Oxidation of High Yield Strength Metals Tungsten and Rhenium in High-Pressure High-Temperature Experiments of Carbon Dioxide and Carbonates

The laser-heating diamond-anvil cell technique enables direct investigations of materials under high pressures and temperatures, usually confining the samples with high yield strength W and Re gaskets. This work presents experimental data that evidences the chemical reactivity between these refractory metals and CO2 or carbonates at temperatures above 1300 °C and pressures above 6 GPa. Metal oxides and diamond are identified as reaction products. Recommendations to minimize non-desired chemical reactions in high-pressure high-temperature experiments are given

Making the invisible visible: improved electrospray ion formation of metalloporphyrins/-phthalocyanines by attachment of the formate anion (HCOO-)

A protocol is developed for the coordination of the formate anion (HCOO-) to neutral metalloporphyrins (Pors) and -phthalocyanines (Pcs) containing divalent metals as a means to improve their ion formation in electrospray ionization (ESI). This method is particularly useful when the oxidation of the neutral metallomacrocycle fails. While focusing on Zn(II)Pors and Zn(II)Pcs, we show that formate is also readily attached to Mn(II), Mg(II) and Co(II)Pcs. However, for the Co(II)Pc secondary reactions can be observed. Upon collision-induced dissociation (CID), Zn(II)Por/Pc·formate supramolecular complexes can undergo the loss of CO2 in combination with transfer of a hydride anion (H-) to the zinc metal center. Further dissociation leads to electron transfer and hydrogen atom loss, generating a route to the radical anion of the Zn(II)Por/Pc without the need for electrochemical reduction, although the Zn(II)Por/Pc may have a too low electron affinity to allow electron transfer directly from the formate anion. In addition to single Por molecules, multi Por arrays were successfully analyzed by this method. In this case, multiple addition of formate occurs, giving rise to multiply charged species. In these multi Por arrays, complexation of the formate anion occurs by two surrounding Por units (sandwich). Therefore, the maximum attainment of formate anions in these arrays corresponds to the number of such sandwich complexes rather than the number of porphyrin moieties. The same bonding motif leads to dimers of the composition [(Zn(II)Por/Pc)2·HCOO]-. In these, the formate anion can act as a structural probe, allowing the distinction of isomeric ions with the formate bridging two macrocycles or being attached to a dimer of directly connected macrocycles.Financial support from the Deutsche Forschungsgemeinschaft (DFG)-SFB 953 “Synthetic Carbon Allotropes”, the MINECO, Spain (CTQ-2014-52869-P) and the Comunidad de Madrid (S2013/MIT-2841 FOTOCARBON, T.T.) is acknowledged

Clonality and timing of relapsing colorectal cancer metastasis revealed through whole-genome single-cell sequencing

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGRecurrence of tumor cells following local and systemic therapy is a significant hurdle in cancer. Most patients with metastatic colorectal cancer (mCRC) will relapse, despite resection of the metastatic lesions. A better understanding of the evolutionary history of recurrent lesions is required to identify the spatial and temporal patterns of metastatic progression and expose the genetic and evolutionary determinants of therapeutic resistance. With this goal in mind, here we leveraged a unique single-cell whole-genome sequencing dataset from recurrent hepatic lesions of an mCRC patient. Our phylogenetic analysis confirms that the treatment induced a severe demographic bottleneck in the liver metastasis but also that a previously diverged lineage survived this surgery, possibly after migration to a different site in the liver. This lineage evolved very slowly for two years under adjuvant drug therapy and diversified again in a very short period. We identified several non-silent mutations specific to this lineage and inferred a substantial contribution of chemotherapy to the overall, genome-wide mutational burden. All in all, our study suggests that mCRC subclones can migrate locally and evade resection, keep evolving despite rounds of chemotherapy, and re-expand explosively.Ministerio de Ciencia e Innovación | Ref. PID2019-106247GB-I00AXA Research FundAsociación Española Contra el CáncerXunta de Galicia | Ref. ED481A-2018/30

The Process of Replication Target Selection in Psychology: What to Consider?

Increased execution of replication studies contributes to the effort to restore credibility of empirical research. However, a second generation of problems arises: the number of potential replication targets is at a serious mismatch with available resources. Given limited resources, replication target selection should be well justified, systematic, and transparently communicated. At present the discussion on what to consider when selecting a replication target is limited to theoretical discussion, self-reported justifications, and a few formalized suggestions. In this Registered Report, we proposed a study involving the scientific community to create a list of considerations for consultation when selecting a replication target in psychology. We employed a modified Delphi approach. First, we constructed a preliminary list of considerations. Second, we surveyed psychologists who previously selected a replication target with regards to their considerations. Third, we incorporated the results into the preliminary list of considerations and sent the updated list to a group of individuals knowledgeable about concerns regarding replication target selection. Over the course of several rounds, we established consensus regarding what to consider when selecting a replication target

Post-tilleyite, a dense calcium silicate-carbonate phase

Calcium carbonate is a relevant constituent of the Earth´s crust that is transferred into the deep Earth through the subduction process. Its chemical interaction with calcium-rich silicates at high temperatures give rise to the formation of mixed silicate-carbonate minerals, but the structural behavior of these phases under compression is not known. Here we report the existence of a dense polymorph of Ca5(Si2O7)(CO3)2 tilleyite above 8 GPa. We have structurally characterized the two phases at high pressures and temperatures, determined their equations of state and analyzed the evolution of the polyhedral units under compression. This has been possible thanks to the agreement between our powder and single-crystal XRD experiments, Raman spectroscopy measurements and ab-initio simulations. The presence of multiple cation sites, with variable volume and coordination number (6-9) and different polyhedral compressibilities, together with the observation of significant amounts of alumina in compositions of some natural tilleyite assemblages, suggests that post-tilleyite structure has the potential to accommodate cations with different sizes and valencies.We are thankful for the financial support received from the Spanish Ministry of Economy and Competitiveness through national projects PGC2018-097520-A-100, MAT2016-75586-4-3-P and MAT2015-71070-REDC (MALTA Consolider)

Nirmatrelvir/ritonavir in COVID-19 patients with haematological malignancies: a report from the EPICOVIDEHA registry

Background: Nirmatrelvir/ritonavir treatment decreases the hospitalisation rate in immunocompetent patients with COVID-19, but data on efficacy in patients with haematological malignancy are scarce. Here, we describe the outcome of nirmatrelvir/ritonavir treatment in a large cohort of the latter patients. Methods: This is a retrospective cohort study from the multicentre EPICOVIDEHA registry (NCT04733729) on patients with haematological malignancy, who were diagnosed with COVID-19 between January and September 2022. Patients receiving nirmatrelvir/ritonavir were compared to those who did not. A logistic regression was run to determine factors associated with nirmatrelvir/ritonavir administration in our sample. Mortality between treatment groups was assessed with Kaplan-Meier survival plots after matching all the patients with a propensity score. Additionally, a Cox regression was modelled to detect factors associated with mortality in patients receiving nirmatrelvir/ritonavir. Findings: A total of 1859 patients were analysed, 117 (6%) were treated with nirmatrelvir/ritonavir, 1742 (94%) were treated otherwise. Of 117 patients receiving nirmatrelvir/ritonavir, 80% had received ≥1 anti-SARS-CoV-2 vaccine dose before COVID-19 onset, 13% of which received a 2nd vaccine booster. 5% were admitted to ICU. Nirmatrelvir/ritonavir treatment was associated with the presence of extrapulmonary symptoms at COVID-19 onset, for example anosmia, fever, rhinitis, or sinusitis (aOR 2.509, 95%CI 1.448-4.347) and 2nd vaccine booster (aOR 3.624, 95%CI 1.619-8.109). Chronic pulmonary disease (aOR 0.261, 95%CI 0.093-0.732) and obesity (aOR 0.105, 95%CI 0.014-0.776) were not associated with nirmatrelvir/ritonavir use. After propensity score matching, day-30 mortality rate in patients treated with nirmatrelvir/ritonavir was 2%, significantly lower than in patients with SARS-CoV-2 directed treatment other than nirmatrelvir/ritonavir (11%, p = 0.036). No factor was observed explaining the mortality difference in patients after nirmatrelvir/ritonavir administration. Interpretation: Haematological malignancy patients were more likely to receive nirmatrelvir/ritonavir when reporting extrapulmonary symptoms or 2nd vaccine booster at COVID-19 onset, as opposed to chronic pulmonary disease and obesity. The mortality rate in patients treated with nirmatrelvir/ritonavir was lower than in patients with targeted drugs other than nirmatrelvir/ritonavir. Funding: EPICOVIDEHA has received funds from Optics COMMIT (COVID-19 Unmet Medical Needs and Associated Research Extension) COVID-19 RFP program by GILEAD Science, United States (Project 2020-8223)

Age, Successive Waves, Immunization, and Mortality in Elderly COVID-19 Haematological Patients: EPICOVIDEHA Findings

Introduction: elderly patients with haematologic malignancies face the highest risk of severe COVID-19 outcomes. The infection impact in different age groups remains unstudied in detail. Methods: We analysed elderly patients (age groups: 65-70, 71-75, 76-80 and >80 years old) with hematologic malignancies included in the EPICOVIDEHA registry between January 2020 and July 2022. Univariable and multivariable Cox regression models were conducted to identify factors influencing death in COVID-19 patients with haematological malignancy. results: the study included data from 3,603 elderly patients (aged 65 or older) with haematological malignancy, with a majority being male (58.1%) and a significant proportion having comorbidities. The patients were divided into four age groups, and the analysis assessed COVID-19 outcomes, vaccination status, and other variables in relation to age and pandemic waves.tThe 90-day survival rate for patients with COVID-19 was 71.2%, with significant differences between groups. The pandemic waves had varying impacts, with the first wave affecting patients over 80 years old, the second being more severe in 65-70, and the third being the least severe in all age groups. factors contributing to 90-day mortality included age, comorbidities, lymphopenia, active malignancy, acute leukaemia, less than three vaccine doses, severe COVID-19, and using only corticosteroids as treatment. Conclusions: These data underscore the heterogeneity of elderly haematological patients, highlight the different impact of COVID waves and the pivotal importance of vaccination, and may help in planning future healthcare efforts

Nanochannels for Supramolecular Organisation of Dyes

The supramolecular organisation of molecules, complexes or clusters is a fruitful concept for the design of systems exhibiting specific macroscopic properties. The encapsulation of guest species into the pores or channels of host materials presents a challenging approach to the preparation of novel chemical and optical materials. Zeolite L has been shown to be an ideal host for the supramolecular organisation of organic dyes. A new hierarchy of structural ordering can be achieved by either arranging the zeolite L crystals into densely packed, oriented monolayers or by interfacing them to the environment via molecules bound to the edges of the crystals. These concepts are reviewed here, as well as some potential applications

Novel phthalocyanine-based stopcock for zeolite L

We report the first phthalocyanine-based stopcock for selective adsorption to the channel entrances of zeolite L and realisation of a new electronic dipole moment coupling situation.Depto. de Química en Ciencias FarmacéuticasFac. de FarmaciaTRUEpu