A US perspective on closing the carbon cycle to defossilize difficult-to-electrify segments of our economy.

Electrification to reduce or eliminate greenhouse gas emissions is essential to mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult to electrify and/or will continue to use carbon as a key component, including areas in aviation, heavy-duty and marine transportation, and the chemical industry. In this Roadmap, we explore how multidisciplinary approaches will enable us to close the carbon cycle and create a circular economy by defossilizing these difficult-to-electrify areas and those that will continue to need carbon. We discuss two approaches for this: developing carbon alternatives and improving our ability to reuse carbon, enabled by separations. Furthermore, we posit that co-design and use-driven fundamental science are essential to reach aggressive greenhouse gas reduction targets.

The effects of language proficiency and awareness of time limit in animated vs. text-based situational judgment tests.

BACKGROUND: Situational Judgment Tests (SJTs) are commonly used in medical school admissions. However, it has been consistently found that native speakers tend to score higher on SJTs than non-native speakers, which can be particularly problematic in the admission context due to the potential risk of limited fairness. Besides type of SJT, awareness of time limit may play a role in subgroup differences in the context of cognitive load theory. This study examined the influence of SJT type and awareness of time limit against the background of language proficiency in a quasi high-stakes setting. METHODS: Participants (N = 875), applicants and students in healthcare-related study programs, completed an online study that involved two SJTs: one with a text-based stimulus and response format (HAM-SJT) and another with a video-animated stimulus and media-supported response format (Social Shapes Test, SST). They were randomly assigned to a test condition in which they were either informed about a time limit or not. In a multilevel model analysis, we examined the main effects and interactions of the predictors (test type, language proficiency and awareness of time limit) on test performance (overall, response percentage). RESULTS: There were significant main effects on overall test performance for language proficiency in favor of native speakers and for awareness of time limit in favor of being aware of the time limit. Furthermore, an interaction between language proficiency and test type was found, indicating that subgroup differences are smaller for the animated SJT than for the text-based SJT. No interaction effects on overall test performance were found that included awareness of time limit. CONCLUSION: A SJT with video-animated stimuli and a media-supported response format can reduce subgroup differences in overall test performance between native and non-native speakers in a quasi high-stakes setting. Awareness of time limit is equally important for high and low performance, regardless of language proficiency or test type.

A Mathematical Algorithm for Dried Blood Spot Quality Assessment and Results concerning Quality from a Newborn Screening Program.

BACKGROUND: In addition to newborn screening, dried blood spots (DBSs) are used for a wide variety of analytes for clinical, epidemiological, and research purposes. Guidelines on DBS collection, storage, and transport are available, but it is suggested that each laboratory should establish its own acceptance criteria. METHODS: An optical scanning device was developed to assess the quality of DBSs received in the newborn screening laboratory from 11 maternity wards between 2013 and 2018. The algorithm was adjusted to agree with the visual examination consensus of experienced laboratory personnel. Once validated, the algorithm was used to categorize DBS specimens as either proper or improper. Improper DBS specimens were further divided based on 4 types of specimen defects. RESULTS: In total, 27 301 DBSs were analyzed. Compared with an annual DBS rejection rate of about 1%, automated scanning rejected 26.96% of the specimens as having at least one defect. The most common specimen defect was multi-spotting (ragged DBS, 19.13%). Among maternity wards, improper specimen rates varied greatly between 5.70% and 49.92%. CONCLUSIONS: Improper specimen rates, as well as the dominant type of defect(s), are mainly institution-dependent, with various maternity wards consistently showing specific patterns of both parameters over time. Although validated in agreement with experienced laboratory personnel consensus, automated analysis rejects significantly more specimens. While continuous staff training, specimen quality monitoring, and problem-reporting to maternities is recommended, a thorough quality assessment strategy should also be implemented by every newborn screening laboratory. An important role in this regard may be played by automation in the form of optical scanning devices.

Beyond n-dopants for organic semiconductors: use of bibenzo[d]imidazoles in UV-promoted dehalogenation reactions of organic halides.

2,2'-Bis(4-dimethylaminophenyl)- and 2,2'-dicyclohexyl-1,1',3,3'-tetramethyl-2,2',3,3'-tetrahydro-2,2'-bibenzo[d]imidazole ((N-DMBI)2 and (Cyc-DMBI)2) are quite strong reductants with effective potentials of ca. -2 V vs ferrocenium/ferrocene, yet are relatively stable to air due to the coupling of redox and bond-breaking processes. Here, we examine their use in accomplishing electron transfer-induced bond-cleavage reactions, specifically dehalogenations. The dimers reduce halides that have reduction potentials less cathodic than ca. -2 V vs ferrocenium/ferrocene, especially under UV photoexcitation (using a 365 nm LED). In the case of benzyl halides, the products are bibenzyl derivatives, whereas aryl halides are reduced to the corresponding arenes. The potentials of the halides that can be reduced in this way, quantum-chemical calculations, and steady-state and transient absorption spectroscopy suggest that UV irradiation accelerates the reactions via cleavage of the dimers to the corresponding radical monomers.

German Physicians and Medical Students Do Not Represent the Population They Serve.

Medical professionals who represent the communities they serve are in a better position to understand patients' social circumstances and communicate in a more patient-centered way. International studies show limited diversity and underrepresentation of certain social groups in the population of physicians and medical students. We designed an observational study to investigate the cultural and socio-economic diversity of physicians and medical applicants in comparison to the general population in Germany. We invited 15,195 physicians in Hamburg and 11,287 medical applicants in Germany to participate in an online survey between June and August 2022. The lower three quintiles of objective socio-economic background (SEB) were vastly underrepresented in all subsamples of the study and in particular amongst applicants and students admitted in Hamburg: 57.9% of physicians and 73.8% of medical students in Hamburg originate from the top quintile of SEB. The Turkish and Polish communities were particularly underrepresented in the group of physicians from Hamburg and medical applicants and students in Germany (p = 0.02; p < 0.001). In line with existing evidence, the vast majority of physicians and medical students come from the most affluent households when entering medical school. Widening participation strategies are needed to facilitate fairer access to the study of medicine in Germany.

On the Temperature Sensitivity of Electrochemical Reaction Thermodynamics.

Herein, we report a method to estimate the thermodynamic potentials of electrochemical reactions at different temperatures. We use a two-term Taylor series approximation of thermodynamic potential as a function of temperature, and we calculate the temperature sensitivity for a family of twenty seven known half reactions. We further analyze pairs of cathode and anode half-cells to pinpoint optimal voltage matches and discuss implications of changes in temperature on overall cell voltages. Using these observations, we look forward to increased interest in temperature and idealized half-reaction pairing as experimental choices for the optimization of electrochemical processes.

Persistent severe visual field impairment is associated with obesity and tumour invasiveness, but not with pituitary dysfunction, in patients with craniopharyngioma.

PURPOSE: Craniopharyngiomas (CP) are benign tumours of the sellar region. Hypopituitarism, visual deficits, hypothalamic damage with consequent obesity and related increased cardiovascular risk, are complications due to the tumour itself or secondary to treatment strategy. We retrospectively correlated visual field status with clinical, neuroradiological, histopathological features and management strategy, in a single-centre cohort of patients with CP. METHODS: Thirty-four patients (16 M; median age 27.2 ± 21.8 yrs) with CP were included. We evaluated visual field status, assessed by means of standard automated perimetry and expressed as mean deviation (MD), at last follow-up visit (median 14 ± 11.7 yrs). MD has been correlated with clinical, radiological, histological data and treatment modalities. RESULTS: In univariate analysis worst eye MD was significantly associated with panhypopituitarism (p 0.010). In multivariable linear regression, panhypopituitarism (p 0.008), CP recurrence (p 0.020) and DI (p 0.004) were found to be the main independent predictors of a worse visual field outcome. When stratifying patients according to the degree of visual field impairment (MD < -12 dB Vs MD > -12 dB), the main independent predictors of worse visual field outcome were older age at diagnosis (p 0.010), CP histological subtype (p 0.004), invasiveness (p 0.04), CP recurrence (p 0.035), DI (p 0.002) and weight at last follow-up (p 0.012). CONCLUSION: In CP patients the long-term ophthalmological impairment is frequent, especially at older age, and strictly related to tumour invasiveness and recurrence, and associated to pituitary disfunction and obesity.

Method comparison between Alinity hq and Sysmex XT-4000i in an emergency laboratory.

Due to technological advancements, haematology analysers are becoming increasingly more complex. Before introducing new analyzers, laboratories must compare the agreement between the new and the old instruments. This study aimed to quantify the method agreement between Sysmex XT-4000i and Alinity hq analysers in order to establish whether they can be used interchangeably. A total of 415 complete blood counts (CBC) from adult patients of the Emergency Clinical County Hospital of Târgu Mureș, Romania, were analysed within 4 h from the collection on Sysmex XT-4000i (considered the reference method), then on Alinity hq. Statistical analysis consisted of outlier removal, Spearman Correlation, Bland-Altman test, and Passing-Bablok regression. For each CBC parameter, the analytical difference between methods was compared with the Reference Change Value (RCV) at medical decision levels (MDL). Despite using different technologies, the instruments have a good agreement regarding cell differentiation and counting. Cell counting and haemoglobin measurement showed a good agreement at all (Medical Decision Limits) MDLs. The analytical difference between methods surpassed the (Reference Change Value) RCV with 1.2% at the 14% MDL of HCT and with 0.2% at the 100 fL MDL of MCV. This study can not tell whether Sysmex or Alinity is superior, only if the two methods agree. The poorer agreement observed for RBC indices, especially MCHC, suggests an accumulation of differences caused by the different working principles of the two methods. However, it is reasonable to assume that such small differences will not affect clinical decision-making and patient outcome.

Recent synthetic methods involving carbon radicals generated by electrochemical catalysis.

Driven by a resurgence of interest in electrode-driven synthetic methods, this paper covers recent activity in the field of mediated electrochemical and photoelectrochemical bond activation, inclusive of C-H, C-C, C-N, and other C-heteroatom bonds.

Predictive energetic tuning of C-Nucleophiles for the electrochemical capture of carbon dioxide.

This work maps the thermodynamics of electrochemically generated C-nucleophiles for reactive capture of CO2. We identify a linear relationship between the pKa, the reduction potential of a protonated nucleophile (E red ), and the nucleophile's free energy of CO2 binding ( Δ G b i n d ). Through synergistic experiments and computations, this study establishes a three-parameter correlation described by the equation Δ G b i n d = - 0.78 p K a + 4.28 E r e d + 20.95 for a series of twelve imidazol(in)ium/N-heterocyclic carbene pairs with an R 2 of 0.92. The correlation allows us to predict the Δ G b i n d of C-nucleophiles to CO2 using reduction potentials or pKas of imidazol(in)ium cations. The carbenes in this study were found to exhibit a wide range CO2 binding strengths, from strongly CO2 binding to nonspontaneous. This observation suggests that the Δ G b i n d of imidazol(in)ium-based carbenes is tunable to a desired strength by appropriate structural changes. This work sets the stage for systematic energetic tuning of electrochemically enabled reactive separations.

Reliability and validity of new online selection tests for midwifery students.

BACKGROUND AND OBJECTIVE: Newly created midwifery bachelor programmes attract an increasing number of applicants. Hence, educators have moved away from traditional non-standardised selection methods and started developing new tools for the admission of students. Researchers have expressed concerns around the validity of such selection measures and their ability to identify the appropriate candidates. The objective of this study was to develop and implement selection procedures for a new midwifery Bachelor of Science degree in Hamburg, Germany, and assess their psychometric properties. DESIGN: This is a mixed-methods longitudinal study on the reliability, validity and acceptability of newly developed selection criteria. SETTING: The newly established midwifery bachelor of science in Hamburg, Germany. PARTICIPANTS: Upon completion of their online application, all midwifery applicants were invited by email to participate in our research project and thereby informed of its purpose and voluntary nature of their participation. The total number of candidates who took the test was 366, of which 309 agreed to take part in this study. Sixty-five applicants were eventually admitted to the midwifery Bachelor programme, of which 59 were included in the study. MEASUREMENTS AND FINDINGS: We developed two tests for cognitive ability (HAM-Mid I and II) and adapted one test for personal and professional characteristics (Casper - Computer-based Assessment for Sampling Personal Characteristics). Due to the Covid pandemic, we implemented the tests online instead of on site as initially planned. HAM-Mid I had the lowest (Cronbach's Alpha = 0.38) whereas Casper had the highest internal consistency (Cronbach's Alpha = 0.77) of all three tests. Age, previous academic achievement and native tongue were significantly associated with applicants' performance on HAM-Mid II and Casper admission tests. HAM-Mid II was associated with students' performance in the first year midwifery exam (r = 0.31, p < 0.05). Overall evaluation of HAM-Mid II and Casper was good while HAM-Mid I received a more negative feedback. KEY CONCLUSIONS: Evidence on the reliability and predictive validity of the newly developed tests suggests that the applied admission criteria are appropriate for an objective selection of bachelor midwifery students. IMPLICATIONS FOR PRACTICE: The interests of university and clinical stakeholders of a midwifery bachelor degree can be represented through the development of tests for the assessment of cognitive ability and personal and professional characteristics.

Attitude and communication skills of German medical students.

OBJECTIVE: While the development of communication competencies in medical schools plays a pivotal role in the curriculum, studies show that students' communication skills and patient-centred attitudes may vary based on gender and ethnicity. The goal of this study was to investigate the socio-demographic factors that influence medical students' communication abilities and, more specifically, to what extent their attitude toward communication skills learning and patient orientation associate with communication abilities. Our population included medical students admitted in 2017. Used tools included a communication score, the patient-provider orientation and communication skills attitudes scales. RESULTS: Three hundred and sixty-five students participated in the study (56.4% female, 85.2% German native speakers, mean age 24.2 ± 3.5 years). Female and German native speaking students had a better communication skills OSCE performance, were more patient-oriented and had more positive attitudes toward communication skills learning than male and non-native speaking students. There was a significant association between gender, native tongue, attitudes towards communication skills learning and communication skills OSCE performance. In conclusion, to support medical students to improve their communication proficiency and attitudes towards the importance of clear communication and patient-oriented care, medical educators should consider teaching and assessment strategies that address socio-cultural aspects of communication.

How good are medical students at communicating risk? An implementation study at three German medical schools.

OBJECTIVE: To assess the objective and subjective risk communication skills of medical students in three universities in Germany METHODS: We developed a risk communication skills Objective Structured Clinical Examination (OSCE) station and implemented it in three medical schools in Germany. 596 students contributed data to a risk communication checklist and a risk communication self-assessment. Multiple linear regression models were used to identify factors associated with the risk communication OSCE performance. RESULTS: Participants in our study achieved on average 73.5% of the total risk communication skills score, which did not differ between locations (F(2-595) = 1.96; p = 0.142). The mean objective performance of students who assessed their skills as poor was significantly worse than the performance of students who assessed their skills as good (t(520) = -5.01, p < 0.001). The risk communication skills score was associated with native language but not with gender nor General Point Average (p < 0.001). CONCLUSIONS: Medical students demonstrated acceptable risk communication skills scores and were able to self-assess their performance. However, selected communication techniques should be re-emphasised in the undergraduate medical curriculum. PRACTICE IMPLICATIONS: Our research identified shortcomings in particular subgroups that can be addressed through tailored curriculum interventions.

Humoral Immune Response to SARS-CoV-2 Vaccination after a Booster Vaccine Dose in Two Kidney Transplant Recipients with Fabry Disease and Variable Secondary Immunosuppressive Regimens.

The urgent need to fight the COVID-19 pandemic has accelerated the development of vaccines against SARS-CoV-2 and approval processes. Initial analysis of two-dose regimens with mRNA vaccines reported up to 95% efficacy against the original strain of the SARS-CoV-2 virus. Challenges arose with the appearance of new strains of the virus, and reports that solid organ transplant recipients may have reduced vaccination success rates after a two-dose mRNA vaccination regimen encouraged health authorities to recommend a booster in immunocompromised patients. Fabry disease is an X-linked inherited lysosomal disorder, which may lead to chronic end-stage renal disease. We report on two patients with advanced Fabry disease, renal graft and adjunctive immunosuppressive therapies who exhibited variable humoral vaccination-related immune responses against SARS-CoV-2 after three vaccine doses. The first patient developed mild COVID-19 infection, while the second patient did not seroconvert after three shots of an mRNA vaccine. Both cases emphasize that patients with Fabry disease and renal graft are susceptible to develop a weak response to COVID-19 vaccination and highlight the importance of maintaining barrier protection measures. Vaccination of family members should be encouraged to lower the risk of viral transmission to immunocompromised, transplanted patients, including vaccinated ones.

Application-specific thermodynamic favorability zones for direct air capture of carbon dioxide.

An increased interest in the capture and conversion of carbon dioxide into valuable chemical products is fueled by impending societal and ecological consequences of increasing CO2 concentration in the atmosphere. This work utilizes Lackner's thermodynamic calculations for the capture of carbon dioxide from the atmosphere based on a single sorbent approximation to map thermodynamic favorability zones compatible with various applications. When a minimal amount of CO2 is removed from the air stream, -4.64 kcal mol-1 is estimated as the maximum free energy of binding for sorption to occur in atmospheric conditions at 1 atm pressure and room temperature. When complete scrubbing of CO2 from a dilute source is desired, a more negative free energy of sorption is needed, with an estimated -10.92 kcal mol-1 required for close to complete CO2 removal from the stream.

Long-term cardiometabolic outcome in patients with pituitary adenoma diagnosed in chilhood and adolescence.

PURPOSE: Pituitary adenomas (PAs) rarely occur in childhood and adolescence. Management of PAs in this critical age can be particularly challenging considering the auxological sequelae and potential long-term cardiometabolic consequences. We aimed to describe the clinical characteristics of patients with PA aged < 18years at diagnosis and during long-term follow-up, focusing on the prevalence of cardio-metabolic comorbidities and the impact of different therapeutic strategies. METHODS: Clinical data at diagnosis and at last follow-up visit (mean 10.3 ± 9.2 years) of 101 patients aged < 18 years with PA, referred to our University Hospital from 1990 to 2017, were retrospectively evaluated. RESULTS: At diagnosis, 11.9% of patients presented with pituitary hormone deficiencies, whose number was positively correlated with pituitary tumor diameter (p < 0.001). At diagnosis, 26.7% of patients were overweight and 15.8% were obese. In patients with hypercortisolism or GH excess the prevalence of obesity was more than 2-fold greater than in general population. No correlation was found between pituitary tumor size and BMI. At baseline, the greater the number of pituitary hormone deficits, the higher BMI (p = 0.039). In prolactinoma patients still on medical therapy at last visit, BMI was higher than at baseline. CONCLUSION: We found an increased prevalence of overweight/obesity only in pediatric and adolescent patients with GH- or ACTH-secreting PA. Regarding cardio-metabolic comorbidities other than obesity/overweight, we have not found anything worth of mention. The remission of hypercortisolism positively impacted on BMI, while medical therapy in patients with prolactinoma seemed unable to avoid weight gain, suggesting a careful metabolic management of these patients.

Chemical and Electrochemical Recycling of End-Use Poly(ethylene terephthalate) (PET) Plastics in Batch, Microwave and Electrochemical Reactors.

This work describes new methods for the chemical recycling of end-use poly(ethylene terephthalate) (PET) in batch, microwave and electrochemical reactors. The reactions are based on basic hydrolysis of the ester moieties in the polymer framework and occur under mild reaction conditions with low-cost reagents. We report end-use PET depolymerization in refluxing methanol with added NaOH with 75% yield of terephthalic acid in batch after 12 h, while yields up to 65% can be observed after only 40 min under microwave irradiation at 85 °C. Using basic conditions produced in the electrochemical reduction of protic solvents, electrolytic experiments have been shown to produce 17% terephthalic acid after 1 h of electrolysis at -2.2 V vs. Ag/AgCl in 50% water/methanol mixtures with NaCl as a supporting electrolyte. The latter method avoids the use of caustic solutions containing high-concentration NaOH at the outset, thus proving the concept for a novel, environmentally benign method for the electrochemical recycling of end-use PET based on low-cost solvents (water and methanol) and reagents (NaCl and electricity).

Metalloradical intermediates in electrocatalytic reduction of CO2 to CO: Mn versus Re bis-N-heterocyclic carbene pincers.

This work examines the relative reactivities of ReI and MnI tricarbonyl pyridine-2,6-bis-N-heterocyclic carbene pincers M(CO)3CNCBnX (M = Re, Mn and X = Cl and Br) towards catalysis for the electrochemical conversion of CO2 to CO. Unlike prior well-studied group VII catalysts, Mn(CO)3CNCBnX is extraordinarily active, while the new Re(CO)3CNCBnX complex surprisingly does not exhibit catalytic response. DFT calculations shed light on this puzzling behavior and show that the redox-active pyridine-2,6-bis-N-heterocyclic carbene ligand facilitates the reduction of the ground-state complexes; however, the extent of electronic delocalization in the reduced intermediates differs in the degree of metalloradical character. The highly-active Mn(CO)3CNCBnX complex proceeds through an intermediate with nucleophilic metalloradical character in which 66% of the unpaired electron spin resides on Mn. In contrast, Re(CO)3CNCBnX reduction proceeds through an intermediate with less metalloradical character in which only 38% of the unpaired spin is localized on Re with the remainder delocalized over the ligand. The energetic penalty of the electron delocalization of an electron on the ligand affects the M-CO bond strengths and related kinetic barriers. We discuss these observations in the context of turnover-enabling effects in CO2 reductions mediated by group VII NHC pincer molecular electrocatalysts.

Quantitative analysis of the distribution and mixing of cellulose nanocrystals in thermoplastic composites using Raman chemical imaging.

Cellulose nanofibers hold much promise for enhancing the mechanical properties of composites owing to their uniquely high stiffness and strength. One major issue limiting this performance however is the dispersion and mixing of cellulose nanofibers within thermoplastic resins. A combination of Raman imaging and chemical analysis has been used to quantify the distribution and mixing of cellulose nanocrystals (CNCs) in a polyethylene-matrix composite. Large area spectral imaging provides information about the effect of a compatibilizer - namely poly(ethylene oxide) (PEO) and maleated polyethylene (MAPE) - on the distribution of CNCs in the thermoplastic matrix. High-resolution images enable quantification of the degree of mixing between the CNCs and HDPE. Lower resolution images, but with greater spatial spread, allow quantification of the distribution of the CNCs. It is shown that the CNCs tend to agglomerate, with little increase in distribution even with the use of the compatibilizer. A shift in the position of characteristic Raman bands indicates the formation of hydrogen bonding between the PEO compatibilizer and the CNCs, which in turn is thought to affect the distribution of aggregates of the reinforcing phase.

The health literacy dyad: the contribution of future GPs in England.

BACKGROUND: Health literacy studies have primarily focused on the cognitive and social skills of individuals needed to gain access to, understand, and use health information. This area of study is undergoing a paradigm shift with increased attention being paid to the skills of practitioners and an examination of their contribution to the link between literacy and health outcomes. The aim of this study was to describe the health literacy related competencies of General Practice (GP) trainees who will soon be responsible for the clinical encounter. METHODS: A cross-sectional survey of a convenience sample of 206 GP trainees was conducted online. Univariate and bivariate analysis methods were used to describe GP trainees' health literacy-related competencies. RESULTS: GP trainees overestimated the numeracy and literacy levels of the English population and did not regard the improvement of patient health literacy as a GP responsibility. GP trainees rated their general communication skills highly but the skills that are important for patients in health decision-making such as coaching skills, explaining risk and using visual aids to clarify were rated low. CONCLUSION: This study demonstrates that health literacy is insufficiently addressed in the undergraduate and postgraduate medical education of GPs to enable them to fulfil the core competence which is part of building an effective partnership with patients.