Evaluating a Rapid Field Assessment System for Anticoagulant Rodenticide Exposure of Raptors.

Anticoagulant rodenticides (ARs) are commonly used to control rodent pests. However, worldwide, their use is associated with secondary and tertiary poisoning of nontarget species, especially predatory and scavenging birds. No medical device can rapidly test for AR exposure of avian wildlife. Prothrombin time (PT) is a useful biomarker for AR exposure, and multiple commercially available point-of-care (POC) devices measure PT of humans, and domestic and companion mammals. We evaluated the potential of one commercially available POC device, the Coag-Sense® PT/INR Monitoring System, to rapidly detect AR exposure of living birds of prey. The Coag-Sense device delivered repeatable PT measurements on avian blood samples collected from four species of raptors trapped during migration (Intraclass Correlation Coefficient > 0.9; overall intra-sample variation CV: 5.7%). However, PT measurements reported by the Coag-Sense system from 81 ferruginous hawk (Buteo regalis) nestlings were not correlated to those measured by a one-stage laboratory avian PT assay (r = - 0.017, p = 0.88). Although precise, the lack of agreement in PT estimates from the Coag-Sense device and the laboratory assay indicates that this device is not suitable for detecting potential AR exposure of birds of prey. The lack of suitability may be related to the use of a mammalian reagent in the clotting reaction, suggesting that the device may perform better in testing mammalian wildlife.

High-fidelity profiling and modeling of heterogeneity in wastewater systems using milli-electrode array (MEA): Toward high-efficiency and energy-saving operation.

High energy consumption is a critical problem for wastewater treatment systems currently monitored using conventional "single point" probes and operated with manual or automatic open-loop control strategies, exhibiting significant time lag. This challenge is addressed in this study by profiling the variation of three critical water quality parameters (conductivity, temperature and pH) along the depth of a reactor at high spatiotemporal resolution in a real-time mode using flat thin milli-electrode array (MEA) sensors. The profiling accurately captured the heterogeneous status of the reactor under transient shocks (conductivity and pH) and slow lingering shock (temperature), providing an effective dataset to optimize the chemical dosage and energy requirement of wastewater treatment systems. Transient shock models were developed to validate the MEA profiles and calculate mass transfer coefficients. Monte Carlo simulation revealed high-resolution MEA profiling combined with fast closed-loop control strategies can save 59.50% of energy consumption (Temperature and oxygen consumption controls) and 45.29% of chemical dosage, and reach 16.28% performance improvement over the benchmark (defined with ideal conditions), compared with traditional "single-point" sensors that could only monitor the entire system through a single process state. This study demonstrated the capability of MEA sensors to profile reactor heterogeneity, visualize the variation of water quality at high resolution, provide complete datasets for accurate control, and ultimately lead to energy-saving operation with high resilience.

Dexamethasone Increases Cisplatin-Loaded Nanocarrier Delivery and Efficacy in Metastatic Breast Cancer by Normalizing the Tumor Microenvironment.

Dexamethasone is a glucocorticoid steroid with anti-inflammatory properties used to treat many diseases, including cancer, in which it helps manage various side effects of chemo-, radio-, and immunotherapies. Here, we investigate the tumor microenvironment (TME)-normalizing effects of dexamethasone in metastatic murine breast cancer (BC). Dexamethasone normalizes vessels and the extracellular matrix, thereby reducing interstitial fluid pressure, tissue stiffness, and solid stress. In turn, the penetration of 13 and 32 nm dextrans, which represent nanocarriers (NCs), is increased. A mechanistic model of fluid and macromolecule transport in tumors predicts that dexamethasone increases NC penetration by increasing interstitial hydraulic conductivity without significantly reducing the effective pore diameter of the vessel wall. Also, dexamethasone increases the tumor accumulation and efficacy of ∼30 nm polymeric micelles containing cisplatin (CDDP/m) against murine models of primary BC and spontaneous BC lung metastasis, which also feature a TME with abnormal mechanical properties. These results suggest that pretreatment with dexamethasone before NC administration could increase efficacy against primary tumors and metastases.

Monomeric thorium chalcogenolates with bipyridine and terpyridine ligands.

Thorium chalcogenolates Th(ER)4 react with 2,2'-bipyridine (bipy) to form complexes with the stoichiometry (bipy)2Th(ER)4 (E = S, Se; R = Ph, C6F5). All four compounds have been isolated and characterized by spectroscopic methods and low-temperature single crystal X-ray diffraction. Two of the products, (bipy)2Th(SC6F5)4 and (bipy)2Th(SeC6F5)4, crystallize with lattice solvent, (bipy)2Th(SPh)4 crystallizes with no lattice solvent, and the selenolate (bipy)2Th(SePh)4 crystallizes in two phases, with and without lattice solvent. In all four compounds the available volume for coordination bounded by the two bipy ligands is large enough to allow significant conformational flexibility of thiolate or selenolate ligands. 77Se NMR confirms that the structures of the selenolate products are the same in pyridine solution and in the solid state. Attempts to prepare analogous derivatives with 2,2',6',2''-terpyridine (terpy) were successful only in the isolation of (terpy)(py)Th(SPh)4, the first terpy compound of thorium. These materials are thermochromic, with color attributed to ligand-to-ligand charge transfer excitations.

Organosoluble tetravalent actinide di- and trifluorides.

Soluble molecular actinide(iv) fluorides can be prepared in high yield via redox or metathesis reactions of silver fluorides with actinide compounds containing ancillary iodide or fluorinated thiolate ligands. Two compounds, (py)4UF2I2·2py and (py)7Th2F5(SC6F5)3·2py were isolated and characterized by conventional methods, powder and low temperature single crystal X-ray diffraction.

Tetrametallic Thorium Compounds with Th4E4 (E = S, Se) Cubane Cores.

Tetrametallic thorium compounds with a Th4E4 core (E = S, Se) having a distorted cubane structure can be prepared by ligand-based reductions of elemental E with thorium chalcogenolates, prepared by in situ oxidation of Th metal with a 3:1 mixture of PhEEPh and F5C6EEC6F5. Four compounds, (py)8Th4S4(µ2-SPh)4(SC6F5)4, (py)8Th4S4(µ2-SPh)4(SeC6F5)4, (py)8Th4Se4(µ2-SePh)4(SeC6F5)4, and (py)8Th4Se4(µ2-SePh)4(SC6F5)4, were isolated and characterized by NMR spectroscopy and X-ray diffraction. These compounds clearly demonstrate the chemical impact of ring fluorination, with the less-nucleophilic EC6F5 ligands occupying the terminal binding sites and the EPh ligands bridging two metal centers. For this series of compounds, crystal packing and intermolecular π···π and H-bonding interactions result in a consistent motif and crystallization in a body-centered tetragonal unit cell. Solution-state 77Se NMR spectroscopy reveals that the solid-state structures are maintained in pyridine.