Ant-Plant Mutualism in Palm Peat Swamp Forests: A Study of Host and Epiphyte Diversity in Ant Gardens.

Mutualisms characterized by reciprocal benefits between species are a fundamental relationship of tropical ecosystems. Ant Gardens (AGs) represent an interesting ant-plant mutualism, involving specialized interactions between vascular epiphytes and ants. While this relationship has been extensively studied in various tropical regions, the available information on Peruvian ecosystems is limited.

C≡N and N≡O Bond Cleavages of Acetonitrile and Nitrosyl Ligands at a Dimolybdenum Center to Render Ethylidyne and Acetamidinate Ligands.

Extended reduction of [MoCp(μ-Cl)(μ-PBu)(NO)] () with Na(Hg) in acetonitrile (MeCN) at room temperature resulted in an unprecedented full cleavage of the C≡N bond of a coordinated MeCN molecule to yield the vinylidene derivative Na[MoCp(μ-PBu)(μ-CCH)(NO)], which upon protonation with (NH)PF gave the ethylidyne complex [MoCp(μ-PBu)(μ-CMe)(NO)] [Mo1-Mo2 = 2.9218(2) Å] in a selective and reversible way. Controlled reduction of at 273 K yielded instead, after protonation, the 30-electron acetamidinate complex [MoCp(μ-PBu)(μ-κ:κ'-HNCMeNH)(μ-NO)]PF [Mo1-Mo2 = 2.

E-H Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Hydrogen and p-Block Element Hydrides.

Reactions of complexes [MoMCp(μ-PMes*)(CO)] with H and several p-block element (E) hydrides mostly resulted in the cleavage of E-H bonds under mild conditions [M = Re () and Mn (); Mes* = 2,4,6-CHBu]. The reaction with H (ca. 4 atm) proceeded even at 295 K to give the hydrides [MoMCp(μ-H)(μ-PHMes*)(CO)].

P2X7 Receptor Regulates Collagen Expression in Human Intestinal Fibroblasts: Relevance in Intestinal Fibrosis.

Intestinal fibrosis is a common complication that affects more than 50% of Crohn´s Disease (CD) patients. There is no pharmacological treatment against this complication, with surgery being the only option. Due to the unknown role of P2X7 in intestinal fibrosis, we aim to analyze the relevance of this receptor in CD complications.

Cycloaddition and C-S Bond Cleavage Processes in Reactions of Heterometallic Phosphinidene-Bridged MoRe and MoMn Complexes with Alkynes and Phenyl Isothiocyanate.

Reactions of [MoReCp(μ-PMes*)(CO)] with internal alkynes RC≡CR yielded the phosphapropenylidene-bridged complexes [MoReCp(μ-κ:η-PMes*CRCR)(CO)] (Mes* = 2,4,6-CHBu; R = COMe, Ph). Terminal alkynes HC≡CR gave mixtures of isomers [MoReCp(μ-κ:η-PMes*CHCR)(CO)] and [MoReCp(μ-κ:η-PMes*CRCH)(CO)], with the first isomer being major (R = COMe) or unique (R = Bu), indicating the relevance of steric repulsions during the [2 + 2] cycloaddition step between Mo=P and C≡C bonds in these reactions. Similar reactions were observed for [MoMnCp(μ-PMes*)(CO)].

Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Sulfur and Selenium: From Chalcogenophosphinidene- to Trithiophosphonate-Bridged Derivatives.

Reactions of [MoReCp(μ-PR*)(CO)] with S were strongly dependent on experimental conditions (R* = 2,4,6-CHBu). When using 1 equiv of sulfur, complex [MoReCp(μ-η:κ-SPR*)(CO)] was slowly formed at 313 K, with a thiophosphinidene ligand unexpectedly bridging the dimetal center in the novel μ-κ:η coordination mode, as opposed to the μ-κ:η mode usually found in related complexes. The latter underwent fast decarbonylation at 363 K to give [MoReCp(μ-η:η-SPR*)(CO)], with a six-electron donor thiophosphinidene ligand rearranged into the rare μ-η:η coordination mode.

Abacavir causes leukocyte/platelet crosstalk by activating neutrophil P2X7 receptors thus releasing soluble lectin-like oxidized low-density lipoprotein receptor-1.

Background And Purpose: Abacavir, an antiretroviral drug used in HIV therapy associated with myocardial infarction, promotes thrombosis through P2X7 receptors. The role of platelets as pro-thrombotic cells is acknowledged whereas that of neutrophils-due to their secretory capacity-is gaining recognition. This study analyses the role of neutrophils-specifically the secretome of abacavir-treated neutrophils (SN )-in platelet activation that precedes thrombosis.

P-C, P-N, and M-N Bond Formation Processes in Reactions of Heterometallic Phosphinidene-Bridged MoMn and MoRe Complexes with Diazoalkanes and Organic Azides to Build Three- to Five-Membered Phosphametallacycles.

Reactions of the heterometallic MoRe complex [MoReCp(μ-PR*)(CO)] and its MoMn analogue with some small molecules having N-N multiple bonds, such as diazoalkanes and organic azides, were investigated (R* = 2,4,6-CHBu). Reactions with excess ethyl diazoacetate proceeded slowly and with concomitant denitrogenation to give complexes [MoMCp(μ-η:κ-PR*CHCOEt)(CO)], which display a bridging phosphaalkene ligand in a novel μ-η:κ coordination mode, while reactions with other diazoalkanes resulted only in the decomposition of the organic reagent. The MoRe complex reacted with benzyl- or -tolyl azide at room temperature to give the green complexes [MoReCp(μ-η:κ-PR*NR)(CO)] [R = Bn, -tol], which display bridging phosphatriazadiene ligands in a novel 6-electron donor coordination mode as a result of a formal [2 + 1] cycloaddition of the terminal N atom of the azide to the Mo-P double bond of the parent complex, followed by coordination of the distal NR nitrogen to the rhenium center.

Chemistry of a Nitrosyl Ligand κ:η-Bridging a Ditungsten Center: Rearrangement and N-O Bond Cleavage Reactions.

The novel nitrosyl-bridged complex [WCp(μ-PBu)(μ-κ:η-NO)(CO)(NO)](BAr) [Ar = 3,5-CH(CF)] was prepared in a multistep procedure starting from the hydride [WCp(μ-H)(μ-PBu)(CO)] and involving the new complexes [WCp(μ-PBu)(CO)](BF), [WCp(μ-PBu)(CO)(NO)](BAr), and [W(μ-κ:η-CH)Cp(μ-PBu)(CO)(NO)] as intermediates, which follow from reactions with HBF·OEt, NO, and MeNO·2HO, respectively. The nitrosyl-bridged cation easily added chloride upon reaction with [N(PPh)]Cl, with concomitant NO rearrangement into the terminal coordination mode, to give [WClCp(μ-PBu)(CO)(NO)], and underwent N-O and W-W bond cleavages upon the addition of CNBu to give the mononuclear phosphinoimido complex [WCp(NPBu)(CNBu)](BAr). Another N-O bond cleavage was induced upon photochemical decarbonylation at 243 K, which gave the oxo- and phosphinito-bridged nitrido complex [WCp(N)(μ-O)(μ-OPBu)(NO)](BAr), likely resulting from a N-O bond cleavage step following decarbonylation.

Macrophages Modulate Hepatic Injury Involving NLRP3 Inflammasome: The Example of Efavirenz.

Drug-induced liver injury (DILI) constitutes a clinical challenge due to the incomplete characterization of the mechanisms involved and potential risk factors. Efavirenz, an anti-HIV drug, induces deleterious actions in hepatocytes that could underlie induction of the NLRP3 inflammasome, an important regulator of inflammatory responses during liver injury. We assessed the potential of efavirenz to modulate the inflammatory and fibrogenic responses of major liver cell types involved in DILI.

Role of Neutrophil Extracellular Traps in COVID-19 Progression: An Insight for Effective Treatment.

The coronavirus disease 2019 (COVID-19), caused by SARS-CoV-2, has resulted in a pandemic with over 270 million confirmed cases and 5.3 million deaths worldwide. In some cases, the infection leads to acute respiratory distress syndrome (ARDS), which is triggered by a cytokine storm and multiple organ failure.

Hypercholesterolemic patients have higher eryptosis and erythrocyte adhesion to human endothelium independently of statin therapy.

Background: Phosphatidylserine (PS) externalization out of the membrane facilitates the eryptotic erythrocytes (EE) binding to endothelial cells (EC), potentially leading to atherosclerosis. Thus, the levels of eryptosis and interactions of EE-EC in hypercholesterolemic patients, either non-medicated or medicated, compared with healthy subjects were studied.

Methods: A total of 56 subjects clustered into three groups: (control (n = 20), hypercholesterolemic non-treated (HCNT) (n = 15), and statin-treated (HCT) (n = 21)) were enrolled in this cross-sectional study.

Electronic Structure and Donor Ability of an Unsaturated Triphosphorus-Bridged Dimolybdenum Complex.

The triphosphorus complex [MoCp(μ-η:η-P)(μ-PBu)] was prepared in 83% yield by reacting the methyl complex [MoCp(μ-κ:η-CH)(μ-PBu)(μ-CO)] with P at 333 K, a process also giving small amounts of the methyldiphosphenyl complex [MoCp(μ-η:η-PMe)(μ-PBu)(CO)]. The latter could be better prepared by first reacting the anionic complex Na[MoCp(μ-PBu)(μ-CO)] with P to give the diphosphorus derivative Na[MoCp(μ-η:η-P)(μ-PBu)(CO)] and further reaction of the latter with MeI. Density functional theory calculations on the title complex revealed that its triphosphorus group can be viewed as an allylic-like P ligand acting as a six-electron donor via the external P atoms, while coordination of the internal P atom involves donation from the π orbital of the ligand and back-donation to its π* orbital, both interactions having a weakening effect on the Mo-Mo and P-P connections.

The Neutrophil Secretome as a Crucial Link between Inflammation and Thrombosis.

Cardiovascular diseases are a leading cause of death. Blood-cell interactions and endothelial dysfunction are fundamental in thrombus formation, and so further knowledge of the pathways involved in such cellular crosstalk could lead to new therapeutical approaches. Neutrophils are secretory cells that release well-known soluble inflammatory signaling mediators and other complex cellular structures whose role is not fully understood.

Abacavir Increases Purinergic P2X7 Receptor Activation by ATP: Does a Pro-inflammatory Synergism Underlie Its Cardiovascular Toxicity?

The cardiovascular toxicity of Abacavir is related to its purinergic structure. Purinergic P2X7-receptors (P2X7R), characterized by activation by high concentrations of ATP and with high plasticity, seem implicated. We appraise the nature of the interplay between Abacavir and P2X7R in generating vascular inflammation.

Structural and Functional Basis for Understanding the Biological Significance of P2X7 Receptor.

The P2X7 receptor (P2X7R) possesses a unique structure associated to an as yet not fully understood mechanism of action that facilitates cell permeability to large ionic molecules through the receptor itself and/or nearby membrane proteins. High extracellular adenosine triphosphate (ATP) levels-inexistent in physiological conditions-are required for the receptor to be triggered and contribute to its role in cell damage signaling. The inconsistent data on its activation pathways and the few studies performed in natively expressed human P2X7R have led us to review the structure, activation pathways, and specific cellular location of P2X7R in order to analyze its biological relevance.

Efficient Synthesis and Multisite Reactivity of a Phosphinidene-Bridged Mo-Re Complex. A Platform Combining Nucleophilic and Electrophilic Features.

The heterometallic complex [MoReCp(μ-PR*)(CO)] () was prepared in 60% overall yield from -[MoCp(PHR*)(CO)] via a three-step procedure involving complexes -[MoCp(PClR*)(CO)] and [MoReCp(μ-PR*)(CO)] as intermediate species (R* = 2,4,6-CHBu). The PR* ligand in displays a novel asymmetric interaction with the dimetal center, involving a double bond with one atom (Mo) and a dative single bond with the other one (Re). Compound underwent thermal isomerization involving a C-H bond cleavage to yield the hydride [MoReCp(μ-H){μ-P(CHCMe)CHBu}(CO)] and reacted with I to give [MoReCpI(μ-PR*)(CO)], which displays a symmetrical phosphinidene bridge.

Leukocyte-Endothelium Interaction Is Associated with Fat Mass in Children.

Objective: To study leukocyte-endothelium interaction, a measure of the initial phase of atheromatosis, in children with overweight or obesity.

Study Design: A prospective study was conducted in 77 children aged 7-16 years; 47 were children with overweight/obesity and 30 were normal weight. Polymorphonuclear neutrophils (PMNs) and peripheral blood mononuclear cells were isolated from venous blood samples and the interaction of leukocytes over a monolayer of human umbilical vein endothelial cells was analyzed using flow chamber microscopy.

P-N and N-Mo Bond Formation Processes in the Reactions of a Pyramidal Phosphinidene-Bridged Dimolybdenum Complex with Diazoalkanes and Organic Azides.

The reactivity of the complex [MoCp(μ-κ:κ,η-PCH)(CO)(η-HMes*)(PMe)] () toward different diazoalkanes and organic azides was investigated. The pyramidal phosphinidene ligand in displayed a strong nucleophilicity, enabling these reactions to proceed rapidly even below room temperature. Thus, reacted rapidly at 253 K with different diazoalkanes NCRR' (R,R' = H,H, Ph,Ph, H,COEt) to give the corresponding P:P-bridged phosphadiazadiene derivatives as major products which, however, could not be isolated.

A reproducible and safe at-home allogeneic haematopoietic cell transplant program: first experience in Central and Southern Europe.

In 2015, we implemented an at-home allogeneic haematopoietic cell transplant (allo-HCT) program. Between 2015 and 2018, 252 patients underwent allo-HCT; 41 patients underwent allo-HCT in the at-home program (46% myeloablative; 63% unrelated donor; 32% posttransplant cyclophosphamide), and these patients were compared with 39 in-patients; safety, capacity to release beds for other programs, and economic efficiency cost were evaluated. We observed a lower incidence of febrile neutropenia in the at-home group compared with that in the in-patient group (32% versus 90%; p < 0.

Malnutrition impairs mitochondrial function and leukocyte activation.

Background: The aim of this study was to evaluate markers of inflammation, oxidative stress and endothelial function in a disease-related malnutrition (DRM) outpatient population.

Methods: For this cross-sectional study, a total of 83 subjects were included and clustered in 3 groups: 34 with normonutrition (NN), 21 with DRM without inflammation (DRM-I) and 28 with DRM and inflammation (DRM + I). Nutritional diagnosis was conducted for all subjects according to ASPEN.

Coordination and Dehydrogenation of Diphosphine-Borane PhPCHPPh·BH at a Heterometallic MoRe Center to Give an Agostic Boryl-Bridged Derivative.

The coordination chemistry of the title diphosphine-borane adduct at heterometallic MoRe centers was examined through its reactions with the hydride complex [MoReCp(μ-H)(μ-PCy)(CO)(NCMe)] (Cp = η-CH). The latter reacted rapidly with stoichiometric amounts of dppm·BH (dppm = PhPCHPPh) in refluxing toluene solution, with displacement of the nitrile ligand, to give [MoReCp(μ-H)(μ-PCy)(CO)(κ-dppm·BH)], with a -bound diphosphine-borane ligand arranged to the PCy group. Decarbonylation of the latter complex was accomplished rapidly upon irradiation with visible-UV light in toluene solution at 263 K, to give the agostic derivative [MoReCp(μ-H)(μ-PCy)(CO)(κ,η-dppm·BH)] as major product (Mo-Re = 3.