Strategic synthesis of [Cu2], [Cu4] and [Cu5] complexes: inhibition and triggering of ligand arm hydrolysis and self-aggregation by chosen ancillary bridges

The Schiff base ligand HL1 ({2,6-bis(allylimino)methyl}-4-methylphenol) having no coordinating donor arm has been examined for its reaction medium and ancillary bridge dependent reactivity for hierarchical family of CuII complexes. The ligand showed unique reactivity pattern toward CuII in solution. The bridging nature of in situ generated HO− ions in absence and presence of externally added carboxylates (RCOO−; R= CF3, C6H5 and CH3) has been utilized to produce complexes {[Cu2(µ–L2)2(H2O)]2[Cu2(µ–L2)2(H2O)2](ClO4)6} (1) (HL2 = 3-{(allylimino)methyl}-2-hydroxy-5-methylbenzaldehyde), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CCF3)4] (2), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CC6H5)4]∙H2O (3), [Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)2(H2O)4][Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)3(H2O)](ClO4)3∙2C2H5OH (4). Absence of carboxylate anions did not yield HO− ions in situ and triggered single ligand arm hydrolysis. The formation of tetra- and pentanuclear aggregates as well as ligand hydrolyzed dinulcear products has been rationalized to identify the possible roles of carboxylate anions in solution. Detailed characterization of the complexes in the solid state and in solution have been carried out using spectroscopic measurements, X-ray crystallography, variable temperature magnetic measurements and functional behavior. In MeOH solutions at 298 K, the complexes 1-4 showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) saturated with O2 of air

Nitro­furan­toin methanol monosolvate

The anti­biotic nitro­furan­toin {systematic name: (E)-1-[(5-nitro-2-fur­yl)methyl­idene­amino]­imidazolidine-2,4-dione} crys­tallizes as a methanol monosolvate, C8H6N4O5·CH4O. The nitro­furan­toin mol­ecule adopts a nearly planar conformation (r.m.s. deviation = 0.0344 Å). Hydrogen bonds involve the co-operative N—H⋯O—H⋯O heterosynthons between the cyclic imide of nitro­furan­toin and methanol O—H groups. There are also C—H⋯O hydrogen bonds involving the nitro­furan­toin mol­ecules which support the key hydrogen-bonding synthon. The overall crystal packing is further assisted by weak C—H⋯O inter­actions, giving a herringbone pattern

Guillain-Barré syndrome and COVID-19: an observational multicentre study from two Italian hotspot regions

Objective: Single cases and small series of Guillain-Barré syndrome (GBS) have been reported during the SARS-CoV-2 outbreak worldwide. We evaluated incidence and clinical features of GBS in a cohort of patients from two regions of northern Italy with the highest number of patients with COVID-19. Methods: GBS cases diagnosed in 12 referral hospitals from Lombardy and Veneto in March and April 2020 were retrospectively collected. As a control population, GBS diagnosed in March and April 2019 in the same hospitals were considered. Results: Incidence of GBS in March and April 2020 was 0.202/100 000/month (estimated rate 2.43/100 000/year) vs 0.077/100 000/month (estimated rate 0.93/100 000/year) in the same months of 2019 with a 2.6-fold increase. Estimated incidence of GBS in COVID-19-positive patients was 47.9/100 000 and in the COVID-19-positive hospitalised patients was 236/100 000. COVID-19-positive patients with GBS, when compared with COVID-19-negative subjects, showed lower MRC sum score (26.3±18.3 vs 41.4±14.8, p=0.006), higher frequency of demyelinating subtype (76.6% vs 35.3%, p=0.011), more frequent low blood pressure (50% vs 11.8%, p=0.017) and higher rate of admission to intensive care unit (66.6% vs 17.6%, p=0.002). Conclusions: This study shows an increased incidence of GBS during the COVID-19 outbreak in northern Italy, supporting a pathogenic link. COVID-19-associated GBS is predominantly demyelinating and seems to be more severe than non-COVID-19 GBS, although it is likely that in some patients the systemic impairment due to COVID-19 might have contributed to the severity of the whole clinical picture

4-(E)-2-[3-(3-[(E)-2-(4-cyanophenyl)-1-diazenyl]hexahydro-1-pyrimidinylm ethyl)hexahydro-1-pyrimidinyl]-1diazenylbenzonitrile: X-ray crystal structure

Methyl 4-((E)- 2-{3-[(3 - {( E)- 2-[ 4-( methoxycarbonyl) phenyl]- 1-diazenyl}-5, 5-dimethyl hexahydro-1-pyrimidinyl) methyl]- 5, 5-dimethylhexahydro-1- pyrimidinyl}-1-diazenyl) benzoate ( 1) has been synthesized by reaction of a mixture of formaldehyde and 2,2- dimethyl-1,3-propanediamine with p-methoxycarbonylbenzenediazonium chloride. The crystal structure of 1 has been determined by single crystal X-ray diffraction analysis. The crystals of 1 displayed problems of disorder; the asymmetric unit is built up by two independent molecules, which display disorder within a methoxycarbonyl group. The two independent molecules in the asymmetric unit are very similar, differing only slightly about the mutual orientation of the aryltriazenyl groups. With respect to the N-C-N bridge between the hexahydropyrimidinyl rings, the two equivalent fragments containing the triazene moieties are in a cis orientation. The N-N single bonds, in the range 1.319( 4) - 1.348( 4) &ANGS;, and the N=N double bonds, in the range 1.255( 5) - 1.275( 4) &ANGS;, indicate significant conjugations within the triazene moieties. All the hexahydropyrimidine six-membered rings adopt a chair conformation as shown by their puckering parameters. The crystal packing is determined only by simple van der Waals interactions. The crystal structure of 1 is compared with the previously reported structure of the unbranched hexahydropyrimidine analogue 2

An X-Ray Crystallographic Study of the Novel Aminal bis-(p-Ethoxycarbonylphenylamino-)methane

The crystal structure of bis-(p-Ethoxycarbonylphenylamino-methane (1) has been determined by single crystal X-ray diffraction analysis. The bis-aminal (1) molecule is V-shaped and situated on a twofold axis passing through C1 with the phenyl rings forming a dihedral angle of 70.2(1). The carboxylate and phenyl groups are coplanar. The crystal structure of 1 is compared with the structure of the closely related aminals, 2–5. Crystal data: 1 C19H22N2O4, tetragonal, space group I41cd (N.110), a = 20.4760(7) A ˚ ´,b = 20.4760(7) A ˚ ´,c = 8.2984(3) A ˚ , and V = 3477.7(2) A ˚ 3, for Z = 8

CRYSTAL-STRUCTURE OF SQUARE-PLANAR [1,2-BIS(PHENYLSULFANYL)ETHANE]DIHALOGENPLATINUM(II) COMPLEXES - CIS-CHELATE EFFECT AND MUTUAL TRANS INFLUENCE

The crystal structures of six isomorphous [1,2-bis(phenylsulfanyl)ethane]dihalogenoplatinum(II) square-planar neutral complexes, i.e. dichloro (1), dibromo (2), diiodo (3), chlorobromo (4), chloroiodo (5) and bromoiodo (6) species, have been determined by the single-crystal X-ray diffraction technique. Crystals are monoclinic, space group P2(1)/c, Z=4, and their structures have been solved from three-dimensional counter data by Patterson and Fourier methods. Mixed dihalogeno species are disordered as far as the positions of the two halides are concerned and refinements have been carried out with occupancies of 0.5. The platinum atom is coordinated by means of the two sulfur atoms of the bidentate ligand and two halogen atoms in cis position. Comparison with other classes of platinum(II) complexes, carrying either chelating or monodentate thioetheric ligands and halides, allows to estimate a cis-chelate effect as well as the mutual trans influence of the different ligands

Biotransformation of cortisone with Rhodococcus rhodnii: Synthesis of new steroids

Cortisone is a steroid widely used as an anti-inflammatory drug able to suppress the immune system, thus reducing inflammation and attendant pain and swelling at the site of an injury. Due to its numerous side effects, especially in prolonged and high-dose therapies, the development of the pharmaceutical industry is currently aimed at finding new compounds with similar activities but with minor or no side effects. Biotransformations are an important methodology towards more sustainable industrial processes, according to the principles of “green chemistry”. In this work, the biotransformation of cortisone with Rhodococcus rhodnii DSM 43960 to give two new steroids, i.e., 1,9β,17,21-tetrahydoxy-4-methyl-19-nor-9β-pregna-1,3,5(10)-trien-11,20-dione and 1,9β,17,20β,21- pentahydoxy-4-methyl-19-nor-9β-pregna-1,3,5(10)-trien-11-one, is reported. These new steroids have been fully characterized