The intense far-red absorption and emission features have made silicon phthalocyanines (SiPcs) distinct from the structurally related porphyrin analogues. Unlike most other phthalocyanines, SiPcs ...possess two additional axial bonds which reduce aggregation in solution and can be synthetically tailored, thereby creating further scope for modulation of optical, chemical and electronic properties. Multiple synthetic strategies have been employed for facile construction of symmetrical or unsymmetrical SiPc variants bearing desired substitutents at the axial and the aromatic ring positions. The overarching motive of this concise review article is to highlight and summarize the key synthetic routes and the fast-emerging applications of SiPcs in photouncaging techniques, photothermal and photoimmunotherapy, photovoltaics, optoelectronics and photocatalysis.
Their unique axial bonds and NIR optical properties have made silicon phthalocyanines (SiPcs) valuable compounds. Herein, we present key synthetic strategies and emerging applications of SiPcs over the past decade.
The Turkana Low-Level Jet (LLJ) was discovered in the early 1980s, yet there are still questions about the primary forcing mechanisms that drive and sustain the jet throughout the year. A few studies ...have addressed these questions, but most focus on numerical simulations of mechanical forcing mechanisms, such as orography, channeling flow, and monsoon background flow. No studies have shown the effects of thermal forcing from differential heating in the regions in and around the Turkana Channel. This paper uses National Centers for Environmental Prediction (NCEP) Climate Forecast System Reanalysis (CFSR) data and the National Aeronautics and Space Administration (NASA) Modern-Era Retrospective Analysis for Research and Applications (MERRA) data in order to analyze and find relationships between temperature gradients and the strength of the Turkana LLJ. In addition to temperature, potential temperature, divergence, wind magnitude, wind fields, and vertical motion are also examined. This analysis attempts to show that thermal forcing is one of the most important factors, if not the primary factor, in the initiation and maintenance of the jet and propose that more research and model simulations should be implemented to determine the contributions from thermal forcing.
Lead halide perovskites have emerged as a promising class of semiconductors; however, they suffer from issues related to lead toxicity and instability. We report results of a first-principles-based ...design of heavy-metal-based oxynitrides as alternatives to lead halide perovskites. We have used density functional theory calculations to search a vast composition space of ABO2N and ABON2 compounds, where B is a p-block cation and A is an alkaline, alkali-earth, rare-earth, or transition metal cation, and identify 10 new ABO2N oxynitride semiconductors that we expect to be formable. Specifically, we discover a new family of ferroelectric semiconductors with A 3+SnO2N stoichiometry (A = Y, Eu, La, In, and Sc) in the LuMnO3-type structure, which combine the strong bonding of metal oxides with the low carrier effective mass and small, tunable band gaps of the lead halide perovskites. These tin oxynitrides have predicted direct band gaps ranging from 1.6 to 3.3 eV and a sizable electric polarization up to 17 μC/cm2, which is predicted to be switchable by an external electric field through a nonpolar phase. With their unique combination of polarization, low carrier effective mass, and band gaps spanning the entire visible spectrum, we expect ASnO2N ferroelectric semiconductors will find useful applications as photovoltaics and photocatalysts as well as for optoelectronics.
Patient-centred communication and empathy are key enablers for patient-centred care. However, several studies suggest a downward trend regarding the empathic communication skills of physicians during ...medical residency. It is known that communication training can have a positive effect on patient-centred communication, empathy and relational skills. Training residents in patient-centred communication and empathy can be an opportunity to improve the patient-centred care. To evaluate the training a tri-focal perspective will be used.
A 3-day training was developed to improve residents' patient-centred communication and empathy skills at an academic medical health centre, in the Netherlands. The training included: (1) the basics of patient-centred communication and empathy (through presentations, scientific literature), (2) practicing with actors, and (3) reflecting on residents' video recorded consultations (by themselves and communication experts). A pilot study with a pre-post design was conducted to evaluate the training from patient and observer perspectives. Semi-structured interviews were used to get insight into residents' perspective. Nine residents from different specialities followed the training and enrolled in the pilot study. During two random days consultations between residents and patients were video recorded. Patients were asked to fill in two questionnaires, indicating their perspective on residents' empathy and communication skills before as well as after the consultation. All video recorded consultations were coded to rate residents' communication skills, empathy, computer use and agenda-setting. Statistical analysis were performed using multilevel analysis.
A total of 137 eligible patients took part in the pilot study. Trained residents showed significant improvement in patient-rated empathy scores. According to observers, residents' computer use improved significantly after the training. The communication skills of trained residents did not improve significantly. Agenda setting by residents showed a downward trend. Almost all residents were satisfied with the training, especially with the video-feedback.
A brief training significantly increased residents' empathy scores according to patients and significantly decreased residents' computer use according to observers. These findings indicate that the quality of patient-centred care can be improved by integrating patient-centred communication into residency programs, at an academic medical health centre. The ultimate goal is to structurally embed the training in residents' education program.
Objective Recently it was shown that the relative lack of diagnostic interventions conducted in women contributed to the negative association between female sex and diagnosed disease. However, it ...remains unknown whether women and men presenting with common somatic symptoms obtain disease diagnoses in an equal frequency after diagnostic interventions were performed in general practice. Methods We used primary care registration data from the Dutch Family Medicine Network. We used generalized linear mixed-effect models to assess the association between diagnostic interventions and disease diagnoses, when patients presented with common somatic symptoms. We analyzed sex-by-diagnostic intervention interaction terms to assess whether the association between diagnostic interventions and disease diagnoses differed between female and male patients. Results We analyzed 34,268 episodes of care (61.4% female). Physical examinations and specialist referrals were associated with more disease diagnoses (OR = 2.32; 95%CI = 2.17-2.49 and OR = 1.38; 95%CI = 1.27-1.49. respectively), whereas laboratory diagnostics were associated with fewer disease diagnoses (OR = 0.50; 95%C1 = 0.47-0.54). Interaction terms showed that women presenting with back pain, tiredness, arm and/or leg symptoms and tingling extremities received significantly fewer disease diagnoses after diagnostic interventions were performed than men. We found no significant interaction term that indicated that men receive fewer disease diagnosis after a diagnostic intervention than women. Conclusion Especially when women present with back pain, tiredness, arm and/or leg symptoms and tingling extremities, CPs should be aware that diagnostic interventions yield less disease diagnoses in female patients than in men. However, performing fewer diagnostic interventions in women with these symptoms will further exacerbate sex differences in diagnosed disease.
Multiferroic materials with simultaneous magnetic and ferroelectric ordering that persist above room temperature are rare. Using first-principles density functional theory calculations, we ...demonstrate fluorination of oxygen-deficient AA′Fe2O5 perovskites, where A and A′ are cations with +3 and +2 oxidation states, respectively, and have a layered ordering, as an effective strategy to obtain room-temperature multiferroics. We show that by controlling the size of the A and A′ cations, it is possible to stabilize a noncentrosymmetric phase arising due to the hybrid improper ferroelectricity mechanism, with polarization as high as 13 μC/cm2. The fluorination also stabilizes Fe in +3 oxidation state, which results in superexchange interactions that are strong enough to sustain magnetic order well above room temperature. We also show the presence of a magnetoelectric coupling wherein the switching mode that reverses the direction of the spontaneous polarization also affects the strength of the magnetic interactions. The results show that low-temperature fluorination of anion-deficient perovskites with layered cation ordering can be an effective approach to design new multiferroics.
Carbon nanotubes carry the promise of enhancing the poor out-of-plane mechanical performance of fiber reinforced polymer composites (FRPs). The present study is aimed to investigate the effect of ...adding multi-walled carbon nanotubes (MWCNTs) to the epoxy matrix of a carbon fiber reinforced composite (CFRP) on the composites’ damping performance, impact resistance and impact damage progression. Two sets of CFRPs with their matrices comprising MWCNTs–epoxy and neat epoxy, respectively, were fabricated and mechanically tested under tensile, Quasi-static punch test, vibration and intermediate velocity impact (IVI) environments. While the tensile failure strain of the carbon fiber reinforced epoxy–MWCNT composite increased, its tensile modulus and strength remained almost unaffected. Dynamic mechanical analysis (DMA) was employed to measure the damping performance of the two composite systems. The composite samples containing MWCNTs retained higher damping indicating their greater capability to attenuate impact shocks generated during an impact phenomenon. The samples were subjected to out-of-plane impact (at ∼100ms−1) from which the energy dissipation capacity of the composites was evaluated. Incorporating MWCNTs into the CFRP increased the absorbed impact energy by 21%. The punch test provided valuable information on the damage mechanics of the ballistic impact of the composite panels. It also contrasted the effect of high-stain-rate on the impact test. The consequences of adding MWCNTs to the matrix of CFRPs on the impact progressive damage and energy absorption were discussed in terms of the damage mechanisms and the dynamic damping behavior of the composites. To better comprehend the effect of adding CNTs on the impact damage mechanisms, X-ray radiography was carried out on the impacted panels. It was shown that the addition of MWCNTs to the matrix of a CFRP improves its inter- and intra-laminar mechanical performance yielding a better impact resistance. It was confirmed that the impact failure behavior of the studied composite systems could be predicted from the quasi-static and dynamic mechanical tests.
Coronavirus disease 2019 (COVID-19) results in debilitating long-term symptoms, often referred to as Post-Acute Sequelae of SARS-CoV-2 Infection (PASC), in a substantial subgroup of patients. One of ...the most prevalent symptoms following COVID-19 is severe fatigue. Prompt delivery of cognitive behavioural therapy (CBT), an evidence-based treatment that has shown benefit in reducing severe fatigue in other conditions, may reduce post-COVID-19 fatigue. Based on an existing CBT protocol, a blended intervention of 17 weeks, Fit after COVID, was developed to treat severe fatigue after the acute phase of infection with SARS-CoV-2.
The ReCOVer study is a multicentre 2-arm randomised controlled trial (RCT) to test the efficacy of Fit after COVID on severe post-infectious fatigue. Participants are eligible if they report severe fatigue 3 up to and including 12 months following COVID-19. One hundred and fourteen participants will be randomised to either Fit after COVID or care as usual (ratio 1:1). The primary outcome, the fatigue severity subscale of the Checklist Individual Strength (CIS-fatigue), is assessed in both groups before randomisation (T0), directly post CBT or following care as usual (T1), and at follow-up 6 months after the second assessment (T2). In addition, a long-term follow-up (T3), 12 months after the second assessment, is performed in the CBT group only. The primary objective is to investigate whether CBT will lead to a significantly lower mean fatigue severity score measured with the CIS-fatigue across the first two follow-up assessments (T1 and T2) as compared to care as usual. Secondary objectives are to determine the proportion of participants no longer being severely fatigued (operationalised in different ways) at T1 and T2 and to investigate changes in physical and social functioning, in the number and severity of somatic symptoms and in problems concentrating across T1 and T2.
This is the first trial testing a cognitive behavioural intervention targeting severe fatigue after COVID-19. If Fit after COVID is effective in reducing fatigue severity following COVID-19, this intervention could contribute to alleviating the long-term health consequences of COVID-19 by relieving one of its most prevalent and distressing long-term symptoms.
Netherlands Trial Register NL8947 . Registered on 14 October 2020.
Objective Women are reported to consult general practitioners (GPs) more frequently than men. However, previous studies on sex differences in help-seeking behaviour for somatic symptoms do not ...distinguish between sex and gender, do not account for sex differences in presented symptoms, and are often conducted in clinical settings, automatically excluding non-help seekers. Therefore, we assess the independent associations of sex and gender with primary care help-seeking for somatic symptoms in the general population. Method Records from the longitudinal population-based Lifelines Cohort Study were linked to routine electronic health records from GPs. We applied generalized linear mixed-effect models to assess whether participants' sex and gender, operationalized by a novel gender index, were associated with consulting GPs, while adjusting for participants' presented symptom(s), age, presence of chronic disease and educational level. In post-hoc analyses we assessed whether gender-related variables, such as mean paid working days per week, were associated with help-seeking behaviour. Results Of the 20,187 individuals with linked data. 8325 participants (67.5% female; mean age = 44.5 SD = 12-9)) reported at least one new-onset somatic symptom and 255 (3.1%) hereof consulted the GP. Female sex was positively associated with consulting the GP (OR = 1.78; 95X01 = 1.13-2.80), whereas feminine gender was not significantly associated with this (OR = 0.67; 95X01 = 0.39-1.16). More paid working days negatively associated with help-seeking (OR = 0.95; 95X01 = 0.91 -0.98). Conclusion The results suggest that female sex rather than feminine gender associated with primary care help-seeking behaviour for somatic symptoms. Nevertheless, clinicians should be aware that gender-related variables, such as mean paid working days may associate with help-seeking behaviour.
Defect engineering is a strategy that has been widely used to design active semiconductor photocatalysts. However, understanding the role of defects, such as oxygen vacancies, in controlling ...photocatalytic activity remains a challenge. Here, we report the use of chemically triggered fluorogenic probes to study the spatial distribution of active regions in individual tungsten oxide nanowires using super-resolution fluorescence microscopy. The nanowires show significant heterogeneity along their lengths for the photocatalytic generation of hydroxyl radicals. Through quantitative, coordinate-based colocalization of multiple probe molecules activated by the same nanowires, we demonstrate that the nanoscale regions most active for the photocatalytic generation of hydroxyl radicals also possess a greater concentration of oxygen vacancies. Chemical modifications to remove or block access to surface oxygen vacancies, supported by calculations of binding energies of adsorbates to different surface sites on tungsten oxide, show how these defects control catalytic activity at both the ensemble and single-particle levels. These findings reveal that clusters of oxygen vacancies activate surface-adsorbed water molecules toward photo-oxidation to produce hydroxyl radicals, a critical intermediate in several photocatalytic reactions.
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