Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution.

Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3-8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6-8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T' phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T' phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T'-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T'-MoS2 a mass activity of 85 ± 23 A [Formula: see text] at the overpotential of -50 mV and a mass-normalized exchange current density of 127 A [Formula: see text] and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T'-TMDs will also be effective supports for other catalysts targeting other important reactions.

Phase Engineering of Nanomaterials: Transition Metal Dichalcogenides.

Crystal phase, a critical structural characteristic beyond the morphology, size, dimension, facet, etc., determines the physicochemical properties of nanomaterials. As a group of layered nanomaterials with polymorphs, transition metal dichalcogenides (TMDs) have attracted intensive research attention due to their phase-dependent properties. Therefore, great efforts have been devoted to the phase engineering of TMDs to synthesize TMDs with controlled phases, especially unconventional/metastable phases, for various applications in electronics, optoelectronics, catalysis, biomedicine, energy storage and conversion, and ferroelectrics. Considering the significant progress in the synthesis and applications of TMDs, we believe that a comprehensive review on the phase engineering of TMDs is critical to promote their fundamental studies and practical applications. This Review aims to provide a comprehensive introduction and discussion on the crystal structures, synthetic strategies, and phase-dependent properties and applications of TMDs. Finally, our perspectives on the challenges and opportunities in phase engineering of TMDs will also be discussed.

Reversible Semimetal-Semiconductor Transition of Unconventional-Phase WS2 Nanosheets.

Phase transition with band gap modulation of materials has gained intensive research attention due to its various applications, including memories, neuromorphic computing, and transistors. As a powerful strategy to tune the crystal phase of transition-metal dichalcogenides (TMDs), the phase transition of TMDs provides opportunities to prepare new phases of TMDs for exploring their phase-dependent property, function, and application. However, the previously reported phase transition of TMDs is mainly irreversible. Here, we report a reversible phase transition in the semimetallic 1T'-WS2 driven by proton intercalation and deintercalation, resulting in a newly discovered semiconducting WS2 with a novel unconventional phase, denoted as the 1T'd phase. Impressively, an on/off ratio of >106 has been achieved during the phase transition of WS2 from the semimetallic 1T' phase to the semiconducting 1T'd phase. Our work not only provides a unique insight into the phase transition of TMDs via proton intercalation but also opens up possibilities to tune their physicochemical properties for various applications.

TOETVA: a single surgeon's learning curve and a case report of CASTLE thyroid tumor.

BACKGROUND: Owing to the lack of visible scars, the transoral endoscopic thyroidectomy vestibular approach (TOETVA) offers superior aesthetic outcomes compared to conventional thyroidectomy. Carcinoma showing thymus-like differentiation (CASTLE) represents a rare thyroid gland neoplasm. This study aimed to explore the TOETVA learning curve and present a case report of CASTLE. METHODS: A study with precise 1:1 matching was conducted to assess the procedure safety and cancer control outcomes of TOETVA in comparison to conventional surgery between May 2020 and May 2023. Cumulative sum analysis was employed to optimally fit the learning curve. Subsequently, a case report of CASTLE treated with TOETVA surgery was presented. RESULTS: The mean operative time was longer in the TOETVA group than in the open group. The TOETVA group had a higher incidence of skin numbness and excellent cosmetic outcomes compared to the open group. The learning curves for work area preparation, unilateral thyroid lobectomy, and the entire surgical process were 59, 28, and 50 cases, respectively. There were no differences between the learning and proficient groups, except for operative time, intraoperative blood loss, and drainage volume on the first postoperative day. CONCLUSIONS: A comprehensive analysis of the TOETVA learning curve utilizing cumulative and analytical methods demonstrated the feasibility of TOETVA with regards to surgical integrity, safety, and oncological safety. This study's findings suggest that a surgeon's cumulative number of TOETVA cases exceeding 50 can reach the mastery stage. Moreover, diagnosing CASTLE is challenging and necessitates immunohistochemical detection of relatively specific markers associated with thymic epithelial tumors.

ATP synthase subunit e is a shrimp growth-associated breeding marker.

Penaeus vannamei is one of the most popular aquaculture species in the world. This species is featured with its fast-growing and delicious taste, which drives people develop various strains. During this process identification of trait-associated markers could effectively increase breeding efficiency. Driven by this, we tried to screen fast-growing key regulators via a FACS-based high throughput method, in which 2-NBDG was applied as a fluorescent indicator for direct glucose uptake measurement. Totally six candidate genes were screened out followed by in vitro validation in 293T cells. After that, the correlation between these genes and shrimp growing was further verified in a hybrid lineage. The expression level of two genes including ATP synthase subunit e and inhibitor of apoptosis protein showed some correlation with shrimp growth speed. Furthermore, we tested these two candidate markers in various lineages and confirmed that ATP synthase subunit e could be a shrimp growth-associated breeding marker.

Seeded Synthesis of Unconventional 2H-Phase Pd Alloy Nanomaterials for Highly Efficient Oxygen Reduction.

Crystal phase engineering of noble-metal-based alloy nanomaterials paves a new way to the rational synthesis of high-performance catalysts for various applications. However, the controlled preparation of noble-metal-based alloy nanomaterials with unconventional crystal phases still remains a great challenge due to their thermodynamically unstable nature. Herein, we develop a robust and general seeded method to synthesize PdCu alloy nanomaterials with unconventional hexagonal close-packed (hcp, 2H type) phase and also tunable Cu contents. Moreover, galvanic replacement of Cu by Pt can be further conducted to prepare unconventional trimetallic 2H-PdCuPt nanomaterials. Impressively, 2H-Pd67Cu33 nanoparticles possess a high mass activity of 0.87 A mg-1Pd at 0.9 V (vs reversible hydrogen electrode (RHE)) in electrochemical oxygen reduction reaction (ORR) under alkaline condition, which is 2.5 times that of the conventional face-centered cubic (fcc) Pd69Cu31 counterpart, revealing the important role of crystal phase on determining the ORR performance. After the incorporation of Pt, the obtained 2H-Pd71Cu22Pt7 catalyst shows a significantly enhanced mass activity of 1.92 A mg-1Pd+Pt at 0.9 V (vs RHE), which is 19.2 and 8.7 times those of commercial Pt/C and Pd/C, placing it among the best reported Pd-based ORR electrocatalysts under alkaline conditions.

A Wearable Head Mounted Display Bio-Signals Pad System for Emotion Recognition.

Multimodal bio-signals acquisition based on wearable devices and using virtual reality (VR) as stimulus source are promising techniques in emotion recognition research field. Numerous studies have shown that emotional states can be better evoked through Immersive Virtual Environments (IVE). The main goal of this paper is to provide researchers with a system for emotion recognition in VR environments. In this paper, we present a wearable forehead bio-signals acquisition pad which is attached to Head-Mounted Displays (HMD), termed HMD Bio Pad. This system can simultaneously record emotion-related two-channel electroencephalography (EEG), one-channel electrodermal activity (EDA), photoplethysmograph (PPG) and skin temperature (SKT) signals. In addition, we develop a human-computer interaction (HCI) interface which researchers can carry out emotion recognition research using VR HMD as stimulus presentation device. To evaluate the performance of the proposed system, we conducted different experiments to validate the multimodal bio-signals quality, respectively. To validate EEG signal, we have assessed the performance in terms of EEG eyes-blink task and eyes-open and eyes-closed task. The EEG eyes-blink task indicates that the proposed system can achieve comparable EEG signal quality in comparison to the dedicated bio-signals measuring device. The eyes-open and eyes-closed task proves that the proposed system can efficiently record alpha rhythm. Then we used signal-to-noise ratio (SNR) and Skin Conductance Reaction (SCR) signal to validate the performance for EDA acquisition system. A filtered EDA signal, with a high mean SNR of 28.52 dB, is plotted on HCI interface. Moreover, the SCR signal related to stimulus response can be correctly extracted from EDA signal. The SKT acquisition system has been validated effectively by the temperature change experiment when subjects are in unpleasant emotion. The pulse rate (PR) estimated from PPG signal achieved the low mean average absolute error (AAE), which is 1.12 beats per minute (BPM) over 8 recordings. In summary, the proposed HMD Bio Pad offers a portable, comfortable and easy-to-wear device for recording bio-signals. The proposed system could contribute to emotion recognition research in VR environments.

Dynamic Restructuring of Cu-Doped SnS2 Nanoflowers for Highly Selective Electrochemical CO2 Reduction to Formate.

With ever-increasing energy consumption and continuous rise in atmospheric CO2 concentration, electrochemical reduction of CO2 into chemicals/fuels is becoming a promising yet challenging solution. Sn-based materials are identified as attractive electrocatalysts for the CO2 reduction reaction (CO2 RR) to formate but suffer from insufficient selectivity and activity, especially at large cathodic current densities. Herein, we demonstrate that Cu-doped SnS2 nanoflowers can undergo in situ dynamic restructuring to generate catalytically active S-doped Cu/Sn alloy for highly selective electrochemical CO2 RR to formate over a wide potential window. Theoretical thermodynamic analysis of reaction energetics indicates that the optimal electronic structure of the Sn active site can be regulated by both S-doping and Cu-alloying to favor formate formation, while the CO and H2 pathways will be suppressed. Our findings provide a rational strategy for electronic modulation of metal active site(s) for the design of active and selective electrocatalysts towards CO2 RR.

Ethylene Selectivity in Electrocatalytic CO2 Reduction on Cu Nanomaterials: A Crystal Phase-Dependent Study.

The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO2 reduction reaction (CO2RR) to produce high-value hydrocarbons. However, studies to date are limited to the conventional face-centered cubic (fcc) Cu. Here, we report a crystal phase-dependent catalytic behavior of Cu, after the successful synthesis of high-purity 4H Cu and heterophase 4H/fcc Cu using the 4H and 4H/fcc Au as templates, respectively. Remarkably, the obtained unconventional crystal structures of Cu exhibit enhanced overall activity and higher ethylene (C2H4) selectivity in CO2RR compared to the fcc Cu. Density functional theory calculations suggest that the 4H phase and 4H/fcc interface of Cu favor the C2H4 formation pathway compared to the fcc Cu, leading to the crystal phase-dependent C2H4 selectivity. This study demonstrates the importance of crystal phase engineering of metal nanocatalysts for electrocatalytic reactions, offering a new strategy to prepare novel catalysts with unconventional phases for various applications.

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles.

Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO2RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochemical cells.

Symmetry-Breaking Synthesis of Multicomponent Nanoparticles.

Multicomponent nanoparticles (MCNs) composed of disparate inorganic colloidal components have attracted great attention from researchers in both the academic and industrial community, because of their unique properties and diverse applications in energy conversion and storage; heterogeneous catalysis; optics and electronics; and biomedical imaging, diagnosis, and therapy. Compared with single-component nanoparticles (NPs), new or advanced properties of MCNs arise from the synergistic effect between their constituent components and the presence of nanoscale interfaces between distinct materials within the particles. Consequently, the spatial arrangement of nanoscale domains of MCNs becomes equally important in property or function control of MCNs as their size, shape, and composition, if not more. In particular, compositionally asymmetric MCNs may outperform their symmetric counterparts in many of their applications. To this end, the seed-mediated growth (SMG) method, which involves depositing a second material onto seed NPs, has been considered as the most common strategy for the synthesis of asymmetric MCNs with desired complexity. In this approach, the control of symmetry breaking during MCN growth is usually achieved by manipulating the growth kinetics or using seed NPs with asymmetric shapes or surfaces. Although great progress has been made in the past decade, there remains a challenge to control the shape, orientation and organization of colloidal components of MCNs with a high yield and reproducibility. Recently, several unconventional methods have been developed as an important addition to the synthetic toolbox for the production of complex MCNs that otherwise may not be readily attainable. This Account summarizes recent advancements on the development of unconventional synthetic strategies for breaking the growth symmetry in the synthesis of asymmetric MCNs. We start with a brief discussion of the achievements and limitations of the conventional strategies for symmetry breaking synthesis. In the subsequent section, we present three unconventional approaches toward symmetry-breaking synthesis of asymmetric MCNs, namely, surface-protected growth, interface-guided growth, and welding-induced synthesis. First, we discuss how commonly used soft agents (e.g., collapsed polymer) and hard agents (e.g., silica) can be asymmetrically coated on seed NPs to template the asymmetric growth of secondary material, generating a broad range of MCNs with complex architectures. The unique features and key factors of this surface-protected synthesis are discussed from the viewpoints of the surface chemistry of seed NPs. We further discuss the use of a solid/liquid or liquid/liquid interface to guide the synthesis of Janus or more complex MCNs through two general mechanisms; that is, selective blocking or impeding the access of precursors to one side of seed NPs and interfacial reaction-enabled generation of asymmetric seeds for further growth. Finally, we discuss a symmetry-breaking method beyond the SMG mechanism, directed welding of as-synthesized single-component NPs. Moreover, we discuss how the unique structural symmetry and compositional arrangement of these MCNs significantly alter the physical and chemical properties of MCNs, thus facilitating their performance in exemplary applications of photocatalysis and electrocatalysis. We finally conclude this Account with a summary of recent progress and our future perspective on the future challenges.

Oxytocin and CD38 in the paraventricular nucleus play a critical role in paternal aggression in mice.

In mammals, the development of healthy offspring requires maternal care. Behavior by lactating mothers toward other individuals is an important component of maternal aggression. However, it is unclear whether fathers display aggression primed by pups (an external factor), and the protection mechanism is poorly understood. To address this question, we examined paternal aggression in the ICR mouse strain. We found that sires exposed to cues from pups and lactating dams showed stronger aggression toward intruders than did sires that were deprived of family cues or exposed to nonlactating mates. c-Fos immunohistochemistry showed that cells in both the paraventricular and supraoptic nuclei (PVN and SON, respectively) in the hypothalamus of sires exposed to any cues were highly activated. However, c-Fos activation in oxytocinergic neurons was increased only in sires exposed to pup cues and solely in the PVN. In Cd38-knockout sires, the presence of pups induced no or reduced parental aggression; however, this phenotype was recovered, that is, aggression increased to the wild-type level, after intraperitoneal administration of oxytocin (OT). Specific c-Fos activation patterns induced by pup cues were not found in the PVN of knockout sires. These results demonstrate that the PVN is one of the primary hypothalamic areas involved in paternal aggression and suggest that a CD38-dependent OT mechanism in oxytocinergic neurons is critical for part of the behavior associated with the protection of offspring by nurturing male mice.

Two-dimensional metal-organic framework nanosheets: synthesis and applications.

Two-dimensional (2D) metal-organic framework (MOF) nanosheets are attracting increasing research attention due to their unique properties originating from their ultrathin thickness, large surface area and high surface-to-volume atom ratios. Many great advances have been made in the synthesis and application of 2D MOF nanosheets over the past few years. In this review, we summarize the recent advances in the synthesis of 2D MOF nanosheets by using top-down methods, e.g. sonication exfoliation, mechanical exfoliation, Li-intercalation exfoliation and chemical exfoliation, and bottom-up methods, i.e. interfacial synthesis, three-layer synthesis, surfactant-assisted synthesis, modulated synthesis, and sonication synthesis. In addition, the recent progress in 2D MOF nanosheet-based nanocomposites is also briefly introduced. The potential applications of 2D MOF nanosheets in gas separation, energy conversion and storage, catalysis, sensors and biomedicine are discussed. Finally, we give our personal insights into the challenges and opportunities for the future research of 2D MOF nanosheets and their composites.

Adjusting the Reduction Potential of Electrons by Quantum Confinement for Selective Photoreduction of CO2 to Methanol.

The production of CH3 OH from the photocatalytic CO2 reduction reaction (PCRR) presents a promising route for the clean utilization of renewable resources, but charge recombination, an unsatisfying stability and a poor selectivity limit its practical application. In this paper, we present the design and fabrication of 0D/2D materials with polymeric C3 N4 nanosheets and CdSe quantum dots (QDs) to enhance the separation and reduce the diffusion length of charge carriers. The rapid outflow of carriers also restrains self-corrosion and consequently enhances the stability. Furthermore, based on quantum confinement effects of the QDs, the energy of the electrons could be adjusted to a level that inhibits the hydrogen evolution reaction (HER, the main competitive reaction to PCRR) and improves the selectivity and activity for CH3 OH production from the PCRR. The band structures of photocatalysts with various CdSe particle sizes were also investigated quantitatively to establish the relationship between the band energy and the photocatalytic performance.

Morphological and Compositional Design of Pd-Cu Bimetallic Nanocatalysts with Controllable Product Selectivity toward CO2 Electroreduction.

Electrochemical conversion of carbon dioxide (electrochemical reduction of carbon dioxide) to value-added products is a promising way to solve CO2 emission problems. This paper describes a facile one-pot approach to synthesize palladium-copper (Pd-Cu) bimetallic catalysts with different structures. Highly efficient performance and tunable product distributions are achieved due to a coordinative function of both enriched low-coordinated sites and composition effects. The concave rhombic dodecahedral Cu3 Pd (CRD-Cu3 Pd) decreases the onset potential for methane (CH4 ) by 200 mV and shows a sevenfold CH4 current density at -1.2 V (vs reversible hydrogen electrode) compared to Cu foil. The flower-like Pd3 Cu (FL-Pd3 Cu) exhibits high faradaic efficiency toward CO in a wide potential range from -0.7 to -1.3 V, and reaches a fourfold CO current density at -1.3 V compared to commercial Pd black. Tafel plots and density functional theory calculations suggest that both the introduction of high-index facets and alloying contribute to the enhanced CH4 current of CRD-Cu3 Pd, while the alloy effect is responsible for high CO selectivity of FL-Pd3 Cu.

Surviving High-Temperature Calcination: ZrO2 -Induced Hematite Nanotubes for Photoelectrochemical Water Oxidation.

Nanotubular Fe2 O3 is a promising photoanode material, and producing morphologies that withstand high-temperature calcination (HTC) is urgently needed to enhance the photoelectrochemical (PEC) performance. This work describes the design and fabrication of Fe2 O3 nanotube arrays that survive HTC for the first time. By introducing a ZrO2 shell on hydrothermal FeOOH nanorods by atomic layer deposition, subsequent high-temperature solid-state reaction converts FeOOH-ZrO2 nanorods to ZrO2 -induced Fe2 O3 nanotubes (Zr-Fe2 O3 NTs). The structural evolution of the hematite nanotubes is systematically explored. As a result of the nanostructuring and shortened charge collection distance, the nanotube photoanode shows a greatly improved PEC water oxidation activity, exhibiting a photocurrent density of 1.5 mA cm-2 at 1.23 V (vs. reversible hydrogen electrode, RHE), which is the highest among hematite nanotube photoanodes without co-catalysts. Furthermore, a Co-Pi decorated Zr-Fe2 O3 NT photoanode reveals an enhanced onset potential of 0.65 V (vs. RHE) and a photocurrent of 1.87 mA cm-2 (at 1.23 V vs. RHE).

Synthesis of Platinum Nanotubes and Nanorings via Simultaneous Metal Alloying and Etching.

Metallic nanotubes represent a class of hollow nanostructures with unique catalytic properties. However, the wet-chemical synthesis of metallic nanotubes remains a substantial challenge, especially for those with dimensions below 50 nm. This communication describes a simultaneous alloying-etching strategy for the synthesis of Pt nanotubes with open ends by selective etching Au core from coaxial Au/Pt nanorods. This approach can be extended for the preparation of Pt nanorings when Saturn-like Au core/Pt shell nanoparticles are used. The diameter and wall thickness of both nanotubes and nanorings can be readily controlled in the range of 14-37 nm and 2-32 nm, respectively. We further demonstrated that the nanotubes with ultrathin side walls showed superior catalytic performance in oxygen reduction reaction.

Thin Heterojunctions and Spatially Separated Cocatalysts To Simultaneously Reduce Bulk and Surface Recombination in Photocatalysts.

Efficient charge separation and light absorption are crucial for solar energy conversion over solid photocatalysts. This paper describes the construction of Pt@TiO2 @In2 O3 @MnOx mesoporous hollow spheres (PTIM-MSs) for highly efficient photocatalytic oxidation. TiO2 -In2 O3 double-layered shells were selectively decorated with Pt nanoparticles and MnOx on the inner and outer surfaces, respectively. The spatially separated cocatalysts drive electrons and holes near the surface to flow in opposite directions, while the thin heterogeneous shell separates the charges generated in the bulk phase. The synergy between the thin heterojunctions and the spatially separated cocatalysts can simultaneously reduce bulk and surface/subsurface recombination. In2 O3 also serves as a sensitizer to enhance light absorption. The PTIM-MSs exhibit high photocatalytic activity for both water and alcohol oxidation.

Magneto-Plasmonic Janus Vesicles for Magnetic Field-Enhanced Photoacoustic and Magnetic Resonance Imaging of Tumors.

Magneto-plasmonic Janus vesicles (JVs) integrated with gold nanoparticles (AuNPs) and magnetic NPs (MNPs) were prepared asymmetrically in the membrane for in vivo cancer imaging. The hybrid JVs were produced by coassembling a mixture of hydrophobic MNPs, free amphiphilic block copolymers (BCPs), and AuNPs tethered with amphiphilic BCPs. Depending on the size and content of NPs, the JVs acquired spherical or hemispherical shapes. Among them, hemispherical JVs containing 50 nm AuNPs and 15 nm MNPs showed a strong absorption in the near-infrared (NIR) window and enhanced the transverse relaxation (T2 ) contrast effect, as a result of the ordering and dense packing of AuNPs and MNPs in the membrane. The magneto-plasmonic JVs were used as drug delivery vehicles, from which the release of a payload can be triggered by NIR light and the release rate can be modulated by a magnetic field. Moreover, the JVs were applied as imaging agents for in vivo bimodal photoacoustic (PA) and magnetic resonance (MR) imaging of tumors by intravenous injection. With an external magnetic field, the accumulation of the JVs in tumors was significantly increased, leading to a signal enhancement of approximately 2-3 times in the PA and MR imaging, compared with control groups without a magnetic field.

Heterogeneous-Structure-Based AuNBs@TiO2 Nano-Photosensitizers for Computed Tomography Imaging Guided NIR-II Photodynamic Therapy and Cancer Metastatic Prevention.

Photodynamic therapy (PDT) is a minimally invasive cancer treatment that, despite its significant attention, faces limitations in penetration depth, which restrict its effectiveness. Herein, it is found that gold nanobipyramid (AuNBs) coated with TiO2 can form a core-shell heterogeneous structure (AuNBs@TiO2) with strong absorption at second near infrared (NIR-II) region. A substantial quantity of reactive oxygen species (ROS), including singlet oxygen (1O2), superoxide anion radicals, and hydroxyl radicals, can be rapidly generated when subjecting the AuNBs@TiO2 aqueous suspension to 1064 nm laser irradiation. The quantum yield for sensitization of 1O2 by AuNBs@TiO2 is 0.36 at 1064 nm light excitation. In addition, the Au element as high-Z atoms in the nanosystem can improve the ability of computed tomographic (CT) imaging. As compared to commercial iohexol, the AuNBs@TiO2 nanoparticle exhibits significantly better CT imaging effect, which can be used to guide PDT. In addition, the nano-photosensitizer shows a remarkable therapeutic effect against established solid tumors and prevents tumor metastasis and potentiates immune checkpoint blockade therapy. More importantly, here the great potentials of AuNBs@TiO2 are highlighted as a theranostic platform for CT-guided cancer photodynamic immunotherapy.