The Joint Initiative for Teaching and Learning on Global Health Challenges and One Health experience on implementing an online collaborative course.

The "Joint Initiative for Teaching and Learning on Global Health Challenges and One Health" piloted the online course "Global Health Challenges and One Health in 2021. The present work documents this experience, lessons learned, and the future outlook of the course. A descriptive study was conducted based on the evaluations performed with the enrolled students and course coordinators.

The impact of strict measures as a result of the COVID-19 pandemic on the spatial pattern of the demand for police: case study Antwerp (Belgium).

COVID-19 impacts the daily lives of millions of people. This radical change in our daily activities affected many aspects of life, but acted as well as a natural experiment for research into the spatial distribution of 911 calls. We analyse the impact of the COVID-19 measures on the spatial pattern of police interventions.

Assessment of binding potencies of polychlorinated biphenyls and polybrominated diphenyl ethers with Baikal seal and mouse constitutive androstane receptors: Comparisons across species and congeners.

The present study evaluated the binding potencies (equilibrium dissociation constant: K) of polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) with the constitutive androstane receptor (CAR)_ligand binding domain (LBD) of the Baikal seal (bsCAR_LBD) and mouse (mCAR_LBD) using a surface plasmon resonance (SPR) biosensor. The binding affinities of individual congeners with mCAR_LBD tended to be higher than those with bsCAR_LBD but the differences were within the same order of magnitude. Notably, PBDE congeners showed higher binding affinities for both CAR_LBDs than PCB congeners.

Polycyclic aromatic hydrocarbons in airborne particulate matter samples from Hanoi, Vietnam: Particle size distribution, aryl hydrocarbon ligand receptor activity, and implication for cancer risk assessment.

Concentrations and profiles of unsubstituted and methylated polycyclic aromatic hydrocarbons (PAHs and Me-PAHs) were analyzed in airborne particulate matter (PM) samples collected from high-traffic roads in Hanoi urban area. Levels of PAHs and Me-PAHs ranged from 210 to 660 (average 420) ng/m in total PM, and these pollutants were mainly associated with fine particles (PM) rather than coarser ones (PM and PM). Proportions of high-molecular-weight compounds (i.

Hydrolysis of Metal Dioxides Differentiates d-block from f-block Elements: Pa(V) as a 6d Transition Metal; Pr(V) as a 4f "Lanthanyl".

Gas-phase reactions of pentavalent metal dioxide cations MO with water were studied experimentally for M = V, Nb, Ta, Pr, Pa, U, Pu, and Am. Addition of two HO can occur by adsorption to yield hydrate (HO)MO or by hydrolysis to yield hydroxide M(OH). Displacement of HO by acetone indicates hydrates for Pr, U, Pu, and Am, whereas nondisplacement indicates hydroxides for Nb, Ta, and Pa.

Soil and sediment contamination by unsubstituted and methylated polycyclic aromatic hydrocarbons in an informal e-waste recycling area, northern Vietnam: Occurrence, source apportionment, and risk assessment.

Improper processing activities of e-waste are potential sources of polycylic aromatic hydrocarbons (PAHs) and their derivatives, however, information about the environmental occurrence and adverse impacts of these toxic substances is still limited for informal e-waste recycling areas in Vietnam and Southeast Asia. In this study, unsubstituted and methylated PAHs were determined in surface soil and river sediment samples collected from a rural village with informal e-waste recycling activities in northern Vietnam. Total levels of PAHs and MePAHs decreased in the order: workshop soil (median 2900; range 870-42,000 ng g) > open burning soil (2400; 840-4200 ng g) > paddy field soil (1200; range 530-6700 ng g) > river sediment samples (750; 370-2500 ng g).

Coordination of 2,2'-(Trifluoroazanediyl)bis(,'-dimethylacetamide) with U(VI), Nd(III), and Np(V): A Thermodynamic and Structural Study.

Thermodynamic properties of the complexation of 2,2'-(trifluoroazanediyl)bis(,'-dimethylacetamide) (CFABDMA) with U(VI), Nd(III), and Np(V) have been studied in 1.0 M NaNO at 25 °C. Equilibrium constants of the complexation were determined by potentiometry and spectrophotometry.

Activation of Water by Pentavalent Actinide Dioxide Cations: Characteristic Curium Revealed by a Reactivity Turn after Americium.

Swapping of an oxygen atom of water with that of a pentavalent actinide dioxide cation, AnO also called an "actinyl", requires activation of an An-O bond. It was previously found that such oxo exchange in the gas phase occurs for the first two actinyls, PaO and UO, but not the next two, NpO and PuO. The An-O bond dissociation energies (BDEs) decrease from PaO to PuO, such that the observation of a parallel decrease in the An-O bond reactivity is intriguing.

Pentavalent Curium, Berkelium, and Californium in Nitrate Complexes: Extending Actinide Chemistry and Oxidation States.

Pentavalent actinyl nitrate complexes AnO(NO) were produced by elimination of two NO from An(NO) for An = Pu, Am, Cm, Bk, and Cf. Density functional theory (B3LYP) and relativistic multireference (CASPT2) calculations confirmed the AnO(NO) as AnO actinyl moieties coordinated by nitrates. Computations of alternative AnO(NO) and AnO(NO) revealed significantly higher energies.

Complexation of NpO with Amine-Functionalized Diacetamide Ligands in Aqueous Solution: Thermodynamic, Structural, and Computational Studies.

Complexation of Np(V) with three structurally related amine-functionalized diacetamide ligands, including 2,2'-azanediylbis( N, N'-dimethylacetamide) (ABDMA), 2,2'-(methylazanediyl)bis( N, N'-dimethylacetamide) (MABDMA), and 2,2'-(benzylazanediyl)bis( N, N'-dimethylacetamide) (BnABDMA), in aqueous solutions was investigated. The stability constants of two successive complexes, namely, NpOL and NpOL, where L stands for the ligands, were determined by absorption spectrophotometry. The results suggest that the stability constants of corresponding Np(V) complexes follow the trend: MABDMA > ABDMA ≈ BnABDMA.

Thermodynamic, Structural, and Computational Investigation on the Complexation between UO and Amine-Functionalized Diacetamide Ligands in Aqueous Solution.

The stability constants (log β), enthalpies of complexation (ΔH), and entropies of complexation (ΔS) for the complexes of uranium(VI) with a series of amine-functionalized diaetamide ligands, 2,2'-benzylazanediylbis(N,N'-dimethylacetamide) (BnABDMA), 2,2'-azanediylbis(N,N'-dimethylacetamide) (ABDMA), and 2,2'-methylazanediylbis(N,N'-dimethylacetamide) (MABDMA), in aqueous solution were determined by potentiometry and calorimetry. Electronspray ionization mass spectrometry was used to verify the presence of uranium(VI) complexes in solution. The thermodynamic data indicate that the binding strengths of the three ligands with UO follow the order BnABDMA < ABDMA < MABDMA, parallel to the order of the protonation constants as well as the order of the stability of the Nd complexes, suggesting that the complexation of UO with the ligands consist predominantly of electrostatic interactions.

Heptavalent Actinide Tetroxides NpO and PuO: Oxidation of Pu(V) to Pu(VII) by Adding an Electron to PuO.

The highest known actinide oxidation states are Np(VII) and Pu(VII), both of which have been identified in solution and solid compounds. Recently a molecular Np(VII) complex, NpO(NO), was prepared and characterized in the gas phase. In accord with the lower stability of heptavalent Pu, no Pu(VII) molecular species has been identified.

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

Actinyl chemistry is extended beyond Cm to BkO and CfO through transfer of an O atom from NO to BkO or CfO , establishing a surprisingly high lower limit of 73 kcal mol for the dissociation energies, D[O-(BkO )] and D[O-(CfO )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO )].

Cleaving Off Uranyl Oxygens through Chelation: A Mechanistic Study in the Gas Phase.

Recent efforts to activate the strong uranium-oxygen bonds in the dioxo uranyl cation have been limited to single oxo-group activation through either uranyl reduction and functionalization in solution, or by collision induced dissociation (CID) in the gas-phase, using mass spectrometry (MS). Here, we report and investigate the surprising double activation of uranyl by an organic ligand, 3,4,3-LI(CAM), leading to the formation of a formal U chelate in the gas-phase. The cleavage of both uranyl oxo bonds was experimentally evidenced by CID, using deuterium and O isotopic substitutions, and by infrared multiple photon dissociation (IRMPD) spectroscopy.

An enhanced bioluminescence-based Annexin V probe for apoptosis detection in vitro and in vivo.

The process of controlled cellular death known as apoptosis has an important central role not only in normal homeostatic maintenance of tissues, but also in numerous diseases such as cancer, neurodegenerative, autoimmune, and cardiovascular diseases. As a result, new technologies with the capability to selectively detect apoptotic cells represent a central focus of research for the study of these conditions. We have developed a new biosensor for the detection of apoptotic cells, incorporating the targeted selectivity for apoptotic cells from Annexin V with the sensitivity of bioluminescence signal generation from a serum-stable mutant of Renilla luciferase (RLuc8).

Transcriptional regulatory proteins as biosensing tools.

We have developed sensing systems employing different classes of transcriptional regulatory proteins genetically and chemically modified to incorporate a fluorescent reporter molecule for detection of arsenic, hydroxylated polychlorinated biphenyls (OH-PCBs), and cyclic AMP (cAMP). These are the first examples of optical sensing systems based on transcriptional regulatory proteins.

A Uranyl Peroxide Dimer in the Gas Phase.

The gas-phase uranyl peroxide dimer, [(UO)(O)(L)] where L = 2,2'-trifluoroethylazanediyl)bis(N,N'-dimethylacetamide), was synthesized by electrospray ionization of a solution of UO and L. Collision-induced dissociation of this dimer resulted in endothermic O atom elimination to give [(UO)(O)(L)], which was found to spontaneously react with water via exothermic hydrolytic chemisorption to yield [(UO)(OH)(L)]. Density functional theory computations of the energies for the gas-phase reactions are in accord with observations.

Heptavalent Neptunium in a Gas-Phase Complex: (NpO)(NO).

A central goal of chemistry is to achieve ultimate oxidation states, including in gas-phase complexes with no condensed phase perturbations. In the case of the actinide elements, the highest established oxidation states are labile Pu(VII) and somewhat more stable Np(VII). We have synthesized and characterized gas-phase AnO(NO) complexes for An = U, Np, and Pu by endothermic NO elimination from AnO(NO).

Divalent and trivalent gas-phase coordination complexes of californium: evaluating the stability of Cf(ii).

The divalent oxidation state is increasingly stable relative to the trivalent state for the later actinide elements, with californium the first actinide to exhibit divalent chemistry under moderate conditions. Although there is evidence for divalent Cf in solution and solid compounds, there are no reports of discrete complexes in which Cf(II) is coordinated by anionic ligands. Described here is the divalent Cf methanesulfinate coordination complex, Cf(II)(CH3SO2)3(-), prepared in the gas phase by reductive elimination of CH3SO2 from Cf(III)(CH3SO2)4(-).

Thermodynamic study of the complexation between Nd(3+) and functionalized diacetamide ligands in solution.

A series of amine functionalized ligands, including 2,2'-(benzylazanediyl)bis(N,N'-dimethylacetamide) (BnABDMA), 2,2'-azanediylbis(N,N'-dimethylacetamide) (ABDMA), and 2,2'-(methylazanediyl)bis(N,N'-dimethylacetamide) (MABDMA), are synthesized for the thermodynamic study of their complexation with Nd(3+) ions. Their complexation in solution is investigated using potentiometry, spectrophotometry, calorimetry, and electrospray ionization mass spectrometry. The results suggest that these ligands act as tridentate ligands.

Structural and spectroscopic studies of a rare non-oxido V(v) complex crystallized from aqueous solution.

A non-oxido V(v) complex with glutaroimide-dioxime (HL), a ligand for recovering uranium from seawater, was synthesized from aqueous solution as Na[V(L)]·2HO, and the structure determined by X-ray diffraction. It is the first non-oxido V(v) complex that has been directly synthesized in and crystallized from aqueous solution. The distorted octahedral structure contains two fully deprotonated ligands (L) coordinating to V, each in a tridentate mode the imide N ( = 1.

Activation of carbon dioxide by a terminal uranium-nitrogen bond in the gas-phase: a demonstration of the principle of microscopic reversibility.

Activation of CO2 is demonstrated by its spontaneous dissociative reaction with the gas-phase anion complex NUOCl2(-), which can be considered as NUO(+) coordinated by two chloride anion ligands. This reaction was previously predicted by density functional theory to occur exothermically, without barriers above the reactant energy. The present results demonstrate the validity of the prediction of microscopic reversibility, and provide a rare case of spontaneous dissociative addition of CO2 to a gas-phase complex.

Oxidation of Actinyl(V) Complexes by the Addition of Nitrogen Dioxide Is Revealed via the Replacement of Acetate by Nitrite.

The gas-phase complexes AnO2(CH3CO2)2(-) are actinyl(V) cores, An(V)O2(+) (An = U, Np, Pu), coordinated by two acetate anion ligands. Whereas the addition of O2 to U(V)O2(CH3CO2)2(-) exothermically produces the superoxide complex U(VI)O2(O2)(CH3CO2)2(-), this oxidation does not occur for Np(V)O2(CH3CO2)2(-) or Pu(V)O2(CH3CO2)2(-) because of the higher reduction potentials for Np(V) and Pu(V). It is demonstrated that NO2 is a more effective electron-withdrawing oxidant than O2, with the result that all three An(V)O2(CH3CO2)2(-) exothermically react with NO2 to form nitrite complexes, An(VI)O2(CH3CO2)2(NO2)(-).

Vibrational State-Selective Resonant Two-Photon Photoelectron Spectroscopy of AuS(-) via a Spin-Forbidden Excited State.

Vibrational state-selective resonant two-photon photoelectron spectra have been obtained via a triplet intermediate state ((3)Σ(-)) of AuS(-) near its detachment threshold using high-resolution photoelectron imaging of cryogenically cooled AuS(-) anions. Four vibrational levels of the (3)Σ(-) excited state are observed to be below the detachment threshold. Resonant two-photon absorptions through these levels yield vibrational state-selective photoelectron spectra to the (2)Σ final state of neutral AuS with broad and drastically different Franck-Condon distributions, reflecting the symmetries of the vibrational wave functions of the (3)Σ(-) intermediate state.