Hydrogen-bond landscapes, geometry and energetics of squaric acid and its mono- and dianions: a Cambridge Structural Database, IsoStar and computational study

As part of a programme of work to extend central-group coverage in the Cambridge Crystallographic Data Centre's (CCDC) IsoStar knowledge base of intermolecular interactions, we have studied the hydrogen-bonding abilities of squaric acid (H(2)SQ) and its mono-and dianions (HSQ(-) and SQ(2-)) using the Cambridge Structural Database (CSD) along with dispersion-corrected density functional theory (DFT-D) calculations for a range of hydrogen-bonded dimers. The -OH and -C=O groups of H(2)SQ, HSQ(-) and SQ(2-) are potent donors and acceptors, as indicated by their hydrogenbond geometries in available crystal structures in the CSD, and by the attractive energies calculated for their dimers with acetone and methanol, which were used as model acceptors and donors. The two anions have sufficient examples in the CSD for their addition as new central groups in IsoStar. It is also shown that charge-and resonance-assisted hydrogen bonds involving H(2)SQ and HSQ(-) are similar in strength to those made by carboxylate COO- acceptors, while hydrogen bonds made by the dianion SQ(2-) are somewhat stronger. The study reinforces the value of squaric acid and its anions as cocrystal formers and their actual and potential importance as isosteric replacements for carboxylic acid and carboxylate functions

Synthesis and Reactivity of Mixed-Ligand Palladium(II) Organometallic Complexes with Phosphites and Bis(pyrazol-1-yl)methane

New cationic organometallic palladium(II) complexes of general formula [PdMe(NN)P(OR)3]ClO4 {NN = bis(pyrazol-1-yl)methane (BPM) and bis(3,5-dimethylpyrazol-1-yl)methane (Me2BPM); P(OR)3 = phosphites} have been synthesized and characterized. The isolation of the intermediate reaction products has highlighted the formation mechanism of these species. By reacting [PdMe(BPM)P(OEt)3]ClO4 with the Cl- and SeCN- ions the neutral species PdClMe(BPM)P(OEt)3 and PdMe(SeCN)(BPM)P(OEt)3 have been prepared, the last one as a mixture of isomers. The NMR data suggest that these neutral complexes are stabilized by an anagostic interaction between a hydrogen atom of the BPM methylene bridge and the palladium center. The reaction of [PdMe(BPM)P(OEt)3]ClO4 with CO and tosylmethyl isocyanide allowed the isolation of the corresponding insertion products. Preliminary studies showed that the cationic acyl complex [Pd(COMe)(BPM)P(OEt)3]ClO4 is an active catalyst toward styrene polymerization in the presence of CO

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

Genetic Variability and Admixture Zones in the Italian Populations of Turkey Oak (<i>Quercus cerris</i> L.)

The Turkey oak (Quercus cerris L.) is widely distributed in Italy, where it is the ecologically dominant oak on sandy and acidic soil. In this work, we analysed 23 natural populations by means of eight SSR (microsatellite) markers, to obtain the first synthetic map of genetic variability for this species and to study its dispersion during the Holocene, due to the possibility that at least one refugium during the Last Glacial Maximum was in Italy. The analyses showed a good amount of genetic variability together with fair differentiation between populations, as indicated by FST = 0.059. A Bayesian analysis of the amount of admixture among populations revealed the presence of four putative gene pools of origin and a rough subdivision of the populations according to their geographic location, as confirmed by the spatial analysis. No evidence for the existence of putative refugial populations was found; however, this study paves the way for the planning of conservation strategies also with regard to the relationship between Turkey oak and other oak species in Italy

Phenological and genetic characterization of Mediterranean plants at the peripheral range: the case of Cistus albidus near Lake Garda

The potential effects of climate change on the distribution of Mediterranean plants at their peripheral range make them extremely vulnerable to environmental fluctuations. The northern-most Italian population of Cistus albidus provides an outstanding case for study, as it grows at the extreme northern edge of its range and because phenological data have been available since the early XIX century. In the period 2012\u20132017, we analysed the population demography and spatial structure, growth and flowering phenology, and genetic variability to understand the history, current state and possible evolution of this population. Lastly, the population data were tested for association with environmental factors. The population studied consists of plants on average 10 years old, showing the highest growth rates in spring and autumn. Anthesis starts in April and ends in early June and is significantly dependent on temperature. High levels of genetic variability are present (average He\u2009=\u20090.471), with heterozygote excess detected at four loci out of five. Bayesian analysis does not support any genetic structuring of the population. The aggregated pattern in the distribution of individuals and their phenological traits, together with the absence of genetic structuring, seem to suggest that this extreme geographical population is not currently endangered

Anti-N-methyl-d-aspartate receptor encephalitis causing a prolonged depressive disorder evolving to inflammatory brain disease.

10nonenoneMariotto S; Tamburin S; Salviati A; Ferrari S; ZOCCARATO, MARCO; GIOMETTO, BRUNO; Bertolasi L; Alessandrini F; Benedetti MD; Monaco S.Mariotto, S; Tamburin, S; Salviati, A; Ferrari, S; Zoccarato, Marco; Giometto, Bruno; Bertolasi, L; Alessandrini, F; Benedetti, Md; Monaco, S

A last stand in the Po valley: Genetic structure and gene flow patterns in Ulmus minor and U. pumila

Background and Aims Ulmus minor has been severely affected by Dutch elm disease (DED). The introduction into Europe of the exotic Ulmus pumila, highly tolerant to DED, has resulted in it widely replacing native U. minor populations. Morphological and genetic evidence of hybridization has been reported, and thus there is a need for assessment of interspecific gene flow patterns in natural populations. This work therefore aimed at studying pollen gene flow in a remnant U. minor stand surrounded by trees of both species scattered across an agricultural landscape. Methods All trees from a small natural stand (350 in number) and the surrounding agricultural area within a 5-km radius (89) were genotyped at six microsatellite loci. Trees were morphologically characterized as U. minor, U. pumila or intermediate phenotypes, and morphological identification was compared with Bayesian clustering of genotypes. For paternity analysis, seeds were collected in two consecutive years from 20 and 28 mother trees. Maximum likelihood paternity assignment was used to elucidate intra- and interspecific gene flow patterns. Key Results Genetic structure analyses indicated the presence of two genetic clusters only partially matching the morphological identification. The paternity analysis results were consistent between the two consecutive years of sampling and showed high pollen immigration rates ( 3c0 80) and mean pollination distances ( 3c3 km), and a skewed distribution of reproductive success. Few intercluster pollinations and putative hybrid individuals were found. Conclusions Pollen gene flow is not impeded in the fragmented agricultural landscape investigated. High pollen immigration and extensive pollen dispersal distances are probably counteracting the potential loss of genetic variation caused by isolation. Some evidence was also found that U. minor and U. pumila can hybridize when in sympatry. Although hybridization might have beneficial effects on both species, remnant U. minor populations represent a valuable source of genetic diversity that needs to be preserved

Chelate polypyridine ligand rearrangement in Au(III) complexes

The reaction of gold(III) neutral complexes AuBr(CN)2(N–N) {N–N = 2,20-bipyridine (bpy), 5,50- dimethyl-2,20-bipyridine (Me2bpy), 1,10-phenanthroline (phen)} with a stoichiometric amount of K[AuCl4] 2H2O in nitromethane at room temperature led to the formation of 1:1 electrolytes which were characterized by NMR and IR spectroscopy, conductivity measurements, elemental analyses and X-ray diffraction. Both the anions and the cations of these salts are singly charged square-planar Au(III) complexes and the cations have general formula [AuCl2(N–N)]+. A hypothesis on the possible reaction mechanisms is presented to give an explanation for the formation of the reaction products