Optoelectronic Properties of Carbon-Bound Boron Difluoride Hydrazone Dimers

The creation of dimeric boron difluoride complexes of chelating N-donor ligands is a proven strategy for the enhancement of the optoelectronic properties of fluorescent dyes. We report dimers based on the boron difluoride hydrazone (BODIHY) framework, which offer unique and sometimes unexpected substituent-dependent absorption, emission, and electrochemical properties. BODIHY dimers have low-energy absorption bands (lmax = 421 to 479 nm, e = 17,200 to 39,900 M−1 cm−1) that are red-shifted relative to monomeric analogues. THF solutions of these dimers exhibit aggregation-induced emission upon addition of water, with emission enhancement factors ranging from 5 to 18. Thin films of BODIHY dimers are weakly emissive as a result of the inner-filter effect, attributed to intermolecular p-type interactions. BODIHY dimers are redox-active and display two one-electron oxidation and two one-electron reduction waves that strongly depend on the N-aryl substituents. These properties are rationalized using density-functional theory calculations and X-ray crystallography experiments

Robot-aided assessment of wrist proprioception

Introduction: Impaired proprioception severely affects the control of gross and fine motor function. However, clinical assessment of proprioceptive deficits and its impact on motor function has been difficult to elucidate. Recent advances in haptic robotic interfaces designed for sensorimotor rehabilitation enabled the use of such devices for the assessment of proprioceptive function. Purpose: This study evaluated the feasibility of a wrist robot system to determine proprioceptive discrimination thresholds for two different DoFs of the wrist. Specifically, we sought to accomplish three aims: first, to establish data validity; second, to show that the system is sensitive to detect small differences in acuity; third, to establish test–retest reliability over repeated testing. Methodology: Eleven healthy adult subjects experienced two passive wrist movements and had to verbally indicate which movement had the larger amplitude. Based on a subject’s response data, a psychometric function was fitted and the wrist acuity threshold was established at the 75% correct response level. A subset of five subjects repeated the experimentation three times (T1, T2, and T3) to determine the test–retest reliability. Results: Mean threshold for wrist flexion was 2.15° ± 0.43° and 1.52° ± 0.36° for abduction. Encoder resolutions were 0.0075° (flexion–extension) and 0.0032° (abduction–adduction). Motor resolutions were 0.2°(flexion–extension) and 0.3° (abduction–adduction). Reliability coefficients were rT2-T1 = 0.986 and rT3-T2 = 0.971. Conclusion: We currently lack established norm data on the proprioceptive acuity of the wrist to establish direct validity. However, the magnitude of our reported thresholds is physiological, plausible, and well in line with available threshold data obtained at the elbow joint. Moreover, system has high resolution and is sensitive enough to detect small differences in acuity. Finally, the system produces reliable data over repeated testing

Optoelectronic, Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λmax = 427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended p-conjugated groups cause a red shift, whereas electron-withdrawing groups result in a blue shift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λPL = 525–578 nm) with quantum yields of up to 18% and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (Eox1 = 0.62–1.02 V vs. Fc/Fc+) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state

High-Resolution Anoscopy Surveillance After Anal Squamous Cell Carcinoma: High-Grade Squamous Intraepithelial Lesion Detection and Treatment May Influence Local Recurrence

BACKGROUND: Local recurrence is a significant risk after anal squamous cell carcinoma. OBJECTIVES: This study aimed to examine the occurrence of high-grade squamous intraepithelial lesions and local recurrence after anal cancer at surveillance with high-resolution anoscopy. DESIGN: This is a retrospective observational study. SETTING: This study was conducted at an anogenital neoplasia referral center. PATIENTS: There were 76 anal/perianal cancers from 1998 to 2018. Sixty-three patients were eligible and 3 were excluded, for a total of 60 patients; 35 of 60 (58%) patients were male. INTERVENTION: High-resolution anoscopy after chemoradiation or excision only for anal squamous cell carcinoma was performed. MAIN OUTCOME MEASURES: The primary outcomes measured were local recurrence and high-grade squamous intraepithelial lesion detection rates. RESULTS: Sixty patients, 27% HIV positive, underwent surveillance over a median 42 (range 7-240) months of follow-up. Seven had had a prior local recurrence at study entry so were analyzed separately. Thirty of 53 underwent chemoradiation (57%) and 23 of 53 underwent excision alone (43%); 33 had perianal cancer and 20 had anal cancer. Ten of 30 of the chemoradiation group had had stage 1 (33%) disease in comparison with 22 of 23 of the excision only group (96%, p < 0.001). OUTCOMES: High-grade squamous intraepithelial lesions were detected in 4 of 30 (13%) patients after chemoradiation and in 17 of 23 (74%) patients after excision only (p < 0.001). Twenty of 21 (95%) high-grade lesions were treated with ablation. Six of 7 (86%) patients with prior local recurrence had high-grade squamous intraepithelial lesions over a median of 21 months follow-up. One local recurrence (T1N0M0) occurred during surveillance after primary chemoradiation (0.56/1000 person-months), none occurred after excision only, and 2 of 7 with prior local recurrence developed further local recurrence (6.86/1000 person-months). All 3 local recurrences occurred after treatment of high-grade squamous intraepithelial lesions. There were no metastases, abdominoperineal excisions, or deaths from anal squamous cell carcinoma. LIMITATIONS: Retrospective data were used for this study. CONCLUSIONS: High-grade squamous intraepithelial lesions after anal squamous cell carcinoma are more common after excision only than after chemoradiation. Local recurrence is low in this high-resolution anoscopy surveillance group in which high-grade squamous intraepithelial disease was ablated. Excision of small perianal cancers appears safe; however, a subset of patients is at excess risk

Aroma characterization of mold resistant basewines for sparkling wine produced in a warm-temperate area at two different altitudes

In a recent context where consumers pay an increasing attention to sustainability and eco-friendly aspects in the decision-making process, the use of the resistant varieties in the winesector have returned to the attention. In this context, the use of mould-resistant grape varietieswould be an opportunity for sparkling wine producers as it can reduced the pesticideutilization in grape management and hence production costs. However, the use of the resistant varieties to produce the base wine may be strongly infl uenceddue to its requirements for a particular balance between sugars and acidity to ensure thequality of the fi nal product. In addition, the aromatic profi le of base wine plays a crucial rolein the perception of the quality of the sparkling wine. This work aims to study the volatile composition of base wines produced from fi ve resistantvarieties (Bronner, Solaris, Johanniter, Souvignier Gris, Vinera) cultivated in two experimentalvineyards located in Trentino (IT): one situated on the valley bottom and one in the hill. Theresults were comparing with those of Chardonnay, the main variety used in this areanowadays for this product, cultivated in the same plots. The volatiles were extracted from thebase wines and the GC-MS/MS analysis allowed to quantify the aromatic compoundsbelonging to six different chemical classes: acetates, ethyl esters, alcohols, fatty acids, terpenesand norisoprenoids. Among the varieties, Souvignier Gris was characterised by methyl salicylate and 1-hexanol,while Solaris stood out for the concentration of β-damascone, acetates and ethyl esters.Bronner showed signifi cant contents of some grape-derived metabolites, such as β-damasconeand linalool. This terpene was also present in higher quantities in Solaris and Johanniter.Regarding the location, acetates and ethyl esters were higher in base wines of the valleybottom and fatty acids, higher alcohols and terpenes in the hilly plot wines

A robot-aided visuomotor wrist training induces motor and proprioceptive learning that transfers to the untrained ipsilateral elbow

Background: Learning of a visuomotor task not only leads to changes in motor performance but also improves proprioceptive function of the trained joint/limb system. Such sensorimotor learning may show intra-joint transfer that is observable at a previously untrained degrees of freedom of the trained joint. Objective: Here, we examined if and to what extent such learning transfers to neighboring joints of the same limb and whether such transfer is observable in the motor as well as in the proprioceptive domain. Documenting such intra-limb transfer of sensorimotor learning holds promise for the neurorehabilitation of an impaired joint by training the neighboring joints. Methods: Using a robotic exoskeleton, 15 healthy young adults (18-35 years) underwent a visuomotor training that required them to make continuous, increasingly precise, small amplitude wrist movements. Wrist and elbow position sense just-noticeable-difference (JND) thresholds and spatial movement accuracy error (MAE) at wrist and elbow in an untrained pointing task were assessed before and immediately after, as well as 24&nbsp;h after training. Results: First, all participants showed evidence of proprioceptive and motor learning in both trained and untrained joints. The mean JND threshold decreased significantly by 30% in trained wrist (M: 1.26° to 0.88°) and by 35% in untrained elbow (M: 1.96° to 1.28°). Second, mean MAE in untrained pointing task reduced by 20% in trained wrist and the untrained elbow. Third, after 24&nbsp;h the gains in proprioceptive learning persisted at both joints, while transferred motor learning gains had decayed to such extent that they were no longer significant at the group level. Conclusion: Our findings document that a one-time sensorimotor training induces rapid learning gains in proprioceptive acuity and untrained sensorimotor performance at the practiced joint. Importantly, these gains transfer almost fully to the neighboring, proximal joint/limb system

FINJ: A Fault Injection Tool for HPC Systems

We present FINJ, a high-level fault injection tool for High-Performance Computing (HPC) systems, with a focus on the management of complex experiments. FINJ provides support for custom workloads and allows generation of anomalous conditions through the use of fault-triggering executable programs. FINJ can also be integrated seamlessly with most other lower-level fault injection tools, allowing users to create and monitor a variety of highly-complex and diverse fault conditions in HPC systems that would be difficult to recreate in practice. FINJ is suitable for experiments involving many, potentially interacting nodes, making it a very versatile design and evaluation tool.Comment: To be presented at the 11th Resilience Workshop in the 2018 Euro-Par conferenc