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Classical and ab initio molecular dynamics (MD) simulations have been performed for electrolytes based on LiTFSI and NaTFSI solutions in ethylene carbonate and its mono- and difluoro derivatives. Differences between electrolytes with Li+ or Na+ ions and the effect of fluorination on the structure and transport properties have been analyzed. The observed differences are related to the strength of Me+-carbonate binding, which is weaker for the Na+ cation and/or fluorinated solvents. Infrared spectra have been computed from ab initio MD and density functional tight binding (DFTB) MD trajectories. The changes of vibrational frequencies have been related to the local structure of the electrolyte and to interactions between salt cations and solvent molecules. The frequency shifts obtained from the AIMD simulations agree with experimental data, whereas DFTB underestimates Na+-carbonate interactions.

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A new, dynamic diastereomeric crystallization method has been developed, in which the mother liquors are continuously separated, racemized over a fixed-bed catalyst, and recirculated to the crystallizer in a resolution-racemization-recycle (R3) process. Separating the racemization from crystallization overcomes problems of using catalysts in situ, that suffer conflicting sets of conditions, inhibition, and separation. Continuous racemization has been achieved through the covalent attachment of [IrCp*I2]2 SCRAM catalyst to Wang resin solid support to give a fixed-bed catalyst. One tertiary and a variety of secondary optically enriched amines have been racemized efficiently, with residence times compatible with the crystallization (2.25-30 min). The catalyst demonstrates lower turnover (TOF) than the homogeneous analogue but with reuse shows a long lifetime (e.g., 40 recycles, 190 h) giving acceptable turnover number (TON) (up to 4907). The slow release of methylamine during racemization of N-methyl amines was found to inactivate the catalyst, which could be partially reactivated using hydroiodic acid. Dynamic crystallization is achieved in the R3 process through the continual removal of the more soluble diastereomer and supply of the less soluble one. The solubility of the diastereomers was determined, and the difference correlates to the rate of resolution but is also affected by the rates of racemization, crystal growth, and dissolution. A variety of cyclic and acyclic amine salts were resolved using mandelic acid (MA) and ditoluoyl tartaric acid (DTTA) with higher resolvability (S = yield × d.e.) than the simple diastereomeric crystallization alone. Comparing resolvabilities, resolutions were 1.6-44 times more effective with the R3 process than batch, though one case was worse. Further investigation of this revealed an unusual thermodynamic switching behavior: rac-N-methylphenethylamine was initially resolved as an (S,S)-bis-alkylammonium tartrate crystal but over time became the equivalent (R,S) salt. Thermal, mixing, concentration, stoichiometry, and seeding conditions were all found to affect the onset of the switching behavior which is only associated with difunctional resolving reagents.

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Chiral carbon dots (CDs) integrated the advantages of achiral CDs and the unique chiral property, which expand the prospect of the biological applications of CDs. However, the structure control and the origin of chirality for chiral CDs remain unclear. Herein, chiral CDs were obtained by thermal polymerization of chiral amino acids and citric acid, and their handedness of chirality could be controlled by adjusting the reaction temperature, which leads to different kinds of surface modifications. With aliphatic amino acids as a chiral source, all of the CDs that reacted at different temperatures (90-200 °C) have the same handedness of the chiral source. But with aromatic amino acids as a chiral source, CDs with maintained or inversed handedness compared with the chiral source could be obtained by adjusting the reaction temperature. Below a temperature of 120 °C, the chiral source was modified with CDs by esterification and transferred the handedness of chirality; at high temperatures (above 150 °C), which mainly connected by amidation accompanying with the formation of rigid structure generated by the π conjugation between the aromatic nucleus of chiral source and the carbon core of CDs, caused the inversing of the chiral signal. Further, we investigated the chiral effects of CDs on the glucose oxidase activity for a highly sensitive electrochemical biosensor.

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Early intensive applied behaviour analysis-based interventions are designed to support young autistic children’s learning and development. Unfortunately, the available evidence about the effectiveness of these interventions remains unclear. Several reviews have focused on the published findings rather than contacting the authors to collect and analyse data about the individual participants in the original studies. Also, most of the studies were carried out by groups involved in delivering the interventions leading to the potential bias in interpreting the results. Our research team (supported by an international advisory group) carried out an independent individual patient data review by collecting the original participant data from the authors of the studies, to examine the effectiveness of these interventions. The results suggested that early intensive applied behaviour analysis-based interventions might lead to some changes in children’s cognitive ability (intelligence quotient) and everyday life skills after 2 years, compared with standard treatments. However, all the studies had problems with the way they were designed. Also, few of the studies looked at outcomes that have been described as most important to autistic people or followed children beyond 2 years. We think that further systematic reviews of the existing evidence are unlikely to add to the findings of our review. Furthermore, we recommend that future research should investigate which types of supports and interventions are most effective for children and families, prioritising outcomes measures that are meaningful for the autism community and include, wherever possible, longer-term follow-up.

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The purpose of this study was to compare Korean immigrant families and Canadian families of children with autism in their perceptions and definitions of family quality of life. Interviews were done with 13 Korean immigrant parents and 12 Canadian parents of children with autism living in BC, Canada. For Korean immigrant families, three themes were identified: family cohesiveness, value orientation, and acceptance from society. For Canadian families, themes comprising family interactions, support, emotional well-being, individual characteristics, and comparisons to other families were essential elements in defining their family quality of life. The findings emphasize how differences in culture may impact how we understand and assess family functioning and quality of life. If research informing the development of these tools lacks cross-cultural perspectives, service providers and professionals may fail to address these families' unique needs.

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To identify patient-reported outcomes (PROs) and other clinical outcome measures (contrast sensitivity (CS), low-luminance visual acuity (LLVA) and reading acuity or reading speed (RA-RS)), relevant to patients with age-related macular degeneration (AMD) or diabetic retinopathy (DR), which would be recommended for use in clinical practice.

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Thyroid cancer is usually diagnosed both with imaging techniques and transdermal biopsy. Laboratory tests are also included in the initial work-up.

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In tonal languages such as Mandarin, both lexical tone and sentence intonation are primarily signaled by F0. Their F0 encodings are sometimes in conflict and sometimes in congruency. The present study investigated how tone and intonation, with F0 encodings in conflict or in congruency, are processed and how semantic context may affect their processing. To this end, tone and intonation identification experiments were conducted in both semantically neutral and constraining contexts. Results showed that the overall performance of tone identification was better than that of intonation. Specifically, tone identification was seldom affected by intonation information irrespective of semantic contexts. However, intonation identification, particularly question intonation, was susceptible to the final lexical tone identity and affected by the semantic context. In the semantically neutral context, questions ending with a rising tone and a falling tone were equally difficult to identify. In the semantically constraining context, questions ending with a falling tone were much better identified than those ending with a rising tone. This perceptual asymmetry suggests that top-down information provided by the semantically constraining context can play a facilitating role for listeners to disentangle intonational information from tonal information, but mainly in sentences with the lexical falling tone in the final position.

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Glioblastoma is invariably deadly and is characterized by extensive vascularization and macrophage-dominant immunosuppression; nevertheless, anti-angiogenesis has so far failed to prolong overall survival of patients. Regardless of the problems in clinical development, the rationale for the application of anti-angiogenics in glioblastoma remains. Areas covered: Mechanisms of glioblastoma resistance to anti-angiogenic agents are discussed, including vessel co-option and amplification of hypoxic signaling in response to vessel destruction. The modulation of GSC and tumor-associated macrophages by dysfunctional tumor vessels and by hypoxia are outlined. Pharmacologic approaches to sensitizing glioblastomas to anti-angiogenics and evidence for the cooperation of anti-angiogenics with immunotherapy approaches are summarized. Database search: https://pubmed.ncbi.nlm.nih.gov prior to December 12, 2020. Expert opinion: Despite drawbacks in the clinical development of vascular endothelial growth factor A (VEGF)-targeted agents, there is still rationale for the use of anti-angiogenics. The better understanding of vascular co-option and adverse effects of blood vessel destruction guides to improve strategies for vascular targeting. The pivotal role of the vasculature and of angiogenic factors such as VEGF for the induction and maintenance of immunosuppression in glioblastoma supports the use of anti-angiogenics in combination with immunotherapy. Proinflammatory repolarization of perivascular and perinecrotic tumor-associated macrophages is probably paramount for overcoming treatment resistance to virtually any treatment.

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Maturation failure remains a major clinical problem of distal arteriovenous fistula (AVF). Early failure (EF) is associated with the small size of the veins. For about 10 years we have used in more than 1000 fistulas, the Vessels Pre-Dilatation (VPD) to increase the recruitment of small veins for creating distal AVFs. The purpose of this study is to highlight if the VPD can reduce the incidence of EF or failure to mature (FTM) in AVFs created with small veins. Data of all the consecutive patients directly admitted to our Department for their first distal AVF from January to December 2019 were collected. The patients were divided in two groups, one with a vein diameter after the tourniquet ⩽2.0 mm (G1) and one >2 mm (G2). Both in G1 then in G2 the vessels had undergone VPD. Immediate failure (IF), EF, FTM, delayed or arrested maturation rate (DAM), unassisted AVFs and matured AFVs were evaluated. The patients recruited totalled 104, 37 in G1, and 67 in G2. The two groups were homogeneous in age, incidence of diabetes, obesity, heart disease, peripheral vasculopathy, and race. Female were more numerous in G1 (51% vs 12%, p < 0.001). In G1 and G2 occurred respectively 3 IF versus zero (p < 0.05), 10 EF (29%) versus 6 (9%) (p < 0.05), 6 DAM (16%) versus 6 (9%), 21 unassisted AVFs (57%) versus 57 (85%) (p < 0.01). Dividing the patients into groups of unassisted and assisted AVFs, female and low vein diameter are more represented in the assisted group. There were 32 matured AVFs (86%) in G1 and 65 (97%) in G2. In order to increase the incidence of the distal AVF, the PDV allows to include small veins. However, more patients require further interventions to achieve maturation of the fistula.