Synthesis of Hollowed Polyoxometalate with a Flipped VO Unit by the Elimination of a Centered Organic Molecule.

Mechanistic understanding of the formation of clusters plays a role in designing the structure-dependent properties. Based on the fact that anions act as templates to form spherical polyoxovanadates, various structures were reported by changing anions in the synthetic solution. In this work, another factor in the formation of spherical polyoxometalates was demonstrated.

Controlling the symmetry of hexamonodentate 3d-transition metal complexes through symmetry propagation from high-symmetry Ti-Mo and Zr-Mo clusters hydrogen-bonding interactions.

The symmetry of one of the simplest hexamonodentate complexes, [M(HO)] (M = Fe, Co, Ni, and Zn), was controlled by tuning interactions in the second coordination sphere. Highly symmetric Ti-Mo or Zr-Mo cluster cations acted as symmetry templates, imposing a crystallographic trigonal coordination geometry in the hexamonodentate complexes through intermolecular hydrogen-bonding interactions. Magnetic measurements revealed that the ideal trigonal symmetry results in weak spin-orbit coupling for high-spin Fe complexes, despite the T-term ground state in the octahedral geometry.

Human iPSC-liver organoid transplantation reduces fibrosis through immunomodulation.

Donor organ shortages for transplantation remain a serious global concern, and alternative treatment is in high demand. Fetal cells and tissues have considerable therapeutic potential as, for example, organoid technology that uses human induced pluripotent stem cells (hiPSCs) to generate unlimited human fetal-like cells and tissues. We previously reported the in vivo vascularization of early fetal liver-like hiPSC-derived liver buds (LBs) and subsquent improved survival of recipient mice with subacute liver failure.

Reactivity control of nitrate-incorporating octadecavanadates by changing the oxidation state and metal substitution.

Clarification and control of the active sites at the atomic/molecular level are important to develop nanocatalysts. The catalytic performance of two oxidation states of nitrate-incorporating octadecavanadates, [VO(NO)] (V18) and [VO(NO)] (V18ox), and a copper-substituted one, [CuVO(NO)] (Cu2V16), in selective oxidation was investigated. Both V18 and V18ox possessed the same double-helical structures and one of two tetravalent vanadium sites of V18 was oxidized in V18ox.

Integration of Kupffer cells into human iPSC-derived liver organoids for modeling liver dysfunction in sepsis.

Maximizing the potential of human liver organoids (LOs) for modeling human septic liver requires the integration of innate immune cells, particularly resident macrophage Kupffer cells. In this study, we present a strategy to generate LOs containing Kupffer cells (KuLOs) by recapitulating fetal liver hematopoiesis using human induced pluripotent stem cell (hiPSC)-derived erythro-myeloid progenitors (EMPs), the origin of tissue-resident macrophages, and hiPSC-derived LOs. Remarkably, LOs actively promote EMP hematopoiesis toward myeloid and erythroid lineages.

Effect of Smoke Evacuator on Reduction of Volatile Organic Compounds and Particles in Surgical Smoke: A Randomized Controlled Trial.

Background: Surgical smoke is an occupational health problem and is increasingly recognized as a potential source of virus transmission. Dedicated smoke evacuators are used to protect against surgical smoke exposure. We tested the hypothesis that using smoke evacuators would reduce volatile organic compounds and the number of particles in surgical smoke during the laparotomy procedure.

A data-informed timeline for hospital discharge with a reasonably low risk of unplanned readmission after open and minimally invasive liver resections.

Background: Postoperative complications following liver resection remain high, ranging from 20% to 50%. Patients are hospitalized for a certain period of time following liver resection because of the risk of postoperative complications. We hypothesized that the risk of complications decreases with each complication-free postoperative day after open and minimally invasive liver resections and can be stratified using a recently reported three-level complexity classification.

Mechanistic insights into template-driven polyoxovanadate self-assembly: the role of internal and external templates.

The self-assembly of molecular metal oxides, polyoxometalates (POMs), can be controlled using internal or, more rarely, external templates. Here, we explore how the interplay between internal templates (halides, oxoanions) and organic external templates (protonated cyclene species) affect the self-assembly of a model polyoxovanadate cluster, [VOX] (X = Cl, Br, NO). A combination of crystallographic analyses, spectroscopic studies and as well as solid-state V NMR spectroscopy provide critical insights into the initial formation of an intermediate vanadate species formed during the process.

Evaluation of fibrinogen concentration by clot firmness using a dielectric blood coagulation test system.

Purpose: To determine if fibrinogen concentration can be evaluated by dielectric permittivity changes in dielectric blood coagulation testing (DBCM) during cardiovascular surgery with cardiopulmonary bypass (CPB).

Methods: We performed a single-center prospective observational study at a university hospital. One hundred patients undergoing cardiovascular surgery with CPB were enrolled.

Synthesis of Water-Soluble Planar Cobalt(II), Nickel(II), and Copper(II) Hydroxo Clusters Using a (1,4,7-Triazacyclononane)cobalt(III) Complex as a Hydrolysis-Terminating Group.

We report on a group of planar cobalt(II), nickel(II), and copper(II) hydroxo clusters that have a definite composition and are water-soluble: [{Co(tacn)(OH)}Co(OH)](NO)(CFSO)·10HO (), [{Co(tacn)(OH)}Ni(OH)](NO)(CFSO)·10HO (), [{Co(tacn)(OH)}Ni(OH)](BNPP)·6CHNO·8HO [; BNPP = bis(-nitrophenyl)phosphate], [{Co(tacn)(OH)}Ni(OH)(OH)](SO)(CFSO)·30HO (), [{Co(tacn)(OH)}Ni(OH)(OH)](SO)(CFSO)·44HO (), [{Co(tacn)(OH)}Co(OH)(OH)](SO)(CFSO)·4HO (), [{Co(tacn)(OH)}Ni(OH)(OH)](SO)(CFSO)·4HO (), and [{Co(tacn)(OH)}Cu(OH)](ClO)·5HO (), where tacn is 1,4,7-triazacyclononane. The peripheral of each metal hydroxo cluster plane is chemically protected by the coordination of {Co(tacn)(OH)} groups to prevent further hydrolysis. These clusters were synthesized by the reaction of an equimolar amount of [Co(tacn)(OH)] and cobalt, nickel, or copper salt at pH values in the range of 6.

Synthesis of cyanooxovanadate and cyanosilylation of ketones.

The cyanosilylation was performed by using metavanadate catalysts, and measurements revealed the formation of [VO(CN)] and [VOTMS] under reaction conditions. The reaction of [VO(CN)], trimethylsilyl cyanide (TMSCN), and water afforded [VOTMS] and CN, which reacted with ketones to yield the corresponding cyanohydrin trimethylsilyl ethers over [VO(CN)]. Compound [VO(CN)] showed high catalytic performance for cyanosilylation of various carbonyl compounds.

Selective Formation of Intramolecular Hydrogen-Bonding Palladium(II) Complexes with Nucleosides Using Unsymmetrical Tridentate Ligands.

Three palladium(II) complexes with amino-amidato-phenolato-type tridentate ligands were synthesized and characterized by H NMR spectroscopy and X-ray crystallography. The strategic arrangement of a hydrogen-bond donor and acceptor adjacent to the substitution site of the Pd complex allowed the selective coordination of nucleosides. Among two pyrimidine-nucleosides, cytidine and 5-methyluridine, cytidine was successfully coordinated to the Pd complex while 5-methyluridne was not.

Human Pluripotent Stem Cell-Derived Hepatocyte-Like Cells and Organoids for Liver Disease and Therapy.

Liver disease is a global health issue that has caused an economic burden worldwide. Organ transplantation is the only effective therapy for end-stage liver disease; however, it has been hampered by a shortage of donors. Human pluripotent stem cells (hPSCs) have been widely used for studying liver biology and pathology as well as facilitating the development of alternative therapies.

Isolation of a Nitromethane Anion in the Calix-Shaped Inorganic Cage.

A calix-shaped polyoxometalate, [VO] (), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by to form [VO(CN)].

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity.

Dodecavanadate, [V O ] (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br was inserted into V12, inducing the inversion of one of the VO square pyramids to form [V O (Br )] (V12(Br2)).

Effects of neural stem cell transplantation in Alzheimer's disease models.

Currently there are no therapies for treating Alzheimer's disease (AD) that can effectively halt disease progression. Existing drugs such as acetylcholinesterase inhibitors or NMDA receptor antagonists offers only symptomatic benefit. More recently, transplantation of neural stem cells (NSCs) to treat neurodegenerative diseases, including AD, has been investigated as a new therapeutic approach.

Artificial bioinorganic clusters of dinuclear 3d-transition metal ions coordinated by an inorganic coordination ligand.

A new biologically relevant cubane-type artificial inorganic ligand was developed to support 3d-transition metal ions of Mn(II), Co(II), Ni(II), Zn(II), Fe(III), and also In(III). All of the reactions produce dinuclear cationic clusters of [({Co(tacn)}HMoO∙HO){M(HO)}] (M = Mn (4Mn), Co (4Co), Ni (4Ni), Zn (4Zn), n = 2; M = Fe (5), In (6), n = 4), where tacn is the abbreviation of 1,4,7-triazacyclononane ligand. Clusters 4 do not dissolve in any solvents at all to prevent the recrystallization or the further characterization whereas the high solubility of clusters 5 and 6 allowed us to characterize the solution state properties.

Evaluation of the chemo- and shape-selective association of a bowl-type dodecavanadate cage with an electron-rich group.

The host-guest interaction between a half spherical-type dodecavanadate (V12) and a neutral molecule guest was evaluated by monitoring the flip of a VO unit caused by the presence or absence of a guest in the cavity of V12. In N,N-dimethylformamide (DMF), V12 adopted the guest-free form (V12-free). By the addition of several guest molecules, such as acetonitrile, nitromethane, and dichloromethane, the structural conversion to the guest-inserted form (V12(guest)) was observed with the affinity constants of 137 ± 10 M, 0.

Synthesis and structural characterization of tube-type tetradecavanadates.

By the reaction of ammonium perchlorate with anion-incorporated bowl-type dodecavanadates, viz. [VO(X)] [X = N (1), OCN and NO], tube-type tetradecavanadates, viz. (NH)[VO(X)] [X = N (2), OCN (3) and NO (4)] were synthesized.

Solid-State Umbrella-type Inversion of a VO Square-Pyramidal Unit in a Bowl-type Dodecavanadate Induced by Insertion and Elimination of a Guest Molecule.

Design of cavities for a target molecule and the elucidation of the corresponding host-guest interactions are important for molecular manipulation. A discrete dodecavanadate bowl, [V O ] (V12), with an entrance diameter of 4.4 Å and an electron-rich guest at the center of the bowl, was stabilized by electrostatic interactions.

Strategic Isolation of a Polyoxocation Mimicking Vanadium(V) Oxide Layered-Structure by Stacking of [HVO] Anions Bridged by (1,4,7-Triazacyclononane)Co(III) Complexes.

An isolation of a vanadium(V) oxide cluster mimicking VO layered structure was achieved formulated as [{Co(tacn)}VO(OH)] () (tacn = 1,4,7-triazacyclononane). From the V NMR spectra of the reaction mixtures, we optimized the reaction condition in terms of a molar ratio of VO and [Co(tacn)(HO)] as well as a pH value. Cluster is stable in a wide range of pH values from 1.

Synthesis of cationic molybdenum-cobalt heterometallic clusters protected against hydrolysis by macrocyclic triazacyclononane complexes.

Four kinds of cobalt-polyoxomolybdenum clusters were synthesized by a combination of polyoxomolybdates and a Co-tacn (tacn = 1,4,7-triazacyclononane) complex. The heterometallic polynuclear clusters were obtained by the reaction of Na2MoO4 and [Co(tacn)(H2O)3](CF3SO3)3·H2O in water. The peripherals of polyoxomolybdates are capped by thermodynamically stable [Co(tacn)]3+ protecting groups to prevent further hydrolysis and condensation reactions.

Simultaneous assessment of blood coagulation and hematocrit levels in dielectric blood coagulometry.

Background: In a whole blood coagulation test, the concentration of any in vitro diagnostic agent in plasma is dependent on the hematocrit level but its impact on the test result is unknown.

Objective: The aim of this work was to clarify the effects of reagent concentration, particularly Ca2+, and to find a method for hematocrit estimation compatible with the coagulation test.

Methods: Whole blood coagulation tests by dielectric blood coagulometry (DBCM) and rotational thromboelastometry were performed with various concentrations of Ca2+ or on samples with different hematocrit levels.

Small-Molecule Anion Recognition by a Shape-Responsive Bowl-Type Dodecavanadate.

A dodecavanadate, [V O ] , is an inorganic bowl-type host with a cavity entrance with a diameter of 4.4 Å in the optimized structure. Linear, bent, and trigonal planar anions are tested as guest anions and the formation of host-guest complexes, [V O (X)] (X=CN , OCN , NO , NO , HCO , and CH CO ), were confirmed by X-ray crystallographic analyses and a V NMR spectroscopy study.

A Bowl-Type Dodecavanadate as a Halide Receptor.

The dodecavanadate framework, [VO], exhibits a unique bowl-type structure with an open molecular oxide cage having a cavity diameter of 4.4 Å, and different synthetic paths were required to construct the bowl-type structure with a different guest. A new dodecavanadate, {(-CH)N}[VO(CHNO)] (), is synthesized with a nitromethane guest, which is stacked above the entrance of the hemisphere rather than fully occupying the cavity, and it enables a guest-capturing reaction, while retaining the anionic cage structure.