Aqua­(4,4′-bipyridine-κN)bis­(1,4-dioxo-1,4-dihydronaphthalen-2-olato-κ2 O 1,O 2)zinc 4,4′-bipyridine mono­solvate dihydrate

The reaction of 2-hy­droxy-1,4-naphtho­quinone and 4,4′-bipyridine with zinc acetate produced the title compound, [Zn(C10H5O3)2(C10H8N2)(H2O)]·C10H8N2·2H2O. The bond lengths and angles around the metal atom indicate a deviation from octa­hedral geometry. The two naphtho­quinone ligands coordinate in a cis fashion, with the 4,4′-bipyridine ligand and the water mol­ecules completing the coordination sphere of the metal atom. The asymmetric unit contains also one free 4,4′-bipyridine mol­ecule and two uncoordinated water mol­ecules. These mol­ecules make contacts with the complex through O—H⋯N and O—H⋯O hydrogen bonds, creating a layer two-dimensional network parallel to (121)

Asymmetric zinc(II) complexes as functional and structural models for phosphoesterases

We report two asymmetric ligands for the generation of structural and functional dinuclear metal complexes as phosphoesterase mimics. Two zinc(II) complexes, [Zn-2(CH(3)L4)(CH3CO2)(2)](+) (CH(3)HL4 = 2-(((2methoxyethyl)(pyridin-2-ylmethyl) amino) methyl)-4-methyl-6-(((pyridin-2-ylmethyl) amino) methyl)phenol) and [Zn-2(CH(3)L5)(CH3CO2)(2)](+) (CH(3)HL5 = 2-(((2-methoxyethyl)(pyridine-2-ylmethyl) amino)methyl)- 4-methyl-6-(((pyridin-2-ylmethyl)(4-vinylbenzyl) amino) methyl) phenol) were synthesized and characterized by X-ray crystallography. The structures showed that the ligands enforce a mixed 6,5-coordinate environment in the solid state. H-1-, C-13-and P-31-NMR, mass spectrometry and infrared spectroscopy were used to further characterize the compounds in the solid state and in solution. The zinc(II) complexes hydrolyzed the organophosphate substrate bis-(2,4-dinitrophenol) phosphate (BDNPP), the nucleophile proposed to be a terminal water molecule (pK(a) 7.2). The ligand CH3HL4 was immobilised on Merrifield resin and its zinc(II) complex generated. Infrared spectroscopy, microanalysis and XPS measurements confirmed successful immobilisation, with a catalyst loading of similar to 1.45 mmol g(-1) resin. The resin bound complex was active towards BDNPP and displayed similar pH dependence to the complex in solution

A New Heterobinuclear FeIIICuII Complex with a Single Terminal FeIII–O(phenolate) Bond. Relevance to Purple Acid Phosphatases and Nucleases

A novel heterobinuclear mixed valence complex [Fe^IIICu^II(BPBPMP)(OAc)_2]ClO_4, 1, with the unsymmetrical N_5O_2 donor ligand 2-bis[{(2-pyridylmethyl)aminomethyl}-6-{(2-hydroxybenzyl)(2-pyridylmethyl)} aminomethyl]-4-methylphenol (H_2BPBPMP) has been synthesized and characterized. A combination of data from mass spectrometry, potentiometric titrations, X-ray absorption and electron paramagnetic resonance spectroscopy, as well as kinetics measurements indicates that in ethanol/water solutions an [Fe^III-(nu)OH-Cu^IIOH_2]+ species is generated which is the likely catalyst for 2,4-bis(dinitrophenyl)phosphate and DNA hydrolysis. Insofar as the data are consistent with the presence of an Fe_III-bound hydroxide acting as a nucleophile during catalysis, 1 presents a suitable mimic for the hydrolytic enzyme purple acid phosphatase. Notably, 1 is significantly more reactive than its isostructural homologues with different metal composition (Fe^IIIM^II, where M^II is Zn^II, Mn^II, Ni^II,or Fe^II). Of particular interest is the observation that cleavage of double-stranded plasmid DNA occurs even at very low concentrations of 1 (2.5 nuM), under physiological conditions (optimum pH of 7.0), with a rate enhancement of 2.7 x 10^7 over the uncatalyzed reaction. Thus, 1 is one of the most effective model complexes to date, mimicking the function of nucleases

COVID-19 severity and thrombo-inflammatory response linked to ethnicity

Although there is strong evidence that SARS-CoV-2 infection is associated with adverse outcomes in certain ethnic groups, the association of disease severity and risk factors such as comorbidities and biomarkers with racial disparities remains undefined. This retrospective study between March 2020 and February 2021 explores COVID-19 risk factors as predictors for patients’ disease progression through country comparison. Disease severity predictors in Germany and Japan were cardiovascular-associated comorbidities, dementia, and age. We adjusted age, sex, body mass index, and history of cardiovascular disease comorbidity in the country cohorts using a propensity score matching (PSM) technique to reduce the influence of differences in sample size and the surprisingly young, lean Japanese cohort. Analysis of the 170 PSM pairs confirmed that 65.29% of German and 85.29% of Japanese patients were in the uncomplicated phase. More German than Japanese patients were admitted in the complicated and critical phase. Ethnic differences were identified in patients without cardiovascular comorbidities. Japanese patients in the uncomplicated phase presented a suppressed inflammatory response and coagulopathy with hypocoagulation. In contrast, German patients exhibited a hyperactive inflammatory response and coagulopathy with hypercoagulation. These differences were less pronounced in patients in the complicated phase or with cardiovascular diseases. Coagulation/fibrinolysis-associated biomarkers rather than inflammatory-related biomarkers predicted disease severity in patients with cardiovascular comorbidities: platelet counts were associated with severe illness in German patients. In contrast, high D-dimer and fibrinogen levels predicted disease severity in Japanese patients. Our comparative study indicates that ethnicity influences COVID-19-associated biomarker expression linked to the inflammatory and coagulation (thrombo-inflammatory) response. Future studies will be necessary to determine whether these differences contributed to the less severe disease progression observed in Japanese COVID-19 patients compared with those in Germany

The role of Zn-OR and Zn-OH nucleophiles and the influence of para-substituents in the reactions of binuclear phosphatase mimetics

Analogues of the ligand 2,2'-(2-hydroxy-5-methyl-1,3-phenylene)bis(methylene)bis((pyridin-2-ylmethyl)azanediyl)diethanol (CH(3)H(3)L1) are described. Complexation of these analogues, 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-methylphenol (CH(3)HL2), 4-bromo-2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (BrHL2), 2,6-bis(((2-methoxyethyl)(pyridin-2-ylmethyl)amino)methyl)-4-nitrophenol (NO(2)HL2) and 4-methyl-2,6-bis(((2-phenoxyethyl)(pyridin-2-ylmethyl)amino)methyl)phenol (CH(3)HL3) with zinc(II) acetate afforded [Zn-2(CH(3)L2)(CH3COO)(2)](PF6), [Zn-2(NO(2)L2)(CH3COO)(2)](PF6), [Zn-2(BrL2)(CH3COO)(2)](PF6) and [Zn-2(CH(3)L3)(CH3COO)(2)](PF6), in addition to [Zn-4(CH(3)L2)(2)(NO2C6H5OPO3)(2)(H2O)(2)](PF6)(2) and [Zn-4(BrL2)(2)(PO3F)(2)(H2O)(2)](PF6)(2). The complexes were characterized using H-1 and C-13 NMR spectroscopy, mass spectrometry, microanalysis, and X-ray crystallography. The complexes contain either a coordinated methyl-(L2 ligands) or phenyl-(L3 ligand) ether, replacing the potentially nucleophilic coordinated alcohol in the previously reported complex [Zn-2(CH(3)HL1)(CH3COO)(H2O)](PF6). Functional studies of the zinc complexes with the substrate bis(2,4-dinitrophenyl) phosphate (BDNPP) showed them to be competent catalysts with, for example, [Zn-2(CH(3)L2)](+), k(cat) = 5.70 +/- 0.04 x 10(-3) s(-1) (K-m = 20.8 +/- 5.0 mM) and [Zn-2(CH(3)L3)](+), kcat = 3.60 +/- 0.04 x 10(-3) s(-1) (K-m = 18.9 +/- 3.5 mM). Catalytically relevant pK(a)s of 6.7 and 7.7 were observed for the zinc(II) complexes of CH(3)L2(-) and CH(3)L3(-), respectively. Electron donating para-substituents enhance the rate of hydrolysis of BDNPP such that k(cat) p-CH3 > p-Br > p-NO2. Use of a solvent mixture containing H2O18/H2O16 in the reaction with BDNPP showed that for [Zn-2(CH(3)L2)(CH3COO)(2)](PF6) and [Zn-2(NO(2)L2)(CH3COO)(2)](PF6), as well as [Zn-2(CH(3)HL1)(CH3COO)(H2O)](PF6), the O-18 label was incorporated in the product of the hydrolysis suggesting that the nucleophile involved in the hydrolysis reaction was a Zn-OH moiety. The results are discussed with respect to the potential nucleophilic species (coordinated deprotonated alcohol versus coordinated hydroxide)

Covid-19 triage in the emergency department 2.0: how analytics and AI transform a human-made algorithm for the prediction of clinical pathways

The Covid-19 pandemic has pushed many hospitals to their capacity limits. Therefore, a triage of patients has been discussed controversially primarily through an ethical perspective. The term triage contains many aspects such as urgency of treatment, severity of the disease and pre-existing conditions, access to critical care, or the classification of patients regarding subsequent clinical pathways starting from the emergency department. The determination of the pathways is important not only for patient care, but also for capacity planning in hospitals. We examine the performance of a human-made triage algorithm for clinical pathways which is considered a guideline for emergency departments in Germany based on a large multicenter dataset with over 4,000 European Covid-19 patients from the LEOSS registry. We find an accuracy of 28 percent and approximately 15 percent sensitivity for the ward class. The results serve as a benchmark for our extensions including an additional category of palliative care as a new label, analytics, AI, XAI, and interactive techniques. We find significant potential of analytics and AI in Covid-19 triage regarding accuracy, sensitivity, and other performance metrics whilst our interactive human-AI algorithm shows superior performance with approximately 73 percent accuracy and up to 76 percent sensitivity. The results are independent of the data preparation process regarding the imputation of missing values or grouping of comorbidities. In addition, we find that the consideration of an additional label palliative care does not improve the results