Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes

The mechanism of the platinum-catalysed dihydroalkoxylation of allenes to give acetals has been studied experimentally and by computational methods. Our findings further explain divergent reactivity encountered for platinum- and gold-vinyl intermediates after the first nucleophilic attack onto the coordinated allene, as well as provide new details on the catalytic cycle with platinum, uncovering enol ethers as resting states of the catalytic cycle, a S(E)Ox process via Pt(V)-H as the final protodemetallation step after the second nucleophilic attack when neutral platinum complexes are used, and a fast acid promoted addition of methanol to enol ethers when cationic platinum complexes are employed

A Small Non-Coding RNA Modulates Expression of Pilus-1 Type in Streptococcus pneumoniae

Streptococcus pneumoniae is a major cause of morbidity and mortality worldwide, and about 30% of the pneumococcal clinical isolates show type I pili-like structures. These long proteinaceous polymers extending from the bacterial surface are encoded by pilus islet 1 and play major roles in adhesion and host colonization. Pili expression is bistable and is controlled by the transcriptional activator RlrA. In this work, we demonstrate that the previously identified small noncoding RNA srn135 also participates in pilus regulation. Our findings show that srn135 is generated upon processing of the 5'-UTR region of rrgA messenger and its deletion prevents the synthesis of RrgA, the main pili adhesin. Moreover, overexpression of srn135 increases the expression of all pili genes and rises the percentage of piliated bacteria within a clonal population. This regulation is mediated by the stabilization of rlrA mRNA since higher levels of srn135 increase its half-life to 165%. Our findings suggest that srn135 has a dual role in pilus expression acting both in cis- (on the RrgA levels) and in trans- (modulating the levels of RlrA) and contributes to the delicate balance between pili expressing and non-expressing bacteria.This research was funded by Fondo de Investigación Sanitaria (FIS), grant number PI11/00656, and Ministerio de Economía, Industria y Competitividad, grant number BIO2017-82951-R.” P.A. was the recipient of a contract funded by the FIS project PI11/00656 and A.G.-S. was the recipient of a contract funded by Instituto de Salud Carlos III (CA10/1103).S

DNA methylation and adaptive response in forest tree species

Progressive increase of temperatures as well as longer seasonal drought periods revealed by climate studies correspond to fast environmental changes that forest species face with their actual genetic background. Natural selective processes cannot develop an adaptive response within this time frame. Thus the capability of forest tree species to adapt to the new environments will depend on their genetic background, but also rely on their phenotypic plasticity. Several reports have shown the involvement of epigenetic modifiers as the basis of the phenotypic plasticity, and in particular to the adaptation to abiotic stresses. DNA methylation (methylation of cytosine residues)is one the most important epigenetic modification in eukaryotes. Itis involved in specific biological processes such as gene transcription regulation, gene silencing, mobile element control or genome imprinting.Therefore, there is a great interest in analyzing cytosine methylation levels and distribution within the genom

Enriched mannose glycosylation contributes to Act d 2 allergenicity.

Allergens are responsible for the Th2 response in patients as part of complex mixtures of proteins, fatty acids and other molecules. Plant allergens have hitherto been included in several protein families that share no common biochemical features. Their physical, biochemical and immunological characteristics have been widely studied, but no definite conclusion has been reached about what makes a protein an allergen. N-glycosylation is characteristic of plant allergen sources but is not present in mammals

Unravelling mechanistic insights in the platinum-catalysed dihydroalkoxylation of allenes

The mechanism of the platinum-catalysed dihydroalkoxylation of allenes to give acetals has been studied experimentally and by computational methods. Our findings further explain divergent reactivity encountered for platinum- and gold-vinyl intermediates after the first nucleophilic attack onto the coordinated allene, as well as provide new details on the catalytic cycle with platinum, uncovering enol ethers as resting states of the catalytic cycle, a S(E)Ox process via Pt(V)-H as the final protodemetallation step after the second nucleophilic attack when neutral platinum complexes are used, and a fast acid promoted addition of methanol to enol ethers when cationic platinum complexes are employed

Use of Oral Sirolimus in Paediatric Patients with Serious Vascular Anomalies: Case Report

Background Pediatric vascular anomalies comprise a heterogeneous group of clinical disorders of varying severity. These anomalies are divided into vascular tumors or vascular malformations. Different therapeutic strategies have been used depending on the pathology in question. In recent years, mammalian target of rapamycin (mTOR) inhibitors have been explored as a therapeutic option in patients with complex vascular anomalies that fail to respond to conventional therapies. Case Report Two patients affected by complicated vascular anomalies were treated with sirolimus. Case 1: fourteen-month-old male patient with primary congenital lymphedema in the right arm. Case 2: boy aged two years and eight months, diagnosed with a non-respectable cervical aposiform hemangioendothelioma (KHE). Both patients received sirolimus at doses of 0.8 mg/m2/12 h during 12 and 13 months respectively. Monitoring plasma sirolimus concentrations made it possible to safely deal with problems associated with the medication. Both patients experiment an important improvement of their pathology, maintained after suspending treatment. No adverse effects related to treatment with sirolimus were observed. Conclusion Oral sirolimus proved to be an effective strategy in the treatment of complicated vascular anomalies in our pediatric population