complex and cannot be predicted by theory. The blends can be strongly influenced by processing conditions, which can introduce non-equilibrium states. Currently, nanocomposite devices are designed through cycles of experimental trial and error. Machine learning (ML) methods are a compelling alternative because they can use existing datasets to map high-dimensional spaces. These methods do not rely on known relationships between parameters, so they are suited to complex systems without a solid theoretical foundation. Here, a dataset of 595 microscopy images of nanocomposite thin films is used to train a series of ML models. Correlations between the input and output parameters are examined, providing new insights into the system. Finally, the most successful ML model is used to predict the structures of new nanocomposite compositions. The results confirm that ML techniques can be used to improve the efficiency of nanocomposite device design. More broadly, the current study suggests some of the advantages and challenges associated with applying ML to complex systems.

Orbital Angular Momentum from Self-Assembled Concentric Nanoparticle Rings.

Ring-shaped nanostructures can focus, filter, and manipulate electromagnetic waves, but are challenging to incorporate into devices using standard nanofabrication techniques. Directed self-assembly (DSA) of block copolymers (BCPs) on lithographically patterned templates has successfully been used to fabricate concentric rings and spirals as etching masks. However, this method is limited by BCP phase behavior and material selection. Here, a straightforward approach to generate ring-shaped nanoparticle assemblies in thin films of supramolecular nanocomposites is demonstrated. DSA is used to guide the formation of concentric rings with radii spanning 150-1150 nm and ring widths spanning 30-60 nm. When plasmonic nanoparticles are used, ring nanodevice arrays can be fabricated in one step, and the completed devices produce high-quality orbital angular momentum (OAM). Nanocomposite DSA simplifies and streamlines nanofabrication by producing metal structures without etching or deposition steps; it also introduces interparticle coupling as a new design axis. Detailed analysis of the nanoparticle ring assemblies confirms that the supramolecular system self-regulates the spatial distribution of its components, and thus exhibits a degree of flexibility absent in DSA of BCPs alone, where structures are determined by polymer-pattern incommensurability. The present studies also provide guidelines for developing self-regulating DSA as an alternative to incommensurability-driven methods.

Surgical Cross-Training With Surgery Naive Learners: Implications for Resident Training.

OBJECTIVE: While current literature has explored the transferability of laparoscopic surgical skills to robotic surgery, this study looks to investigate the transferability of surgical skills between robotic surgical simulation and simulated traditional laparoscopy. DESIGN: Participants completed a survey regarding prior surgery exposure and other confounding factors including previous video game experience and self-assessed hand-eye coordination. Following orientation to the laparoscopic simulator (LS) and robotic surgical simulator (RoSS), participants were timed performing the Balloon Grasp and Ball Drop tasks on the RoSS and the Peg Transfer and Ball Drop tasks on the LS. Participants were then randomized to either the laparoscopic or RoSS arm and timed performing the Ball Drop task 10 times and then reassessed performing the Ball Drop using the unpracticed modality. SETTING: Clinical Simulation Laboratory at the University of Vermont PARTICIPANTS: A total of 31 medical students with limited experience in laparoscopic and robotic surgery. RESULTS: There were no statistically significant differences in the demographics or prior surgical and videogame experience between the participants in the laparoscopic and robotic arms of the study (X2 = 0.72, p = 0.75). Timed initial assessment of the RoSS Balloon Grasp (p = 0.84) and Ball Drop (p = 0.79) tasks and the LS Peg Transfer (p = 0.14) and Ball Drop (p = 0.44) tasks were not statistically different between the 2 arms. The simulator modality which was practiced yielded the greatest improvement. The degree of improvement on the unpracticed modality was not statistically different between the groups (p = 0.57), and it was not significantly better than 2 rounds of sequential practice on the practiced modality (LS, p = 0.98 and RoSS, p = 0.55). CONCLUSIONS: With practice, both groups increased surgical skill on the unpracticed modality. However, this degree of improvement was equal, suggesting there is no transferability of skills between laparoscopy and robotics.

The Other Side of Medical Student Mistreatment: Teaching Cultural Competency Across the Generational Divide.

Introduction: Medical student mistreatment continues to be a significant problem despite increased awareness and longitudinal efforts to address the issue. Through audience discussions of a previously published film depicting learner mistreatment, we identified challenges created by student behaviors that negatively impact the learning environment. In addition, the need to address cultural competency in a multigenerational clinical environment became apparent. Methods: We created a film of three vignettes based on perspectives shared in focus groups by faculty, residents, nurses, and staff who work with medical students. We used this film to develop student and faculty curricula elucidating generational differences in behaviors and expectations while also exploring the learner's role in creating a more positive learning environment. Results: Our film was presented to medical education professionals at faculty development workshops and meetings, clerkship students at orientation sessions, residents as part of residents-as-teachers curricula, and faculty at departmental grand rounds. Evaluation data from 176 students and 42 faculty showed that a majority of our participants believed the film accurately reflected challenges they faced in the learning environment and felt better equipped to address them. Discussion: Film is an effective way to stimulate discussion about complex interactions in the clinical learning environment. Divergent perspectives on behaviors depicted in the film served as a stimulus to create targeted curricula for faculty and student education. Stimulating dialogue through film may enhance understanding and empathy among disparate groups, which is likely to be a necessary step for lasting change.

An Exploratory Analysis of Public Awareness and Perception of Ionizing Radiation and Guide to Public Health Practice in Vermont.

Exposure to ionizing radiation has potential for acute and chronic health effects. Within the general public of the United States, there may be a discrepancy between perceived and actual health risks. In conjunction with the Vermont Department of Health, a survey designed to assess public perception and knowledge of ionizing radiation was administered at 6 Vermont locations (n = 169). Descriptive and inferential statistical analyses were conducted. Eighty percent of respondents underestimated the contribution of medical imaging tests to total ionizing radiation exposure. Although only thirty-nine percent of participants were confident in their healthcare professional's knowledge of ionizing radiation, most would prefer to receive information from their healthcare professional. Only one-third of individuals who received a medical imaging test in the past year were educated by their healthcare professional about the risks of these tests. Those who tested their home for radon were twice as likely to choose radon as the greatest ionizing radiation risk to self. Although respondents had an above-average education level, there were many misperceptions of actual risks of exposure to ionizing radiation, particularly of medical imaging tests. Educating healthcare professionals would therefore have a profound and positive impact on public understanding of ionizing radiation.

Development of a dense SNP-based linkage map of an apple rootstock progeny using the Malus Infinium whole genome genotyping array.

BACKGROUND: A whole-genome genotyping array has previously been developed for Malus using SNP data from 28 Malus genotypes. This array offers the prospect of high throughput genotyping and linkage map development for any given Malus progeny. To test the applicability of the array for mapping in diverse Malus genotypes, we applied the array to the construction of a SNP-based linkage map of an apple rootstock progeny. RESULTS: Of the 7,867 Malus SNP markers on the array, 1,823 (23.2%) were heterozygous in one of the two parents of the progeny, 1,007 (12.8%) were heterozygous in both parental genotypes, whilst just 2.8% of the 921 Pyrus SNPs were heterozygous. A linkage map spanning 1,282.2 cM was produced comprising 2,272 SNP markers, 306 SSR markers and the S-locus. The length of the M432 linkage map was increased by 52.7 cM with the addition of the SNP markers, whilst marker density increased from 3.8 cM/marker to 0.5 cM/marker. Just three regions in excess of 10 cM remain where no markers were mapped. We compared the positions of the mapped SNP markers on the M432 map with their predicted positions on the 'Golden Delicious' genome sequence. A total of 311 markers (13.7% of all mapped markers) mapped to positions that conflicted with their predicted positions on the 'Golden Delicious' pseudo-chromosomes, indicating the presence of paralogous genomic regions or mis-assignments of genome sequence contigs during the assembly and anchoring of the genome sequence. CONCLUSIONS: We incorporated data for the 2,272 SNP markers onto the map of the M432 progeny and have presented the most complete and saturated map of the full 17 linkage groups of M. pumila to date. The data were generated rapidly in a high-throughput semi-automated pipeline, permitting significant savings in time and cost over linkage map construction using microsatellites. The application of the array will permit linkage maps to be developed for QTL analyses in a cost-effective manner, and the identification of SNPs that have been assigned erroneous positions on the 'Golden Delicious' reference sequence will assist in the continued improvement of the genome sequence assembly for that variety.