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Cu0-mediated atom transfer radical polymerization (ATRP) in aqueous media is extended to tertiary amine-pendant methacrylate polymers with poly([2-dimethylamino]ethyl methacrylate) (PDMAEMA) servin...

Two-coordinate carbene-M

The formation of dendrites is the bottleneck to harvest the high theoretical capacities of metal anodes such as Li, Na, Mg, and Zn batteries. The critical current density, interfacial instabilities, and the characteristic of the solid-electrolyte interface (SEI) layer play a major role in the formation mechanisms of dendrites. In this study, we investigated the impact of the SEI layer on the electroplating of zinc metals in organic and aqueous electrolytes by using electrochemical techniques coupled with electron microscopy and X-ray photoelectron spectroscopy. First, the electrochemical response of Zn plating in organic or aqueous electrolytes was compared with the ones for Li and Na metal plating by using analogous perchlorate salt dissolved in the same organic solvent. Under similar charge conditions, the cycle life of the metal electrodes was longer in the order of Zn (aqueous) > Li > Zn (organic) > Na. The impact of the SEI layer is then investigated by electroplating Zn in aqueous for 20 cycles, and then switching it to organic electrolytes and vice versa. In organic electrolytes, the cycle life of the PAO-Zinc is almost three-fold longer than the as-received zinc electrodes. PAO stands for pre-cycled in aqueous electrolyte for twenty times. Overall, our study demonstrated the impact of surface chemistry and morphology on the formation of Zn dendrites. The methodology established here can be used to study the impact of electrolyte salt and additives on the formation of dendrites on metal electrodes.

BACKGROUND: Procedural aspects and complications of gastrojejunostomy insertion are important considerations in the use of levodopa-carbidopa intestinal gel therapy (LCIG) and may limit uptake. We describe our experience of using per-oral image guided gastrojejunostomy (PIG-J) which avoids the need for endoscopy and routine sedation in percutaneous endoscopic gastrojejunostomy (PEG-J) and allows more secure tube placement than radiologically inserted gastrojejunostomy techniques. METHODS: We describe a case series of 32 patients undergoing PIG-J insertion for LCIG therapy in a single centre. Under local anaesthetic, a fluoroscopy-guided gastric puncture allows access for the guidewire which is then used to pull through the gastrostomy tube allowing for secure fixation, followed by placement of the gastrojejunal extension. RESULTS: Between December 2015 to April 2020, 32/34 patients referred for PIG-J underwent this procedure successfully, 2 cases unsuccessful due to technical considerations. One patient developed delirium following successful implantation. Ten patients (31%) required a replacement tube due to blockage or displacement within the first 12 months of placement, including 2 patients who needed more than one replacement. Minor complications occurred in 10 other patients (31%), including infection (9 patients); a small haematoma not requiring intervention who later developed an infection (1 patient); and peri-stomal acid leakage (1 patient). CONCLUSION: In summary, PIG-J insertion is safe with a similar complication rate to traditional PEG-J, well tolerated and effective for use in LCIG administration. This may widen access to LCIG for PD patients who may not be suitable or unable to tolerate PEG-J.

Due to the theragnostic potential of mesoporous silica nanoparticles (MSNs), these were extensively investigated as a novel approach to improve clinical outcomes. Boasting an impressive array of formulations and modifications, MSNs demonstrate significant in vivo efficacy when used to identify or treat myriad malignant diseases in preclinical models. As MSNs continue transitioning into clinical trials, a thorough understanding of the characteristics of effective MSNs is necessary. This review highlights recent discoveries and advances in MSN understanding and technology. Specific focus is given to cancer theragnostic approaches using MSNs. Characteristics of MSNs such as size, shape, and surface properties are discussed in relation to effective nanomedicine practice and projected clinical efficacy. Additionally, tumor-targeting options used with MSNs are presented with extensive discussion on active-targeting molecules. Methods for decreasing MSN toxicity, improving site-specific delivery, and controlling release of loaded molecules are further explained. Challenges facing the field and translation to clinical environments are presented alongside potential avenues for continuing investigations.

Through a field experiment set among licensed therapists (N = 425), we found nuanced evidence of heterosexist discrimination at the entry point of mental health services for a fictitious White, pre...

Method: We used consensual qualitative research (CQR) to investigate the experiences of therapist trainees who had a rupture with a client. Results: Of 21 trainees who were tracked weekly, 14 experienced a rupture and were interviewed 1 week after the rupture and again 2 weeks later about antecedents, repair attempts, and consequences. Trainees typically reported experiencing tension at the beginning of the rupture session and difficult emotions during the rupture (e.g., anger, depleted self-efficacy). Conclusion: Trainees typically tried to repair the rupture by using immediacy or facilitating exploration about the conflict. Trainees typically reported both negative (e.g., strained therapeutic relationship) and positive consequences (e.g., therapeutic work became more productive). Trainees seemed to be less aware of withdrawal than confrontational ruptures. Implications are that trainees could benefit from learning more about ruptures including how to regulate negative emotions toward clients and acquiring more rupture-repair tools, as well as realizing that ruptures can have some positive as well as negative aspects.

Rare-earth (RE) coordination polymers are infinitely tailorable to yield luminescent materials for various applications. Here we described the synthesis of a heterometallic rare-earth coordination compound ((CH 3 ) 2 SO) 3 (RE)NbO(C 2 O 4 ) 3 ((CH 3 ) 2 SO) = dimethylsulfoxide, DMSO, (C 2 O 2 = oxalate), (RE=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb). The structure was obtained from single crystal X-ray diffraction of the La analogue. The Nb˭O and DMSO terminal-bonding character guides assembly of an open framework structure with noncentrosymmetric RE-coordination geometry, and large spacing between the RE centers. A second structure was observed by PXRD for the smaller rare earths (Dy, Ho, Er, Yb); this structure has not yet been determined. The materials were further characterized using FTIR, and photoluminescence measurements. Characteristic excitation and emission transitions were observed for RE = Nd, Sm, Eu, and Tb. Quantum yield (QY) measurements were performed by exciting Eu and Tb analoges at 394 nm (QY 66%) and 464 nm (QY 71%) for Eu; and 370 nm (QY=40%) for Tb. We attribute the high QY and bright luminescence to two main structure-function properties of the system; namely the absence of water in the structure, and absence of concentration quenching.

The framework of intersectionality is a powerful analytical tool for making sense of how interlocking systems of privilege and oppression are experienced by individuals and groups. Despite the long history of the concept, intersectionality has only recently gained attention in psychology. We conducted a content analysis to assess counseling psychology's engagement with an intersectional perspective. All articles published in the Journal of Counseling Psychology (n = 4,800) and The Counseling Psychologist (n = 1,915) from their first issues until July 2016 were reviewed to identify conceptual and empirical work focused on intersectionality. A total of 40 articles were identified and examined for themes. Limitations and future directions are discussed. (PsycINFO Database Record

DNA vaccination is an attractive technology, based on its well-established manufacturing process, safety profile, adaptability to rapidly combat pandemic pathogens, and stability at ambient temperature; however an optimal delivery method of DNA remains to be determined. As pigs are a relevant model for humans, we comparatively evaluated the efficiency of vaccine DNA delivery in vivo to pigs using dissolvable microneedle patches, intradermal inoculation with needle (ID), surface electroporation (EP), with DNA associated or not to cationic poly-lactic-co-glycolic acid nanoparticles (NPs). We used a luciferase encoding plasmid (pLuc) as a reporter and vaccine plasmids encoding antigens from the Porcine Reproductive and Respiratory Syndrome Virus (PRRSV), a clinically-significant swine arterivirus. Patches were successful at inducing luciferase expression in skin although at lower level than EP. EP induced the cutaneaous recruitment of granulocytes, of MHC2posCD172Apos myeloid cells and type 1 conventional dendritic cells, in association with local production of IL-1β, IL-8 and IL-17; these local responses were more limited with ID and undetectable with patches. The addition of NP to EP especially promoted the recruitment of the MHC2posCD172Apos CD163int and CD163neg myeloid subsets. Notably we obtained the strongest and broadest IFNγ T-cell response against a panel of PRRSV antigens with DNA + NPs delivered by EP, whereas patches and ID were ineffective. The anti-PRRSV IgG responses were the highest with EP administration independently of NPs, mild with ID, and undetectable with patches. These results contrast with the immunogenicity and efficacy previously induced in mice with patches. This study concludes that successful DNA vaccine administration in skin can be achieved in pigs with electroporation and patches, but only the former induces local inflammation, humoral and cellular immunity, with the highest potency when NPs were used. This finding shows the importance of evaluating the delivery and immunogenicity of DNA vaccines beyond the mouse model in a preclinical model relevant to human such as pig and reveals that EP with DNA combined to NP induces strong immunogenicity.

Thermochemical ester bond cleavage in the phospholipid phosphatidylcholine (PC) was evaluated at reaction temperatures between ca. 20-60 °C using a series of lithium and zinc halides: lithium chloride, lithium bromide, lithium iodide, zinc chloride, zinc bromide, and zinc iodide. Hydroxides, produced via reaction between lithium or zinc halides and potassium hydroxide (KOH), attacked and cleaved selective phosphate and carbonyl ester bonds found in PC. Cleavage reaction efficacy was studied over a wide range of reaction conditions, 2 and 4 hours at 21, 30, 50 and 60 °C, using attenuated total reflectance and transmission FTIR (ATR-FTIR) spectroscopy. FTIR spectral analysis of neat (unreacted) and reacted PC showed qualitative and quantitative evidence of carbonyl and phosphonyl ester bond cleavage as indicated by the appearance and increase in the asymmetric carboxylate anion stretch (∼1577 cm-1) and symmetric phosphonyl dianion stretch (∼1010 cm-1) peaks, respectively. Ester cleavage in PC was demonstrated under extremely mild conditions using lithium hydroxide. In addition, the hydrolysis was found to be selective, leaving the zwitterionic phosphorylcholine group intact. Reaction time and temperature had little to no effect in promoting hydroxide attack on the ester bonds found in PC. Finally, the results of this study show that a non-enzymatic cleavage reaction methodology based on lithium hydroxide can be used for selective ester hydrolysis under extremely mild conditions. This ester hydrolysis method allows for a fast, low temperature, and selective cleavage using a chemical catalyst.

Session Poster P06 Vaccination; International audience

Critical consciousness (CC) has been heralded as an antidote to oppression. Developed by the Brazilian educator, Paulo Freire, CC represents the process by which individuals gain awareness of societal inequities and subsequently take action to dismantle the systems and institutions that sustain them. Empirically supported instruments intended to assess this important construct have only been recently introduced to the literature and have focused specifically on racism, classism, and heterosexism. The purpose of this project was to develop a psychometrically sound measure of CC that expands assessment into sexism, cissexism (genderism/transphobia), and ableism. Two studies with a total of 569 observations provided initial reliability and validity evidence on the Contemporary Critical Consciousness Measure II (CCCMII). Results from exploratory and confirmatory factor analyses suggest that the final 37-item CCCMII provides a general index of CC as well as assesses CC associated with sexism and ableism above and beyond the general factor. Results support the internal consistency and factor structure of the measure. Expected relationships between the CCCMII and existing measures of sexism, cissexism, and ableism provide evidence for the validity of the instrument. Limitations, future directions for research, and counseling implications are discussed. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

Scopo: Nell'ambito del progetto e-Rés@mont (Interreg Alcotra) è stato sviluppato un sistema di teleconsulto per migliorare l'assistenza sanitaria per turisti e residenti in montagna. Metodi: In 5 rifugi della Valle d'Aosta e presso 2 distretti sanitari (1533 - 3500 metri) 5 infermieri formati erano disponibili per valutare pazienti tramite raccolta della storia clinica e di parametri fisiologici, elettrocardiogramma, ecografia. Il sistema forniva un sistema di video-conferenza realizzato ad-hoc e permetteva, tramite tablet dotato di connessione mobile, di registrare e inviare le informazioni a un medico all'ospedale di Aosta. In caso di connessione non disponibile, un sistema di supporto alle decisioni forniva all'infermiere score di rischio per valutare la gravità e decidere di chiamare il sistema di emergenza. Tutti i dati registrati e salvati localmente alla riconnessione venivano inviati all'ospedale. Il sistema permetteva anche la valutazione automatica del male acuto di alta quota in base al Lake Louise Score. Risultati: Nel periodo estivo e invernale del 2017 sono stati effettuati 702 teleconsulti. Il 100% dei casi è stato correttamente ricevuto in ospedale e nei casi necessari è stata effettuata anche una valutazione specialistica. Il tempo medio di diagnosi è stato di 32 minuti: 333 codici bianchi, 356 gialli, 13 rossi; in 12 casi questo sistema ha evitato inappropriati interventi di soccorso in elicottero. Conclusioni: Il teleconsulto e-Res@mont è stato efficace nei trattamenti di emergenza, soprattutto per la riduzione dei tempi di valutazione in aree remote. Ulteriori studi sono necessari per valutare l'impatto sulla spesa sanitaria e sulle lista di attesa.

In recent years, there has been an increase in the attendance of people at high altitudes for both tourism and work, so high-altitude diseases represent a non-negligible public health problem. This research examined cross-sectional and prospective associations of lifestyle, individual risk factors, and acute mountain sickness (AMS) in a community-based sample recruited in the cross-border area (Switzerland, Italy, and France Alps). Questionnaires were administered in the five mountain locations in Aosta Valley between 1500 and 3500 m. Data were analyzed from 1002 subjects (males 68.7%, females 31.3%; mean age 42 ± 14 years) in a cross-sectional study (session T0) and from 1112 interviews in a longitudinal study on three consecutive days (session T1-T2-T3), n = 631 in T1, n = 300 in T2, and n = 181 in T3. According to Lake Louise Score self-reported, at session T0, 35.9% of the subjects were classified as mild AMS and 17.5% as moderate-severe AMS. Among the subjects enrolled in the prospective study, 36.5% were classified as mild or moderate/severe AMS in at least one of the 3 days. Predisposing factors to AMS detected in the prospective study were gender (male; odds ratio [OR] = 1.4, confidence interval [CI]: 2.9-11.7; p = 0.001), history of strenuous physical activity (>3 times per week) (OR = 3.1, CI: 2.1-8.7; p = 0.001), smoking >5 cigarettes per day (OR = 2.4, CI: 2.0-6.5; p = 0.001), difficulty sleeping (

Tobacco industry marketing is a primary factor influencing cigarette smoking behavior and the cigarette pack has become an important marketing vehicle for tobacco companies. Standardized "plain" cigarette packaging is advocated as a public health policy to prevent and reduce morbidity and mortality caused by smoking by reducing youth smoking initiation and promoting cessation among smokers. Plain packaging was implemented in Australia in December 2012, and several other countries are considering doing so, but each faces foreseeable legal resistance from opponents to such measures. Tobacco companies have challenged these public health policies, citing international trade agreements and intellectual property laws. Decision-making in these court cases will hinge in part on whether the evidence indicates the public health benefits of plain packaging outweigh any potential harm to tobacco manufacturers' interests. We reviewed the available evidence in support of plain packaging, finding evidence from observational, experimental, and population-based studies. Results indicate that plain packaging can reduce positive perceptions of smoking and dissuade tobacco use. Governments deciding to implement plain cigarette packaging measures can rely on this evidence to help make a strong case that plain packaging plays an important role in the context of comprehensive smoking prevention efforts.

QS-21, a saponin extracted from the tree Quillaja saponaria Molina, is a vaccine adjuvant which has been shown to elicit robust antibody and cell-mediated immune responses in a variety of preclinical and clinical studies [1]. Its purification from the natural source is a lengthy and difficult process. The commercially available saponin mixture Quil-A® is a fraction of the bark extract containing a variety of saponins, including QS-21. In order to facilitate access to QS-21 at laboratory-scale amounts, we propose here a method of purification of QS-21 starting from Quil-A®. In addition, we describe a protocol to appropriately formulate QS-21 into cholesterol-containing, neutral liposomes which are known to decrease QS-21's hemolytic activity while retaining the adjuvant effect. Methods for the physicochemical characterization of purified QS-21 and of the QS-21/liposome formulations are also described.

Metallacrowns are a versatile class of inorganic compounds with uses in several areas of chemistry. Students engage in a multiweek, upper-division inorganic laboratory that explores four different metallacrown compounds: FeIII(O2CCH3)3[9-MCFeIII(N)shi-3](CH3OH)3·3CH3OH, MnII(O2CCH3)2[12-MCMnIII(N)shi-4](C3H7NO)6·2C3H7NO, [(CH3)4N]2{CuII[12-MCCuII(N)shi-4]}·C3H7NO, and MnII(O2CCH3)2[15-MCMnIII(N)shi-5](C5H5N)6·CH3OH. The syntheses are straightforward, and the compounds are characterized by cyclic voltammetry, solid-state magnetic susceptibility, FT-IR, UV–vis, and paramagnetically shifted 1H NMR. Students are provided with a research-like experience in which they can successfully synthesize a metallacrown, conduct a literature search, develop characterization parameters based on departmental resources, interpret experimental results and compare them to the primary literature, analyze the crystallographic structures of the compounds, and finally present an oral seminar detailing their results and analysis.