Synthesis and Properties of Cobalt/Nickel-Iron-Antimony(III, V)-Oxo Tartrate Cluster-Based Compounds.

Two types of isostructural iron-cobalt/nickel-antimony-oxo tartrate cluster-based compounds, namely (H3O)(Me2NH2)[M(H2O)6]2[FeII2SbIII12(µ4-O)3(µ3-O)8(tta)6]·6H2O (M = Co (1); Ni (3)), H5/3[Co2.5FeII4/3FeIII3(H2O)13SbV1/3FeIII2/3(µ4-O)2(µ3-O)4SbIII6(µ3-O)2(tta)6]·2H2O (2) and H2[Ni2.25FeII1.5FeIII3(H2O)14SbV0.25FeIII0.75(µ4-O)2(µ3-O)4SbIII6(µ3-O)2(tta)6]·2H2O (4) (H4tta = tartaric acid) were synthesized via simple solvothermal reactions. All the clusters in the structures adopt sandwich configurations, that is, bilayer sandwich configuration in 1 and 3 and monolayer sandwich configuration in 2 and 4. Interestingly, the monolayer sandwiched compounds 2 and 4 represent rare examples of cluster-based compounds containing mixed-valence Sb(III, V), whose center of the intermediate layer is the co-occupied [FexSbV1-x]. This is different from that of previously reported sandwich-type antimony-oxo clusters in which the center position is either occupied by a transition metal ion or a Sb(V) alone. Thus, the discovery of title compounds 2 and 4 makes the evolution of center metal ion more complete, that is, from M, MxSbV1-x to SbV. All the title compounds were fully characterized, and the photocatalysis, proton conduction and magnetism of compounds 2 and 4 were studied.

Structural Evolution and Properties of Praseodymium Antimony Oxochlorides Based on a Chain-like Tertiary Building Unit.

Unveiling the structural evolution of single-crystalline compounds based on certain building units may help greatly in guiding the design of complex structures. Herein, a series of praseodymium antimony oxohalide crystals have been isolated under solvothermal conditions via adjusting the solvents used, that is, [HN(CH2CH3)3][FeII(2,2'-bpy)3][Pr4Sb12O18Cl15]·EtOH (1) (2,2'-bpy = 2,2'-bipyridine), [HN(CH2CH3)3][FeII(2,2'-bpy)3]2[Pr4Sb12O18Cl14)2Cl]·N(CH2CH3)3·2H2O (2), and (H3O)[Pr4Sb12O18Cl12.5(TEOA)0.5]·2.5EtOH (3) (TEOA = mono-deprotonated triethanolamine anion). Single-crystal X-ray diffraction analysis revealed that all the three structures feature an anionic zig-zag chain of [Pr4Sb12O18Cl15-x]n as the tertiary building unit (TBU), which is formed by interconnections of praseodymium antimony oxochloride clusters (denoted as {Pr4Sb12}) as secondary building units. Interestingly, different arrangements or linkages of chain-like TBUs result in one-dimensional, two-dimensional layered, and three-dimensional structures of 1, 2, and 3, respectively, thus demonstrating clearly the structural evolution of metal oxohalide crystals. The title compounds have been characterized by elemental analysis, powder X-ray diffraction, thermogravimetric analysis, and UV-Vis spectroscopy, and the photodegradation for methyl blue in an aqueous solution of compound 1 has been preliminarily studied. This work offers a way to deeply understand the assembly process of intricate lanthanide-antimony(III) oxohalide structures at the atomic level.

Profiling of extracellular vesicle-bound miRNA to identify candidate biomarkers of chronic alcohol drinking in nonhuman primates.

BACKGROUND: Long-term alcohol drinking is associated with numerous health complications including susceptibility to infection, cancer, and organ damage. However, due to the complex nature of human drinking behavior, it has been challenging to identify reliable biomarkers of alcohol drinking behavior prior to signs of overt organ damage. Recently, extracellular vesicle-bound microRNAs (EV-miRNAs) have been found to be consistent biomarkers of conditions that include cancer and liver disease. METHODS: In this study, we profiled the plasma EV-miRNA content by miRNA-Seq from 80 nonhuman primates after 12 months of voluntary alcohol drinking. RESULTS: We identified a list of up- and downregulated EV-miRNA candidate biomarkers of heavy drinking and those positively correlated with ethanol dose. We overexpressed these candidate miRNAs in control primary peripheral immune cells to assess their potential functional mechanisms. We found that overexpression of miR-155, miR-154, miR-34c, miR-450a, and miR-204 led to increased production of the inflammatory cytokines TNFα or IL-6 in peripheral blood mononuclear cells after stimulation. CONCLUSION: This exploratory study identified several EV-miRNAs that could serve as biomarkers of long-term alcohol drinking and provide a mechanism to explain alcohol-induced peripheral inflammation.

Nonparametric matrix response regression with application to brain imaging data analysis.

With the rapid growth of neuroimaging technologies, a great effort has been dedicated recently to investigate the dynamic changes in brain activity. Examples include time course calcium imaging and dynamic brain functional connectivity. In this paper, we propose a novel nonparametric matrix response regression model to characterize the nonlinear association between 2D image outcomes and predictors such as time and patient information. Our estimation procedure can be formulated as a nuclear norm regularization problem, which can capture the underlying low-rank structure of the dynamic 2D images. We present a computationally efficient algorithm, derive the asymptotic theory, and show that the method outperforms other existing approaches in simulations. We then apply the proposed method to a calcium imaging study for estimating the change of fluorescent intensities of neurons, and an electroencephalography study for a comparison in the dynamic connectivity covariance matrices between alcoholic and control individuals. For both studies, the method leads to a substantial improvement in prediction error.

Perceptions of cruise travel during the COVID-19 pandemic: Market recovery strategies for cruise businesses in North America.

The study aims to identify consumer perceptions of the cruise industry amid the COVID-19 pandemic and seeks to provide market recovery strategies for cruise businesses. The relationship between perceptions among cruise experience and COVID-19 financial status groups were explored. The results of analyses of data from 759 respondents indicated that travel constraints negatively influence behavioral intention through negativity bias. Further, perceived crisis management positively affects behavioral intention through attitude-trust. New consumers' behavioral intention is significantly affected by the negativity bias, and the perceived crisis management manipulates the trust of financial-affected consumers.

Maximum aerodynamic force production by the wandering glider dragonfly (Pantala flavescens, Libellulidae).

Maximum whole-body force production can influence behavioral outcomes for volant taxa, and may also be relevant to aerodynamic optimization in microair vehicles. Here, we describe a new method for measuring maximum force production in free-flying animals, and present associated data for the wandering glider dragonfly. Flight trajectories were repeatedly acquired from pull-up responses by insects dropped in mid-air with submaximal loads attached beneath the center of body mass. Forces were estimated from calculations of the maximum time-averaged acceleration through time, and multiple estimates were obtained per individual so as to statistically facilitate approximation of maximum capacity through use of the Weibull distribution. On a group level, wandering glider dragonflies were here estimated to be capable of producing total aerodynamic force equal to ∼4.3 times their own body weight, a value which significantly exceeds earlier estimates made for load-lifting dragonflies, and also for other volant taxa in sustained vertical load-lifting experiments. Maximum force production varied isometrically with body mass. Falling and recovery flight with submaximal load represents a new context for evaluating limits to force production by flying animals.

A Bayesian nonparametric approach for handling item and examinee heterogeneity in assessment data.

We propose a novel nonparametric Bayesian item response theory model that estimates clusters at the question level, while simultaneously allowing for heterogeneity at the examinee level under each question cluster, characterized by a mixture of binomial distributions. The main contribution of this work is threefold. First, we present our new model and demonstrate that it is identifiable under a set of conditions. Second, we show that our model can correctly identify question-level clusters asymptotically, and the parameters of interest that measure the proficiency of examinees in solving certain questions can be estimated at a n rate (up to a log term). Third, we present a tractable sampling algorithm to obtain valid posterior samples from our proposed model. Compared to the existing methods, our model manages to reveal the multi-dimensionality of the examinees' proficiency level in handling different types of questions parsimoniously by imposing a nested clustering structure. The proposed model is evaluated via a series of simulations as well as apply it to an English proficiency assessment data set. This data analysis example nicely illustrates how our model can be used by test makers to distinguish different types of students and aid in the design of future tests.

Experimental Investigation on Aerodynamic Performance of Inclined Hovering with Asymmetric Wing Rotation.

This study presents a model experiment method that can accurately reproduce the flapping motion of insect wings and measure related unsteady aerodynamic data in real time. This method is applied to investigate the aerodynamic characteristics of inclined hovering, which distinguishes it from normal hovering by having asymmetric wing rotation during the two half strokes. In the study of the aerodynamic influence of the downstroke rotational angle, it is found that the rotational angle affects lift generation by changing the angle between the wing surface and the horizontal plane in the mid-downstroke. When the wing is almost parallel to the horizontal plane in the mid-downstroke, the vortex structure can maintain structural integrity and a large magnitude, which is conducive to the generation of high lift. In the study of the aerodynamic effect of the upstroke rotational angle, the windward conversion mechanism is proposed to explain the influence of the upstroke rotational angle on the direction and magnitude of thrust. Obtaining the rotational angle that is most conducive to maintaining the flight state of hovering in the present study can provide guidance for the structural design and kinematic control of micro aerial vehicles.

New group IIIA metal phosphate-oxalates containing dimethylammonium cations with proton conductivity.

Three new group IIIA metal phosphate-oxalate (MPO) compounds, namely [(CH3)2NH2]2[M2(HPO4)2(H2PO4)2(C2O4)] (M = Al (1), Ga (2)) and [(CH3)2NH2]2[In2(HPO4)2(H2PO4)2(C2O4)]·H2O (3), have been synthesized. Their crystal structures feature an anionic layer with the sql topology net. In particular, 1 displays a proton conductivity (σ) of 9.09 × 10-3 S cm-1 at 85 °C and under 98% relative humidity, which is the highest among MPOs. This study not only endows the main group metal-based MPO family with new members, but also contributes to further understanding of the structure-directing roles of amines and provides a feasible idea for improving the proton conductivity of MPOs.

All-in-one treatment: Capture and immobilization of 137Cs by ultra-stable inorganic solid acid materials HMMoO6·nH2O (M = Ta, Nb).

Capture and immobilization of 137Cs is urgent for radioactive contamination remediation and spent fuel treatment. Herein, an effective all-in-one treatment method to simultaneously adsorb and immobilize Cs+ without high-temperature treatment is proposed. According to the strategy of incorporating high-valency metal ions into molybdates to increase the material stability and affinity towards radionuclides, layered HMMoO6·nH2O (M = Ta (1), Nb (2)) are prepared. Both materials exhibit excellent acid resistance (even 15 mol/L HNO3). They maintain remarkable adsorption capacity for Cs+ in 1 mol/L HNO3 solutions and can selectively capture Cs+ under excessive competitive ions. Furthermore, they show successful cleanup for actual 137Cs-liquid-wastes generated during industrial production. In particular, adsorbed Cs+ can be firmly immobilized in interlayer spaces of materials due to the highly stable anionic framework. The removal mechanism is attributed to ion exchange between Cs+ and interlayer H+ by multiple characterizations. Study of the structure-function relationship shows that the occurrence of Cs+ ion exchange is closely related to plate-like layered structure. This work develops an efficient all-in-one treatment method for capturing and immobilizing radiocesium by ultra-stable inorganic solid acid materials with low energy consumption and high safety for radionuclide remediation.

More applicable quantification of non-CO2 greenhouse gas emissions from wastewater treatment plants by on-site plant-integrated measurements.

Wastewater treatment is an important source of non-CO2 greenhouse gases (GHGs). However, current quantification of these GHG emissions mainly employs unit-based measurements, where emissions from individual process units are identified, leading to large uncertainties of overall emissions. Here we introduce plant-integrated measurements, where emissions from the whole plant are measured through the off-gas pipelines of the enclosed facility, to quantify methane (CH4) and nitrous oxide (N2O) emissions from an underground municipal wastewater treatment plant (WWTP) in southern China. Our results show that the primary oxic tank contributes the largest in total CH4 and N2O emissions, with an average fraction of over 80 % and over 90 %, respectively. This can be attributed to the vigorous aeration process, which facilitates the transfer of dissolved CH4 and N2O from the liquid phase to the atmosphere through intensive air stripping. The plant-integrated measurements yield around 3-9 times higher emission factors of CH4 and N2O than the unit-based measurements. This difference in emission accounting is attributed to both varying survey durations of the two approaches and the omission of uncertain emission sources during unit-based measurements. The comparison between these two approaches indicates that plant-integrated measurements are more applicable for emission quantification of the whole plant whereas unit-based measurements provide insights into the emission characteristics of individual process units. More plant-integrated measurements are needed in the future for more accurate emission accounting of WWTPs.

Mixed-valence compounds based on heterometallic-oxo-clusters containing Sb(III,V): crystal structures and proton conduction.

Two isostructural Co(Cd)-antimony-oxo tartrate cluster-based compounds with a one-dimensional (1-D) belt-like structure, namely H9.2[Co(H2O)6]{M0.5(H2O)3.5{M'(H2O)4[SbVO6[Co4.2(H2O)5SbIII6(µ3-O)2(tta)6]]}}2·nH2O (M = Co, M' = Co, n = 9 (1); M = Cd0.39/Co0.61, M' = Cd0.24/Co0.76, n = 7 (2); H4tta = tartaric acid), have been synthesized by solvothermal methods. It is noteworthy that the relatively rare mixed-valence Sb(III,V) exists in the structures. The anionic clusters in both compounds appear to be in a sandwich configuration; the top and bottom layers are based on {Sb3(µ3-O)(tta)3} brackets, and the intermediate layer is occupied by {SbVO6[Co4.2(H2O)5]}. The title compounds have been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, elemental analyses, thermogravimetric analyses, and UV-Vis spectroscopy. We chose compound 2 as a representative to test its proton conductivity, and the results show that the conductivity can reach 1.42 × 10-3 S cm-1 at 85 °C under 98% relative humidity.

Genomic Alterations and Tumor Mutation Burden in Merkel Cell Carcinoma.

Importance: Merkel cell carcinoma (MCC) is a rare and highly aggressive cutaneous neuroendocrine carcinoma with increasing incidence. Cytotoxic chemotherapy and checkpoint inhibitors provide treatment options in the metastatic setting; however, there are no approved or standard of care targeted therapy treatment options. Objective: To identify actionable alterations annotated by the OncoKB database therapeutic evidence level in association with tumor mutation burden (TMB). Design, Setting, and Participants: This is a retrospective, cross-sectional study using data from the American Association for Cancer Research Genomics Evidence Neoplasia Information Exchange, a multicenter international cancer consortium database. Patients with MCC were enrolled in participating institutions between 2017 and 2022. Data from version 11.0 of the database were released in January 2022 and analyzed from April to June 2022. Main Outcomes and Measures: The main outcome was the percentage of patients with high TMB and OncoKB level 3B and 4 alterations. Results: A total of 324 tumor samples from 313 patients with MCC (107 women [34.2%]; 287 White patients [91.7%]; 7 Black patients [2.2%]) were cataloged in the database. The median (range) number of alterations was 4.0 (0.0-178.0), with a mean (SD) of 13.6 (21.2) alterations. Oncogenic alterations represented 20.2% of all alterations (862 of 4259 alterations). Tissue originated from primary tumor in 55.0% of patients (172 patients) vs metastasis in 39.6% (124 patients). TMB-high (≥10 mutations per megabase) was present in 26.2% of cases (82 patients). Next-generation sequencing identified 55 patients (17.6%) with a level 3B variation for a Food and Drug Administration-approved drug for use in a biomarker-approved indication or approved drug in another indication. An additional 8.6% of patients (27 patients) had a level 4 variation. Actionable alterations were more common among high TMB cases, with 37 of 82 patients (45.1%) harboring level 3 alterations compared with only 18 of 231 patients (7.8%) with low TMB. The most common level 3B gene variants included PIK3CA (12 patients [3.8%]), BRCA1/2 (13 patients [4.2%]), ATM (7 patients [2.2%]), HRAS (5 patients [1.6%]), and TSC1/2 (6 patients [1.9%]). The most common level 4 variants include PTEN (13 patients [4.1%]), ARID1A (9 patients [2.9%]), NF1 (7 patients [2.2%]), and CDKN2A (7 patients [2.2%]). Copy number alterations and fusions were infrequent. In 61.0% of cases (191 cases), a PanCancer pathway was altered, and 39.9% (125 cases) had alterations in multiple pathways. Commonly altered pathways were RTK-RAS (119 patients [38.0%]), TP53 (103 patients [32.9%]), cell cycle (104 patients [33.2%]), PI3K (99 patients [31.6%]), and NOTCH (93 patients [29.7%]). In addition, oncogenic DNA mismatch repair gene alterations were present in 8.0% of cases (25 patients). Conclusions and Relevance: In this cross-sectional retrospective study of alterations and TMB in MCC, a minority of patients had potentially actionable alterations. These findings support the investigation of targeted therapies as single agent or in combination with immunotherapy or cytotoxic chemotherapy in selected MCC populations.

Kinematics and Aerodynamics of Dragonflies (Pantala flavescens, Libellulidae) in Climbing Flight.

This study presents a detailed analysis of dragonflies' climbing flight by integratinghigh-speed photogrammetry, three-dimensional reconstruction, and computational fluid dynamics. In this study, a dragonfly's climbing flight is captured by two high-speed cameras with orthogonal optical axes. Through feature point matching and three-dimensional reconstruction, the body kinematics and wing kinematics of 22 dragonflies in climbing flight are accurately captured. Experimental results show that the climbing angles (η) are distributed from 10° to 80° and are concentrated within two ranges, 60°-70° (36%) and 20°-30° (32%), which are defined as large angle climb (LAC) and small angle climb (SAC), respectively. In order to study the aerodynamic mechanism of the climbing flight based on the biological observation results, the kinematic parameters of the dragonfly during LAC and SAC are selected for analysis and numerical simulation. The results show that the climbing angle η and wing kinematics are related. There are considerable differences in wing kinematics during climbing with different η, while the wing kinematics are unchanged during climbing with similar η. With the increase in η, the phase difference (λ) between the forewing and the hind wing decreases and the amplitude of the positional angle (θ mean) of the hind wing increases, while θ mean of the forewing remains almost unchanged. Through numerical simulation of LAC and SAC, it can be found that during the climb with different η, the different wing kinematics have a significant influence on aerodynamic performance. During SAC, the increase in λ and the decrease in θ mean of the hind wing weaken the aerodynamic disturbance of the forewing by the vortex wing of the hind wing, thus improving the flight efficiency.

Tandem-wing interactions on aerodynamic performance inspired by dragonfly hovering.

Dragonflies possess two pairs of wings and the interactions between forewing (FW) and hindwing (HW) play an important role in dragonfly flight. The effects of tandem-wing (TW) interactions on the aerodynamic performance of dragonfly hovering have been investigated. Numerical simulations of single-wing hovering without interactions and TW hovering with interactions are conducted and compared. It is found that the TW interactions reduce the lift coefficient of FW and HW by 7.36% and 20.25% and also decrease the aerodynamic power and efficiency. The above effects are mainly caused by the interaction between the vortex structures of the FW and the HW, which makes the pressure of the wing surface and the flow field near the wings change. During the observations of dragonfly flight, it is found that the phase difference (γ) is not fixed. To explore the influence of phase difference on aerodynamic performance, TW hovering with different phase differences is studied. The results show that at γ = 22.5°, dragonflies produce the maximum lift which is more than 20% of the body weight with high efficiency; at γ = 180°, dragonflies generate the same lift as the body weight.

Bilayer MoOX/CrOX Passivating Contact Targeting Highly Stable Silicon Heterojunction Solar Cells.

Molybdenum oxide (MoOX, X < 3) has been successfully demonstrated as an efficient passivating hole-selective contact in crystalline Si (c-Si) heterojunction solar cells because of its large bandgap (∼3.2 eV) and work function (∼6.9 eV). However, the severe performance degradation coming from the instability of the MoOX and its interfaces has not been well addressed. In this work, we started with a c-Si(p)/MoOX heterojunction solar cell that yielded a power conversion efficiency (PCE) of 15.86%, in which the MoOX film was synthesized by industry-compatible atomic layer deposition (ALD). The initial PCE dropped to 10.20% after 2 days because of severe migration of O and Ag at the MoOX/Ag interface. We solved this by the insertion of a CrOX layer between the MoOX layer and the Ag electrode. The solar cell was found to be stable for more than 8 months in air because of the suppression of interface degradation. Our work demonstrates an effective way of improving the stability of silicon solar cells with transition metal oxide carrier selective contacts.

Experimental and Numerical Investigation on Dragonfly Wing and Body Motion during Voluntary Take-off.

We present a detailed analysis of the voluntary take-off procedure of a dragonfly. The motions of the body and wings are recorded using two high-speed cameras at Beihang University. The experimental results show that the dragonfly becomes airborne after approximately one wingbeat and then leaves the ground. During this process, the maximum vertical acceleration could reach 20 m/s2. Evidence also shows that acceleration is generated only by the aerodynamic force induced by the flapping of wings. The dragonfly voluntary take-off procedure is divided into four phases with distinctive features. The variation in phase difference between the forewing and hindwing and angle of attack in the down-stroke are calculated to explain the different features of the four phases. In terms of the key parameters of flapping, the phase difference increases from approximately 0 to 110 degrees; the angle of attack in down-stroke reaches the maximum at first and then decreases in the following take-off procedure. Due to experimental limitations, 2-D simulations are conducted using the immersed boundary method. The results indicate that the phase difference and the angle of attack are highly correlated with the unsteady fluid field around the dragonfly's wings and body, which determines the generation of aerodynamic forces.