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Nanoparticle assemblies have generated intense interest because of their novel optical, electronic, and magnetic properties that open up numerous opportunities in fundamental and applied nanophotonics, -electronics, and -magnetics. However, despite the great scientific and technological potential of these structures, it remains an outstanding challenge to reliably fabricate such assemblies with both nanometer-level structural control and precise spatial arrangements on a macroscopic scale. It is the combination of these two features that is key to realizing nanoparticle assemblies' potential, particular for device applications. To address this challenge, we propose a hierarchical assembly approach consisting of both template-particle and particle-particle interactions, whereby the former ensures precise addressability of assemblies on a surface and the latter provides nanometer-level structural control. Template-particle interactions are harnessed via chemical-pattern-directed assembly, and the particle-particle interactions are controlled using DNA-directed self-assembly. To demonstrate the potential of this hierarchical assembly approach, we demonstrate the fabrication of a particularly fascinating assembly: the nanoparticle heterodimer, which possesses a surprisingly rich set of plasmonic properties and is a promising candidate to enable a variety of imaging and sensing applications. Each heterodimer is placed on the surface at predetermined locations, and the precise control of the nanogaps is confirmed by far-field scattering measurements of individual dimers. We further demonstrate that the gap size can be effectively tuned by varying the DNA length. By correlating measured spectra with finite-difference time-domain (FDTD) simulations, we determine the gap sizes to be 4.2 and 5.0 nm-with subnm deviation-for the two DNA lengths investigated. This is one of the best gap uniformities ever demonstrated for surface-bound nanoparticle assemblies. The estimated surface-enhanced Raman scattering (SERS) enhancement factor of these heterodimers is on the order of 105-106 with high reproducibility and predictable polarization-dependence. This hierarchical fabrication technique-employing both template-particle and particle-particle interactions-constitutes a novel platform for the realization of functional nanoparticle assemblies on surfaces and thereby creates new opportunities to implement these structures in a variety of applications.
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The efficacy with which solvent vapor annealing (SVA) can control block copolymer self-assembly has so far been demonstrated primarily for the simplest class of copolymer, the linear diblock copolymer. Adding a third distinct block-thereby creating a triblock terpolymer-not only provides convenient access to complex continuous network morphologies, particularly the gyroid phases, but also opens up a route toward the fabrication of novel nanoscale devices such as optical metamaterials. Such applications, however, require the generation of well-ordered 3D continuous networks, which in turn requires a detailed understanding of the SVA process in terpolymer network morphologies. Here, in situ grazing-incidence small-angle X-ray scattering (GISAXS) is employed to study the self-assembly of a gyroid-forming triblock terpolymer during SVA, revealing the effects of several key SVA parameters on the morphology, lateral order, and, in particular, its preservation in the dried film. The robustness of the terpolymer gyroid morphology is a key requirement for successful SVA, allowing the exploration of annealing parameters which may enable the generation of films with long-range order, e.g., for optical metamaterial applications.
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PURPOSE: Health care inequities persist, and it is difficult to teach health professions students effectively about implicit bias, structural inequities, and caring for patients from underrepresented or minoritized backgrounds. Improvisational theater (improv), where performers create everything in a spontaneous and unplanned manner, may help teach health professions trainees about advancing health equity. Core improv skills, discussion, and self-reflection can help improve communication; build trustworthy relationships with patients; and address bias, racism, oppressive systems, and structural inequities. METHOD: Authors integrated a 90-minute virtual improv workshop using basic exercises into a required course for first-year medical students at University of Chicago in 2020. Sixty randomly chosen students took the workshop and 37 (62%) responded to Likert-scale and open-ended questions about strengths, impact, and areas for improvement. Eleven students participated in structured interviews about their experience. RESULTS: Twenty-eight (76%) of 37 students rated the workshop as very good or excellent, and 31 (84%) would recommend it to others. Over 80% of students perceived their listening and observation skills improved, and that the workshop would help them take better care of patients with experiences different than their own. Six (16%) students experienced stress during the workshop but 36 (97%) felt safe. Eleven (30%) students agreed there were meaningful discussions about systemic inequities. Qualitative interview analysis showed that students thought the workshop helped develop interpersonal skills (communication, relationship building, empathy); helped personal growth (insights into perception of self and others, ability to adapt to unexpected situations); and felt safe. Students noted the workshop helped them to be in the moment with patients and respond to the unexpected in ways more traditional communication curricula have not. The authors developed a conceptual model relating improv skills and equity teaching methods to advancing health equity. CONCLUSIONS: Improv theater exercises can complement traditional communication curricula to advance health equity.
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Educação Médica , Equidade em Saúde , Estudantes de Ciências da Saúde , Estudantes de Medicina , Humanos , Relações Médico-Paciente , Currículo , ComunicaçãoRESUMO
Ninety-minute virtual workshops that used improvisational comedy, standup comedy, graphic medicine, and Theatre of the Oppressed were implemented in 2020 within a required health equity course at the University of Chicago Pritzker School of Medicine to train 90 first-year medical students in advancing health equity. Learning objectives were to (1) deepen understanding of diverse human experiences by developing relationship skills, such as empathy, active listening, engagement, and observation; (2) recognize how diverse patients perceive students and how students perceive them to gain insight into one's identity and how intersectional systems of oppression can stigmatize and marginalize different identities; and (3) engage in free, frank, fearless, and safe conversations about structural racism, colonialism, White and other social privileges, and systemic factors that lead to health inequities. With a 61% (109/180 [90 students × 2 workshops per student]) survey response rate, 72% of respondents thought workshops were very good or excellent, and 83% agreed or strongly agreed they would recommend workshops to others. Key recommendations are to (1) incorporate experiential storytelling and discussion; (2) define clear learning goals for each workshop, map exercises to these goals, and explain their relevance to students; and (3) create a safe, courageous, brave space for exploration and discussion. For health equity, transformation happens as students share their perspectives of curriculum content from their intersectional identities, experiences, and varied privileges; are challenged by others' perspectives; and attempt to understand how others can experience the same content differently. The arts create a powerful form of sharing beyond routine conversations or discussions, which is critical for honest dialogue on difficult topics, such as racism, homophobia, and White privilege and other social privileges. Educators should enable students to have the space, time, and courage to share their true perspectives and engage in authentic discussions that may be uncomfortable but transformative.
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Drama , Equidade em Saúde , Estudantes de Medicina , Humanos , Currículo , EmpatiaRESUMO
Liquid crystal blue phases (BPs) are three-dimensional soft crystals with unit cell sizes orders of magnitude larger than those of classic, atomic crystals. The directed self-assembly of BPs on chemically patterned surfaces uniquely enables detailed in situ resonant soft x-ray scattering measurements of martensitic phase transformations in these systems. The formation of twin lamellae is explicitly identified during the BPII-to-BPI transformation, further corroborating the martensitic nature of this transformation and broadening the analogy between soft and atomic crystal diffusionless phase transformations to include their strain-release mechanisms.
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Optical metamaterials offer the tantalizing possibility of creating extraordinary optical properties through the careful design and arrangement of subwavelength structural units. Gyroid-structured optical metamaterials possess a chiral, cubic, and triply periodic bulk morphology that exhibits a redshifted effective plasma frequency. They also exhibit a strong linear dichroism, the origin of which is not yet understood. Here, the interaction of light with gold gyroid optical metamaterials is studied and a strong correlation between the surface morphology and its linear dichroism is found. The termination of the gyroid surface breaks the cubic symmetry of the bulk lattice and gives rise to the observed wavelength- and polarization-dependent reflection. The results show that light couples into both localized and propagating plasmon modes associated with anisotropic surface protrusions and the gaps between such protrusions. The localized surface modes give rise to the anisotropic optical response, creating the linear dichroism. Simulated reflection spectra are highly sensitive to minute details of these surface terminations, down to the nanometer level, and can be understood with analogy to the optical properties of a 2D anisotropic metasurface atop a 3D isotropic metamaterial. This pronounced sensitivity to the subwavelength surface morphology has significant consequences for both the design and application of optical metamaterials.
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Engineering the grain boundaries of crystalline materials represents an enduring challenge, particularly in the case of soft materials. Grain boundaries, however, can provide preferential sites for chemical reactions, adsorption processes, nucleation of phase transitions, and mechanical transformations. In this work, "soft heteroepitaxy" is used to exert precise control over the lattice orientation of three-dimensional liquid crystalline soft crystals, thereby granting the ability to sculpt the grain boundaries between them. Since these soft crystals are liquid-like in nature, the heteroepitaxy approach introduced here provides a clear strategy to accurately mold liquid-liquid interfaces in structured liquids with a hitherto unavailable level of precision.
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Block copolymer (BCP) self-assembly is a promising route to manufacture functional nanomaterials for applications from nanolithography to optical metamaterials. Self-assembled cubic morphologies cannot, however, be conveniently optically characterized in the lab due to their structural isotropy. Here, the aligned crystallization behavior of a semicrystalline-amorphous polyisoprene-b-polystyrene-b-poly(ethylene oxide) (ISO) triblock terpolymer was utilized to visualize the grain structure of the cubic microphase-separated morphology. Upon quenching from a solvent swollen state, ISO first self-assembles into an alternating gyroid morphology, in the confinement of which the PEO crystallizes preferentially along the least tortuous pathways of the single gyroid morphology with grain sizes of hundreds of micrometers. Strikingly, the resulting anisotropic alignment of PEO crystallites gives rise to a unique optical birefringence of the alternating gyroid domains, which allows imaging of the self-assembled grain structure by optical microscopy alone. This study provides insight into polymer crystallization within a tortuous three-dimensional network and establishes a useful method for the optical visualization of cubic BCP morphologies that serve as functional nanomaterial templates.
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Gold gyroid optical metamaterials are known to possess a reduced plasma frequency and linear dichroism imparted by their intricate subwavelength single gyroid morphology. The anisotropic optical properties are, however, only evident when a large individual gyroid domain is investigated. Multidomain gyroid metamaterials, fabricated using a polyisoprene-b-polystyrene-b-poly(ethylene oxide) triblock terpolymer and consisting of multiple small gyroid domains with random orientation and handedness, instead exhibit isotropic optical properties. Comparing three effective medium models, we here show that the specular reflectance spectra of such multidomain gyroid optical metamaterials can be accurately modeled over a broad range of incident angles by a Bruggeman effective medium consisting of a random wire array. This model accurately reproduces previously published results tracking the variation in normal incidence reflectance spectra of gold gyroid optical metamaterials as a function of host refractive index and volume fill fraction of gold. The effective permittivity derived from this theory confirms the change in sign of the real part of the permittivity in the visible spectral region (so, that gold gyroid metamaterials exhibit both dielectric and metallic behavior at optical wavelengths). That a Bruggeman effective medium can accurately model the experimental reflectance spectra implies that small multidomain gold gyroid optical metamaterials behave both qualitatively and quantitatively as an amorphous composite of gold and air (i.e., nanoporous gold) and that coherent electromagnetic contributions arising from the subwavelength gyroid symmetry are not dominant.
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By incorporating feedback around systems we wish to manipulate, it is possible to improve their performance and robustness properties to meet pre-specified design objectives. For decades control engineers have been successfully implementing feedback controllers for complex mechanical and electrical systems such as aircraft and sports cars. Natural biological systems use feedback extensively for regulation and adaptation but apart from the most basic designs, there is no systematic framework for designing feedback controllers in Synthetic Biology. In this paper we describe how classical approaches from linear control theory can be used to close the loop. This includes the design of genetic circuits using feedback control and the presentation of a biological phase lag controller.
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Engenharia Genética/métodos , Modelos Biológicos , Biologia Sintética/métodosRESUMO
Public policy requires public support, which in turn implies a need to enable the public not just to understand policy but also to be engaged in its development. Where complex science and technology issues are involved in policy making, this takes time, so it is important to identify emerging issues of this type and prepare engagement plans. In our horizon scanning exercise, we used a modified Delphi technique. A wide group of people with interests in the science and policy interface (drawn from policy makers, policy adviser, practitioners, the private sector and academics) elicited a long list of emergent policy issues in which science and technology would feature strongly and which would also necessitate public engagement as policies are developed. This was then refined to a short list of top priorities for policy makers. Thirty issues were identified within broad areas of business and technology; energy and environment; government, politics and education; health, healthcare, population and aging; information, communication, infrastructure and transport; and public safety and national security.