Gas-Phase Reactions of Doubly Charged Lanthanide Cations with Alkanes and Alkenes. Trends in Metal(2+) Reactivity

The gas-phase reactivity of doubly-charged lanthanide cations, Ln2+ (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), with alkanes (methane, ethane, propane, n-butane) and alkenes (ethene, propene, 1-butene) was studied by Fourier transform ion cyclotron resonance mass spectrometry. The reaction products consisted of different combinations of doubly-charged organometallic ions?adducts or species formed via metal-ion-induced hydrogen, dihydrogen, alkyl, or alkane eliminations from the hydrocarbons?and singly-charged ions that resulted from electron, hydride, or methide transfers from the hydrocarbons to the metal ions. The only lanthanide cations capable of activating the hydrocarbons to form doubly-charged organometallic ions were La2+, Ce2+, Gd2+, and Tb2+, which have ground-state or low-lying d1 electronic configurations. Lu2+, with an accessible d1 electronic configuration but a rather high electron affinity, reacted only through transfer channels. The remaining Ln2+ reacted via transfer channels or adduct formation. The different accessibilities of d1 electronic configurations and the range of electron affinities of the Ln2+ cations allowed for a detailed analysis of the trends for metal(2+) reactivity and the conditions for occurrence of bond activation, adduct formation, and electron, hydride, and methide transfers

Managing the cancer backlog: a national population-based study of patient mobility, waiting times and ‘spare capacity’ for cancer surgery

Background: Waiting times for cancer treatments continue to increase in many countries. In this study we estimated potential ‘spare surgical capacity’ in the English NHS and identified regions more likely to have spare capacity based on patterns of patient mobility (the extent to which patients receive surgery at hospitals other than their nearest). Methods: We identified patients who had an elective breast or colorectal cancer surgical resection between January 2016 and December 2018. We estimated each hospital's ‘maximum surgical capacity’ as the maximum 6-month moving average of its surgical volume. ‘Spare surgical capacity’ was estimated as the difference between maximum surgical capacity and observed surgical volume. We assessed the association between spare surgical capacity and whether a hospital performed more or fewer procedures than expected due to patient mobility as well as the association between spare surgical capacity and whether or not waiting times targets for treatment were likely to be met. Findings: 100,585 and 49,445 patients underwent breast and colorectal cancer surgery respectively. 67 of 166 hospitals (40.4%) providing breast cancer surgery and 82 of 163 hospitals (50.3%) providing colorectal cancer surgery used less than 80% of their maximum surgical capacity. Hospitals with a ‘net loss’ of patients to hospitals further away had more potential spare capacity than hospitals with a ‘net gain’ of patients (p < 0.001 for breast and p = 0.01 for colorectal cancer). At the national level, we projected an annual potential spare capacity of 8389 breast cancer and 4262 colorectal cancer surgical procedures, approximately 25% of the volumes actually performed. Interpretation: Spare surgical capacity potentially exists in the present configuration of hospitals providing cancer surgery and requires regional allocation for efficient utilisation. Funding: National Institute for Health Research

Association between COVID-19 burden and delays to diagnosis and treatment of cancer patients in England

BACKGROUND: The COVID-19 pandemic has been highly disruptive for cancer care. Here, we examined the effect COVID-19 had on performance of the 62-day Cancer Waiting Time (CWT) target set by the National Health Service (NHS) in England. METHODS: Data were retrospectively obtained on COVID-19 hospitalisations and CWT for NHS hospitals in England (n = 121). We produced a 'COVID-19 burden' to describe the proportion of each provider's beds occupied with COVID-19 patients. COVID-19 burden was examined against CWT performance for 1st April - 30th May 2020 (Wave 1), and 1st October - 30th November 2020 (Wave 2). Two-tailed Spearman correlations were used to identify relationships between COVID-19 burden and CWT performance amongst different referral (i.e., 2-week-wait (2 W W) and internal specialist) and tumour types. Significantly correlated variables were further examined using linear regression models. RESULTS: COVID-19 burden was negatively associated with the percentage of 2 W W pathway referrals that met the CWT target in Wave 1 (r= -0.30, p = 0.001) and Wave 2 (r= -0.21, p = 0.02). These associations were supported by the results from our linear regression models (B for wave 1: -0.71; 95 %CI: -1.03 to -0.40; B for wave 2: -0.38; 95 %CI: -0.68 to -0.07). No associations were found between COVID-19 burden and internal specialist referrals or tumour type. CONCLUSION: Increased COVID-19 burden was associated with lower compliance with CWT targets amongst urgent referrals from primary care in England. This will likely be an ongoing issue due to the backlog of patients awaiting investigations and treatment. POLICY SUMMARY: As the number of cancer referrals improve, we highlight the need for changes to primary and secondary care to manage the backlog within cancer diagnostic services to alleviate the impact of COVID-19

The impact of national non-pharmaceutical interventions ('lockdowns') on the presentation of cancer patients.

One of the most ignored aspects of the COVID-19 pandemic has been the impact of public health measures by governments on wider health and welfare. From March 2020, hospitals in the UK saw a dramatic reduction in patients with cancer presenting due to multifactorial reasons. The impact of the pandemic on patients with cancer in the South East London Cancer Alliance was studied. The specific aims were (1) to examine the reduction in cancer diagnoses during the first wave of the pandemic and (2) to examine the stage of diagnosis of patients with cancer presenting during the pandemic compared with that of patients presenting before the pandemic. There was an 18.2% reduction in new cancer diagnoses (an estimate of 987 cancers), when compared with 2019. This fall in cancer diagnoses was most marked in patients with prostate (51.4%), gynaecological (29.7%), breast (29.5%) and lung (23.4%) cancers. There was an overall 3.9% increase in advanced stage presentation (Stages 3 and 4), with an overall 6.8% increase in Stage 4 cancers during this period. The greatest shifts were seen in lung (increase of 6.3%, with an 11.2% increase in Stage 4 cancer alone) and colorectal (5.4%) cancers. For prostate cancer, there was an increase in 3.8% in those presenting with Stage 4 disease. For breast cancer, there was an 8% reduction in patients diagnosed with Stage 1 cancer with commensurate increases in the proportion of those with Stage 2 disease. The experiences in cancer are a salient warning that pandemic control measures and policy need to balance all health and welfare. Alternative strategies need to be adopted during further waves of the current and any future pandemic to ensure that patients with cancer are prioritised for diagnosis and treatment to prevent late-stage presentation and an increase in avoidable deaths

Unwanted sex due to intoxication among Australians aged 16–69 years

Intoxication can be a factor in unwanted sex, but research on the extent of the issue in both women and men is limited. We assessed the prevalence, correlates, and 10-year time-trends of unwanted sex due to intoxication among a representative sample of 4,279 women and 3,875 men aged 16–69 years in Australia and considered how these vary by gender. In 2012–13, 16% of women and 10% of men reported ever having had a sexual experience when they “did not want to because they were too drunk or high at the time.” For both women and men, this was associated with younger age, bisexual activity, and reports of lifetime injection drug use, sexually transmitted infections, and forced sex. Among women only, it was associated with drinking above guideline levels and ever having terminated a pregnancy. Among men only, it was associated with current tobacco smoking, elevated psychosocial distress, and poor general health. Compared with 2001–02 data, fewer men reported unwanted intoxicated sex, while there were no changes for women as a whole. Interpreting these findings through an intersectional assemblage framework supports stronger understanding of the multiple factors influencing sexuality and substance use with implications for promoting equity, safety, and sexual health

COVID-19 Risk Factors for Cancer Patients: A First Report with Comparator Data from COVID-19 Negative Cancer Patients

none32siSimple SummaryThe COVID-19 pandemic has had a detrimental impact on cancer patients globally. Whilst there are several studies looking at the potential risk factors for COVID-19 disease and related death, most of these include non-cancerous patients as the COVID-19 negative comparator group, meaning it is difficult to draw hard conclusions as to the implications for cancer patients. In our study, we utilized data from over 2000 cancer patients from a large tertiary Cancer Centre in London. In summary, our study found that patients who are male, of Black or Asian ethnicity, or with a hematological malignancy are at an increased risk of COVID-19. The use of cancer patients as the COVID-19 negative comparator group is a major advantage to the study as it means we can better understand the true impact of COVID-19 on cancer patients and identify which factors pose the biggest risk to their likelihood of infection with SARS-CoV2.Very few studies investigating COVID-19 in cancer patients have included cancer patients as controls. We aimed to identify factors associated with the risk of testing positive for SARS CoV2 infection in a cohort of cancer patients. We analyzed data from all cancer patients swabbed for COVID-19 between 1(st) March and 31(st) July 2020 at Guy's Cancer Centre. We conducted logistic regression analyses to identify which factors were associated with a positive COVID-19 test. Results: Of the 2152 patients tested for COVID-19, 190 (9%) tested positive. Male sex, black ethnicity, and hematological cancer type were positively associated with risk of COVID-19 (OR = 1.85, 95%CI:1.37-2.51; OR = 1.93, 95%CI:1.31-2.84; OR = 2.29, 95%CI:1.45-3.62, respectively) as compared to females, white ethnicity, or solid cancer type, respectively. Male, Asian ethnicity, and hematological cancer type were associated with an increased risk of severe COVID-19 (OR = 3.12, 95%CI:1.58-6.14; OR = 2.97, 95%CI:1.00-8.93; OR = 2.43, 95%CI:1.00-5.90, respectively). This study is one of the first to compare the risk of COVID-19 incidence and severity in cancer patients when including cancer patients as controls. Results from this study have echoed those of previous reports, that patients who are male, of black or Asian ethnicity, or with a hematological malignancy are at an increased risk of COVID-19.openRussell, Beth; Moss, Charlotte L; Palmer, Kieran; Sylva, Rushan; D'Souza, Andrea; Wylie, Harriet; Haire, Anna; Cahill, Fidelma; Steel, Renee; Hoyes, Angela; Wilson, Isabelle; Macneil, Alyson; Shifa, Belul; Monroy-Iglesias, Maria J; Papa, Sophie; Irshad, Sheeba; Ross, Paul; Spicer, James; Kordasti, Shahram; Crawley, Danielle; Zaki, Kamarul; Sita-Lumsden, Ailsa; Josephs, Debra; Enting, Deborah; Swampillai, Angela; Sawyer, Elinor; Fields, Paul; Wrench, David; Rigg, Anne; Sullivan, Richard; Van Hemelrijck, Mieke; Dolly, SaoirseRussell, Beth; Moss, Charlotte L; Palmer, Kieran; Sylva, Rushan; D'Souza, Andrea; Wylie, Harriet; Haire, Anna; Cahill, Fidelma; Steel, Renee; Hoyes, Angela; Wilson, Isabelle; Macneil, Alyson; Shifa, Belul; Monroy-Iglesias, Maria J; Papa, Sophie; Irshad, Sheeba; Ross, Paul; Spicer, James; Kordasti, Shahram; Crawley, Danielle; Zaki, Kamarul; Sita-Lumsden, Ailsa; Josephs, Debra; Enting, Deborah; Swampillai, Angela; Sawyer, Elinor; Fields, Paul; Wrench, David; Rigg, Anne; Sullivan, Richard; Van Hemelrijck, Mieke; Dolly, Saoirs

Environmental Management Science Program Report Progress Report Plutonium Speciation, Solubilization, and Migration in Soils

The DOE is currently conducting cleanup activities at its nuclear weapons development sites, many of which have accumulated plutonium in soils for 50 years. To properly control Pu migration in soils within Federal sites and onto public lands, better evaluate the public risk, and design effective remediation strategies, a fundamental understanding of Pu speciation and environmental transport is needed. The key scientific goals of this project are: to determine Pu concentrations and speciation at a contaminated DOE site; to study the formation, stability, and structural and spectroscopic features of environmentally relevant Pu species; to determine the mechanism(s) of interaction between Pu and Mn/Fe minerals and the potential release of Pu via redox cycling; and to model the environmental behavior of plutonium. Our long-term goal is to use characterization, thermodynamic, mineral interaction, and mobility data to develop better models of radionuclide transport and risk assessment, and to enable the development of science based decontamination strategies. This research will fill important gaps between basic actinide science and the problems impeding site clean-up, plutonium disposition, and accurate risk assessment. Information gained will allow for the development of technologies and clean-up approaches targeting particular plutonium contaminants and improved assessment of risks associated with actinide migration, site remediation, and decontamination. By combining very specific study of plutonium at the Rocky Flats Environmental Technology Site (RFETS), a well-characterized contaminated site, with laboratory studies on the most important plutonium and mineral component systems, we will provide essential knowledge of contaminant characteristics and distinguish critical geochemical processes and mechanisms