Plasmonic Response of Complex Nanoparticle Assemblies.

Optical properties of nanoparticle assemblies reflect distinctive characteristics of their building blocks and spatial organization, giving rise to emergent phenomena. Integrated experimental and computational studies have established design principles connecting the structure to properties for assembled clusters and superlattices. However, conventional electromagnetic simulations are too computationally expensive to treat more complex assemblies. Here we establish a fast, materials agnostic method to simulate the optical response of large nanoparticle assemblies incorporating both structural and compositional complexity. This many-bodied, mutual polarization method resolves limitations of established approaches, achieving rapid, accurate convergence for configurations including thousands of nanoparticles, with some overlapping. We demonstrate these capabilities by reproducing experimental trends and uncovering far- and near-field mechanisms governing the optical response of plasmonic semiconductor nanocrystal assemblies including structurally complex gel networks and compositionally complex mixed binary superlattices. This broadly applicable framework will facilitate the design of complex, hierarchically structured, and dynamic assemblies for desired optical characteristics.

Modular mixing in plasmonic metal oxide nanocrystal gels with thermoreversible links.

Gelation offers a powerful strategy to assemble plasmonic nanocrystal networks incorporating both the distinctive optical properties of constituent building blocks and customizable collective properties. Beyond what a single-component assembly can offer, the characteristics of nanocrystal networks can be tuned in a broader range when two or more components are intimately combined. Here, we demonstrate mixed nanocrystal gel networks using thermoresponsive metal-terpyridine links that enable rapid gel assembly and disassembly with thermal cycling. Plasmonic indium oxide nanocrystals with different sizes, doping concentrations, and shapes are reliably intermixed in linked gel assemblies, exhibiting collective infrared absorption that reflects the contributions of each component while also deviating systematically from a linear combination of the spectra for single-component gels. We extend a many-bodied, mutual polarization method to simulate the optical response of mixed nanocrystal gels, reproducing the experimental trends with no free parameters and revealing that spectral deviations originate from cross-coupling between nanocrystals with distinct plasmonic properties. Our thermoreversible linking strategy directs the assembly of mixed nanocrystal gels with continuously tunable far- and near-field optical properties that are distinct from those of the building blocks or mixed close-packed structures.

Assembling Inorganic Nanocrystal Gels.

Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network-structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advantages in terms of gel stability, reversibility, or tunability and presents new opportunities for the design of reconfigurable materials and fueled assemblies.

Surface Electrochemistry of Carbon Electrodes and Faradaic Reactions in Capacitive Deionization.

Recent advances in electrochemical desalination techniques have paved way for utilization of saline water. In particular, capacitive deionization (CDI) enables removal of salts with high energy efficiency and economic feasibility, while its applicability has been challenged by degradation of carbon electrodes in long-term operations. Herein, we report a thorough investigation on the surface electrochemistry of carbon electrodes and Faradaic reactions that are responsible for stability issues of CDI systems. By using bare and membrane CDI (MCDI) as model systems, we identified various electrochemical reactions of carbon electrodes with water or oxygen, with thermodynamics and kinetics governed by the electrode potential and pH. As a result, a complete overview of the Faradaic reactions taking place in CDI was constructed by tracing the physicochemical changes occurring in CDI and MCDI systems.

Thermally Cross-Linkable Styrene-Based Host Materials for Solution-Processed Organic Light-Emitting Diodes.

Thermally cross-linkable host materials, DV-TPACZ, DV-TPADBCZ, and TV-TPBI, were designed and synthesized for solution-processed organic light-emitting diodes (OLEDs). The synthesized styrene-functionalized host materials were thermally cross-linked by curing at 150-200 °C without using a polymerization initiator. Excellent solvent resistance was observed for all cured host films. They exhibited low highest occupied molecular orbital energy levels of 5.4-5.7 eV, which indicated a low hole injection barrier from the hole transport layer to the emissive layer. A solution-processed red phosphorescent OLED with 5 wt% (MPHMQ)2Ir (tmd) dopant in the thermally cross-linkable DV-TPACZ host exhibited a current efficiency of 5.3 cd/A, power efficiency of 3.2 lm/W, and external quantum efficiency of 3.6%.

The Time Point-Specific Effect of Beta-Adrenergic Blockade in Attenuating High Fat Diet-Induced Obesity and Bone Loss.

We aimed to clarify the key factor determining the effect of beta blocker attenuating high fat diet- induced obesity and bone loss. Six-week-old C57BL/6 male mice were assigned to groups reflecting different relative onset of obesity and beta blocker administration, different diet (control vs. high fat), and treatment (vehicle vs. beta blocker: propranolol). Mice in Group 1 were fed a control diet (CON) or high fat diet (HIGH) with vehicle or propranolol for 12 weeks. Mice in Group 2 were fed a CON or HIGH without pharmaceutical treatment for the first 12 weeks, followed by another 12 weeks of treatment with vehicle or propranolol. Mice in Group 3 were fed a CON without pharmaceutical treatment for the first 12 weeks, followed by stratification into diet-based subgroups and another 12 weeks of treatment with vehicle or propranolol. Propranolol attenuated the HIGH-induced increase in body weight/fat mass in Group 1 mice and in Group 3 mice, but not in Group 2 mice. Propranolol mitigated HIGH-induced reduction in femoral trabecular bone mineral density and bone architecture deterioration in Group 1 mice but not in Group 2 mice. HIGH feeding in Group 3 did not compromise skeletal integrity. Taken together, propranolol attenuates HIGH-induced body weight increases while weight gain is in progress but not once obesity has already been established. HIGH feeding during the growth period results in compromised bone mass/architecture; which can be attenuated by propranolol administration during the growth period, but not by propranolol administration after obesity has already been established.

Ultrafast Flow Synthesis of o-Functionalized Benzenesulfonyl Fluorides and Subsequent SuFEx Connections via Lithiated Chemistry.

Herein we present a flow-based, rapid, and straightforward approach to synthesize diverse functionalized sulfonyl fluorides by harnessing an aryllithium intermediate. The aryllithium intermediate was fully utilized under optimized conditions (0.016 s, -18 °C) to afford various functionalized sulfonyl fluorides and also intramolecular SuFEx cyclization products in high yields (27-94%). Furthermore, the integrated synthesis incorporating subsequent SuFEx connections with even unstable organolithium nucleophiles facilitated one-flow molecular assembly in high yields (42-72%).

Visual Guidance for User Placement in Avatar-Mediated Telepresence between Dissimilar Spaces.

Rapid advances in technology gradually realize immersive mixed-reality (MR) telepresence between distant spaces. This paper presents a novel visual guidance system for avatar-mediated telepresence, directing users to optimal placements that facilitate the clear transfer of gaze and pointing contexts through remote avatars in dissimilar spaces, where the spatial relationship between the remote avatar and the interaction targets may differ from that of the local user. Representing the spatial relationship between the user/avatar and interaction targets with angle-based interaction features, we assign recommendation scores of sampled local placements as their maximum feature similarity with remote placements. These scores are visualized as color-coded 2D sectors to inform the users of better placements for interaction with selected targets. In addition, virtual objects of the remote space are overlapped with the local space for the user to better understand the recommendations. We examine whether the proposed score measure agrees with the actual user perception of the partner's interaction context and find a score threshold for recommendation through user experiments in virtual reality (VR). A subsequent user study in VR investigates the effectiveness and perceptual overload of different combinations of visualizations. Finally, we conduct a user study in an MR telepresence scenario to evaluate the effectiveness of our method in real-world applications.

Illuminating Disorder: Optical Properties of Complex Plasmonic Assemblies.

The optical properties of disordered plasmonic nanoparticle assemblies can be continuously tuned through the structural organization and composition of their colloidal building blocks. However, progress in the design and experimental realization of these materials has been limited by challenges associated with controlling and characterizing disordered assemblies and predicting their optical properties. This Perspective discusses integrated studies of experimental assembly of disordered optical materials, such as doped metal oxide nanocrystal gels and metasurfaces, with electromagnetic computations on large-scale simulated structures. The simulations prove vital for connecting experimental parameters to disordered structural motifs and optical properties, revealing structure-property relations that inform design choices. Opportunities are identified for optimizing optical property designs for disordered materials using computational inverse methods and tools from machine learning.

Toward microfluidic continuous-flow and intelligent downstream processing of biopharmaceuticals.

Biopharmaceuticals have emerged as powerful therapeutic agents, revolutionizing the treatment landscape for various diseases, including cancer, infectious diseases, autoimmune and genetic disorders. These biotherapeutics pave the way for precision medicine with their unique and targeted capabilities. The production of high-quality biologics entails intricate manufacturing processes, including cell culture, fermentation, purification, and formulation, necessitating specialized facilities and expertise. These complex processes are subject to rigorous regulatory oversight to evaluate the safety, efficacy, and quality of biotherapeutics prior to clinical approval. Consequently, these drugs undergo extensive purification unit operations to achieve high purity by effectively removing impurities and contaminants. The field of personalized precision medicine necessitates the development of novel and highly efficient technologies. Microfluidic technology addresses unmet needs by enabling precise and compact separation, allowing rapid, integrated and continuous purification modules. Moreover, the integration of intelligent biomanufacturing systems with miniaturized devices presents an opportunity to significantly enhance the robustness of complex downstream processing of biopharmaceuticals, with the benefits of automation and advanced control. This allows seamless data exchange, real-time monitoring, and synchronization of purification steps, leading to improved process efficiency, data management, and decision-making. Integrating autonomous systems into biopharmaceutical purification ensures adherence to regulatory standards, such as good manufacturing practice (GMP), positioning the industry to effectively address emerging market demands for personalized precision nano-medicines. This perspective review will emphasize on the significance, challenges, and prospects associated with the adoption of continuous, integrated, and intelligent methodologies in small-scale downstream processing for various types of biologics. By utilizing microfluidic technology and intelligent systems, purification processes can be enhanced for increased efficiency, cost-effectiveness, and regulatory compliance, shaping the future of biopharmaceutical production and enabling the development of personalized and targeted therapies.

Structural Control of Plasmon Resonance in Molecularly Linked Metal Oxide Nanocrystal Gel Assemblies.

Nanocrystal gels exhibit collective optical phenomena based on interactions among their constituent building blocks. However, their inherently disordered structures have made it challenging to understand, predict, or design properties such as optical absorption spectra that are sensitive to the coupling between the plasmon resonances of the individual nanocrystals. Here, we bring indium tin oxide nanocrystal gels under chemical control and show that their infrared absorption can be predicted and systematically tuned by selecting the nanocrystal sizes and compositions and molecular structures of the link-mediating surface ligands. Thermoreversible assemblies with metal-terpyridine links form reproducible gel architectures, enabling us to derive a plasmon ruler that governs the spectral shifts upon gelation, predicated on the nanocrystal and ligand compositions. This empirical guide is validated using large-scale, many-bodied simulations to compute the optical spectra of gels with varied structural parameters. Based on the derived plasmon ruler, we design and demonstrate a nanocrystal mixture whose spectrum exhibits distinctive line narrowing upon assembly.

Effective Hard-Sphere Repulsions between Oleate-Capped Colloidal Metal Oxide Nanocrystals.

Nanocrystal interactions in solvent influence colloidal stability and dictate self-assembly outcomes. Small-angle X-ray scattering is used to study how dilute oleate-capped In2O3 nanocrystals with 7-19 nm core diameters interact when dispersed in a series of nonpolar solvents. Osmotic second virial coefficient analysis finds toluene-dispersed nanocrystals in this size range interact like effective hard spheres with diameters comprising the inorganic core and a ligand-solvent corona with a core-size independent thickness. Hard-sphere-like structure factors are similarly observed for nanocrystals with a 9.7 nm core diameter dispersed in all the solvents investigated. Nanocrystal hydrodynamic diameters from dynamic light scattering measurements correlate with thermodynamic diameters obtained from the osmotic second virial coefficient analysis for all samples. The ability to prepare nanoscale building blocks of different sizes, and dispersed in a variety of solvents, with effective hard-sphere repulsions provides a foundation for assembly, where secondary linking or depletant molecules can be deliberately added to customize interactions to form superstructures such as gel networks or superlattices.

Colorimetric quantification of linking in thermoreversible nanocrystal gel assemblies.

Nanocrystal gels can be responsive, tunable materials, but designing their structure and properties is challenging. By using reversibly bonded molecular linkers, gelation can be realized under conditions predicted by thermodynamics. However, simulations have offered the only microscopic insights, with no experimental means to monitor linking leading to gelation. We introduce a metal coordination linkage with a distinct optical signature allowing us to quantify linking in situ and establish structural and thermodynamic bases for assembly. Because of coupling between linked indium tin oxide nanocrystals, their infrared absorption shifts abruptly at a chemically tunable gelation temperature. We quantify bonding spectroscopically and use molecular simulation to understand temperature-dependent bonding motifs, revealing that gel formation is governed by reaching a critical number of effective links that extend the nanocrystal network. Microscopic insights from our colorimetric linking chemistry enable switchable gels based on thermodynamic principles, opening the door to rational design of programmable nanocrystal networks.

Scalable Subsecond Synthesis of Drug Scaffolds via Aryllithium Intermediates by Numbered-up 3D-Printed Metal Microreactors.

Continuous-flow microreactors enable ultrafast chemistry; however, their small capacity restricts industrial-level productivity of pharmaceutical compounds. In this work, scale-up subsecond synthesis of drug scaffolds was achieved via a 16 numbered-up printed metal microreactor (16N-PMR) assembly to render high productivity up to 20 g for 10 min operation. Initially, ultrafast synthetic chemistry of unstable lithiated intermediates in the halogen-lithium exchange reactions of three aryl halides and subsequent reactions with diverse electrophiles were carried out using a single microreactor (SMR). Larger production of the ultrafast synthesis was achieved by devising a monolithic module of 4 numbered-up 3D-printed metal microreactor (4N-PMR) that was integrated by laminating four SMRs and four bifurcation flow distributors in a compact manner. Eventually, the 16N-PMR system for the scalable subsecond synthesis of three drug scaffolds was assembled by stacking four monolithic modules of 4N-PMRs.

Safety and Effectiveness of Darunavir in Korean Patients with Human Immunodeficiency Virus 1 Infection: A Post-Marketing Observational Study.

We aimed to evaluate the safety and effectiveness of darunavir (DRV) in the treatment of human immunodeficiency virus-1 (HIV-1) infection in Korea. From October 29, 2010, 225 eligible patients with HIV-1 infection receiving DRV were enrolled. DRV was administered with other antiretroviral agents, and followed for 24 weeks. The primary objective was safety evaluation, and effectiveness was assessed by viral load and CD4 T cell counts after 12 weeks and 24 weeks. Adverse drug reactions occurred in 18 patients (9.2%); diarrhea was the most common. Viral load was controlled (<400 copies/mL) in 90.9% of patients. CD4 T cell counts were increased 45.0/mm³ significantly at Week 12 (P = 0.0002), and 70.5/mm³ at Week 24 (P <0.0001). DRV safety and effectiveness was consistent with previous studies.

Impact of Interferon-Based Treatment on Quality of Life and Work-Related Productivity of Korean Patients with Chronic Hepatitis C.

Background/Aims: Chronic hepatitis C virus (HCV) infections put patients at risk of serious liver disease and adversely affects patient quality of life (QoL). MOSAIC (International Multicenter Prospective Observational Study to Evaluate the Epidemiology, Humanistic and Economic Outcomes of Treatment for Chronic Hepatitis C Virus) was a prospective, non-interventional, international, multicenter study that aimed to describe the epidemiology of the infection, the impact of the infection on health-related QoL (HRQoL) and daily activities, and healthcare resource use related to HCV and treatment. Here, we present the results on HRQoL and daily activity impairment in consecutively enrolled South Korean patients treated with interferon (IFN)-containing regimens prospectively followed for up to 48 weeks. Methods: General HRQoL, HCV-specific HRQoL, perceived health state, and work/general activity impairments were measured using the EuroQoL 5-dimension 5-level (EQ-5D-5L), HCV patient-reported outcomes (HCV-PRO), EQ-5D Visual Analog Scale, and Work Productivity and Activity Impairment questionnaires, respectively. Results: Thirty-three of the 100 enrolled patients initiated IFN-based treatment, with an intended duration of 24 weeks for 20 patients and 48 weeks for 12 patients; this information was missing for one patient. Fourteen patients (42.4%) prematurely withdrew. After treatment initiation, IFN-treated patients showed a trend towards deterioration of both general (baseline: 0.87±0.103, week 4: 0.77±0.153) and HCV-specific (baseline: 76.2±19.5, week 4: 68.2±22.3) HRQoL. The scores recovered somewhat towards the end of treatment (EOT) (0.84±0.146 for EQ-5D-5L and 70.8±21.9 for HCV-PRO). The perceived health state and work/general activity impairment displayed similar temporal patterns. Conclusions: Initiating IFN-based treatment prompted some deterioration in general and HCV-related HRQoL, accompanied by impaired daily activities and most work productivity measures; however, the HRQoL and productivity scores improved towards the EOT. HRQoL impairment upon treatment initiation likely contributed to treatment discontinuation.

Recent Progress in the Design and Synthesis of Nitrides for Mesoscopic and Perovskite Solar Cells.

With growing concerns about global warming and the energy crisis, a variety of photovoltaic devices have attracted worldwide attention as alternative energy sources. Among them, organic-inorganic hybrid photovoltaics, typically mesoscopic and perovskite solar cells, are promising, owing to their potential for low-cost energy production, which mainly comes from unlimited combinations of materials optimized for each step of solar energy conversion. However, the commercialization of organic-inorganic hybrid solar cells is hampered by costly electrocatalysts or hole-transport materials. Currently, state-of-the-art dye- or quantum-dot-sensitized solar cells and perovskite solar cells necessitate noble metals and high-price polymeric materials. In an attempt to resolve this issue, various kinds of metal compounds have been investigated, and nitrides have been actively reported to possess a number of favorable properties for the aforementioned purpose, such as excellent electrical conductivity and superb electrocatalytic performance. Herein, the use of nitrides as cost-effective electrocatalysts or hole-transport materials in organic-inorganic hybrid solar cells is reviewed. Nitrides with a variety of morphologies and scales are discussed, together with the synergistic effect in the case of diverse composites. In addition, prospects and challenges for applying nitride materials are briefly suggested.

A numbering-up metal microreactor for the high-throughput production of a commercial drug by copper catalysis.

Microreactors are emerging as an efficient, sustainable synthetic tool compared to conventional batch reactors. Here, we present a new numbering-up metal microreactor by integrating a flow distributor and a copper catalytic module for high productivity of a commercial synthetic drug. A flow distributor and an embedded baffle disc were manufactured by CNC machining and 3D printing of stainless steel (S/S), respectively, whereas a catalytic reaction module was composed of 25 copper coiled capillaries configured in parallel. Eventually, the numbering-up microreactor system assembled with functional modules showed uniform flow distribution and high mixing efficiency regardless of clogging, and achieved high-throughput synthesis of the drug "rufinamide", an anticonvulsant medicine, via a Cu(i)-catalyzed azide-alkyne cycloaddition reaction under optimized conditions.

Determinants of Functional Outcomes Using Clinical Pathways for Rehabilitation After Hip Fracture Surgery.

BACKGROUND: This study evaluated functional outcomes using newly established clinical pathways after hip fracture surgery in older adults and analyzed the major determinants of successful functional outcomes in rehabilitation programs using standardized clinical pathways. METHODS: This was a retrospective cohort study performed in a tertiary rehabilitation facility. A total of 220 patients who had received unilateral hip fracture surgery were followed up from immediately after surgery to 6 months postoperatively. Clinical pathways for rehabilitation included early, individualized rehabilitation, education for activities of daily living, review of general medical conditions, and arrangement of discharge settings. One rehabilitation specialist consecutively checked ambulatory function using 3-level grading, and patients were classified into good recovery and poor recovery groups based on ambulatory function at 6 months postoperatively. Logistic regression analysis was performed using 7 representative variables (age, sex, bone mineral density, Mini-Mental Status Examination [MMSE], Berg Balance Scale [BBS], premorbid ambulatory function, and length of hospital stay). RESULTS: A total of 86.8% of patients could walk with or without assistance at 6 months after surgery and 75.5% of patients involved in the rehabilitation program were classified into the good recovery group in this study. the good recovery group showed higher mmse and bbs scores compared with the poor recovery group. the factors in the model most strongly correlated with recovery were mmse and bbs. CONCLUSION: This study showed that a well-designed rehabilitation program could improve ambulatory function in older patients after hip fracture surgery and that cognitive impairment and poor balance control may inhibit the recovery of ambulatory function.

Highly Efficient Bifacial Dye-Sensitized Solar Cells Employing Polymeric Counter Electrodes.

Dye-sensitized solar cells (DSCs) are promising solar energy conversion devices with aesthetically favorable properties such as being colorful and having transparent features. They are also well-known for high and reliable performance even under ambient lighting, and these advantages distinguish DSCs for applications in window-type building-integrated photovoltaics (BIPVs) that utilize photons from both lamplight and sunlight. Therefore, investigations on bifacial DSCs have been done intensively, but further enhancement in performance under back-illumination is essential for practical window-BIPV applications. In this research, highly efficient bifacial DSCs were prepared by a combination of electropolymerized poly(3,4-ethylenedioxythiphene) (PEDOT) counter electrodes (CEs) and cobalt bipyridine redox ([Co(bpy)3]3+/2+) electrolyte, both of which manifested superior transparency when compared with conventional Pt and iodide counterparts, respectively. Keen electrochemical analyses of PEDOT films verified that superior electrical properties were achievable when the thickness of the film was reduced, while their high electrocatalytic activities were unchanged. The combination of the PEDOT thin film and [Co(bpy)3]3+/2+ electrolyte led to an unprecedented power conversion efficiency among bifacial DSCs under back-illumination, which was also over 85% of that obtained under front-illumination. Furthermore, the advantage of the electropolymerization process, which does not require an elevation of temperature, was demonstrated by flexible bifacial DSC applications.