The Impact of Contact Experience on the Attitudes and Beliefs Toward Same-Sex Parents and Their Children Among Kindergarten Teachers.

Intergroup contact is important to reduce prejudice toward sexual minorities. Yet little is known regarding how kindergarten teachers' contact experiences with sexual minority affect their attitudes toward sexual minorities and their beliefs regarding same-sex family parents' parenting skills and same-sex family children's adjustment. This cross-sectional study recruited kindergarten teachers (n = 261; mean age = 38.8 years) in Taiwan in 2021-2022. A self-reported online questionnaire was administered which included questions about quantity and quality of contact experiences with lesbians, gay men (LG) and same-sex families, attitudes toward same-sex families, beliefs regarding same-sex parenting skills, and children's adjustment. Hierarchical multiple regression was used for analysis. The results showed that higher quality of contact with LG was associated with lower prejudice toward LG and with a more positive belief regarding same-sex parents' parenting skills and children's adjustment in same-sex families. The contact experience with same-sex families has an association with positive beliefs regarding same-sex family parents and children. After adjustment of quality of contact, quantity of contact did not show association with attitude toward LG or beliefs regarding same-sex family parents and children. The findings suggest that the quality of contact experience with LG is an important factor to reduce the stereotype against same-sex families.

Engineering nanoscale H supply chain to accelerate methanol synthesis on ZnZrOx.

Metal promotion is the most widely adopted strategy for enhancing the hydrogenation functionality of an oxide catalyst. Typically, metal nanoparticles or dopants are located directly on the catalyst surface to create interfacial synergy with active sites on the oxide, but the enhancement effect may be compromised by insufficient hydrogen delivery to these sites. Here, we introduce a strategy to promote a ZnZrOx methanol synthesis catalyst by incorporating hydrogen activation and delivery functions through optimized integration of ZnZrOx and Pd supported on carbon nanotube (Pd/CNT). The CNT in the Pd/CNT + ZnZrOx system delivers hydrogen activated on Pd to a broad area on the ZnZrOx surface, with an enhancement factor of 10 compared to the conventional Pd-promoted ZnZrOx catalyst, which only transfers hydrogen to Pd-adjacent sites. In CO2 hydrogenation to methanol, Pd/CNT + ZnZrOx exhibits drastically boosted activity-the highest among reported ZnZrOx-based catalysts-and excellent stability over 600 h on stream test, showing potential for practical implementation.

Thiolated Mesoporous Silica Nanoparticles as an Immunoadjuvant to Enhance Efficacy of Intravesical Chemotherapy for Bladder Cancer.

The characteristics of global prevalence and high recurrence of bladder cancer has led numerous efforts to develop new treatments. The spontaneous voiding and degradation of the chemodrug hamper the efficacy and effectiveness of intravesical chemotherapy following tumor resection. Herein, the externally thiolated hollow mesoporous silica nanoparticles (MSN-SH(E)) is fabricated to serve as a platform for improved bladder intravesical therapy. Enhanced mucoadhesive effect of the thiolated nanovector is confirmed with porcine bladder. The permeation-enhancing effect is also verified, and a fragmented distribution pattern of a tight junction protein, claudin-4, indicates the opening of tight junction. Moreover, MSN-SH(E)-associated reprogramming of M2 macrophages to M1-like phenotype is observed in vitro. The antitumor activity of the mitomycin C (MMC)-loaded nanovector (MMC@MSN-SH(E)) is more effective than that of MMC alone in both in vitro and in vivo. In addition, IHC staining is used to analyze IFN-γ, TGF-ß1, and TNF-α. These observations substantiated the significance of MMC@MSN-SH(E) in promoting anticancer activity, holding the great potential for being used in intravesical therapy for non-muscle invasive bladder cancer (NMIBC) due to its mucoadhesivity, enhanced permeation, immunomodulation, and prolonged and very efficient drug exposure.

Tuning the Site-to-Site Interaction in Ru-M (M = Co, Fe, Ni) Diatomic Electrocatalysts to Climb up the Volcano Plot of Oxygen Electroreduction.

The modulating of the geometric and electronic structures of metal-N-C atomic catalysts for improving their performance in catalyzing oxygen reduction reactions (ORRs) is highly desirable yet challenging. We herein report a delicate "encapsulation-substitution" strategy for the synthesis of paired metal sites in N-doped carbon. With the regulation of the d-orbital energy level, a significant increment in oxygen electroreduction activity was demonstrated in Ru-Co diatomic catalyst (DAC) compared with other diatomic (Ru-Fe and Ru-Ni) and single-atomic counterparts. The Ru-Co DAC efficiently reduces oxygen with a halfwave potential of 0.895 V vs RHE and a turnover frequency of 2.424 s-1 at 0.7 V, establishing optimal thermodynamic and kinetic behaviors in the triple-phase reaction under practical conditions. Moreover, the Ru-Co DAC electrode displays bifunctional activity in a gas diffusion Zn-air battery with a small voltage gap of 0.603 V, outperforming the commercial Pt/C|RuO2 catalyst. Our findings provide a clear understanding of site-to-site interaction on ORR and a benchmark evaluation of atomic catalysts with correlations of diatomic structure, energy level, and overall catalytic performance at the subnanometer level.

Dissolution and morphology evolution of mesoporous silica nanoparticles under biologically relevant conditions.

Mesoporous silica nanoparticles (MSN) are promising drug vectors due to their high drug loading capacities, degradability under biologically relevant conditions. The dissolution of MSN has been the focus of several recent studies, most of which have, however, been carried out in the absence of proteins, and do therefore not reflect the conditions prevailing during in vitro or in vivo administration of the particles. Furthermore, typically the dissolution studies are limited with respect to the range of MSN concentrations applied. Here, we report results related to the dissolution kinetics and structural particle evolution for MCM-48 MSN carried out in the presence of proteins, and where the particle concentration has been used as a parameter to cover typical concentrations used in in vitro and in vivo studies involving MSNs. Proteins adsorbing to the MSN surface form a diffusion limiting layer that leads to the intermediate formation of core-shell structured particles upon dissolution. Here, the protein concentration controls the kinetics of this process, as the amount of protein adsorbing to the MSN increase with increasing protein concentration. The results thus also imply that the MSN dissolution kinetics is faster under normally applied in vitro conditions as compared to what can be expected under full serum conditions.

Radiative Relaxation of Gold Nanorods Coated with Mesoporous Silica with Different Porosities upon Nanosecond Photoexcitation Monitored by Time-Resolved Infrared Emission Spectroscopy.

Gold nanorods (AuNRs) have been widely used in photothermal conversion, and a coating of silica (SiO2) provides higher thermal stability, better biocompatibility, and versatile chemical functionalization. In this work, two gold nanorods coated with surfactant-templated mesoporous silica layers of the same thickness but different porosities, and thus different specific surface areas, were prepared. Upon irradiation with 1064 nm nanosecond pulsed laser, the transient infrared emissions of AuNR@SiO2 enveloped the stretching mode of the Si-O-Si bridge (1000-1250 cm-1), the bending mode of adsorbed H2O (1600-1650 cm-1) within the mesoporous silica layer, and blackbody radiation, in terms of an underlying broad band (1000-2000 cm-1) probed with a step-scan Fourier transform spectrometer. The mesoporous silica shell and the adsorbed H2O gained populations of their vibrationally excited states, and the whole AuNR@SiO2 was heated up via the photothermal energy of the core AuNRs. An average temperature after 5-10 µs within 80% of the emission intensity was ca. 200 °C. The decay of the emission at 1000-1250 and 1500-1750 cm-1 was both accelerated, and the blackbody radiation components were negatively correlated with the porosity of the mesoporous silica layer. Higher porosity of the mesoporous silica layer was associated with more effective depopulation of the vibrationally excited states of the silica layers on the AuNRs via the nonradiative thermal conduction of the adsorbed H2O, since H2O has a larger thermal conduction coefficient than that of silica, in concomitance with the accelerated emission kinetics. This work unveils the roles of the porosity, capping materials, and entrapping molecules of a core-shell nanostructure during the thermalization after photoexcitation.

Synergies of Fe Single Atoms and Clusters on N-Doped Carbon Electrocatalyst for pH-Universal Oxygen Reduction.

Single atomic metal-N-C materials have attracted immense interest as promising candidates to replace noble metal-based electrocatalysts for the oxygen reduction reaction (ORR). The coordination environment of metal-N-C active centers plays a critical role in determining their catalytic activity and durability, however, attention is focused only on the coordination of metal atoms. Herein, Fe single atoms and clusters co-embedded in N-doped carbon (Fe/NC) that deliver the synergistic enhancement in pH-universal ORR catalysis via the four-electron pathway are reported. Combining a series of experimental and computational analyses, the geometric and electronic structures of catalytic sites in Fe/NC are revealed and the neighboring Fe clusters are shown to weaken the binding energies of the ORR intermediates on Fe-N sites, hence enhancing both catalytic kinetics and thermodynamics. This strategy provides new insights into the understanding of the mechanism of single atom catalysis.

Targeting triple-negative breast cancer with an aptamer-functionalized nanoformulation: a synergistic treatment that combines photodynamic and bioreductive therapies.

BACKGROUND: Areas of hypoxia are often found in triple-negative breast cancer (TNBC), it is thus more difficult to treat than other types of breast cancer, and may require combination therapies. A new strategy that combined bioreductive therapy with photodynamic therapy (PDT) was developed herein to improve the efficacy of cancer treatment. Our design utilized the characteristics of protoporphyrin IX (PpIX) molecules that reacted and consumed O2 at the tumor site, which led to the production of cytotoxic reactive oxygen species (ROS). The low microenvironmental oxygen levels enabled activation of a bioreductive prodrug, tirapazamine (TPZ), to become a toxic radical. The TPZ radical not only eradicated hypoxic tumor cells, but it also promoted therapeutic efficacy of PDT. RESULTS: To achieve the co-delivery of PpIX and TPZ for advanced breast cancer therapy, thin-shell hollow mesoporous Ia3d silica nanoparticles, designated as MMT-2, was employed herein. This nanocarrier designed to target the human breast cancer cell MDA-MB-231 was functionalized with PpIX and DNA aptamer (LXL-1), and loaded with TPZ, resulting in the formation of TPZ@LXL-1-PpIX-MMT-2 nanoVector. A series of studies confirmed that our nanoVectors (TPZ@LXL-1-PpIX-MMT-2) facilitated in vitro and in vivo targeting, and significantly reduced tumor volume in a xenograft mouse model. Histological analysis also revealed that this nanoVector killed tumor cells in hypoxic regions efficiently. CONCLUSIONS: Taken together, the synergism and efficacy of this new therapeutic design was confirmed. Therefore, we concluded that this new therapeutic strategy, which exploited a complementary combination of PpIX and TPZ, functioned well in both normoxia and hypoxia, and is a promising medical procedure for effective treatment of TNBC.

Zeolite-Encaged Pd-Mn Nanocatalysts for CO2 Hydrogenation and Formic Acid Dehydrogenation.

A CO2 -mediated hydrogen storage energy cycle is a promising way to implement a hydrogen economy, but the exploration of efficient catalysts to achieve this process remains challenging. Herein, sub-nanometer Pd-Mn clusters were encaged within silicalite-1 (S-1) zeolites by a ligand-protected method under direct hydrothermal conditions. The obtained zeolite-encaged metallic nanocatalysts exhibited extraordinary catalytic activity and durability in both CO2 hydrogenation into formate and formic acid (FA) dehydrogenation back to CO2 and hydrogen. Thanks to the formation of ultrasmall metal clusters and the synergic effect of bimetallic components, the PdMn0.6 @S-1 catalyst afforded a formate generation rate of 2151 molformate molPd -1 h-1 at 353 K, and an initial turnover frequency of 6860 mol H 2 molPd -1 h-1 for CO-free FA decomposition at 333 K without any additive. Both values represent the top levels among state-of-the-art heterogeneous catalysts under similar conditions. This work demonstrates that zeolite-encaged metallic catalysts hold great promise to realize CO2 -mediated hydrogen energy cycles in the future that feature fast charge and release kinetics.

Hierarchical zeolites comprising orthogonally stacked bundles of zeolite nanosheets for catalytic and adsorption applications.

The synthesis of hierarchical MFI zeolites comprising orthogonally stacked bundles of zeolite nanosheets using a new type of triblock structure-directing agents (SDAs) was reported. The textural properties, including the degree of nanosheet branching and the spacing between adjacent nanosheets, could be controlled by changing the length of the linkers in the triblock SDAs. The hierarchical pure-silica silicalite-1 materials exhibited high and stable catalytic activity for the vapor-phase Beckmann rearrangement of cyclohexanone oxime with high selectivity of ε-caprolactam. On the other hand, the hierarchical ZSM-5 materials showed high adsorption capacity of Pb2+ ion following a Langmuir-type adsorption behavior. After being deposited with Pd nanoparticles, the hierarchical Pd/ZSM-5 nanocomposites exhibited high activity in the aqueous-phase hydrogenation of phenol to cyclohexanone at room temperature. The results show promise of the disclosed hierarchical zeolites for catalytic and adsorption applications.

Suitability of boric acid as a boron drug for boron neutron capture therapy for hepatoma.

Hepatoma is the second leading cause of cancer death worldwide. Due to the poor outcomes of patients with late diagnosis, newer treatments for hepatoma are still needed. As an emerging therapy, boron neutron capture therapy (BNCT) may be an effective solution in hepatoma management. In this study, boric acid (BA) was used as the boron drug for in vivo analysis of action mechanism. The N1S1 single liver tumor-bearing rat and the VX2 multifocal liver tumor-bearing rabbit models were used to investigate the retention status of BA in the tumor regions during BNCT. The autoradiographic examination showed BA can localize specifically not only in the hepatoma cells but also in tumor blood vessels. Our findings indicate that superior hepatoma targeting could be achieved in BA-mediated BNCT, which supports BA to be a suitable boron drug for BNCT for hepatoma.

Superhydrophobic drug-loaded mesoporous silica nanoparticles capped with ß-cyclodextrin for ultrasound image-guided combined antivascular and chemo-sonodynamic therapy.

Interfacial nanobubbles (INBs) on a superhydrophobic surface has been proposed as a solid cavitation agent for enhancing inertial cavitation dose and ultrasound contrast imaging, but the dispersibility of superhydrophobic particles limits the biomedical application. For this study, we designed superhydrophobic mesoporous silica nanoparticles loaded with the anti-tumor drug Doxorubicin (FMSNs-Dox) for tumor therapy. The ß-cyclodextrin was used to cap the superhydrophobic surface of FMSNs-Dox to reduce aggregation without inhibiting the accumulation of INBs. The mean size and a contact angle of FMSNs-Dox was 217 ± 58 nm and 129 ± 3°, respectively. The INBs cavitation on the surface of FMSNs-Dox during ultrasound sonication disrupted tumor vessels to allow a large amount of drug penetrating and trapping within tumors. The reduced tumor perfusion, histological reactive oxygen species staining, and tumor inhibition demonstrated that FMSNs-Dox sonication combined anti-vascular, sonodynamic and chemical therapies in a simple platform. Moreover, the repeatability of INB cavitation by single-injection FMSNs-Dox with multiple ultrasound sonication provided intratumoral ultrasound contrast-enhanced imaging from day 1-9 (enhancement of 3.84 ± 0.47 dB). Therefore, the characteristics of FMSNs-Dox with slow biodegradation and acoustic-sensitivity presented intratumoral day-scaled lifetime to provide a probability of repeated combination therapy by single-injection.

Study on the dissolution of hollow mesoporous silica nanosphere-supported nanosized platinum oxide in biorelevant media for evaluating its potential as chemotherapeutics.

Platinum oxide (PtOx) nanoparticles (NPs) have been shown to possess anticancer activity by releasing ionic Pt species under biological conditions. However, the dissolution kinetics and the changes in the chemical state of Pt during PtOx dissolution have not yet been studied. To fill this gap, we prepared a composite (designated as PtOx@MMT-2) containing PtOx NPs on hollow mesoporous silica nanospheres and studied the dissolution of the material in different biorelevant media. We found that the release of Pt was retarded due to the adsorption of biomolecules on PtOx NPs during the degradation of host silica. The biomolecules adsorption also lowered the accessibility of PtOx NPs, resulting in the reduced catalase-like activity of the NPs. In line with the results, the cytotoxicity of PtOx@MMT-2, which was positively correlated to the amount of Pt uptake, was reduced by biomolecules adsorption. Our findings should be applicable to other metal (oxide) NPs under biological conditions and may provide implications for the design of nanomaterials for practical therapeutic applications.

Tiny Ni particles dispersed in platelet SBA-15 materials induce high efficiency for CO2 methanation.

In this study, short-channel SBA-15 with a platelet morphology (p-SBA-15) is used to support Ni to effectively enhance catalytic activity and CH4 selectivity during CO2 hydrogenation. The use of p-SBA-15 as a support can result in smaller Ni particle sizes than Ni particles on typical SBA-15 supports because p-SBA-15 possesses a larger surface area and a greater ability to provide metal-support interactions. The Ni/p-SBA-15 materials with tiny Ni particles exhibit enhanced catalytic activity toward CO2 hydrogenation and CH4 formation during CO2 hydrogenation compared to the same Ni loading on a SBA-15 support. The presence of metal-support interaction on the Ni/p-SBA-15 catalyst may increase the possibility of abundance of strongly adsorbing sites for CO and CO2, thus resulting in high reaction rates for CO2 and CO hydrogenation. The reaction kinetics, reaction pathway and active sites were studied and correlated to the high catalytic activity for CO2 hydrogenation to form CH4.

Therapeutic Efficacy and Radiobiological Effects of Boric Acid-mediated BNCT in a VX2 Multifocal Liver Tumor-bearing Rabbit Model.

BACKGROUND/AIM: Most patients with hepatocellular carcinoma (HCC) cannot be treated using traditional therapies. Boron neutron capture therapy (BNCT) may provide a new treatment for HCC. In this study, the therapeutic efficacy and radiobiological effects of boric acid (BA)-mediated BNCT in a VX2 multifocal liver tumor-bearing rabbit model are investigated. MATERIALS AND METHODS: Rabbits were irradiated with neutrons at the Tsing Hua Open Pool Reactor 35 min following an intravenous injection of BA (50 mg 10B/kg BW). The tumor size following BNCT treatment was determined by ultrasonography. The radiobiological effects were identified by histopathological examination. RESULTS: A total of 92.85% of the tumors became undetectable in the rabbits after two fractions of BNCT treatment. The tumor cells were selectively eliminated and the tumor vasculature was collapsed and destroyed after two fractions of BA-mediated BNCT, and no injury to the hepatocytes or blood vessels was observed in the adjacent normal liver regions. CONCLUSION: Liver tumors can be cured by BA-mediated BNCT in the rabbit model of a VX2 multifocal liver tumor. BA-mediated BNCT may be a breakthrough therapy for hepatocellular carcinoma.

Detection of Cigarette Smoke Using a Surface-Acoustic-Wave Gas Sensor with Non-Polymer-Based Oxidized Hollow Mesoporous Carbon Nanospheres.

The objective of this research was to develop a surface-acoustic-wave (SAW) sensor of cigarette smoke to prevent tobacco hazards and to detect cigarette smoke in real time through the adsorption of an ambient tobacco marker. The SAW sensor was coated with oxidized hollow mesoporous carbon nanospheres (O-HMC) as a sensing material of a new type, which replaced a polymer. O-HMC were fabricated using nitric acid to form carboxyl groups on carbon frameworks. The modified conditions of O-HMC were analyzed with Scanning Electron Microscopy (SEM), Fourier transform infrared spectrometry (FTIR), and X-ray diffraction (XRD). The appropriately modified O-HMC are more sensitive than polyacrylic acid and hollow mesoporous carbon nanospheres (PAA-HMC), which is proven by normalization. This increases the sensitivity of a standard tobacco marker (3-ethenylpyridine, 3-EP) from 37.8 to 51.2 Hz/ppm and prevents the drawbacks of a polymer-based sensing material. On filtering particles above 1 µm and using tar to prevent tar adhesion, the SAW sensor detects cigarette smoke with sufficient sensitivity and satisfactory repeatability. Tests, showing satisfactory selectivity to the cigarette smoke marker (3-EP) with interfering gases CH4, CO, and CO2, show that CO and CO2 have a negligible role during the detection of cigarette smoke.

Influence of serum concentration and surface functionalization on the protein adsorption to mesoporous silica nanoparticles.

A study of a protein corona on mesoporous silica nanoparticles (MSNs) at in vitro and in vivo relevant serum concentrations is presented. Three MSNs different in terms of mesoscopic pore arrangement, surface chemistry, and surface roughness were studied. After incubation in either 10% or 100% serum, the hard protein corona-particle complexes were collected and analyzed by DLS, zeta-potential, and TGA, and the corona proteins were analyzed with SDS-PAGE. A good correlation between SDS-PAGE and TG results in terms of total amounts of proteins adsorbed was established. The results demonstrated that more proteins, especially apolipoproteins, were associated with the particles at higher serum concentration regardless of surface chemistry and morphological differences. Also, the mean molecular weight of the adsorbed proteins was clearly lower under full serum conditions modeling in vivo conditions as compared to under dilute conditions modeling in vitro conditions, but functionalization of the MSNs by carboxylic acid functionalities reduced protein adsorption. The influence of the structural characteristics of the MSNs on the protein adsorption was minor.

Decomposition of Large Cu Crystals into Ultrasmall Particles Using Chemical Vapor Deposition and Their Application in Selective Propylene Oxidation.

In this work, we report a novel application of chemical vapor deposition (CVD) in which the calcination and reduction of Cu(thd)2 deposited onto 4.9 wt % Cu/SiO2 induces significant decomposition of 28 nm crystalline Cu into ultrasmall ∼2 nm particles (5.1 wt % Cu/SiO2). The Cu loading slightly increased, but the particle size dramatically decreased. The deposition of Cu(thd)2 onto the Cu surface can initially affect the size reduction of the metallic Cu particles due to charge transfer between Cu(thd)2 and the Cu surface. Thermal treatments, including calcination in air and reduction in H2, can further influence the Cu particle decomposition. The mechanism of change in the Cu particle decomposition was investigated by a variety of experiments, such as X-ray diffraction and in situ X-ray absorption spectroscopy. CVD treatment of Cu/SiO2 can create Cu-rich sites, which effectively enhance the conversion and acrolein yield in selective propylene oxidation. The intermediate associated with propylene oxidation on the Cu catalysts was also examined by IR spectroscopy.

Roles of Textural and Surface Properties of Nanoparticles in Ultrasound-Responsive Systems.

Acoustic inertial cavitation (IC) is a crucial phenomenon for many ultrasound (US)-related applications. This study aimed to investigate the roles of textural and surface properties of NPs in IC generation by combining typical IC detection methods with various types of silica model NPs. Acoustic passive cavitation detection, optical high-speed photography, and US imaging have been used to quantify IC activities (referred to as the IC dose, ICD) and describe the physical characteristics of IC activities from NPs. The results showed that the ICDs from NPs were positively correlated to their surface hydrophobicity and that their external surface hydrophobicity plays a much more crucial role than do the textural properties. The high-speed photography revealed that the sizes of IC-generated bubbles from superhydrophobic NPs ranged from 20-40 µm at 4-6 MPa and collapsed in several microseconds. Bubble clouds monitored with US imaging showed that IC from NPs was consistent with the surface hydrophobicity. The simulation results based on the crevice model of cavitation nuclei correlated well with the experimental results. This study has demonstrated that the surface property, instead of the textural property, of NPs dominated the IC generation, and surface nanobubbles adsorbed on the NP surface have been proposed to be cavitation nuclei.

Effect of Tumor Microenvironment on Selective Uptake of Boric Acid in HepG2 Human Hepatoma Cells.

BACKGROUND: Feasibility and efficacy of boric acid (BA)-mediated boron neutron capture therapy (BNCT) was first demonstrated by eliminating hepatocellular carcinoma (HCC) in a rat model. Furthermore, selective uptake of BA by liver tumor cells was shown in a rabbit model. To gain further insight, this study aimed to investigate the mechanisms of transportation and selective uptake of BA in HepG2 liver tumor cells. MATERIALS AND METHODS: Transportation of BA in HepG2 cells was analyzed by time-course assays and by analyzing the rate of diffusion versus the concentration of BA. The effect of different tumor conditions on BA uptake was studied by treating HepG2 cells with 25 µg 10B/ml BA under different concentrations of glucose, at different pH and in the presence of water-soluble cholesterol. RESULTS: HepG2 cells mainly uptake BA by simple diffusion. Cell membrane permeability may also contribute to tumor-specific uptake of BA. CONCLUSION: The selective uptake of BA was achieved primarily by diffusion, while other factors, such as low pH and increased membrane fluidity, which are hallmarks of HCC, might further enhance BA uptake.