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Laser desorption-ionization mass spectrometry (MS) shows great potential for in situ molecular analysis of planetary surfaces and microanalysis of space-returned samples or (micro)fossils. Coupled with pyrolysis gas chromatography-mass spectrometry (Py-GC-MS) in ESA's ExoMars project, this technique could help assess further the origin of sulfur-bearing organic matter (OM) recently detected on Mars. To unravel this potential, we analyzed sulfurized microbial OM from ca. 150 million year-old carbonates with laser desorption-ionization mass spectrometry (single- and two-step: LDI-MS and L2MS), in comparison with time-of-flight secondary-ion mass spectrometry (ToF-SIMS), gas chromatography-mass spectrometry (GC-MS), and Py-GC-MS. We show that LDI-MS and L2MS readily detect sulfur-bearing moieties such as (alkyl)thiophenes and (alkyl)benzothiophenes. The mineral matrix, however, made the identification of sulfur-bearing molecules challenging in our L2MS experiment. The dominance of small aromatic hydrocarbons (≤14 carbons) in the LDI-MS and L2MS of the extracted soluble and insoluble OM and of the bulk rock is consistent with the low thermal maturity of the sediment and contrasts with the predominance of larger polycyclic aromatic structures commonly observed in meteorites with these techniques. We detected inorganic ions, in particular VO + , in demineralized OM that likely originate from geoporphyrins, which derive from chlorophylls during sediment diagenesis. Finally, insoluble OM yielded distinct compositions compared with extracted soluble OM, with a greater abundance of ions of mass-to-charge ratio ( m / z ) over 175 and additional N-moieties. This highlights the potential of laser-assisted MS to decipher the composition of macromolecular OM, in particular to investigate the preservation of biomacromolecules in microfossils. Studies comparing diverse biogenic and abiogenic OM are needed to further assess the use of this technique to search for biosignatures.

Background: The effectiveness of the COVID-19 vaccine may differ in hemodialysis patients. The aim of this prospective multicenter study was to determine the degree of serological response to the SARS-CoV-2 vaccine in the population of dialysis patients and its association with later SARS-CoV-2 infections., Methods: A blood sample was taken for the determination of COVID-19 serological status (IgG antibodies) in 706 dialysis patients 16 weeks after vaccination with the second dose (Pfizer-BioNTech)., Results: Only 314 (44.5%) hemodialyzed patients had a satisfactory response to the COVID-19 vaccine. Eighty-two patients (11.6%) had a borderline response, while 310 patients (43.9%) had an unsatisfactory (negative) post-vaccinal antibody titer. A longer dialysis vintage had an increased odds ratio (OR) of 1.01 for the occurrence of COVID-19 positivity after vaccination. In the group of subsequently positive patients, 28 patients (13.6%) died from complications of COVID-19. We have found differences in mean survival time between patients with and without appropriate responses to vaccination in favor of patients with a satisfactory serological response., Conclusions: The results showed that the dialysis population will not have the same serological response to the vaccine as the general population. The majority of dialysis patients did not develop a severe clinical picture or die at the time of positivity for COVID-19.

The temporal and spatial variability of pollution pressures of the coastal waters resulting from river discharges is the main cause of eutrophication along the coastline. This study aims to assess the water quality and trophic state of Kastela Bay and the river Jadro estuary located in the Croatian central Adriatic Sea. The trophic assessment is classified using the composite trophic status index (TRIX), originally developed for Italian coastal waters and modified for the eastern central Adriatic Sea using data series from 2012 to 2019 from 13 stations. The impact coming from the river Jadro estuary is analyzed using the loading capacity concept to examine the exchange flows and loading dynamics of nutrients discharged in the Kastela Bay. The results show that the trophic index is larger within the river Jadro estuary and maintains the increased values in the surface layer throughout Kastela Bay. The presented loading capacity concept, accounting for the exchange flows in transitional waters, may help better understand the trophic dynamics of the receiving waters. The loading capacity is changing with the river flow and daily loads from measurements can be used to assess the pattern of impairment., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

It is demonstrated, using tandem mass spectrometry and radio frequency ion trap, that the adsorption of a H atom on the gold dimer cation, Au 2 H + , prevents its dissociation and allows for adsorption of CO. Reaction kinetics are measured by employing a radio frequency ion trap, where Au 2 + and CO interact for a given reaction time. The effect of a hydrogen atom is evaluated by comparing reaction rate constants measured for Au 2 + and Au 2 H + . The theoretical results for the adsorption of CO molecules and their reaction characteristics with Au 2 + and Au 2 H + are found to agree with the experimental findings. The joint investigations provide insights into hydrogen atom adsorption effects and consequent reaction mechanisms.

Single-photon, two-electron photodetachment from nickel phthalocyanine tetrasulfonic acid tetra anions, [NiPc](4-), was examined in the gas-phase using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. This system was chosen since it has a low detachment energy, known charge localization, and well-defined geometrical and electronic structures. A threshold for two-electron loss is observed at 10.2 eV, around 1 eV lower than previously observed double detachment thresholds on multiple charged protein anions. The photodetachment energy of [NiPc](4-) has been previously determined to be 3.5 eV and the photodetachment energy of [NiPc](3-•) is determined in this work to be 4.3 eV. The observed single photon double electron detachment threshold is hence 5.9 eV higher than the energy required for sequential single electron loss. Possible mechanisms are for double photodetachment are discussed. These observations pave the way toward new, exciting experiments for probing double photodetachment at relatively low energies, including correlation measurements on emitted photoelectrons.

UV photodissociation of proline-containing peptide ions leads to unusual product ions. In this paper, we report laser-induced dissociation of a series of proline-containing peptides at 213 nm. We observe specific fragmentation pathways corresponding to the formation of (y-2), (a + 2) and (b + 2) fragment ions. This was not observed at 266 nm or for peptides which do not contain proline residues. In order to obtain insights into the fragmentation dynamics at 213 nm, a small peptide (RPK for arginine-proline-lysine) was studied both theoretically and experimentally. Calculations of absorption spectra and non-adiabatic molecular dynamics (MD) were made. Second and third excited singlet states, S(2) and S(3), lie close to 213 nm. Non-adiabatic MD simulation starting from S(2) and S(3) shows that these transitions are followed by C-C and C-N bond activation close to the proline residue. After this first relaxation step, consecutive rearrangements and proton transfers are required to produce unusual (y-2), (a + 2) and (b + 2) fragment ions. These fragmentation mechanisms were confirmed by H/D exchange experiments.

By developing a new method for synthesizing atomically monodisperse Au15 nanoclusters stabilized with glutathione molecules and using the current state-of-the-art methods for synthesizing monodisperse protected Au25 nanoclusters, we investigated their nonlinear optical (NLO) properties after two-photon absorption. The two-photon emission spectra and the first hyperpolarizabilities of these particles were obtained using, in particular, a hyper-Rayleigh scattering technique. The influence on NLO of the excitation wavelength, the size as well as the nature of the ligands is also explored and discussed. Au15, the smallest stable thiolated gold nanocluster, presents remarkable nonlinear properties with respect to two-photon processes. The two-photon absorption cross-section at 780 nm for Au15 is ∼65,700 GM. This experimental cross-section value points to a quantum yield for two-photon emission of about 3 × 10(-7) at 475 nm for Au15. The first hyperpolarizability β for Au15 clusters (509 × 10(-30) esu), as compared to Au25 clusters (128 × 10(-30) esu), is larger considering the difference in the number of gold atoms. Also, 10(30) β per atom values reported for Au15 and Au25 clusters are more than two orders of magnitude larger than the values reported for Au NPs in the size range 10-50 nm, outlining the quantum cluster regime.

We studied the impact of a food supplementation program (Plan Más Vida (PMV)) on the micronutrient nutritional condition of pregnant women from low-income families 1 year after its implementation. The food program provided supplementary diet (wheat and maize--fortified flour, rice or sugar, and fortified soup). We performed a prospective, nonexperimental, cross-sectional study in the province of Buenos Aires, Argentina, evaluating pregnant women at baseline (n = 164) and 1 year after PMV implementation (n = 108). Biochemical tests (hemogram, ferritin, vitamin A, zinc, and folic acid), anthropometric assessments (weight and height), and dietary surveys (24 h recall) were performed at the two study points. One year after PMV implementation, no significant changes in anthropometric values were observed. Folic acid deficiency and the risk of vitamin A deficiency (retinol, 20-30 μg/dl) decreased significantly (35.8 to 6.1 % and 64 to 41 %, respectively; p < 0.000). Anemia and prevalence of iron and zinc deficiency values did not change. Diet survey results showed that although nutrient intake increased significantly, it was still below recommendations. Implementation of the PMV and of the government nutritional strategies had a high impact on the prevalence of folic acid deficiency. We also observed a decrease in the risk of vitamin A deficiency, and no impact on iron and zinc nutritional status. Adherence to the specific fortified food (soup) was not good and intra-family dilution and distribution of food was high.

This study was conducted to evaluate the impact of a food aid program (Plan Más Vida, PMV) on the micronutrient nutritional condition of lactating mothers 1 year after its implementation. The food program provided supplementary diets (wheat- and maize-fortified flour, rice or sugar, and fortified soup) to low-income families from the province of Buenos Aires, Argentina. A prospective, non-experimental study was carried out to evaluate the micronutrient nutritional status of lactating mothers (n = 178 at baseline and n = 151 after 1 year). Biochemical tests (hemoglobin, ferritin, zinc, vitamin A, and folic acid), anthropometric assessments (weight and height) and dietary surveys (24-h recall) were performed. We found no significant changes in anthropometric values 1 year after the intervention. The risk for vitamin A (retinol 20-30 μg/dl) and folate deficiency significantly decreased 1 year after PMV implementation (56.3 vs. 29.9 and 50.3 vs. 3.4 %, respectively; p < 0.001). Anemia was seen in 25.8 % of lactating mothers at baseline, without statistically significant differences 1 year after (p = 0.439). The nutritional data obtained after assessing the early impact of PMV actions may be useful to provincial health authorities to perform periodic evaluations in the future.

This study was undertaken to evaluate the impact of Plan Más Vida (PMV) on the micronutrient nutritional condition of children aged 1 to 6 years 1 year after PMV implementation. The food program was intended for low-income families from the province of Buenos Aires, Argentina and provided supplementary diets. A prospective, nonexperimental study was carried out. Children (472 at baseline and 474 after 1 year) were divided into two groups (1-2 and 2-6 years of age). Biochemical tests (hemogram, ferritin, zinc, vitamin A, and folic acid), anthropometric assessments (weight and height), and dietary surveys (24-h recall) were performed. Chronic growth retardation (-2 height/age Z-score) was present in 2.8% and 8.7% of 1-2- and 2-6-year-old children, respectively; 14.4% in the former and 8.8% in the latter group had overweight/obesity. No significant changes were recorded 1 year after PMV implementation. Whereas anemia values decreased (55.3% to 39.1%, p = 0.003) and serum zinc values increased in 1-2-year-old children, the risk for vitamin A deficiency decreased significantly in both age groups. The evaluation of the early impact of PMV actions provided important nutritional data that should be used by provincial health authorities to conduct future evaluations.

The carotid artery intima-media thickness (IMT) is an established surrogate marker of vascular risk. We assessed the common femoral artery IMT and its correlation with coronary artery disease (CAD). We also assessed the influence of vascular risk factors on the femoral IMT. Patients (n = 180; mean age 60.4 ± 10.5 years) who had undergone coronary angiography due to symptoms of CAD were enrolled in this study. We found significantly higher values of femoral IMT in patients with CAD than in those without CAD (P = .0000). A strong positive correlation between femoral IMT and the severity of CAD expressed by the Gensini Score (P = .0000) was observed. There was a positive correlation between femoral IMT and levels of triglycerides (P = .017), body mass index (BMI; P = .036), male gender (P = .0000), and smoking (P = .028). There was a negative correlation between femoral IMT and the level of high-density lipoprotein-cholesterol (P = .001). Femoral IMT could be a novel cardiovascular risk marker.