α-(Aminomethyl)acrylates as acceptors in radical-polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping.

We demonstrate that α-(aminomethyl)acrylates are suitable acceptors for 1,4-additions of dialkylzincs in aerobic conditions. The air-promoted radical-polar crossover process involves the 1,4-addition of an alkyl radical followed by homolytic substitution at the zinc atom of dialkylzinc. Coordination of the nitrogen atom to zinc enables this SH2 process which represents a rare example of alkylzinc-group transfer to a tertiary α-carbonyl radical. The zinc enolate thus formed readily undergoes ß-fragmentation unless it is trapped by electrophiles in situ. Enolates of substrates having free N-H bonds undergo protodemetalation to provide ultimately the 1,4-addition adduct. In the presence of carbonyl acceptors, aldol condensation occurs providing overall a tandem 1,4-addition-aldol process. When a tert-butanesulfinyl moiety is present on the nitrogen atom, these electrophilic substitution reactions occur with good levels of chiral induction, paving the way to enantioenriched ß2-amino acids and ß2,2-amino acids.

Modular Access to N-Substituted cis 5-Amino-3-hydroxypiperidines.

A sequence of oxidative cleavage/reductive amination/reductive cleavage enables the preparation of N-substituted cis 5-amino-3-hydroxypiperidines from a readily available bicyclic adduct. This new route provides straightforward and versatile access to drug-relevant scaffolds or fragments.

Evidence of VP7 and VP4 intra-lineage diversification in G4P[8] Italian human rotaviruses.

Intragenotypic heterogeneity of co-circulating rotaviruses is remarkable. Sequence and phylogenetic analyses of the rotavirus VP7 and VP4 genes were performed on selected human G4P[8] strains identified in Parma, Northern Italy, during 2004-2005 and 2008-2012. All the strains clustered into lineages Ic (VP7) and P[8]-III (VP4) in different subclusters with a nucleotide sequence variation up to 4 %. VP7 and VP4 amino acid sequences of the Italian rotaviruses showed multiple changes with the corresponding reference strains as well as with vaccine viruses in the neutralizing epitopes. There is concern that the progressive intra-lineage diversification in the VP7 and VP4 through the accumulation of point mutations and amino acid differences between vaccine strains and currently circulating rotaviruses could generate, over the years, vaccine-resistant variants.

Individual and group treatment for patients with acquired brain injury in comprehensive rehabilitation.

PRIMARY OBJECTIVE: The aim of this study was to investigate the hypothesis that group rehabilitation is more effective than individual treatments and provides an improvement in clinical outcomes similar to that achieved by individual treatments alone. RESEARCH DESIGN: Two groups of patients were placed in different rehabilitation settings treated using the same rehabilitation approach. One received only individual treatments and the second group received a combination of both individual and group treatments. The independent variables were measured both pre- and post-treatment and compared between the two groups. METHODS AND PROCEDURES: Seventy-four patients treated with a comprehensive rehabilitation approach were divided into two groups: (a) individual treatment only and, (b) combined treatments (both individual and group). The outcome scales were LCF (Rancho Los Amigos Level of Cognitive Functioning), DRS (Disability Rating Scale) and FIM™ (Functional Independence Measure). RESULTS: The whole sample had obtained statistically significant improvements in all of the outcome scales: LCF (χ(2) = 45.26; p < 0.001), DRS (z = -3.92; p < 0.001) and FIM (z = -4.9; p < 0.001). The comparison between groups did not reveal any pre-treatment difference. Analysis of post-treatment, however, showed a greater improvement in the FIM scale for those in combined individual and group treatment (z = -0.2544, p = 0.01). CONCLUSIONS: Group rehabilitation integrated with individual treatments is more effective than individual treatments alone in improving independence measured by the FIM™ scale. Both groups had obtained statistically significant clinical improvements, the improvement in the FIM™ scale was significantly better in the combined treatment group.

Case report: detection of rotavirus RNA in the cerebrospinal fluid of a child with rotavirus gastroenteritis and meningism.

Although case reports have described detection of rotavirus (RV) in extraintestinal sites such as the liver, kidney, and central nervous system (CNS) of children with RV gastroenteritis, CNS localization in RV infection seems to be rare. RT-PCR and nucleotide sequencing detected a G1P[8] strain in the stool and cerebrospinal fluid (CSF) samples of a patient with concurrent RV-associated enteritis and CNS signs. Upon sequence analysis, the viruses detected in the CSF was identical to the virus detected in the stools. In the VP7- and VP4-based phylogenetic dendograms the strain clustered within the G1-Ic sub-lineage and the P[8]-III lineage. This study supports the hypothesis that RV infection was able to spread from the intestinal tract to the CNS, and likely played a role in the onset of neurological disease.

Functional MRI Studies in Friedreich's Ataxia: A Systematic Review.

Friedreich's ataxia (FRDA) is an inherited neurodegenerative movement disorder with early onset, widespread cerebral and cerebellar pathology, and no cure still available. Functional MRI (fMRI) studies, although currently limited in number, have provided a better understanding of brain changes in people with FRDA. This systematic review aimed to provide a critical overview of the findings and methodologies of all fMRI studies conducted in genetically confirmed FRDA so far, and to offer recommendations for future study designs. About 12 cross-sectional and longitudinal fMRI studies, included 198 FRDA children and young adult patients and, 205 healthy controls (HCs), according to the inclusion criteria. Details regarding GAA triplet expansion and demographic and clinical severity measures were widely reported. fMRI designs included motor and cognitive task paradigms, and resting-state studies, with widespread changes in functionally activated areas and extensive variability in study methodologies. These studies highlight a mixed picture of both hypoactivation and hyperactivation in different cerebral and cerebellar brain regions depending on fMRI design and cohort characteristics. Functional changes often correlate with clinical variables. In aggregate, the findings provide support for cerebro-cerebellar loop damage and the compensatory mechanism hypothesis. Current literature indicates that fMRI is a valuable tool for gaining in vivo insights into FRDA pathology, but addressing that its limitations would be a key to improving the design, interpretation, and generalizability of studies in the future.

A Bespoke Social Network for Deaf Women in Ecuador to Access Information on Sexual and Reproductive Health.

Many deaf women face the lack of numerous resources related to their personal development. The unavailability of proper information on Sexual and Reproductive Health (SRH), in particular, causes problems of sexually transmitted infections, unwanted pregnancy in adolescence, sexual violence, complications during pregnancy, etc. In response to this, we have created a social network that delivers SRH content (verified and validated by experts) to women with different degrees of hearing loss. The site features a recommender system that selects the most relevant pieces of content to deliver to each woman, driven by her individual preferences, needs and levels of knowledge on the different subjects. We report experiments conducted in Cuenca, Ecuador, between 2017 and 2018 with 98 volunteers from low- and middle-income settings, aiming to evaluate the quality and appeal of the contents, the coherence of the methodology followed to create them, and the effectiveness of the content recommendations. The positive results encourage the frequent creation of new content and the refinement of the recommendation logic as the cohort of users expands over time.

Solvatochromism and pH effect on the emission of a triphenylimidazole-phenylacrylonitrile derivative: experimental and DFT studies.

In this work, a study of the photophysical properties in different solvents and at different pH values of a luminogenic compound with a donor-π-acceptor (D-π-A) structure was carried out. The compound (Z)-3-(4-(4,5-diphenyl-1H-imidazol-2-yl)phenyl)-2-phenylacrylonitrile (2) was synthesized and characterized by SCXRD, FT-IR, 1H NMR, 13C NMR, EIMS, UV-Vis absorption and fluorescence. The SCXRD characterization reveals a monoclinic system, P21/c, with Z = 4 and an imidazole core having hydrogen bonding with respect to water molecules present in the asymmetric unit. It leads to a strong π-π-interaction in the solid state. The fluorescence λ max emission of the powder and thin film was observed at 563 nm and 540 nm respectively. Several degrees of positive solvatochromic fluorescence were observed due to different molecular conformations in various solvents. When the pH of the compound was changed with HCl or NaOH, a shift in the wavelength of emission was observed in a reversible manner. At pH 2, the λ max of emission was at 541 nm whereas at pH 14 there were two emissions at 561 nm and 671 nm. Due to their good emission in the solid state, compound 2 was tested as an emitting layer in OLEDs; the devices showed an acceptable performance with a luminance average of 450 cd m-2. The band gap was analyzed by optical absorption, cyclic voltammetry measurement and DFT calculations.

A low molecular weight OLED material: 2-(4-((2-hydroxyethyl)(methyl)amino)benzylidene)malononitrile. Synthesis, crystal structure, thin film morphology, spectroscopic characterization and DFT calculations.

2-(4-((2-Hydroxyethyl)(methyl)amino)benzylidene)malononitrile (HEMABM) was synthesized from 4-[hydroxymethyl(methyl)amino]benzaldehyde and propanedinitrile to obtain a low molecular weight fluorescent material with an efficient solid-state emission and electroluminescence properties comparable to the well-known poly(2-methoxy-5(2'-ethyl)hexoxyphenylenevinylene) (MEH-PPV). The HEMABM was used to prepare an organic light-emitting diode by a solution process. Despite the title compound being a small molecule, it showed optical properties and notable capacity to form a film with smooth morphology (10.81 nm) closer to that of polymer MEH-PPV (10.63 nm). The preparation of the device was by spin coating, the electrical properties such as threshold voltage were about 1.0 V for both HEMABM and MEH-PPV, and the luminance 1300 cd m-2 for HEMABM and 2600 cd m-2 for MEH-PPV. This low molecular weight compound was characterized by SCXRD, IR, NMR, and EI. Besides a quantitative analysis of the intermolecular interactions by PIXEL, density functional theory (DFT) calculations are reported.