Design Principles Research Articles

Interface-modulated kinetic differentials in electron and hole transfer rates as a key design principle for redox photocatalysis by Sb2VO5/QD heterostructures.

The efficient conversion of solar energy to chemical energy represents a critical bottleneck to the energy transition. Photocatalytic splitting of water to generate solar fuels is a promising solution. Semiconductor quantum dots (QDs) are prime candidates for light-harvesting components of photocatalytic heterostructures, given their size-dependent photophysical properties and band-edge energies. A promising series of heterostructured photocatalysts interface QDs with transition-metal oxides which embed midgap electronic states derived from the stereochemically active electron lone pairs of p-block cations. Here, we examine the thermodynamic driving forces and dynamics of charge separation in Sb2VO5/CdSe QD heterostructures, wherein a high density of Sb 5s2-derived midgap states are prospective acceptors for photogenerated holes. Hard-x-ray valence band photoemission spectroscopy measurements of Sb2VO5/CdSe QD heterostructures were used to deduce thermodynamic driving forces for charge separation. Interfacial charge transfer dynamics in the heterostructures were examined as a function of the mode of interfacial connectivity, contrasting heterostructures with direct interfaces assembled by successive ion layer adsorption and reaction (SILAR) and interfaces comprising molecular bridges assembled by linker-assisted assembly (LAA). Transient absorption spectroscopy measurements indicate ultrafast (<2ps) electron and hole transfer in SILAR-derived heterostructures, whereas LAA-derived heterostructures show orders of magnitude differentials in the kinetics of hole (<100ps) and electron (∼1ns) transfer. The interface-modulated kinetic differentials in electron and hole transfer rates underpin the more effective charge separation, reduced charge recombination, and greater photocatalytic efficiency observed for the LAA-derived Sb2VO5/CdSe QD heterostructures.

Mechanical design principles in frustrated thin elastic sheets.

Using a geometric formalism of elasticity theory we develop a systematic theoretical framework for shaping and manipulating the energy landscape of slender solids, and consequently their mechanical response to external perturbations. We formally express global mechanical properties associated with non-Euclidean thin sheets in terms of their local rest lengths and rest curvatures, and we interpret the expressions as both forward and inverse problems for designing the desired mechanical properties. We show that by wisely designing geometric frustration, anomalous mechanical properties can be encoded into a material using accessible experimental techniques. To test the methodology we derive a family of ribbon-springs with extreme mechanical behavior such as tunable, anharmonic, and even vanishing rigidities. The presented formalism can be discretized, offering a new methodology for designing mechanical properties and thus opens a new pathway for the design of both continuum and discrete solids and structures.

Dual Optical Cycling Centers Mounted on an Organic Scaffold: New Insights from Quantum Chemistry Calculations and Symmetry Analysis.

Molecules cooled to ultracold temperatures are desirable for applications in fundamental physics and quantum information science. However, cooling polyatomic molecules with more than six atoms has not yet been achieved. Building on the idea of an optical cycling center (OCC), a moiety supporting a set of localized and isolated electronic states within a polyatomic molecule, molecules with two OCCs (bi-OCCs) may afford better cooling efficiency by doubling the photon scattering rate. By using quantum chemistry calculations, we assess the extent of the coupling of the two OCCs with each other and the molecular scaffold. We show that promising coolable bi-OCC molecules can be proposed by following chemical design principles.

Microfluidic Biochips for Single-Cell Isolation and Single-Cell Analysis of Multiomics and Exosomes.

Single-cell multiomic and exosome analyses are potent tools in various fields, such as cancer research, immunology, neuroscience, microbiology, and drug development. They facilitate the in-depth exploration of biological systems, providing insights into disease mechanisms and aiding in treatment. Single-cell isolation, which is crucial for single-cell analysis, ensures reliable cell isolation and quality control for further downstream analyses. Microfluidic chips are small lightweight systems that facilitate efficient and high-throughput single-cell isolation and real-time single-cell analysis on- or off-chip. Therefore, most current single-cell isolation and analysis technologies are based on the single-cell microfluidic technology. This review offers comprehensive guidance to researchers across different fields on the selection of appropriate microfluidic chip technologies for single-cell isolation and analysis. This review describes the design principles, separation mechanisms, chip characteristics, and cellular effects of various microfluidic chips available for single-cell isolation. Moreover, this review highlights the implications of using this technology for subsequent analyses, including single-cell multiomic and exosome analyses. Finally, the current challenges and future prospects of microfluidic chip technology are outlined for multiplex single-cell isolation and multiomic and exosome analyses.

Synthesis of Styrylbenzazole Photoswitches and Evaluation of their Photochemical Properties.

Styrylbenzazoles form a promising yet under-represented class of photoswitches that can perform a light-driven E-Z isomerization of the central alkene double bond without undergoing irreversible photocyclization, typical of the parent stilbene. In this work, we report the synthesis and photochemical study of 23 styrylbenzazole photoswitches. Their thermal stabilities, quantum yields, maximum absorption wavelengths and photostationary state (PSS) distributions can be tuned by changing the benzazole heterocycle and the substitution pattern on the aryl ring. In particular, we found that push-pull systems show large redshifts of the maximum absorption wavelengths and the highest quantum yields, whereas ortho-substituted styrylbenzazole photoswitches exhibit the most favorable PSS ratios. Taking advantage of both design principles, we produced 2,6-dimethyl-4-(dimethylamino)-styrylbenzothiazole, a thermally stable and efficient P-type photoswitch which displays negative photochromism upon irradiation with visible light up to 470 nm to obtain a near-quantitative isomerization with a very high quantum yield of 59%. Furthermore, 4-hydroxystyrylbenzothiazole was demonstrated to be a pH-sensitive switch which exhibits a 100 nm redshift upon deprotonation. Ortho-methylation of this switch improved the obtained PSS ratio in its deprotonated state from E:Z=53:47 to E:Z=18:82. We anticipate that this relatively unexplored class of photoswitches will form a valuable expansion of the current family of photoswitches.

National Public Health Dashboards: Protocol for a Scoping Review.

The COVID-19 pandemic highlighted the importance of robust public health data systems and the potential utility of data dashboards for ensuring access to critical public health data for diverse groups of stakeholders and decision makers. As dashboards are becoming ubiquitous, it is imperative to consider how they may be best integrated with public health data systems and the decision-making routines of diverse audiences. However, additional progress on the continued development, improvement, and sustainability of these tools requires the integration and synthesis of a largely fragmented scholarship regarding the purpose, design principles and features, successful implementation, and decision-making supports provided by effective public health data dashboards across diverse users and applications. This scoping review aims to provide a descriptive and thematic overview of national public health data dashboards including their purpose, intended audiences, health topics, design elements, impact, and underlying mechanisms of use and usefulness of these tools in decision-making processes. It seeks to identify gaps in the current literature on the topic and provide the first-of-its-kind systematic treatment of actionability as a critical design element of public health data dashboards. The scoping review follows the PRISMA-ScR (Preferred Reporting Items for Systematic Reviews and Meta-Analyses Extension for Scoping Reviews) guidelines. The review considers English-language, peer-reviewed journal papers, conference proceedings, book chapters, and reports that describe the design, implementation, and evaluation of a public health dashboard published between 2000 and 2023. The search strategy covers scholarly databases (CINAHL, PubMed, Medline, and Web of Science) and gray literature sources and uses snowballing techniques. An iterative process of testing for and improving intercoder reliability was implemented to ensure that coders are properly trained to screen documents according to the inclusion criteria prior to beginning the full review of relevant papers. The search process initially identified 2544 documents, including papers located via databases, gray literature searching, and snowballing. Following the removal of duplicate documents (n=1416), nonrelevant items (n=839), and items classified as literature reviews and background information (n=73), 216 documents met the inclusion criteria: US case studies (n=90) and non-US case studies (n=126). Data extraction will focus on key variables, including public health data characteristics; dashboard design elements and functionalities; intended users, usability, logistics, and operation; and indicators of usefulness and impact reported. The scoping review will analyze the goals, design, use, usefulness, and impact of public health data dashboards. The review will also inform the continued development and improvement of these tools by analyzing and synthesizing current practices and lessons emerging from the literature on the topic and proposing a theory-grounded and evidence-informed framework for designing, implementing, and evaluating public health data dashboards. DERR1-10.2196/52843.

Targeted gene delivery systems for T-cell engineering.

T lymphocytes are indispensable for the host systems of defense against pathogens, tumors, and environmental threats. The therapeutic potential of harnessing the cytotoxic properties of T lymphocytes for antigen-specific cell elimination is both evident and efficacious. Genetically engineered T-cells, such as those employed in CAR-T and TCR-T cell therapies, have demonstrated significant clinical benefits in treating cancer and autoimmune disorders. However, the current landscape of T-cell genetic engineering is dominated by strategies that necessitate in vitro T-cell isolation and modification, which introduce complexity and prolong the development timeline of T-cell based immunotherapies. This review explores the complexities of gene delivery systems designed for T cells, covering both viral and nonviral vectors. Viral vectors are known for their high transduction efficiency, yet they face significant limitations, such as potential immunogenicity and the complexities involved in large-scale production. Nonviral vectors, conversely, offer a safer profile and the potential for scalable manufacturing, yet they often struggle with lower transduction efficiency. The pursuit of gene delivery systems that can achieve targeted gene transfer to T cell without the need for isolation represents a significant advancement in the field. This review assesses the design principles and current research progress of such systems, highlighting the potential for in vivo gene modification therapies that could revolutionize T-cell based treatments. By providing a comprehensive analysis of these systems, we aim to contribute valuable insights into the future development of T-cell immunotherapy.

Design Principle and Development Trends of Silicon-Based Anode Binders for Lithium-ion Batteries: A Mini Review

Abstract: Silicon (Si), recognized as a promising alternative material for the anodes of lithium-ion batteries, boasts a high theoretical specific capacity and abundant natural availability. During the preparation of silicon-based anodes, binders play a pivotal role in ensuring the cohesion of silicon particles, conductive agents, and current collectors. The structure and performance of these binders are critical for the mechanical stability, electrical conductivity, and stress dissipation capacity of the anodes. This review initially outlines the structural characteristics of various binders, including linear, branched, and three-dimensional cross-linked types. It then delves into the relationship between the structure and properties of these binders in the context of their application in high-performance lithium-ion batteries, focusing on their mechanical properties, electrical conductivity, and self-healing capabilities. Particular attention is given to the design strategies for binders that facilitate stress dissipation, with an emphasis on integrating multifunctional polymer binders renowned for their superior conductive and self-healing features. Such binders contribute to the formation of a robust three-dimensional network structure via multiple bonding mechanisms, including chemical, non-covalent, and coordination interactions. This configuration significantly enhances the adhesion between silicon particles, thereby facilitating the efficient dissipation of stress, which is a key aspect for ensuring the long-term cycling stability of lithium-ion batteries. Lastly, the paper explores future development directions for silicon anode binders, advocating for a thorough investigation into the synergy of diverse structural and functional combinations, with the aim of advancing the performance and practical application of silicon-based lithium-ion batteries.

Nonclassical Zwitterions as a Design Principle to Reduce Lipophilicity without Impacting Permeability.

The ionization of bioactive molecules impacts many ADME-relevant physicochemical properties, in particular, solubility, lipophilicity, and permeability. Ampholytes contain both acidic and basic groups and are distinguished as ordinary ampholytes and zwitterions. An influential review states that zwitterions only exist if the acidic pKa is significantly lower than the basic pKa. Through concordance of measured and calculated pKa and log P, we show that the zwitterionic behavior of several marketed drugs and natural products occurs despite a low or negative ΔpKa. These nonclassical zwitterions are characterized by a weak acidic and basic pKa and conjugation through an extended aromatic system, often including pseudorings via intramolecular hydrogen bonds. In contrast to most classical zwitterions, nonclassical zwitterions can exhibit excellent permeability. As permeability and lipophilicity are typically correlated, the combination of low lipophilicity and high permeability makes nonclassical zwitterions an attractive design principle in medicinal chemistry.

Robust sliding-mode observer for unbounded state nonlinear systems

Designing a full-state observer for nonlinear systems has always been accompanied by challenges and restrictive constraints. Mainly, applying a state observer in nonlinear systems with non-minimum phase characteristics is more challenging when the limiting constraints are not satisfied due to diverging internal dynamics. In this paper, a robust sliding-mode observer approach has been successfully employed to estimate the states of nonlinear systems with unbounded and diverging dynamics. The design principles of this observer are based on applying a classifying algorithm in single-input single-output and multiple-input multiple-output nonlinear systems. It is noteworthy that this observer is highly robust against disturbance, uncertainty and measurement noise, and its conditions are less conservative compared to previous nonlinear sliding-mode observers. One novel feature of the proposed observer is that while the system's state gets unbounded and diverged in fault-occurring scenarios or critical circumstances, this observer retains accuracy. The efficiency of the proposed observer is verified in the simulation results for two nonlinear industrial systems, including a hydro-turbine power generation plant and a continuous stirred tank reactor.

Porous Crystalline Organic Cages Made by Design

AbstractShape‐persistent organic cages are an intriguing class of molecular porous materials. Through hierarchical molecular design, size and shape of the intrinsic molecular voids are controlled by dynamic covalent chemistry, while pore structure and topology are governed by noncovalent alignment in the solid state. However, the predictable and reliable crystallization of organic cages is still challenging since long‐range superstructures are solely based on weak and rather unidirectional supramolecular interactions. In this tutorial review, we provide a general classification of porous solid‐state materials and discuss specific design principles regarding the dynamic covalent reactions, the small‐molecule building blocks and solid‐state engineering. Furthermore, we introduce the most important analytical techniques for porous materials with a special focus on organic cages.

Design rules for controlling active topological defects

Topological defects play a central role in the physics of many materials, including magnets, superconductors, and liquid crystals. In active fluids, defects become autonomous particles that spontaneously propel from internal active stresses and drive chaotic flows stirring the fluid. The intimate connection between defect textures and active flow suggests that properties of active materials can be engineered by controlling defects, but design principles for their spatiotemporal control remain elusive. Here, we propose a symmetry-based additive strategy for using elementary activity patterns, as active topological tweezers, to create, move, and braid such defects. By combining theory and simulations, we demonstrate how, at the collective level, spatial activity gradients act like electric fields which, when strong enough, induce an inverted topological polarization of defects, akin to a negative susceptibility dielectric. We harness this feature in a dynamic setting to collectively pattern and transport interacting active defects. Our work establishes an additive framework to sculpt flows and manipulate active defects in both space and time, paving the way to design programmable active and living materials for transport, memory, and logic.

Dynamic Hydrogels against Infections: From Design to Applications

Dynamic Hydrogels against Infections: From Design to Applications

From Chemical Drawing to Electronic Properties of Semiconducting Polymers in Bulk: A Tool for Chemical Discovery.

A quantum chemistry (QC)/molecular dynamics (MD) scheme is developed to calculate electronic properties of semiconducting polymers in three steps: (i) constructing the polymer force field through a unified workflow, (ii) equilibrating polymer models, and (iii) calculating electronic structure properties (e.g., density of states and localization length) from the equilibrated models by QC approaches. Notably, as the second step of this scheme is generally the most time-consuming one, we introduce an alternative method to compute thermally averaged electronic properties in bulk, based on the simulation of a polymer chain in the solution of its repeat units, which is shown to reproduce the microstructure of polymer chains and their electrostatic effect (successfully tested for five benchmark polymers) 10 times faster than state-of-the-art methods. In fact, this scheme offers a consistent and speedy way of estimating electronic properties of polymers from their chemical drawings, thus ensuring the availability of a homogeneous set of simulations to derive structure-property relationships and material design principles. As an example, we show how the electrostatic effect of the polymer chain environment can disturb the localized electronic states at the band tails and how this effect is more significant in the case of diketopyrrolopyrrole polymers as compared to indacenodithiophene and dithiopheneindenofluorene ones.

A home health management app designed in the post-epidemic era using empirical evidence based on the demand collection of elderly users

In the context of the epidemic, the daily routines of China’s elderly populace underwent substantial transformations. The implementation of home-based pandemic containment strategies led to heightened levels of social isolation and loneliness, exerting a discernible influence on the subjective well-being of this demographic. Consequently, residing in retirement apartments has emerged as a more advantageous alternative for elderly individuals capable of self-care. To meet their life and emotional needs and improve their sense of well-being, we used the KANO model to design a health management app for the self-care of older persons. We summarised the functional requirements for the self-care of elderly people, distributed questionnaires to generate a list of requirements, and conducted data analysis. We optimised the low-fidelity prototype based on the usability test results combined with relevant interface design elements to implement emotional interaction design practices for older persons’ self-care. Furthermore, we completed a design evaluation and program optimisation of the design practice to guide the final visual design. The research findings identify the core principles of interactive design for elderly users to enable visual design specifications for improving the lives of the elderly population. This research highlights the need to design more appropriate products that meet demographic characteristics. This work contributes to strengthening the connection between elderly people and society while bridging the ‘digital divide’ based on this population’s cautious approach to technologies and declining abilities to learn.

Metal Poly(heptazine imides) as Multifunctional Photocatalysts for Solar Fuel Production

AbstractSolar‐driven photocatalysis employing particulate semiconductors represents a promising approach for sustainable production of valuable chemical feedstock. Metal poly(heptazine imide) (MPHI), a novel 2D ionic carbon nitride, has been recognized as an emerging photocatalyst with distinctive properties. In this minireview, we first delineate the forefront innovations of MPHI photocatalysts, spanning from synthetic strategies and solving structures to the exploration of novel properties. We place special emphasis on the structural design principles aimed at developing high‐performance MPHI systems toward photocatalytic solar fuel production such as H2 evolution, H2O oxidation, H2O2 production and CO2 reduction. Finally, we discuss crucial insights and challenges in leveraging highly active MPHIs for efficient solar‐to‐chemical energy conversion.

Opportunities and Challenges of Integrating Generative Artificial Intelligence in Education

This paper thoroughly examines both the opportunities and obstacles associated with integrating Generative Artificial Intelligence (AI) into educational settings. It explores how Generative AI has the potential to enrich learning experiences, customize education for individuals, and foster creativity. However, it also confronts several challenges including ethical dilemmas, safeguarding data privacy, mitigating algorithmic biases, and reshaping the role of educators. Through a synthesis of theoretical frameworks and empirical research, the paper offers valuable insights into effective strategies for navigating these challenges. It emphasizes the importance of establishing ethical guidelines, ensuring transparency in algorithms, and adopting inclusive design principles during AI integration. Furthermore, the paper underscores the importance of providing educators with adequate training and professional development opportunities to effectively utilize AI tools. Additionally, it advocates for ongoing dialogue among stakeholders—such as educators, policymakers, technologists, and students—to steer responsible AI integration in education. Ultimately, the paper advocates for a collaborative approach that prioritizes human-centric values, equity, and diversity. While Generative AI holds promise for revolutionizing educational practices, its integration requires thoughtful consideration of ethical, social, and pedagogical implications. Through proactive collaboration and partnership, educators can leverage AI's potential to create more immersive, tailored, and equitable learning environments.

Influence of Concrete Compressive Strength on L-Shaped Shear Wall Performance in Buildings within High-Seismicity Zones

Reinforced concrete mid-rise structures are supported by shear walls to withstand lateral forces resulting from earthquakes. In this context, the presence of openings in these walls is essential both functionally and aesthetically. This study employed L-shaped shear walls with varying vertical opening ratios, ranging from 15% to 50%, and compressive strengths ranging from 20MPa to 40MPa in a ten-story building. The study results demonstrate the significant role played by openings and the compressive strength of concrete in reinforced concrete walls to ensure buildings withstand earthquake forces. In this regard, we have developed reference models that adhere to seismic design principles and utilize optimized dimensions for openings based on the compressive strength of the concrete.

Fluid entrapment during forced imbibition in a multidepth microfluidic chip with complex porous geometry

Understanding and controlling fluid entrapment during forced imbibition in porous media is crucial for many natural and industrial applications. However, the microscale physics and macroscopic consequences of fluid entrapment in these geometric-confined porous media remain poorly understood. Here, we introduce a novel multidepth microfluidic chip, which can mitigate the depth confinement of traditional two-dimensional (2-D) microfluidic chips and mimic the wide pore size distribution as natural-occurring three-dimensional (3-D) porous media. Based on microfluidic experiments and direct numerical simulations, we observe the fluid-entrapment scenarios and elucidate the underlying complex interaction between geometric confinement, capillary number and wettability. Increasing depth variation can promote fluid entrapment, whereas increasing capillary number and contact angle yield the opposite effect, which seemingly contradicts conventional expectations in traditional 2-D microfluidic chips. The fluid-entrapment scenario in depth-variable microfluidic chips stems from microscopic interfacial phenomena, classified as snap-off and bypass events. We provide theoretical analyses of these pore-scale events and validate corresponding phase diagrams numerically. It is shown that increasing depth variation triggers snap-off and bypass events. Conversely, a higher capillary number suppresses snap-off events under strong imbibition, and an increased contact angle inhibits bypass events under imbibition. These macroscopic imbibition patterns in microfluidic porous media can be linked with these pore-scale events by improved dynamic pore-network models. Our findings bridge the understanding of forced imbibition between 2-D and 3-D porous media and provide design principles for newly engineered porous media with respect to their desired imbibition behaviours.

Metal Poly(heptazine imides) as Multifunctional Photocatalysts for Solar Fuel Production.

Solar-driven photocatalysis employing particulate semiconductors represents a promising approach for sustainable production of valuable chemical feedstock. Metal poly(heptazine imide) (MPHI), a novel 2D ionic carbon nitride, has been recognized as an emerging photocatalyst with distinctive properties. In this minireview, we first delineate the forefront innovations of MPHI photocatalysts, spanning from synthetic strategies and solving structures to the exploration of novel properties. We place special emphasis on the structural design principles aimed at developing high-performance MPHI systems toward photocatalytic solar fuel production such as H2 evolution, H2O oxidation, H2O2 production and CO2 reduction. Finally, we discuss crucial insights and challenges in leveraging highly active MPHIs for efficient solar-to-chemical energy conversion.