Clinical efficacy of different androgen deprivation therapies for prostate cancer and evaluation based on dynamic-contrast enhanced magnetic resonance imaging.

Objective: To evaluate the clinical efficacy of different androgen deprivation therapies for prostate cancer (PCa) based on dynamic-contrast enhanced magnetic resonance imaging (DCE-MRI). Methods: 104 patients with PCa were studied, all of whom were treated with androgen deprivation therapy. The patients were divided into a continuous group (continuous androgen deprivation therapy) and an intermittent group (intermittent androgen deprivation therapy) by random number table method, 52 cases/group. The therapeutic effect and DCE-MRI indices were compared and the relationship between DCE-MRI indices and clinical efficacy and the evaluation value of therapeutic efficacy were analyzed. Results: The objective response rate (ORR) of the intermittent group was higher than that of the continuous group (p < 0.05), and there was no significant difference in disease control rate (DCR) between the two groups (p > 0.05). After treatment, volume transfer coefficient (Ktrans), reverse transfer constant (Kep), volume fraction (Ve), blood volume (BV), and blood flow (BF) in both groups were lowered, and those in the intermittent group were lower than the continuous group (p < 0.05). Ktrans, Kep, Ve, BF, and BV in the ORR group were lower than those in the non-ORR group (p < 0.05). Ktrans, Kep, Ve, BF, and BV were correlated with the therapeutic effect of PCa (p < 0.05). The AUC value of the combined detection of DCE-MRI indices in evaluating the therapeutic effect of PCa was greater than that of each index alone (p < 0.05). Conclusion: Compared with continuous androgen deprivation therapy, intermittent androgen deprivation therapy has better clinical efficacy in the treatment of PCa, and DCE-MRI indices are related to the treatment efficacy of PCa and have an evaluation value.

Exploring how cation entropy influences electric double layer formation and electrochemical reactivity.

Electric double layers are crucial to energy storage and electrocatalytic device performance. While double layer formation originates in electrostatic interactions, electric double layer properties are governed by a balance of both electrostatic and entropic driving forces. Favorable ion-surface electrostatic interactions attract counterions to charged surfaces to compensate, or "screen," potentials, but the confinement of these same ions from a bulk reservoir to the interface incurs an entropic penalty. Here, we use a dicationic imidazolium ionic liquid and its monovalent analogue to explore how cation valence and entropy influence double layer formation and electrochemical reactivity using CO2 electroreduction as a model reaction. We find that divalent and monovalent cations display similar CO2 reduction kinetics but differ vastly in steady-state reactivity due to rapid electrochemically induced precipitation of insulating dicationic (bi)carbonate films. Using in situ surface-enhanced Raman scattering spectroscopy, we find that potential-dependent cation reorientation occurs at similar potentials between the two ionic liquids, but the introduction of a covalent link in the divalent cation imparts a more ordered double layer structure that favors (bi)carbonate precipitation. In mixed monovalent-divalent electrolytes, we find that the divalent cations dominate interfacial properties by preferentially accumulating at surfaces even at very low relative concentrations. Our findings confirm that ion entropy plays a key role in modulating local electrochemical environments. Furthermore, we highlight how double layer properties are sensitive to the properties of counterions that pay the lowest entropic penalty to accumulate at interfaces. Overall, we illustrate that ion entropy provides a new knob to tune reaction microenvironments and unveil how entropy plays a major role in modulating electrochemical reactivity in mixed ion electrolytes.

Preparation of uniform lignin/titanium dioxide nanoparticles by confined assembly: A multifunctional nanofiller for a waterborne polyurethane wood coating.

We report a facile synthesis for lignin/titanium dioxide (TiO2) nanoparticles (LT NPs) at room temperature by confining assembly of lignin macromolecules. The LT NPs had a uniform nanosize distribution (average diameter âˆ¼ 68 nm) and were directly employed as multifunctional nanofillers to reinforce a waterborne polyurethane wood coating (WBC). X-ray diffraction, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy revealed the mechanism by which formed TiO2 confined lignin assembly. The LT NPs considerably increased the tensile strength of a WBC film from 16.3 MPa to 28.1 MPa. The WBC-LT NPs exhibited excellent ultraviolet (UV) A and UVB blocking performances of 87 % and 98 %, respectively, while maintaining 94 % transmittance in the visible region. Incorporating LT NPs into the WBC enhanced the coating performance (the hardness, adhesion, and abrasion resistance) on wood substrates. A quantitative color and texture analysis revealed that the LT NPs increased the decorativeness of actual wooden products. After nearly 1800 h of UV irradiation, wood coated with the WBC-LT NPs exhibited good color stability, where the original color remained unchanged or even became brighter. In this study, value-added valorization of lignin is enabled by using organic-inorganic nanofillers and insights are gained into developing multifunctional WBCs.

Two-Dimensional Lanthanide Metal-Organic Frameworks as a Platform for Sensing Pollutant and Nitrophenols Reduction.

The discharge of harmful and toxic pollutants in water is destroying the ecosystem balance and human being health at an alarming rate. Therefore, the detection and removal of water pollutants by using stable and efficient materials are significant but challenging. Herein, three novel lanthanide metal-organic frameworks (Ln-MOFs), [La(L)(DMF)2(H2O)2]·H2O (LCUH-104), [Nd(L)(DMF)2(H2O)2]·H2O (LCUH-105), and [Pr(L)(DMF)2(H2O)2]·H2O (LCUH-106) [H3L = 5-(4-(tetrazol-5-yl)phenyl)isophthalic acid (H3TZI)] were solvothermally constructed and structurally characterized. In the three Ln-MOFs, dinuclear metallic clusters {Ln2} were connected by deprotonated tetrazol-containing dicarboxylate TZI3- to obtain a 2D layered framework with a point symbol of {42·84}·{46}. Their excellent chemical and thermal stabilities were beneficial to carry out fluorescence sensing and achieve the catalytic nitrophenols (NPs) reduction. Especially, the incorporation of the nitrogen-rich tetrazole ring into their 2D layered frameworks enables the fabrication of Pd nanocatalysts (Pd NPs@LCUH-104/105/106) and have dramatically enhanced catalytic activity by using the unique metal-support interactions between three Ln-MOFs and the encapsulating palladium nanoparticles (Pd NPs). Specifically, the reduction of NPs (2-NP, 3-NP, and 4-NP) in aqueous solution by Pd NPs@LCUH-104 exhibits exceptional conversion efficiency, remarkable rate constants (k), and outstanding cycling stability. The catalytic rate of Pd NPs@LCUH-104 for 4-NP is nearly 8.5 times more than that of Pd/C (wt 5%) and its turnover frequency value is 0.051 s-1, which indicate its excellent catalytic activity. Meanwhile, LCUH-105, as a multifunctional fluorescence sensor, exhibited excellent fluorescence detection of norfloxacin (NFX) (turn on) and Cr2O72- (turn off) with high selectivity and sensitivity at a low concentration, and the corresponding fluorescence enhancement/quenching mechanism has also been systematically investigated through various detection means and theoretical calculations.

Molecular Imaging Reveals Two Distinct Mixing States of PM2.5 Particles Sampled in a Typical Beijing Winter Pollution Case.

Mixing states of aerosol particles are crucial for understanding the role of aerosols in influencing air quality and climate. However, a fundamental understanding of the complex mixing states is still lacking because most traditional analysis techniques only reveal bulk chemical and physical properties with limited surface and 3-D information. In this research, 3-D molecular imaging enabled by ToF-SIMS was used to elucidate the mixing states of PM2.5 samples obtained from a typical Beijing winter haze event. In light pollution cases, a thin organic layer covers separated inorganic particles; while in serious pollution cases, ion exchange and an organic-inorganic mixing surface on large-area particles were observed. The new results provide key 3-D molecular information of mixing states, which is highly potential for reducing uncertainty and bias in representing aerosol-cloud interactions in current Earth System Models and improving the understanding of aerosols on air quality and human health.

Elucidating the Origin of Plasmon-Generated Hot Holes in Water Oxidation.

Plasmon-generated hot electrons in metal/oxide heterostructures have been used extensively for driving photochemistry. However, little is known about the origin of plasmon-generated hot holes in promoting photochemical reactions. Herein, we discover that, during the nonradiative plasmon decay, the interband excitation rather than the intraband excitation generates energetic hot holes that enable to drive the water oxidation at the Au/TiO2 interface. Distinct from lukewarm holes via the intraband excitation that only remain on Au, hot holes from the interband excitation are found to be transferred from Au into TiO2 and stabilized by surface oxygen atoms on TiO2, making them available to oxidize adsorbed water molecules. Taken together, our studies provide spectroscopic evidence to clarify the photophysical process for exciting plasmon-generated hot holes, unravel their atomic-level accumulation sites to maintain the strong oxidizing power in metal/oxide heterostructures, and affirm their crucial functions in governing photocatalytic oxidation reactions.

Molecular identification of wines using in situ liquid SIMS and PCA analysis.

Composition analysis in wine is gaining increasing attention because it can provide information about the wine quality, source, and nutrition. In this work, in situ liquid secondary ion mass spectrometry (SIMS) was applied to 14 representative wines, including six wines manufactured by a manufacturer in Washington State, United States, four Cabernet Sauvignon wines, and four Chardonnay wines from other different manufacturers and locations. In situ liquid SIMS has the unique advantage of simultaneously examining both organic and inorganic compositions from liquid samples. Principal component analysis (PCA) of SIMS spectra showed that red and white wines can be clearly differentiated according to their aromatic and oxygen-contained organic species. Furthermore, the identities of different wines, especially the same variety of wines, can be enforced with a combination of both organic and inorganic species. Meanwhile, in situ liquid SIMS is sample-friendly, so liquid samples can be directly analyzed without any prior sample dilution or separation. Taken together, we demonstrate the great potential of in situ liquid SIMS in applications related to the molecular investigation of various liquid samples in food science.

Series of Dual Functional Two-Dimensional RE-OFs for Nitrophenol Reduction and Dye Separation.

The rational design and preparation of stable and multifunctional metal-organic frameworks (MOFs) with excellent catalysis and adsorption properties are desirable but are great challenges. The nitrophenol (NP) reduction to aminophenols (APs) by using the catalyst Pd@MOFs is an effective strategy, which has attracted extensive attention in recent years. Here, we report four stable isostructural two-dimensional (2D) rare earth metal-organic frameworks [RE4(AAPA)6(DMA)2 (H2O)4][DMA]3[H2O]8 (namely LCUH-101, RE = Eu, Gd, Tb, Y; AAPA2- = 5-[(anthracen-9-yl-methyl)-amino]-1,3-isophthalate), which feature a 2D layer structure with sql topology of point symbol {44·62} and exhibit excellent chemical stability and thermostability. The as-synthesized Pd@LCUH-101 was utilized for the catalytic reduction of 2/3/4-nitrophenol, which indicates high catalytic activity and recyclability attributed to the synergistic effect between Pd nanoparticles and the 2D layered structure. Of note, the turnover frequency (TOF), the reaction rate constant (k), and the activation energy (Ea) of Pd@LCUH-101 (Eu) in the reduction of 4-NP, respectively, are 1.09 s-1, 2.17 min-1, and 50.2 kJ·mol-1, which show that it has superior catalytic activity. Remarkably, LCUH-101 (Eu, Gd, Tb, and Y) are multifunctional MOFs that can effectively absorb and separate mixed dyes. The appropriate interlayer spacing enables them to efficiently adsorb methylene blue (MB) and rhodamine B (RhB) in aqueous solution, with adsorption capacities of 0.97 and 0.41 g·g-1, respectively, which is one of the highest values among those of the reported MOF-based adsorbers. Meanwhile, LCUH-101 (Eu) can be used for the separation of the dye mixture MB/MO and RhB/MO, and the excellent reusability enables LCUH-101 (Eu) to be used as chromatographic column filters to quickly separate and recover dyes. Therefore, this work provides a new strategy for the exploitation of stable and efficient catalysts for NP reduction and adsorbents for dyes.

Series of TM-OFs as a Platform for Efficient Catalysis and Multifunctional Luminescence Sensing.

Three novel porous transition-metal-organic frameworks (TM-OFs), formulated as [Co3(DCPN)2(µ2-OH2)4(H2O)4](DMF)2 (1), [Cd3(DCPN)2(µ2-OH2)4(H2O)4](DMF)2 (2), and [CdK(DCPN)(DMA)] (3), have been successfully prepared via solvothermal conditions based on a 5-(3',6'-dicarboxylic phenyl) nicotinic carboxylic acid (H3DCPN) ligand. 1 and 2 both have the same porous 3D network structure with the point symbol of {410·614·84}·{45·6}2 based on trinuclear ({Co3} or {Cd3}) clusters, indicating a one-dimensional porous channel, and possess excellent water and thermal stability; 3 also displays a porous 3D network structure with a 4-connected sra topology based on the heteronuclear metal cluster {CdK}. Complex 1 can be used to load Pd nanoparticles (Pd NPs) via a wetness impregnation strategy to obtain Pd@1. The reduction of nitrophenols (2-NP, 3-NP, 4-NP) by Pd@1 in aqueous solution shows outstanding conversion, excellent rate constants (k), and remarkable cycling stability due to the synergistic effect of complex 1 and Pd NPs. Luminescence sensing tests confirmed that 2 is a reliable multifunctional chemical sensor with high selectivity and sensitivity for low concentrations of Fe3+, Cr2O72-, CPFX, and NFX. Specifically, 2 shows a fluorescence enhancement behavior toward fluoroquinolone antibiotics (CPFX and NFX), which has not been reported previously in the literature. Moreover, the rational mechanism of fluorescence sensing was also systematically investigated by various detection means and theoretical calculations.

Series of Stable Anionic Lanthanide Metal-Organic Frameworks as a Platform for Pollutant Separation and Efficient Nanoparticle Catalysis.

Eight new stable porous lanthanide metal-organic frameworks (Ln-OFs), namely, [Ln2(BPTC)2][(CH3)2NH2]2 [Ln = Ho (1), Eu (2), Gd (3), Dy (4), Er (5), Tm (6), Yb (7), Lu (8)], were prepared by 3,3',5,5'-biphenyltetracarboxylic acid (H4BPTC) and lanthanide ions by solvothermal reactions. Complexes 1-8 show a three-dimensional (3D) 6,6-connected network {412·63}·{48·66·8} topology based on binuclear (Ln2) clusters and feature a one-dimensional curving porous channel occupied by exchangeable dimethylamine cations ([(CH3)2NH2]+) in the 3D anionic frameworks. The occupied [(CH3)2NH2]+ in the anionic channels exhibited excellent ion-exchange ability, which is favorable to Pd2+ and cationic dye adsorption. Consequently, 1-8 were used to load Pd nanoparticles to catalyze the reduction of nitrophenols and adsorb and desorb methyl blue (MB). The catalytic reaction efficiencies of Pd@1-8 were higher than that of Pd/C (5 wt %) in the hydrogenation reaction of p-nitrophenol (p-NP). Moreover, Pd@1 exhibited good cycle stability and achieved nearly 100% p-NP conversion after eight cycles. Meanwhile, compound 1 also exhibited a high adsorption ability of MB, possessing an adsorption capacity of 1.41 g·g-1 (second only to 1.49 g·g-1 reported in the literature) selectively over rhodamine B (RhB) and methyl orange (MO) in aqueous solutions. Remarkably, the skeleton of 1 remained stable after four adsorption-desorption cycles of MB in aqueous solution.

Distribution, characteristics, and human exposure to microplastics in mangroves within the Guangdong-Hong Kong-Macao Greater Bay Area.

In this study, three mangroves in the Guangdong-Hong Kong-Macao Greater Bay Area- Qi'ao Island in Zhuhai, Nansha in Guangzhou, and Futian in Shenzhen-were selected for investigating the distribution of microplastics and their characteristics The average microplastic abundance in each descended in the order: Futian (1600 n/kg) > Nansha (1100 n/kg) > Qi'ao Island (440 n/kg), with values from the forest fringe being significantly higher than those in the forest interior. The microplastics were mainly fibers, 1-5 mm in size, and white/black in color; they consisted of polypropylene and polyethylene, with foam and polystyrene accounting for a high proportion in Nansha. The exposure of humans to microplastics in the Futian forest fringe reached 35.95 ng/d·kg; it was one order of magnitude higher than the exposures in Qi'ao Island and Nansha. Furthermore, ingestion accounted for approximately 74% of the total exposure to the human body, dermal contact constitutes 25%, and sediment inhalation accounted for less than 1%.

Largely Enhancing the Blocking Energy Barrier and Temperature of a Linear Cobalt(II) Complex through the Structural Distortion: A Theoretical Exploration.

Complete-active-space self-consistent field and N-electron valence second-order perturbation theory have both been employed to investigate the magnetic anisotropy of one two-coordinate cobalt(II) compound via altering the Co-C bond lengths and twist angle φ. The calculated energy barrier Ueff decreases with the decrease in the Co-C bond lengths due to the gradually increasing interaction between the 3d orbitals of CoII and the coordination ligand field and then to the decrease in the ground orbital angular moment L of CoII. Thus, we cannot improve Ueff simply by shortening the Co-C bond lengths. However, by rotating the twist angle φ from 60 to 0°, it is surprising to find that the energy barrier and blocking temperature can be enhanced up to 1559.1 cm-1 and 90 K, respectively, with φ = 0°, which are prominent even among lanthanide-based single-molecule magnets.

Plasmonic Photoelectrochemistry: In View of Hot Carriers.

Utilizing plasmon-generated hot carriers to drive chemical reactions has emerged as a popular topic in solar photocatalysis. However, a complete description of the underlying mechanism of hot-carrier transfer in photochemical processes remains elusive, particularly for those involving hot holes. Photoelectrochemistry enables to localize hot holes on photoanodes and hot electrons on photocathodes and thus offers an approach to separately explore the hole-transfer dynamics and electron-transfer dynamics. This review summarizes a comprehensive understanding of both hot-hole and hot-electron transfers from photoelectrochemical studies on plasmonic electrodes. Additionally, working principles and applications of spectroelectrochemistry are discussed for plasmonic materials. It is concluded that photoelectrochemistry provides a powerful toolbox to gain mechanistic insights into plasmonic photocatalysis.

Molecular Determination of Organic Adsorption Sites on Smectite during Fe Redox Processes Using ToF-SIMS Analysis.

Turnover of soil organic carbon (SOC) is strongly affected by a balance between mineral protection and microbial degradation. However, the mechanisms controlling the heterogeneous and preferential adsorption of different types of SOC remain elusive. In this work, the heterogeneous adsorption of humic substances (HSs) and microbial carbon (MC) on a clay mineral (nontronite NAu-2) during microbial-mediated Fe redox cycling was determined using time-of-flight secondary ion mass spectrometry (ToF-SIMS). The results revealed that HSs pre-adsorbed on NAu-2 would partially inhibit structural modification of NAu-2 by microbial Fe(III) reduction, thus retarding the subsequent adsorption of MC. In contrast, NAu-2 without precoated HSs adsorbed a significant amount of MC from microbial polysaccharides as a result of Fe(III) reduction. This was attributed to the deposition of a thin Al-rich layer on the clay surface, which provided active sites for MC adsorption. This study provides direct and detailed molecular evidence for the first time to explain the preferential adsorption of MC over HSs on the surface of clay minerals in iron redox processes, which could be critical for the preservation of MC in soil. The results also indicate that ToF-SIMS is a unique tool for understanding complex organic-mineral-microbe interactions.

Origin of Magnetic Relaxation Barriers in a Family of Cobalt(II)-Radical Single-Chain Magnets: Density Functional Theory and Ab Initio Calculations.

Density functional theory (DFT) and ab initio calculations were performed to probe the origin of the magnetic relaxation barriers for two finite single-chain magnets (SCMs) featuring a one-dimension chain, Co(hfac)2(R-NapNIT) (R-NapNIT = 2-(2'-(R-)naphthyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, R = MeO (1) or EtO (2)). Our calculations show that the strong intrachain CoII-CoII exchange coupling interactions transmitted by radicals can contribute much more than ionic anisotropy to the height of the reversal barrier of magnetization for the single-chain magnets (SCMs) with |2E| < |4J/3|. In addition, the anisotropic energy barrier ΔA decreases with the decrease of |2E/J| ratio and finally vanishes in the limit of broad domain walls (|2E| < < |4 J/3|). Therefore, the total magnetic relaxation energy barriers of two SCMs mostly originate from the correlation energy barrier Δξ deriving from the indirect ferromagnetic interaction between CoII-CoII transmitted by the strong CoII-radical antiferromagnetic interactions.

Rationally Designing Metal-Organic Frameworks Based on [Ln2] Magnetic Building Blocks Utilizing 2-Hydroxyisophthalate and Fine-Tuning the Magnetic Properties of Dy Analogues by Terminal Coordinated Solvents.

By utilizing the 2-hydroxyisophthalic acid (H3ipO) ligand, 2D metal-organic frameworks (MOFs) featuring rare Ophenol-bridged [Ln2]-magnetic building blocks (MBBs), [Ln2(ipO)2(DMF)(H2O)] [Ln = Gd (1), Dy (2); DMF = N,N-dimethylformamide], were rationally designed and synthesized. When the reaction solvents that behave as terminal ligands were changed, the coordination geometries of LnIII ions and the arrangement fashion of [Ln2]-MBBs for these MOFs were modified accordingly. Another type of 2D MOF of [Ln2(ipO)2(H2O)4]·2H2O [Ln = Gd (3), Dy (4)] was thus obtained. MOFs 1 and 3 exhibited favorable magnetocaloric effect, whose maximum -ΔSm values reach 30.0 and 31.7 J kg-1 K-1, respectively. None of the single-molecule-magnet (SMM) behavior was observed in 2. However, from 2 to 4, the change of the terminal coordinated solvents brought obvious improvement of the magnetic properties. MOF 4 showed interesting relaxation behavior, in which dual relaxation was only visible under weak direct-current fields, and its highest effective energy barrier (Ueff) reached up to 243 K. Ab initio calculations revealed the tuning mechanism of the terminal coordinated solvents. Their change optimized the arrangements of the magnetic axis of the DyIII centers in both each MBB and the whole framework, thus improving the magnetic anisotropy and magnetic interactions of the system. Significantly, within the [Dy2]-MBBs of 4, the angle made by the individual magnetic axis and Dy···Dy' line is nearly 0°. This case favoring a high SMM performance not only was scarcely achieved in discrete {Ln2}-SMMs with numerous members but also has never been observed in any MBB-based MOFs as far as we know.

Three-Dimensional Mass Spectrometric Imaging of Biological Structures Using a Vacuum-Compatible Microfluidic Device.

Three-dimensional (3D) molecular imaging of biological structures is important for a wide range of research. In recent decades, secondary-ion mass spectrometry (SIMS) has been recognized as a powerful technique for both two-dimensional and 3D molecular imaging. Sample fixations (e.g., chemical fixation and cryogenic fixation methods) are necessary to adapt biological samples to the vacuum condition in the SIMS chamber, which has been demonstrated to be nontrivial and less controllable, thus limiting the wider application of SIMS on 3D molecular analysis of biological samples. Our group recently developed in situ liquid SIMS that offers great opportunities for the molecular study of various liquids and liquid interfaces. In this work, we demonstrate that a further development of the vacuum-compatible microfluidic device used in in situ liquid SIMS provides a convenient freeze-fixation of biological samples and leads to more controllable and convenient 3D molecular imaging. The special design of this new vacuum-compatible liquid chamber allows an easy determination of sputter rates of ice, which is critical for calibrating the depth scale of frozen biological samples. Sputter yield of a 20 keV Ar1800+ ion on ice has been determined as 1500 (±8%) water molecules per Ar1800+ ion, consistent with our results from molecular dynamics simulations. Moreover, using the information of ice sputter yield, we successfully conduct 3D molecular imaging of frozen homogenized milk and observe network structures of interesting organic and inorganic species. Taken together, our results will significantly benefit various research fields relying on 3D molecular imaging of biological structures.

Cooperation of Hot Holes and Surface Adsorbates in Plasmon-Driven Anisotropic Growth of Gold Nanostars.

Light-driven synthesis of plasmonic metal nanostructures has garnered broad scientific interests. Although it has been widely accepted that surface plasmon resonance (SPR)-generated energetic electrons play an essential role in this photochemical process, the exact function of plasmon-generated hot holes in regulating the morphology of nanostructures has not been fully explored. Herein, we discover that those hot holes work with surface adsorbates collectively to control the anisotropic growth of gold (Au) nanostructures. Specifically, it is found that hot holes stabilized by surface adsorbed iodide enable the site-selective oxidative etching of Au0, which leads to nonuniform growths along different lateral directions to form six-pointed Au nanostars. Our studies establish a molecular-level understanding of the mechanism behind the plasmon-driven synthesis of Au nanostars and illustrate the importance of cooperation between charge carriers and surface adsorbates in regulating the morphology evolution of plasmonic nanostructures.

Manipulating Atomic Structures at the Au/TiO2 Interface for O2 Activation.

The metal/oxide interface has been extensively studied due to its importance for heterogeneous catalysis. However, the exact role of interfacial atomic structures in governing catalytic processes still remains elusive. Herein, we demonstrate how the manipulation of atomic structures at the Au/TiO2 interface significantly alters the interfacial electron distribution and prompts O2 activation. It is discovered that at the defect-free Au/TiO2 interface electrons transfer from Ti3+ species into Au nanoparticles (NPs) and further migrate into adsorbed perimeter O2 molecules (i.e., in the form of Au-O-O-Ti), facilitating O2 activation and leading to a ca. 34 times higher CO oxidation activity than that on the oxygen vacancy (Vo)-rich Au/TiO2 interface, at which electrons from Ti3+ species are trapped by interfacial Vo on TiO2 and hardly interact with perimeter O2 molecules. We further reveal that the calcination releases those trapped electrons from interfacial Vo to facilitate O2 activation. Collectively, our results establish an atomic-level description of the underlying mechanism regulating metal/oxide interfaces for the optimization of heterogeneous catalysis.

Experimental Insights into the Growth of Single Truncated Anatase Bipyramids.

Fluorine has been recognized to selectively stabilize anatase titanium dioxide (TiO2 ) crystal facets; however, resolving its physical location at the nanometer scale remains empirically elusive. Here, we provide direct experimental evidence to reveal the spatial distribution of fluorine on single truncated anatase bipyramids (TABs) using nanoscale secondary ion mass spectrometry (NanoSIMS). Fluorine was found to preferentially adsorb on the (001) facet compared to the (101) facet of TABs. Moreover, NanoSIMS depth profiling exhibited a significantly different fluorine distribution between these two facets in the near-surface region, illustrating the essential role of lattice-doped fluorine in the anisotropic crystal growth of TABs.