This article reports the search for nonflammable, stable electrolytes based on ionic liquid (IL) compounds, able to effectively improve the needed safety and reliability of lithium batteries. The ...most significant results are reviewed with the aim of elucidating critical aspects governing the properties of IL electrolytes, including (1) transport properties affecting ionic conductivity and the cycling rate of battery systems, (2) electrochemical/chemical stability toward most conventional electrode materials, and (3) thermal properties determining the range of applicability. Both liquid and polymer electrolytes, adopting ILs as the main component or as an additive to standard electrolyte solutions, are considered. Very promising results, in terms of battery prototype performances in scaled-up configurations, demonstrate the validity of the use of ILs for practical applications. Even though further improvements are necessary, particularly at high current density operations in both lithium-metal and lithium-ion systems, the realization of safer, high-performance batteries based on IL electrolytes is certainly possible. It can be concluded that ILs represent a viable solution to disappointing compromises between energy density and acceptable safety features in lithium batteries.
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EMUNI, FIS, FZAB, GEOZS, GIS, IJS, IMTLJ, KILJ, KISLJ, MFDPS, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, SBMB, SBNM, UKNU, UL, UM, UPUK, VKSCE, ZAGLJ
•Exclusive extraction of copper was attained by leaching with DES at 90 °C.•An extraction yield of 90% for cobalt and only 10% for nickel was reached.•Role of DES degradation during leaching was ...investigated.•Recovered lithium cobalt oxide shows performance equal to commercial material.•DES solution was reused delivering fairly satisfactory leaching performances.
Despite the efforts devoted to the development of new cathodic materials, cobalt-based lithium-ion batteries (LIBs) remain the first choice for many applications, turning cobalt into a critical raw material. Here, we report a method for the selective recovery of cobalt from mixed LIBs electrode materials. The method relies on the application of a green deep eutectic solvent (DES) and yields an extraction of 90% for cobalt and only 10% for nickel. A solvent extraction procedure was optimized to recover cobalt as cobalt oxalate, which was employed to produce lithium cobalt oxide cathode material. This produced cathode material delivered a discharge capacity of 150 mAh g−1 and a capacity retention between 10 and 100 galvanostatic cycles of 83%. Remarkably, the residual DES solution was reused delivering the same cobalt extraction attained using the fresh DES. Cobalt separation constitutes one of the major bottleneck during LIBs recycling, requiring costly and complex hydrometallurgical operations. The demonstrated selectivity of the implemented leaching method, along with the possibility to reuse the residual DES solution, paves the way to a green recycling alternative allowing for the reintroduction of strategic materials into the LIBs production chain.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•Whole-blood interferon-γ-release assay (IGRA) enabled the response to SARS-CoV-2 peptides to be evaluated.•Spike protein was the best stimulus to discriminate COVID-19 from NO-COVID-19.•A ...SARS-CoV-2-specific response is rarely observed in NO-COVID-19 individuals.•This SARS-CoV-2 IGRA has the potential to be a powerful diagnostic tool.
To identify the best experimental approach to detect a SARS-CoV-2-specific T cell response using a whole-blood platform.
Whole-blood from 56 COVID-19 and 23 “NO-COVID-19” individuals were stimulated overnight with different concentrations (0.1 or 1 μg/mL) of SARS-CoV-2 PepTivator® Peptide Pools, including spike (pool S), nucleocapsid (pool N), membrane (pool M), and a MegaPool (MP) of these three peptide pools. ELISA was used to analyse interferon (IFN)-γ levels.
The IFN-γ-response to every SARS-CoV-2 peptide pool was significantly increased in COVID-19 patients compared with NO-COVID-19 individuals. Pool S and MegaPool were the most potent immunogenic stimuli (median: 0.51, IQR: 0.14–2.17; and median: 1.18, IQR: 0.27–4.72, respectively) compared with pools N and M (median: 0.22, IQR: 0.032–1.26; and median: 0.22, IQR: 0.01−0.71, respectively). The whole-blood test based on pool S and MegaPool showed a good sensitivity of 77% and a high specificity of 96%. The IFN-γ-response was mediated by both CD4+ and CD8+ T cells, and independently detected of clinical parameters in both hospitalized and recovered patients.
This easy-to-use assay for detecting SARS-CoV-2-specific T cell responses may be implemented in clinical laboratories as a powerful diagnostic tool.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
•Tumor necrosis factor-α significantly discriminates tuberculosis (TB)-COVID-19 from COVID-19.•SARS-CoV-2-specific response is significantly impaired in patients with TB-COVID-19.•Mycobacterium ...tuberculosis-specific response is significantly reduced in patients with TB-COVID-19.
To characterize the plasma immune profile of patients with tuberculosis (TB)-COVID-19 compared with COVID-19, TB, or healthy controls and to evaluate in vitro the specific responses to SARS-CoV-2 and Mycobacterium tuberculosis (Mtb)-antigens.
We enrolled 119 subjects: 14 TB-COVID-19, 47 COVID-19, 38 TB, and 20 controls. The plasmatic levels of 27 immune factors were measured at baseline using a multiplex assay. The specific response to SARS-CoV-2 and Mtb antigens was evaluated using a home-made whole blood platform and QuantiFERON-Plus tubes, respectively.
We found an immune signature (tumor necrosis factor TNF-α, macrophage inflammatory protein-1β, and interleukin IL-9) associated with TB-COVID-19 coinfection compared with COVID-19 (P <0.05), and TNF-α showed the highest discriminant power. We also found another signature (TNF-α, IL-1β, IL-17A, IL-5, fibroblast growth factor-basic, and granulocyte macrophage colony-stimulating factor GM-CSF) in coinfected patients compared with patients with TB (P <0.05), and among them, TNF-α and granulocyte macrophage colony-stimulating factor showed a non-negligible discriminating ability. Moreover, coinfected patients showed a significantly reduced SARS-CoV-2-specific response compared with COVID-19 for several pro-inflammatory cytokines/chemokines, anti-inflammatory cytokines, and growth factors (P ≤0.05). Furthermore, coinfection negatively affected the Mtb-specific response (P ≤0.05).
We found immune signatures associated with TB-COVID-19 coinfection and observed a major impairment of SARS-CoV-2-specific and, to a lesser extent, the Mtb-specific immune responses. These findings further advance our knowledge of the immunopathology of TB-COVID-19 coinfection.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
Treatment of multi-drug resistant Tuberculosis (MDR-TB) is challenging because it mostly relies on drugs with lower efficacy and greater toxicity than those used for drug-susceptible TB.
Aim of the ...study was to describe the frequency and type of adverse drug reactions in a cohort of MDR-TB patients and their potential impact on treatment outcome.
We conducted a retrospective study in a cohort of MDR-TB patients enrolled at a tertiary referral hospital in Italy from January 2008 to December 2016. The records of patients were reviewed for epidemiological, clinical, microbiological and adverse drug reactions data.
Seventy-four MDR-TB patients (mean age 32 years, 58.1% males, 2 XDR, 12 pre-XDR TB) were extracted from the Institute data base and included in the retrospective study cohort in the evaluation period (January 2008-December 2016). Median length of treatment duration was 20 months (IQR 14-24). Treatment outcome was successful in 57 patients (77%; 51 cured, 6 treatment completed); one patient died and one failed (2.7% overall); 15 patients were lost to follow-up (20.3%). Sixty-six (89.2%) presented adverse drug reactions during the whole treatment period. Total number of adverse drug reactions registered was 409. Three hundred forty-six (84.6%) were classified as adverse events (AEs) and 63 (15.4%) were serious AEs (SAEs). One third of the total adverse drug reactions (134/409; 32.8%) was of gastrointestinal origin, followed by 47/409 (11.5%) ototoxic drug reactions, thirty-five (8.6%) regarded central nervous system and 33 (8.1%) affected the liver. All 63 SAEs required treatment suspension with 61 SAEs out of 63 (96.8%) occurring during the first six months of treatment. Factors associated with unsuccessful treatment outcome were smoking (p = 0.039), alcohol abuse (p = 0.005) and homeless condition (p = 0.044). Neither the number of antitubercular drugs used in different combinations nor the number of AEs showed significant impact on outcome. Patients who completed the treatment experienced a greater number of AEs and SAEs (p < 0.001) if compared to lost to follow-up patients.
Our data demonstrate that, despite the high frequency of adverse drug reactions and long term therapy, the clinical management of MDR-TB patients in a referral center could reach successful treatment according to WHO target, by implementing active and systematic clinical and laboratory assessment to detect, report and manage suspected and confirmed adverse drug reactions.
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DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Recent studies proposed the whole-blood based IFN-γ-release assay to study the antigen-specific SARS-CoV-2 response. Since the early prediction of disease progression could help to assess the optimal ...treatment strategies, an integrated knowledge of T-cell and antibody response lays the foundation to develop biomarkers monitoring the COVID-19. Whole-blood-platform tests based on the immune response detection to SARS-CoV2 peptides is a new approach to discriminate COVID-19-patients from uninfected-individuals and to evaluate the immunogenicity of vaccine candidates, monitoring the immune response in vaccine trial and supporting the serological diagnostics results. Here, we aimed to identify in the whole-blood-platform the best immunogenic viral antigen and the best immune biomarker to identify COVID-19-patients.
Whole-blood was overnight-stimulated with SARS-CoV-2 peptide pools of nucleoprotein-(NP) Membrane-, ORF3a- and Spike-protein. We evaluated: IL-1β, IL-1Ra, IL-2, IL-4, IL-5, IL-6, IL-7, IL-8, IL-9, IL-10, IL-12p70, IL-13, IL- 15, IL-17A, eotaxin, FGF, G-CSF, GM-CSF, IFN-γ, IP-10, MCP-1, MIP-1α, MIP-1β, PDGF, RANTES, TNF-α, VEGF. By a sparse partial least squares discriminant analysis we identified the most important soluble factors discriminating COVID-19- from NO-COVID-19-individuals.
We identified a COVID-19 signature based on six immune factors: IFN-γ, IP-10 and IL-2 induced by Spike; RANTES and IP-10 induced by NP and IL-2 induced by ORF3a. We demonstrated that the test based on IP-10 induced by Spike had the highest AUC (0.85, p < 0.0001) and that the clinical characteristics of the COVID-19-patients did not affect IP-10 production. Finally, we validated the use of IP-10 as biomarker for SARS-CoV2 infection in two additional COVID-19-patients cohorts.
We set-up a whole-blood assay identifying the best antigen to induce a T-cell response and the best biomarkers for SARS-CoV-2 infection evaluating patients with acute COVID-19 and recovered patients. We focused on IP-10, already described as a potential biomarker for other infectious disease such as tuberculosis and HCV. An additional application of this test is the evaluation of immune response in SARS-CoV-2 vaccine trials: the IP-10 detection may define the immunogenicity of a Spike-based vaccine, whereas the immune response to the virus may be evaluated detecting other soluble factors induced by other viral-antigens.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
A study on the interfacial properties between a solid glassy electrolyte, LiI‐Li3PS4 (LPSI), and graphite (MAG) composite electrodes was carried out with the aim of reducing or even eliminating the ...irreversible capacity during the 1st charge‐discharge cycle. The performances of all‐solid‐state MAG|LPSI|Li cells were compared with those of conventional liquid cells. To reinforce a well‐distributed conductive path in MAG as well as at the MAG/LPSI interface, the type of electron conducting additive and the pressure during cell preparation were optimized. Specific functions of the conducting additive were demonstrated, where the sub‐micrometric carbon fibers allowed better galvanostatic performance in the solid‐state configuration by virtue of their high aspect ratio. The coulombic efficiency of solid‐state cells was improved from 46 to 99 % and the reversible capacity value from 100 to 270 mAh g−1, by increasing the pressure from 2 to 4 ton. The interfacial stability of LPSI was also evaluated by impedance spectroscopy of MAG|MAG and Li|Li cells over time. Although ionic resistance of LPSI was higher than a conventional liquid electrolyte, LPSI exhibited controlled interfacial resistance.
Liquid or solid? High interfacial stability of LiI‐Li3PS4 against lithium and graphite anodes was demonstrated by means of impedance spectroscopy and galvanostatic cycling. Moreover, an electron conductive additive in anodes was revealed to have a different role in all‐solid cells compared that in conventional liquid cells.
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FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
•Mycobacterium tuberculosis (Mtb) DNA is detected in the peripheral blood cells of donors with tuberculosis (TB) or TB infection.•Mtb DNA is detected in the peripheral blood cells of donors with ...presumptive TB.•Mtb DNA detection is more frequent in peripheral CD34+ cells.•CD34+ cells may represent a niche for Mtb.•Mtb DNA in peripheral blood cells may be a new microbial biomarker.
To investigate whether Mycobacterium tuberculosis (Mtb) DNA is detected in peripheral blood mononuclear cells (PBMC) of subjects with tuberculosis (TB) or TB infection (TBI) living in a low-burden country.
We prospectively enrolled 57 patients with TB, 41 subjects with TBI, and 39 controls in Rome, Italy. PBMC were isolated, cluster of differentiation (CD)34+ and CD34− cells were immunomagnetic separated, DNA was extracted, and digital polymerase chain reaction for IS6110 and rpoB sequences was used to detect Mtb DNA in PBMC subsets and unfractionated PBMC.
We detected Mtb DNA at a low copy number in CD34+ cells in 4o f 30 (13%) patients with TB, 2 of 24 (8%) subjects with TBI, and 1 of 24 (4%) controls. Mtb DNA was detected in unfractionated PBMC in 3 of 51 (6%) patients with TB, 2 of 38 (5%) subjects with TBI, and 2 of 36 (6%) controls. In CD34− cells, only 1 of 31 (3%) subjects with TBI tested positive for Mtb DNA.
Mtb DNA was detected at low frequencies and levels in the PBMC of subjects with TBI and donors with TB living in a low-burden country. In particular, Mtb DNA was detected more frequently in CD34+ cells, supporting the hypothesis that these cells may represent a Mtb niche. This finding informs biological understanding of Mtb pathogenesis and may support the development of a microbial blood biomarker for Mtb infection.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
► Interesting new material based on Nafion
® doped with sulfated-zirconia filler. ► Membrane exhibits a conductivity of 3
×
10
−3
S
cm
−1 at 120
°C in dry conditions. ► Presence of filler results in ...the deprotonation of Nafion
®’s acid moieties. ► Correlation between molecular relaxations and electric polarizations. ► Effect of water on the conduction mechanism and the molecular relaxations.
An interesting new material based on a Nafion
® membrane doped with a sulfated-zirconia filler is presented. This filler is unique in that the filler itself can contribute to the proton conductivity due to the presence of acidic functionalities on the surface of the filler. The presence of the filler in the membrane results in the deprotonation of Nafion
®’s acid moieties as indicated by the absence of the acid mode at 1475
cm
−1 in the FTIR spectrum. Spectra from DSC, DMA and broadband electric spectroscopy (BES) show the presence of several molecular transitions, two of which are detected in the BES permittivity profiles. The membrane exhibits a reasonably high conductivity (3
×
10
−3
S
cm
−1 at 120
°C) even in completely dry conditions, which makes it a promising material for an anhydrous fuel cell. The conductivity behaviour exhibits a mix of Arrhenius and VTF behaviours and is closely tied to the dielectric relaxations.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
Nafion composite membranes, containing different amounts of mesoporous sulfated titanium oxide (TiO
-SO
) were prepared by solvent-casting and tested in proton exchange membrane fuel cells (PEMFCs), ...operating at very low humidification levels. The TiO
-SO
additive was originally synthesized by a sol-gel method and characterized through x-ray diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and ion exchange capacity (IEC). Peculiar properties of the composite membranes, such as the thermal transitions and ion exchange capacity, were investigated and here discussed. When used as an electrolyte in the fuel cell, the composite membrane guaranteed an improvement with respect to bare Nafion systems at 30% relative humidity and 110 °C, exhibiting higher power and current densities.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
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