Carbocation rearrangement is a powerful tool for converting a simple precursor into a complex molecular scaffold. However, controlling the stereoselectivity of a reaction that involves carbocation rearrangement is challenging and remains elusive. In this study, we demonstrate a novel iridium-catalyzed Wagner-Meerwein rearrangement and asymmetric hydrogenation of carbocation precursors (1-(aryl)-1-(1-methylcyclobutyl/cyclopentyl) ethan-1-ol) for the synthesis of various optically active gem-dimethyl cycloalkanes. Hence, enantiopure gem-dimethyl-containing compounds are important motifs found in many natural products, and some are FDA-approved drugs. Our methodology starts with an iridium-catalyzed formal deoxygenation of tertiary alcohols to generate a tertiary carbocation that triggers the Wagner-Meerwein rearrangement via the ring expansion and alkyl migration cascade to furnish a stable tertiary-benzyl carbocation. Sequential olefination and in situ asymmetric hydrogenation provide access to various gem-dimethyl chiral cycloalkanes in excellent yield (> 99%) and enantioselectivity (ee up to > 99%). Otherwise, establishing a high yield and enantioselectivity in a saturated cyclic hydrocarbon next to a sterically hindered gem-dimethyl group would not be possible by conventional methods.

This study aimed to describe and compare background factors and symptoms at diagnosis of patients with non-advanced or advanced stage lung cancer and patients without cancer, and to develop predictive models identifying key variables that contribute to the detection of early and late-stage lung cancer. Univariate logistic regression and three machine learning algorithms were used. Compared to patients without cancer, six background factors and two symptoms differed in non-advanced lung cancer, while 11 background factors and 19 symptoms differed in advanced cases. The machine learning models showed moderate performance in classifying patients with lung cancer from those without cancer. Notably, top predictors extended beyond classic respiratory symptoms. Demographic and lifestyle factors, particularly age, smoking status, and living situation, remained essential alongside symptoms such as pain, appetite loss, weight reduction, and respiratory problems. These findings support integrating clinical, demographic, and patient-reported symptoms to improve lung cancer risk models and refine referral decisions in screening pathways.

Methyl 2,3-di-O-benzyl-α-d-(4-2H)-glucopyranoside, C21H25DO6, is an intermediate used in synthesis of oligosaccharides. The hexopyranose ring has the 4C1 chair conformation in the crystal structure. The exocyclic groups of the hexose sugar show for the glycosidic torsion angle ϕ =−52.8° and for the hydroxymethyl group the gauche-gauche conformation with ω = −64.7°, one of the two main orientations of the latter group in hexopyranose sugars that have the gluco-configuration, i.e., with an equatorial hydroxyl group at C4. The benzene rings of the benzyl groups are arranged with an angle of 56.9° to each other within the molecule and show intramolecular as well as intermolecular C-H···π interactions. A chain of intermolecular hydrogen bonds exists along the b-axis involving O4 and O6 atoms. The experimentally observed peak in the infrared spectrum at 2159 cm− 1 was ascribed to the stretching of the C4–D4 bond based on DFT calculations.

Purpose This study aimed to explore the experiences of patients with colorectal cancer undergoing surgical treatment, capturing their perspectives from diagnosis through to post-discharge recovery. Methods A qualitative methodology was adopted, utilising semi-structured virtual interviews with ten patients recruited from a specialist colorectal clinic. Interviews were transcribed verbatim, and data analysed by the process of inductive thematic analysis, using interpretive description. Results Themes emerged across the domains of clinical and external, patient-level, and interpersonal and social factors affecting patient experience at diagnosis, surgery, and recovery stages. Clinical and external factors included the impact of the hospital environment, resource limitations, and the attributes of the clinical team, including ward nurses, clinical nurse specialists, and consultant surgeons, in providing compassionate support. Patient-level factors encompassed perceptions and emotional impacts of the diagnosis, and physical challenges post-surgery. Interpersonal and social factors included family support and the psychosocial impact of role changes during recovery. Conclusions Findings highlight the need for comprehensive, compassionate communication and tailored support across the patient journey. Recommendations include enhanced patient education on lifestyle impacts, resources to support family and peer networks, and more attention to psychosocial and emotional challenges in patient-centred care.

BACKGROUND:Research indicates various barriers to cervical cancer screening for transgender people, contributing to cancer inequities. Further research is required to better understand how these barriers affect experiences along the screening trajectory, from engaging with information, through invitation and testing, to receiving test results. Research exploring how transgender people navigate these barriers is also required. AIM:To explore the experiences of cervical cancer screening in Sweden among transgender people who were assigned female at birth, and to identify touchpoints in need of improvement along the cervical cancer screening trajectory. DESIGN:Qualitative interview study inspired by journey mapping. METHODS:Semi-structured interviews (n = 18) and interpretive description analysis. RESULTS:Five phases were identified comprising participants' cervical cancer screening journey, with touchpoints in each phase indicating key experiences, barriers, and strategies to navigate barriers. Experiences of touchpoints were affected by four interrelated dimensions: The embodied person-personal gender identity, relationship with own body, and transition process; System factors-policies, routines, and practices; Gender norms and transphobia; and Prior healthcare experiences. Significant barriers included a lack of trans-specific screening information; an invitation system that does not automatically invite male-registered individuals with a cervix; lack of trans competency among clinics and staff; female-centred clinics; gender dysphoria; anticipation or fear of being mistreated; distrust of healthcare authorities; and participant-staff power dynamics. CONCLUSION:To make cervical cancer screening more equitable for transgender people, barriers need to be addressed by considering the four dimensions that affect these barriers. IMPLICATIONS FOR THE PROFESSION AND/OR PATIENT CARE:Findings show that staff involved in policy and clinical practice can improve transgender people's experiences of cervical cancer screening by promoting agency and self-determination in each screening phase. This involves providing inclusive information, continuing invitations for male-registered individuals with a cervix, enhancing trans-competency, and addressing power dynamics in staff-participant interactions. REPORTING METHOD:The Standards of Reporting Qualitative Research (SRQR). PATIENT OR PUBLIC CONTRIBUTION:Representatives from the Regional Cancer Centre Stockholm-Gotland were involved in the conceptualisation of this study. Representatives from trans and LGBTQI+ organisations, Regional Cancer Centres, and the National Board of Health and Welfare have provided feedback during the analysis and writing phases.

Conversion of carbon dioxide (CO₂) into value-added products is aimed to develop scalable technologies to promote a circular economy. While the electrochemical reduction of CO₂ to carbon monoxide (CO) and formic acid has advanced significantly, a major challenge remains achieving further reduced and more energy-dense products, such as methanol (MeOH), through sustainable pathways. Herein, we report a molecular electrode capable of direct six-electron reduction of CO₂ to MeOH using water as a proton source with a global Faradaic efficiency (FE G ) of 22% and product selectivity of 61% for MeOH. The design consists of an active copper-hydride center surrounded by two closely spaced benzimidazole–hydride units, facilitating the catalytic transfer of three hydrides to produce MeOH. The concurrent formation of formic acid and the absence of formaldehyde suggest that MeOH is generated via a formato pathway. DFT investigations revealed the complete mechanistic pathway, which supports the experimental observations. The morphology and stability of the electrode were evaluated before and after prolonged electrolysis (12 h) experiments using electron microscopic techniques.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

OBJECTIVES:We aimed to determine the prevalence of HIV-related stigma among people with HIV (PWH) in Switzerland. DESIGN:A cross-sectional multicenter study nested within the Swiss HIV Cohort Study (SHCS). METHODS:We included adult PWH enrolled in the SHCS, attending follow-up between March 1, 2020, and January 31, 2021. Inability to speak English, French, German, or Italian was the only exclusion criterion. Participants were invited to complete a validated 12-item HIV-stigma questionnaire comprising four stigma subscales (negative self-image, personalized stigma, disclosure concerns, and concerns regarding public attitudes), plus two healthcare-related stigma items. Questionnaire responses were graded using a four-point Likert-type scale, higher scores indicating higher stigma. "Non-applicable," inferring HIV-status non-disclosure, was possible for personalized stigma; stigma scores from participants answering "non-applicable" to at least one item were analyzed separately. Factors associated with HIV-stigma were identified through multivariable linear models. RESULTS:Of 9643 PWH with a SHCS visit, 5563 participated in the study: 26% were female, 13% Black, and 37% heterosexual; median age was 53 years (interquartile range 44-59); 2067 participants (37%) gave at least one "non-applicable" response. Disclosure concerns had the highest stigma scores and were reported by 4656/5563 (84%). HIV-stigma was reported across all demographic groups. However, being female, Black, and heterosexual were independently associated with higher scores. Higher education and longer follow-up duration were associated with lower scores. Healthcare-related stigma was reported in 37% of participants. CONCLUSION:HIV-stigma was prevalent across all demographic groups. The association with being female and Black suggests that HIV-stigma accentuates preexisting sex and race inequalities.

Lack of the established noninvasive diagnostic biomarkers causes delay in diagnosis of lung cancer (LC). The aim of this study was to explore the association between inflammatory and cancer-associated plasma proteins and LC and thereby discover potential biomarkers. Patients referred for suspected LC and later diagnosed with primary LC, other cancers, or no cancer (NC) were included in this study. Demographic information and plasma samples were collected, and diagnostic information was later retrieved from medical records. Relative quantification of 92 plasma proteins was carried out using the Olink Immuno-Onc-I panel. Association between expression levels of panel of proteins with different diagnoses was assessed using generalized linear model (GLM) with the binomial family and a logit-link function, considering confounder effects of age, gender, smoking, and pulmonary diseases. The analysis showed that the combination of five plasma proteins (CD83, GZMA, GZMB, CD8A, and MMP12) has higher diagnostic performance for primary LC in both early and advanced stages compared with NC. This panel demonstrated lower diagnostic performance for other cancer types. Moreover, inclusion of four proteins (GAL9, PDCD1, CD4, and HO1) to the aforementioned panel significantly increased the diagnostic performance for primary LC in advanced stage as well as for other cancers. Consequently, the collective expression profiles of select plasma proteins, especially when analyzed in conjunction, might have the potential to distinguish individuals with LC from NC. This suggests their utility as predictive biomarkers for identification of LC patients. The synergistic application of these proteins as biomarkers could pave the way for the development of diagnostic tools for early-stage LC detection.

Microporous organic polymers that have three-dimensional connectivity stemming from monomers with tetrahedral or tetrahedron-like geometry can have high surface areas and strong fluorescence. There are however few examples of such polymers based on hindered biaryls, and their fluorescence has not been studied. Hypothesizing that the contortion in a hindered biphenyl moiety would modulate the optical properties of a polymer built from it, we synthesized a meta-enchained polyphenylene from a 2,2ʹ,6,6ʹ-tetramethylbiphenyl-based monomer, in which the two phenyl rings are nearly mutually perpendicular. The polymer was microporous with SBET = 495 m2 g−1. The polymer absorbed near-UV light and emitted blue fluorescence despite the meta-enchainment that would have been expected to break the conjugation. A related copolymer, synthesized from 2,2ʹ,6,6ʹ-tetramethylbiphenyl-based and unsubstituted biphenyl-based monomers, was microporous but not fluorescent.

BackgroundMagnet hospitals, a concept developed in the U.S., have been associated with improved nurse recruitment and retention, and better patient outcomes. Magnet principles may be useful to address workforce challenges in European hospitals, but they have not been implemented or evaluated on a large scale in the European hospital context.ObjectiveThis study aims to explore the initial phase of implementing Magnet principles in 11 acute care hospitals in six European countries. The specific objectives of the study were to investigate the type of work that characterises the early phase of implementation and how implementation leaders engage with their context.MethodsA multinational qualitative study was conducted, with data from 23 semi-structured, one-to-one interviews with implementation leaders in 11 acute care hospitals in six European countries. Thematic analyses guided the analysis of data.FindingsThree themes of core work processes during the early phase of implementing Magnet principles in European hospitals were identified. The first theme, ‘Creating space for Magnet’, describes how work was directed towards creating both political and organisational space for the project. The second theme, ‘Framing to fit: understanding and interpreting Magnet principles’, describes the translational work to understand what the Magnet model entails and how it relates to the local hospital context. Finally, the third theme, ‘Calibrating speed and dose’, describes the strategic work of considering internal and external factors to adjust the process of implementation.ConclusionsThe first phase of implementation was characterised by conceptual and relational work; translating the Magnet concepts, considering the fit into existing structures and practices and making space for Magnet in the local context. Understanding the local context played an important role in shaping and guiding the navigation of professional and organisational tensions. Hospitals employed diverse strategies to either emphasise or downplay the role of nurses and nursing to facilitate progress in the implementation.

The coordination chemistry of N , N ′-dimethylpropyleneurea (dmpu) coordinated metal ions and complexes is reviewed. Dmpu is space-demanding at coordination forcing most metal ions and complexes to adopt lower coordination numbers than in most cases.

Background With access to antiretroviral therapy (ART) HIV infection is a chronic manageable condition and non-sexually transmissible. Yet, many people living with HIV still testify about experiencing HIV-related stigma and discrimination. It is well-documented that HIV-related stigma and discrimination continue to be critical barriers to prevention, treatment, care and quality of life. From an individual stigma-reduction intervention perspective, it is essential to identify individual and interpersonal factors associated with HIV-related stigma manifestations. To address this issue and to expand the literature, the aim of this study was to assess the prevalence of HIV-related stigma manifestations and their associated factors among a diverse sample of people living with HIV in Sweden.Method Data from 1 096 participants were derived from a nationally representative, anonymous cross-sectional survey "Living with HIV in Sweden". HIV-related stigma manifestations were assessed using the validated Swedish 12-item HIV Stigma Scale encompassing four HIV-related stigma manifestations: personalised stigma, concerns with public attitudes towards people living with HIV, concerns with sharing HIV status, and internalized stigma. Variables potentially associated with the HIV-related stigma manifestations were divided into four categories: demographic characteristics, clinical HIV factors, distress and ART adherence, and available emotional HIV-related support. Four multivariable hierarchical linear regression analyses were employed to explore the associations between multiple contributors and HIV-related stigma manifestations.Results The most dominating stigma feature was anticipation of HIV-related stigma. It was manifested in high scores on concerns with sharing HIV status reported by 78% of the participants and high scores on concerns about public attitudes towards people living with HIV reported by 54% of the participants. High scores on personalised stigma and internalized stigma were reported by around one third of the participants respectively. Between 23 and 31% of the variance of the four reported HIV-related stigma manifestations were explained mainly by the same pattern of associated factors including female gender, shorter time since HIV diagnosis, feelings of hopelessness, non-sharing HIV status, and lack of available emotional HIV-related support.Conclusion The most dominating stigma feature was anticipation of stigma. Female gender, shorter time since HIV diagnosis, feelings of hopelessness, non-sharing HIV status, and lack of available emotional HIV-related support constituted potential vulnerability factors of the four HIV-related stigma manifestations. Our findings highlight the vital necessity to support people living with HIV to increase their resilience to stigma in its different forms. Exploring associated factors of HIV-related stigma manifestations may give an indication of what circumstances may increase the risk of stigma burden and factors amenable to targeted interventions. As individual stigma-reductions interventions cannot be performed isolated from HIV-related stigma and discrimination in society, a key challenge is to intensify anti-stigma interventions also on the societal level.

Introduction Clinical research has focused on risk factors and treatment for severe acute respiratory syndrome coronavirus 2 (SARS-COV-2), particularly in people with a comorbidity including the human immunodeficiency virus (HIV), but little attention has been paid to the care pathway. This article aims to show how living with HIV may have been a biopsychosocial burden or boost in care pathways for Covid-19. Method People living with HIV (PLHIV) from 9 clinical centers were invited to participate in this qualitative study. The sampling was purposive with a maximum variation in their sociodemographic profiles. Semi-structured interviews were conducted until data saturation, then coded for thematic analysis, using an inductive general approach. Results We interviewed 34 PLHIV of which 20 had SARS-COV-2 once. They were 24 males, 26 born in France; median age: 55. Twenty had a CD4 number above 500, and all were on antiretroviral therapy (ART). HIV appeared as a burden when Covid-19 symptoms reminded HIV seroconversion, fear of contamination, and triggered questions about ART effectiveness. HIV was not considered relevant when diagnosing Covid-19, caused fear of disclosure when participants sought SARS-COV-2 testing, and its care in hospitals was disrupted by the pandemic. ART-pill fatigue caused avoidance for Covid-19 treatment. As a boost, living with HIV led participants to observe symptoms, to get advice from healthcare professionals, and screening access through them. Some participants could accept the result of screening or a clinical diagnosis out of resilience. Some could consider ART or another drug prescribed by their HIV specialist help them to recover from Covid-19. Conclusion Living with HIV could function as a burden and/or a boost in the care pathways for Covid-19, according to patients’ relationship to their HIV history, comorbidities and representation of ART. Covid-19 in PLHIV needs further qualitative study to gain a more comprehensive assessment of the pandemic’s consequences on their lives and coping strategies.

ObjectivesThe study aimed to investigate the prevalence and factors associated with poor health-related quality of life in adults with cancer in Uganda.MethodsThis cross-sectional study surveyed 385 adult patients (95% response rate) with various cancers at a specialised oncology facility in Uganda. Health-related quality of life was measured using the EORTC QLQ-C30 in the Luganda and English languages. Predetermined validated clinical thresholds were applied to the instrument in order to identify patients with poor health-related quality of life, that is, functional impairments or symptoms warranting concern. Multivariable logistic regression was used to identify factors associated with poor health-related quality of life in six subscales: Physical Function, Role Function, Emotional Function, Social Function, Pain and Fatigue.ResultsThe mean age of the patients was 48 years. The majority self-reported poor functioning ranging between 61% (Emotional Function) to 79% (Physical Function) and symptoms (Fatigue 63%, Pain 80%) at clinically concerning levels. These patients were more likely to be older, without formal education and not currently working. Being an inpatient at the facility and being diagnosed with cervical cancer or leukaemia was a predictor of poor health-related quality of life.ConclusionImprovement of cancer care in East Africa requires a comprehensive and integrated approach that addresses various challenges specific to the region. Such strategies include investment in healthcare infrastructure, for example, clinical guidelines to improve pain management, and patient education and support services. Main findings: The majority of adult patients attending specialized cancer care in Uganda report impaired physical and emotional functioning, and pain, at levels that merit clinical concern.Added knowledge: The large proportion of in- and outpatients with poor self-reported health-related quality of life indicates supportive care needs, exceeding corresponding figures from high-income settings.Global health impact for policy and action: Improvement of cancer care in East Africa requires a comprehensive approach that should include investment in healthcare infrastructure, e.g. clinical guidelines to improve pain management, and patient education and support services.

Objective To test the efficacy of a web-based psychoeducational intervention, Fex-Can Sex, in reducing sexual dysfunction in young adults with cancer. Methods This randomized controlled trial evaluated a 12-week web-based self-help intervention. Young adults aged 19–40 who reported sexual dysfunction 1.5 years after cancer diagnosis were drawn from a population-based cohort. Participants were randomized to an intervention group (IG, n = 72) or a control group (CG, n = 66) that solely received standard care. Primary outcome was assessed by a domain of the Patient Reported Outcome Measures Information Systems® SexFS: “Satisfaction with sex life.” Secondary outcomes included additional SexFS domains, body image (BIS), emotional distress (HADS), health-related quality of life (EORTC QLQ-C30), and self-efficacy related to sex. Surveys were completed at baseline, post-intervention, and three months later. Effects of the intervention were tested with t-tests, and linear mixed models (LMMs), including intention-to-treat and subgroup analyses. Additionally, the IG was asked about their experiences of the program with study-specific questions. Results There were no differences in primary or secondary outcomes between the IG and the CG at post-intervention. Subgroup analyses showed that individuals with greater sexual problems at baseline improved over time, regardless of group allocation. Participants spent a mean time of 20.7 min on the program. The study-specific items showed that the majority of participants in the IG appreciated the program and would recommend it to others. Conclusion The Fex-Can Sex intervention did not show effect on primary and secondary outcomes. Adherence to the intervention was low, and future interventions are recommended to include more interactive components to enhance usage. Clinical trial registration The trial was registered on 25 January, 2016 (trial number: 36621459).

The death literacy index (DLI) was developed in Australia to measure death literacy, a set of experience-based knowledge needed to understand and act on end-of-life (EOL) care options but has not yet been validated outside its original context. The aim of this study was to develop a culturally adapted Swedish-language version of the DLI, the DLI-S, and assess sources of evidence for its validity in a Swedish context. The study involved a multi-step process of translation and cultural adaptation and two validation phases: examining first content and response process validity through expert review (n = 10) and cognitive interviews (n = 10); and second, internal structure validity of DLI-S data collected from an online cross-sectional survey (n = 503). The psychometric evaluation involved analysis of descriptive statistics on item and scale-level, internal consistency and test-retest reliability, and confirmatory factor analysis. During translation and adaptation, changes were made to adjust items to the Swedish context. Additional adjustments were made following findings from the expert review and cognitive interviews. The content validity index exceeded recommended thresholds (S-CVIAve = 0.926). The psychometric evaluation provided support for DLI-S' validity. The hypothesized six-factor model showed good fit (χ2 = 1107.631 p<0.001, CFI = 0.993, TLI = 0.993, RMSEA = 0.064, SRMR = 0.054). High internal consistency reliability was demonstrated for the overall scale (Cronbach's α = 0.94) and each sub-scale (α 0.81-0.92). Test-retest reliability was acceptable, ICC ranging between 0.66-0.85. Through a comprehensive assessment of several sources of evidence, we show that the DLI-S demonstrates satisfactory validity and acceptability to measure death literacy in the Swedish context. There are, however, indications that the sub-scales measuring community capacity perform worse in comparison to other sca and may function differently in Sweden than in the original context. The DLI-S has potential to contribute to research on community-based EOL interventions.

We have developed a new three-component catalytic coupling reaction of alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence of BINOL derivatives. The reaction proceeds with a remarkably high enantio- and diastereoselectivity (up to three contiguous stereocenters) affording tertiary CF3-allenols in a single operational step. The reaction proceeds under mild, neutral, metal-free conditions, which leads to a high level of functional group tolerance.

Ziel/Aim Dynamic PET protocols allow for full quantification of tracer kinetics. With the introduction of long axial field-of-view (LAFOV) PET systems, tracer kinetics of multiple organs of interests can be studied in a single-bed position. These advances enable use of non-linear compartmental kinetic models for estimation of kinetic microparameters from different structures of interest. However, the irreversible 2-tissue-compartment (2TC-3k) might cause artefacts in parametric images when applied to whole-body F-18-FDG datasets. Here, we propose a method that utilizes deep learning-based organ segmentations to select an appropriate kinetic model for each tissue of interest.