The synthesis and detailed characterization of the new spin crossover mononuclear complex FeII(DAPP)(abpt)(ClO4)2, where DAPP = bis(3-aminopropyl)(2-pyridylmethyl)amine and abpt = ...4-amino-3,5-bis(pyridin-2-yl)-1,2,4-triazole, are reported. Variable-temperature magnetic susceptibility measurements and Mössbauer spectroscopy have revealed the occurrence of an abrupt spin transition with a hysteresis loop. The hysteresis width derived from magnetic susceptibility measurements is 10 K, the transition being centered at T c↓ = 171 K for decreasing and T c↑ = 181 K for increasing temperatures. The crystal structure was resolved in the high-spin (293 and 183 K) and low-spin (123 K) states. Both spin-state structures belong to the monoclinic space group P21/n (Z = 4). The thermal spin transition is accompanied by the shortening of the mean Fe−N distances by 0.177 Å. The two main structural characteristics of Fe(DAPP)(abpt)(ClO4)2 are a branched network of intermolecular links in the crystal lattice and the occurrence of two types of order−disorder transitions (in the DAPP ligand and in the perchlorate anions) accompanying the thermal spin change. These features are discussed relative to the magnetic properties of the complex. The electronic structure calculations show that the structural disorder in the DAPP ligand modulates the energy gap between the HS and LS states. In line with previous studies, the order−disorder phenomena and the spin transition in Fe(DAPP)(abpt)(ClO4)2 are found to be interrelated.
A solution to the long-standing problem presented by the oxidative cyclization of a phenolic 3-arylpropionamide to a spirolactam has been developed in this laboratory via oxazoline chemistry. This ...research was motivated by our interest in some novel tricyclic azaspirane natural products formally derived from tyrosine, such as FR901483 and TAN1251C. In this paper, we disclose full details of the total synthesis of these substances.
Infections due to antibiotic-resistant bacteria are threatening modern health care. However, estimating their incidence, complications, and attributable mortality is challenging. We aimed to estimate ...the burden of infections caused by antibiotic-resistant bacteria of public health concern in countries of the EU and European Economic Area (EEA) in 2015, measured in number of cases, attributable deaths, and disability-adjusted life-years (DALYs).
We estimated the incidence of infections with 16 antibiotic resistance–bacterium combinations from European Antimicrobial Resistance Surveillance Network (EARS-Net) 2015 data that was country-corrected for population coverage. We multiplied the number of bloodstream infections (BSIs) by a conversion factor derived from the European Centre for Disease Prevention and Control point prevalence survey of health-care-associated infections in European acute care hospitals in 2011–12 to estimate the number of non-BSIs. We developed disease outcome models for five types of infection on the basis of systematic reviews of the literature.
From EARS-Net data collected between Jan 1, 2015, and Dec 31, 2015, we estimated 671 689 (95% uncertainty interval UI 583 148–763 966) infections with antibiotic-resistant bacteria, of which 63·5% (426 277 of 671 689) were associated with health care. These infections accounted for an estimated 33 110 (28 480–38 430) attributable deaths and 874 541 (768 837–989 068) DALYs. The burden for the EU and EEA was highest in infants (aged <1 year) and people aged 65 years or older, had increased since 2007, and was highest in Italy and Greece.
Our results present the health burden of five types of infection with antibiotic-resistant bacteria expressed, for the first time, in DALYs. The estimated burden of infections with antibiotic-resistant bacteria in the EU and EEA is substantial compared with that of other infectious diseases, and has increased since 2007. Our burden estimates provide useful information for public health decision-makers prioritising interventions for infectious diseases.
European Centre for Disease Prevention and Control.
Dermatophytes are responsible, in majority, for fungal infections of skin, hair and nails, and Trichophyton rubrum is the most frequently isolated dermatophyte in humans. The time for dermatophyte ...growth in culture requires a total of two to four weeks. Molecular methods were developed to improve time to diagnosis and initiation of treatment. We present here an in-house duplex real-time PCR enabling detection of dermatophytes and simultaneous identification of T. rubrum from mycological samples and cultures. The objective of this work was to optimize the fungal DNA extraction method, the detection of dermatophytes and the identification of T. rubrum on a CFX96® (Real-Time PCR Detection System). In addition, the method comparison showed that this new method is more sensitive than the culture and microscopic observations. To conclude, this routinely used method has been accredited ISO 15189 since January 2020 in our laboratory.
•Optimization of a PCR method for the detection of dermatophytes and T. rubrum.•Various extraction and PCR parameters have been assessed.•This PCR, performed on CFX96®, provides results in 4 h.•Performances of this PCR are better than those of culture and microscopic observations.•This in-house PCR is accredited ISO 15189.
Chiral p-tert-butylcalix4arenes functionalized at the lower rim with amino acid residues have been prepared. The 1H and 13C NMR spectra indicate that the macrocycles preferably adopt a cone ...conformation. Calix4arenes bearing amino acid moieties were prepared as a class of receptors selective for anions that are bound through hydrogen bonding with the NH group. The association constants are dependent on the nature of the substituents at the lower rim. Derivative 9 shows the strongest complexation and the largest selectivity for N-tosyl-(l)-alaninate. Finally, a preliminary X-ray crystal study of the difunctionalized receptor 6f shows the “flattened cone” conformation in the solid state.
A survey on the epidemiological situation, surveillance and containment activities for carbapenemase-producing Enterobacteriaceae (CPE) was conducted in European countries in 2018. All 37 ...participating countries reported CPE cases. Since 2015, the epidemiological stage of CPE expansion has increased in 11 countries. Reference laboratory capability, dedicated surveillance and a specific national containment plan are in existence in 33, 27 and 14 countries, respectively. Enhanced control efforts are needed for CPE containment in Europe.
The synthesis and characterization of the new spin crossover mononuclear complex FeII(DPEA)(bim)(ClO4)2·0.5 H2O, where DPEA = (2‐aminoethyl)bis(2‐pyridylmethyl)amine and bim = 2,2‐bisimidazole, are ...reported. Variable‐temperature magnetic susceptibility measurements (77−295 K) reveal the occurrence of a two‐step spin transition. Two steps on the magnetic curve are separated by an inflection point at 200 K, corresponding to about 50% of the complexes that have undergone a thermal spin transition. The first step is centered at 171 K and the second one at 218 K. Mössbauer spectroscopy and X‐ray analysis show that the profile of the magnetic curve is a consequence of the presence of two inequivalent iron(II) molecules in the crystal lattice. The crystal structure was resolved at 293 K (high‐spin form) and at 123 K (low‐spin form). Both spin‐state isomers belong to the monoclinic space group P21/c (Z = 4). The main differences between high‐spin and low‐spin isomers are found in the geometry of the FeN6 core, the shorter Fe−N distances are seen at lower temperatures. Two inequivalent HS molecules at lattice sites 1 and 2 successively undergo a thermal spin transition. The analysis of the mean Fe−N distances for functionally different nitrogen donor atoms show that the two steps of the spin transition can be assigned to the inequivalent lattice sites. The gradual character of the spin transition at both lattice sites is accounted for in terms of intermolecular H‐bonding via the perchlorate ions. At 10 K the light‐induced excited spin state trapping (LIESST) effect is observed within the SQUID magnetometer cavity. Two critical temperatures Tc(LIESST) were recorded (36 K and 21 K) and are attributed to the lattice sites 1 and 2.
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