Dynamic Nanocrystal Superlattices with Thermally Triggerable Lubricating Ligands.

The size-dependent and collective physical properties of nanocrystals (NCs) and their self-assembled superlattices (SLs) enable the study of mesoscale phenomena and the design of metamaterials for a broad range of applications. However, the limited mobility of NC building blocks in dried NCSLs often hampers the potential for employing postdeposition methods to produce high-quality NCSLs. In this study, we present tailored promesogenic ligands that exhibit a lubricating property akin to thermotropic liquid crystals. The lubricating ability of ligands is thermally triggerable, allowing the dry solid NC aggregates deposited on the substrates with poor ordering to be transformed into NCSLs with high crystallinity and preferred orientations. The interplay between the dynamic behavior of NCSLs and the molecular structure of the ligands is elucidated through a comprehensive analysis of their lubricating efficacy using both experimental and simulation approaches. Coarse-grained molecular dynamic modeling suggests that a shielding layer from mesogens prevents the interdigitation of ligand tails, facilitating the sliding between outer shells and consequently enhancing the mobility of NC building blocks. The dynamic organization of NCSLs can also be triggered with high spatial resolution by laser illumination. The principles, kinetics, and utility of lubricating ligands could be generalized to unlock stimuli-responsive metamaterials from NCSLs and contribute to the fabrication of NCSLs.

Self-Assembly of Atomically Aligned Nanoparticle Superlattices from Pt-Fe3O4 Heterodimer Nanoparticles.

Multicomponent nanoparticle superlattices (SLs) promise the integration of nanoparticles (NPs) with remarkable electronic, magnetic, and optical properties into a single structure. Here, we demonstrate that heterodimers consisting of two conjoined NPs can self-assemble into novel multicomponent SLs with a high degree of alignment between the atomic lattices of individual NPs, which has been theorized to lead to a wide variety of remarkable properties. Specifically, by using simulations and experiments, we show that heterodimers composed of larger Fe3O4 domains decorated with a Pt domain at one vertex can self-assemble into an SL with long-range atomic alignment between the Fe3O4 domains of different NPs across the SL. The SLs show an unanticipated decreased coercivity relative to nonassembled NPs. In situ scattering of the self-assembly reveals a two-stage mechanism of self-assembly: translational ordering between NPs develops before atomic alignment. Our experiments and simulation indicate that atomic alignment requires selective epitaxial growth of the smaller domain during heterodimer synthesis and specific size ratios of the heterodimer domains as opposed to specific chemical composition. This composition independence makes the self-assembly principles elucidated here applicable to the future preparation of multicomponent materials with fine structural control.

Enhanced Mercury Accumulation in Riparian Spiders: An Evidence of Insects' Emergence Effect in Aquatic and Upland Terrestrial Crossed Habitat.

Many studies have focused on mercury (Hg) accumulation in both aquatic and terrestrial organisms, but the effects of aquatic Hg on terrestrial organisms have rarely been documented. Here we report the accumulation of Hg in two species of spiders, Argiope bruennichi, inhabiting paddy fields, and Nephila clavata, inhabiting small forests in the riparian zones of two hydroelectric reservoirs in Guiyang, southwest China. The mean concentration of total mercury (THg) was higher in N. clavata (0.38 mg kg-1) than in A. bruennichi (0.20 mg kg-1). The monthly average THg in N. clavata, collected consecutively from May to October, and the highest values for THg in June (1.2 mg kg-1) could be related to the emergence of aquatic insects during early summer, suggesting that emerging insects play a crucial role in the accumulation of Hg in riparian spiders. The high values could also be attributable to the different times of spider sampling or individual differences.

Integrating augmented reality into inquiry-based learning approach in primary science classrooms.

Notwithstanding the advantages of incorporating Augmented Reality (AR) in education, AR's concrete uses as compared to other technologies are not fully recognised. Moreover, many of the existing studies have neglected to examine the impact of pedagogy and its corresponding instructional models, whilst implementing AR in teaching and learning. In leveraging the affordances of AR, an inquiry-based learning framework, referred to as QIMS, was proposed in this study. A learning package was developed on the topic of plant reproduction for primary 5 students (aged 11-12) based on the QIMS framework. Using a quasi-experimental approach, this study evaluated three conditions (AR and QIMS; QIMS; Non-AR and Non-QIMS) for a series of science lessons in a primary school. 117 students took part in this study. The quantitative results showed that although there was no statistically significant difference in students' academic performance when AR was used, students' self-directed learning and creative thinking skills increased significantly after partaking in the QIMS inquiry-based lessons. The usage of AR and QIMS had a significant effect in increasing students' critical thinking and knowledge creation efficacy skills. Moreover, in view of students' academic outcomes, the integration of QIMS and AR proved to be more beneficial to low-progress students. Qualitative analysis of the interview data from teachers and students aids in accounting for the quantitative results and indicate productive implementation strategies. The findings of this study will guide the design of future AR interventions, by providing insights for both researchers and practitioners on how to integrate and implement AR with pedagogical approaches.

Multi-center evaluation of artificial intelligent imaging and clinical models for predicting neoadjuvant chemotherapy response in breast cancer.

BACKGROUND: Neoadjuvant chemotherapy (NAC) plays an important role in the management of locally advanced breast cancer. It allows for downstaging of tumors, potentially allowing for breast conservation. NAC also allows for in-vivo testing of the tumors' response to chemotherapy and provides important prognostic information. There are currently no clearly defined clinical models that incorporate imaging with clinical data to predict response to NAC. Thus, the aim of this work is to develop a predictive AI model based on routine CT imaging and clinical parameters to predict response to NAC. METHODS: The CT scans of 324 patients with NAC from multiple centers in Singapore were used in this study. Four different radiomics models were built for predicting pathological complete response (pCR): first two were based on textural features extracted from peri-tumoral and tumoral regions, the third model based on novel space-resolved radiomics which extract feature maps using voxel-based radiomics and the fourth model based on deep learning (DL). Clinical parameters were included to build a final prognostic model. RESULTS: The best performing models were based on space-resolved and DL approaches. Space-resolved radiomics improves the clinical AUCs of pCR prediction from 0.743 (0.650 to 0.831) to 0.775 (0.685 to 0.860) and our DL model improved it from 0.743 (0.650 to 0.831) to 0.772 (0.685 to 0.853). The tumoral radiomics model performs the worst with no improvement of the AUC from the clinical model. The peri-tumoral combined model gives moderate performance with an AUC of 0.765 (0.671 to 0.855). CONCLUSIONS: Radiomics features extracted from diagnostic CT augment the predictive ability of pCR when combined with clinical features. The novel space-resolved radiomics and DL radiomics approaches outperformed conventional radiomics techniques.

A Temporal and Space Anti-counterfeiting Based on the Four-Modal Luminescent Ba2Zr2Si3O12 Phosphors.

Fluorescent anti-counterfeiting materials have been widely studied due to their high resolution and convenient identification by direct visualization of the color output. To date, the anti-counterfeiting technology of single ultraviolet excitation mode still has security problems because the single mode could be imitated easily. Here, we have successfully developed four modes of anti-counterfeiting from Eu2+ and Er3+ co-doped Ba2Zr2Si3O12 phosphors with photo, long persistent, photo-stimulated, and up-conversion luminescence behavior. The as-fabricated phosphors can emit an intense blue-green luminescence originating from the characteristic transition of Eu2+ ions and exhibit a blue-green long persistent luminescence phenomenon. Moreover, the enhancement of photo-stimulated luminescence that contributed to the effectively increased trap concentration is observed, along with the produced up-conversion phenomenon thanks to the introduction of Er3+ ions. Notably, the fluorescence rapidly changes from blue-green to stable green luminescence with the delay of excitation time under the excitation of a 980 nm laser diode. Herein, this work realizes the fast down- to up-conversion luminescence output over time, which provides the basis for its possible application in advanced multi-mode anti-counterfeiting.

Highly Stable Metal-Free Long-Persistent Luminescent Copolymer for Low Flicker AC-LEDs.

Organic room-temperature long-persistent luminescent materials are promising light-emitting materials for encryption, architectural decoration, organic solar cells, and biomedical applications. However, their unstable structures and thermal- and humidity-induced emission quenching have greatly limited their utility and reliability. Here, we report a metal-free nonconjugated copolymer that possesses stable photoluminescence at both high temperature and humidity. The room-temperature long-persistent luminescence (LPL) of this copolymer lasts for more than 15 s and can be recovered in high humidity conditions by heating to remove moisture. Copolymer LPL can be achieved with various excitation wavelengths, ranging from ultraviolet to near-infrared, and the LPL color can be adjusted accordingly. The high initial LPL intensity and ultrafast filling time of the copolymer makes it suitable for low flicker alternating current-driven light-emitting diodes (AC-LEDs).

Variation from Zero to Negative Thermal Quenching of Phosphor with Assistance of Defect States.

Proper defect states are demonstrated to be beneficial to overcome thermal quenching of the corresponding phosphors. In this work, a cyan-emitting KGaGeO4/Bi3+ phosphor with abundant defect states is reported, the emission intensity of which exhibits an abnormal thermal quenching performance under excitation with different photon energies. A 100% emission intensity is achieved at 393 K under 325 nm excitation compared with that at room temperature, while significantly enhanced intensities of 207% at 393 K and even 351% at 513 K under 365 nm excitation are recorded. The excellent thermal stability performance is confirmed to be not only related to the direct energy transfer from the defect states but also depended on the efficiency of capturing carriers for the trap centers, which is clarified in this work. In addition, the mechanism of the double tunneling process of carriers from trap centers to luminescence centers and luminescence centers to trap centers is studied. These results are believed to provide new insights into the thermal stability of the corresponding fluorescent materials and could inspire studies to further explore novel fluorescent materials with high thermal stability based on defect state engineering.

Light emission from plasmonic nanostructures.

The mechanism of light emission from metallic nanoparticles has been a subject of debate in recent years. Photoluminescence and electronic Raman scattering mechanisms have both been proposed to explain the observed emission from plasmonic nanostructures. Recent results from Stokes and anti-Stokes emission spectroscopy of single gold nanorods using continuous wave laser excitation carried out in our laboratory are summarized here. We show that varying excitation wavelength and power change the energy distribution of hot carriers and impact the emission spectral lineshape. We then examine the role of interband and intraband transitions in the emission lineshape by varying the particle size. We establish a relationship between the single particle emission quantum yield and its corresponding plasmonic resonance quality factor, which we also tune through nanorod crystallinity. Finally, based on anti-Stokes emission, we extract electron temperatures that further suggest a hot carrier based mechanism. The central role of hot carriers in our systematic study on gold nanorods as a model system supports a Purcell effect enhanced hot carrier photoluminescence mechanism. We end with a discussion on the impact of understanding the light emission mechanism on fields utilizing hot carrier distributions, such as photocatalysis and nanothermometry.

Anti-Stokes Emission from Hot Carriers in Gold Nanorods.

The origin of light emission from plasmonic nanoparticles has been strongly debated lately. It is present as the background of surface-enhanced Raman scattering and, despite the low yield, has been used for novel sensing and imaging applications because of its photostability. Although the role of surface plasmons as an enhancing antenna is widely accepted, the main controversy regarding the mechanism of the emission is its assignment to either radiative recombination of hot carriers (photoluminescence) or electronic Raman scattering (inelastic light scattering). We have previously interpreted the Stokes-shifted emission from gold nanorods as the Purcell effect enhanced radiative recombination of hot carriers. Here we specifically focused on the anti-Stokes emission from single gold nanorods of varying aspect ratios with excitation wavelengths below and above the interband transition threshold while still employing continuous wave lasers. Analysis of the intensity ratios between Stokes and anti-Stokes emission yields temperatures that can only be interpreted as originating from the excited electron distribution and not a thermally equilibrated phonon population despite not using pulsed laser excitation. Consistent with this result as well as previous emission studies using ultrafast lasers, the power-dependence of the upconverted emission is nonlinear and gives the average number of participating photons as a function of emission wavelength. Our findings thus show that hot carriers and photoluminescence play a major role in the upconverted emission.

Polycrystallinity of Lithographically Fabricated Plasmonic Nanostructures Dominates Their Acoustic Vibrational Damping.

The study of acoustic vibrations in nanoparticles provides unique and unparalleled insight into their mechanical properties. Electron-beam lithography of nanostructures allows precise manipulation of their acoustic vibration frequencies through control of nanoscale morphology. However, the dissipation of acoustic vibrations in this important class of nanostructures has not yet been examined. Here we report, using single-particle ultrafast transient extinction spectroscopy, the intrinsic damping dynamics in lithographically fabricated plasmonic nanostructures. We find that in stark contrast to chemically synthesized, monocrystalline nanoparticles, acoustic energy dissipation in lithographically fabricated nanostructures is solely dominated by intrinsic damping. A quality factor of Q = 11.3 ± 2.5 is observed for all 147 nanostructures, regardless of size, geometry, frequency, surface adhesion, and mode. This result indicates that the complex Young's modulus of this material is independent of frequency with its imaginary component being approximately 11 times smaller than its real part. Substrate-mediated acoustic vibration damping is strongly suppressed, despite strong binding between the glass substrate and Au nanostructures. We anticipate that these results, characterizing the optomechanical properties of lithographically fabricated metal nanostructures, will help inform their design for applications such as photoacoustic imaging agents, high-frequency resonators, and ultrafast optical switches.

Single-particle absorption spectroscopy by photothermal contrast.

Removing effects of sample heterogeneity through single-molecule and single-particle techniques has advanced many fields. While background free luminescence and scattering spectroscopy is widely used, recording the absorption spectrum only is rather difficult. Here we present an approach capable of recording pure absorption spectra of individual nanostructures. We demonstrate the implementation of single-particle absorption spectroscopy on strongly scattering plasmonic nanoparticles by combining photothermal microscopy with a supercontinuum laser and an innovative calibration procedure that accounts for chromatic aberrations and wavelength-dependent excitation powers. Comparison of the absorption spectra to the scattering spectra of the same individual gold nanoparticles reveals the blueshift of the absorption spectra, as predicted by Mie theory but previously not detectable in extinction measurements that measure the sum of absorption and scattering. By covering a wavelength range of 300 nm, we are furthermore able to record absorption spectra of single gold nanorods with different aspect ratios. We find that the spectral shift between absorption and scattering for the longitudinal plasmon resonance decreases as a function of nanorod aspect ratio, which is in agreement with simulations.

Photochemically engineering the metal-semiconductor interface for room-temperature transfer hydrogenation of nitroarenes with formic acid.

A mild photochemical approach was applied to construct highly coupled metal-semiconductor dyads, which were found to efficiently facilitate the hydrogenation of nitrobenzene. Aniline was produced in excellent yield (>99 %, TOF: 1183) using formic acid as hydrogen source and water as solvent at room temperature. This general and green catalytic process is applicable to a wide range of nitroarenes without the involvement of high-pressure gases or sacrificial additives.

Dynamic multicolor emissions of multimodal phosphors by Mn2+ trace doping in self-activated CaGa4O7.

The manipulation of excitation modes and resultant emission colors in luminescent materials holds pivotal importance for encrypting information in anti-counterfeiting applications. Despite considerable achievements in multimodal and multicolor luminescent materials, existing options generally suffer from static monocolor emission under fixed external stimulation, rendering them vulnerability to replication. Achieving dynamic multimodal luminescence within a single material presents a promising yet challenging solution. Here, we report the development of a phosphor exhibiting dynamic multicolor photoluminescence (PL) and photo-thermo-mechanically responsive multimodal emissions through the incorporation of trace Mn2+ ions into a self-activated CaGa4O7 host. The resulting phosphor offers adjustable emission-color changing rates, controllable via re-excitation intervals and photoexcitation powers. Additionally, it demonstrates temperature-induced color reversal and anti-thermal-quenched emission, alongside reproducible elastic mechanoluminescence (ML) characterized by high mechanical durability. Theoretical calculations elucidate electron transfer pathways dominated by intrinsic interstitial defects and vacancies for dynamic multicolor emission. Mn2+ dopants serve a dual role in stabilizing nearby defects and introducing additional defect levels, enabling flexible multi-responsive luminescence. This developed phosphor facilitates evolutionary color/pattern displays in both temporal and spatial dimensions using readily available tools, offering significant promise for dynamic anticounterfeiting displays and multimode sensing applications.

Training immunophenotyping deep learning models with the same-section ground truth cell label derivation method improves virtual staining accuracy.

Introduction: Deep learning (DL) models predicting biomarker expression in images of hematoxylin and eosin (H&E)-stained tissues can improve access to multi-marker immunophenotyping, crucial for therapeutic monitoring, biomarker discovery, and personalized treatment development. Conventionally, these models are trained on ground truth cell labels derived from IHC-stained tissue sections adjacent to H&E-stained ones, which might be less accurate than labels from the same section. Although many such DL models have been developed, the impact of ground truth cell label derivation methods on their performance has not been studied. Methodology: In this study, we assess the impact of cell label derivation on H&E model performance, with CD3+ T-cells in lung cancer tissues as a proof-of-concept. We compare two Pix2Pix generative adversarial network (P2P-GAN)-based virtual staining models: one trained with cell labels obtained from the same tissue section as the H&E-stained section (the 'same-section' model) and one trained on cell labels from an adjacent tissue section (the 'serial-section' model). Results: We show that the same-section model exhibited significantly improved prediction performance compared to the 'serial-section' model. Furthermore, the same-section model outperformed the serial-section model in stratifying lung cancer patients within a public lung cancer cohort based on survival outcomes, demonstrating its potential clinical utility. Discussion: Collectively, our findings suggest that employing ground truth cell labels obtained through the same-section approach boosts immunophenotyping DL solutions.

DRAC 2022: A public benchmark for diabetic retinopathy analysis on ultra-wide optical coherence tomography angiography images.

We described a challenge named "DRAC - Diabetic Retinopathy Analysis Challenge" in conjunction with the 25th International Conference on Medical Image Computing and Computer Assisted Intervention (MICCAI 2022). Within this challenge, we provided the DRAC datset, an ultra-wide optical coherence tomography angiography (UW-OCTA) dataset (1,103 images), addressing three primary clinical tasks: diabetic retinopathy (DR) lesion segmentation, image quality assessment, and DR grading. The scientific community responded positively to the challenge, with 11, 12, and 13 teams submitting different solutions for these three tasks, respectively. This paper presents a concise summary and analysis of the top-performing solutions and results across all challenge tasks. These solutions could provide practical guidance for developing accurate classification and segmentation models for image quality assessment and DR diagnosis using UW-OCTA images, potentially improving the diagnostic capabilities of healthcare professionals. The dataset has been released to support the development of computer-aided diagnostic systems for DR evaluation.

A B-spline approach to phase unwrapping in tagged cardiac MRI for motion tracking.

A novel B-Spline based approach to phase unwrapping in tagged magnetic resonance images is proposed for cardiac motion tracking. A bicubic B-spline surface is used to model the absolute phase. The phase unwrapping problem is formulated as a mixed integer optimization problem that minimizes the sum of the difference between the spatial gradients of absolute and wrapped phases, and the difference between the rewrapped and wrapped phases. In contrast to the existing techniques for motion tracking, the proposed approach can overcome the limitation of interframe half-tag displacement and increase the robustness of motion tracking. The article further presents a hybrid harmonic phase imaging-B-spline method to take the advantage of the harmonic phase imaging method for small motion and the efficiency of the B-Spline approach for large motion. The proposed approach has been successively applied to a full set of cardiac MRI scans in both long and short axis slices with superior performance when compared with the harmonic phase imaging and quality guided path-following methods.

Chemical and Physical Properties of Photonic Noble-Metal Nanomaterials.

Colloidal noble metal nanoparticles (NPs) are composed of metal cores and organic or inorganic ligand shells. These NPs support size- and shape-dependent plasmonic resonances. They can be assembled from dispersions into artificial metamolecules which have collective plasmonic resonances originating from coupled bright and dark optical electric and magnetic modes that form depending on the size and shape of the constituent NPs and their number, arrangement, and interparticle distance. NPs can also be assembled into extended 2D and 3D metamaterials that are glassy thin films or ordered thin films or crystals, also known as superlattices and supercrystals. The metamaterials have tunable optical properties that depend on the size, shape, and composition of the NPs, and on the number of NP layers and their interparticle distance. Interestingly, strong light-matter interactions in superlattices form plasmon polaritons. Tunable interparticle distances allow designer materials with dielectric functions tailorable from that characteristic of an insulator to that of a metal, and serve as strong optical absorbers or scatterers, respectively. In combination with lithography techniques, these extended assemblies can be patterned to create subwavelength NP superstructures and form large-area 2D and 3D metamaterials that manipulate the amplitude, phase, and polarization of transmitted or reflected light.

IEEE ISMAR 2022 Report: Toward Better Mixed Realities.

On October 21, 2022, the 21st IEEE International Symposium on Mixed and Augmented Reality (ISMAR 2022) was successfully completed in Singapore. ISMAR is the leading international conference in the fields of augmented reality, mixed reality, and virtual reality. This was the first time that ISMAR was held in Southeast Asia and the first time in hybrid mode. ISMAR 2022 achieved a historically high number of papers and attendees, witnessing the steady growth of the community and the scientific contributions. In this article, we report the key outcomes, impressions, research trends, and lessons learned from the conference.

Three-Dimensionally Complex Phase Behavior and Collective Phenomena in Mixtures of Acoustically Powered Chiral Microspinners.

The process of dynamic self-organization of small building blocks is fundamental to the emergent function of living systems and is characteristic of their out-of-equilibrium homeostasis. The ability to control the interactions of synthetic particles in large groups could lead to the realization of analogous macroscopic robotic systems with microscopic complexity. Rotationally induced self-organization has been observed in biological systems and modeled theoretically, but studies of fast, autonomously moving synthetic rotors remain rare. Here, we report switchable, out-of-equilibrium hydrodynamic assembly and phase separation in suspensions of acoustically powered chiral microspinners. Semiquantitative modeling suggests that three-dimensionally (3D) complex spinners interact through viscous and weakly inertial (streaming) flows. The interactions between spinners were studied over a range of densities to construct a phase diagram, which included gaseous dimer pairing at low density, collective rotation and multiphase separation at intermediate densities, and ultimately jamming at high density. The 3D chirality of the spinners leads to self-organization in parallel planes, forming a three-dimensionally hierarchical system that goes beyond the 2D systems that have so far been modeled computationally. Dense mixtures of spinners and passive tracer particles also show active-passive phase separation. These observations are consistent with recent theoretical predictions of the hydrodynamic coupling between rotlets generated by autonomous spinners and provide an exciting experimental window to the study of colloidal active matter and microrobotic systems.