Aluminum–air (Al-air) batteries are promising electrochemical storage systems, because of their practicality, low flammability and no risk of explosion, eco-compatibility, and high energy density. ...However, Al-air batteries realized with liquid electrolytes may present safety concerns, because of leakage, and are unsuitable for miniaturized and portable electronic devices. The transition of the electrolytes for Al-air batteries from aqueous to solid form is an inevitable trend for safety, stability, and possible widespread use. Nevertheless, the manufacturing of new solid electrolytes for Al-air batteries is still a new and largely unexplored field. In fact, the most significant results appeared only in the last decade, with the development of new polymer electrolytes. In this Review, we summarize the most significant findings on polymer electrolytes used in Al-air batteries, particularly emphasizing the cell electrochemical performances and how these relate to the characteristics of the electrolyte.
The influence of formic acid on water cluster aggregation has been investigated experimentally by mass spectrometry and tunable UV laser ionization applied to Na‐doped clusters formed in the ...supersonic expansion of water vapors seeded with formic acid (FA) as well as theoretically using high level quantum chemistry methods. The mass spectra of Na−FA(H2O)n clusters show an enlarging of mass distribution toward heavier clusters with respect to the Na−(H2O)n clusters, suggesting similar mass distribution in neutral clusters and an influence of formic acid in water aggregation. Density functional theory and coupled‐cluster type (DLPNO‐CCSD(T)) calculations have been used to calculate structures and energetics of neutral and ionized Na−FA(H2O)n as well as neutral FA(H2O)n. Na‐doped clusters are characterized by very stable geometries. The theoretical adiabatic ionization potential values match pretty well the measured appearance energies and the calculated first six electronic excited states show Rydberg‐type characters, indicating possible autoionization contributions in the mass spectra. Finally, theoretical calculations on neutral FA(H2O)n clusters show the possibility of similarly stable structures in small clusters containing up to n=4–5 water molecules, where FA interacts significantly with waters. This suggests that FA can compete with water molecules in the starting stage of the aggregation process, by forming stable nucleation seed.
Cluster formation: Water aggregation in presence of formic acid at low concentration was investigated by mass spectrometry/photoionization spectroscopy. Experimental data show the formation of larger clusters in the presence of acid molecules. DFT and coupled‐cluster type (DLPNO‐CCSD(T)) calculations support experimental results and suggest that water molecules aggregate preferentially with acid molecule but mainly in the first stage of cluster formation.
New adjuvant strategies are needed to improve protein-based subunit vaccine immunogenicity. We examined the potential to use nanostructure of 6-O-ascorbyl palmitate to formulate ovalbumin (OVA) ...protein and an oligodeoxynucleotide (CpG-ODN) (OCC). In mice immunized with a single dose, OCC elicited an OVA-specific immune response superior to OVA/CpG-ODN solution (OC). Rheological studies demonstrated OCC's self-assembling viscoelastic properties. Biodistribution studies indicated that OCC prolonged OVA and CpG-ODN retention at injection site and lymph nodes, reducing systemic spread. Flow-cytometry assays demonstrated that OCC promoted OVA and CpG-ODN co-uptake by Ly6ChiCD11bhiCD11c+ monocytes. OCC and OC induced early IFN-γ in lymph nodes, but OCC led to higher concentration. Conversely, mice immunized with OC showed higher serum IFN-γ concentration compared to those immunized with OCC. In mice immunized with OCC, NK1.1+ cells were the IFN-γ major producers, and IFN-γ was essential for OVA-specific IgG2c switching. These findings illustrate how this nanostructure improves vaccine's response.
In a murine model, we explored a novel strategy for formulating vaccine components. The OVA antigen and the CpG-ODN immunostimulant were nanoformulated with a nanostructure formed by self-assembly of ascorbyl palmitate. In parallel, other mice were vaccinated with OVA and CpG-ODN formulated in an aqueous solution. The nanoformulation improved the biodistribution of the vaccine components, favoring their accumulation in the draining lymph node of the injection site over systemic circulation. This profoundly influenced on the overall immune response. Notably, mice vaccinated with the nanoformulation exhibited markedly superior antigen-specific immune responses when compared to those vaccinated with the soluble formulation. Display omitted
The incorporation of aluminum anodes in metal-air galvanic cells is very interesting due to its intrinsic physico-chemical properties that include a high theoretical specific capacity (2.98 Ah g
−1
) ...compared to lithium (3.86 Ah g
−1
), low density, negative standard potential versus the standard hydrogen electrode (SHE), high abundance in the earth's crust, recyclability, and environmental friendliness. In this report, various hydrogels based on xanthan are described that were prepared at different pH values in order to produce solid electrolytes characterized by high ionic conductivity. These electrolytes have been characterized in aluminum-air galvanic cells using Pt/C based air cathodes. The performance of the cells was characterized by discharge tests performed at constant currents across the range from 3 to 6 mA/cm
2
. The ability of recharging the cells was evaluated by determining the electrolyte electrochemical window using cyclic voltammetry (CV) measurements. The ionic conductivity of the hydrogels was determined by electrochemical impedance spectroscopy (EIS). The results evidenced the superior performance of acidic hydrogels in terms of cell capacity and anodic efficiency, due to the capability of xanthan as self-corrosion inhibitor, but the rechargeability was hindered because of the current consuming hydrogen reduction. A larger electrochemical window was observed for neutral hydrogels, but with low cell voltage, and by alkaline electrolytes, but at the expense of the anodic efficiency.
Different commercial carbonaceous materials, two made of activated carbons and one of multiwalled nanotubes, were used to prepare cathodes for primary aluminum-air cells and compared with the more ...expensive platinum-dispersed carbon, usually used as cathode for many types of metal-air cells. The aluminum-air cells used in the electrochemical tests were assembled with alkaline gel polymer electrolytes without any separator. Cells with cathodes made of a cheap activated carbon showed better electrochemical performances than those obtained with platinum-based cathodes. Notably, their discharge capacities were improved and the discharge voltages were always higher than 0.2 V. These improved performances were mainly attributed to the better electrocatalytic activity of the activated carbon as it results from polarization measurements, probably due to the presence of defects, as evidenced from Raman spectra. Three-electrode discharge tests were used to measure the electrode potentials and their impact to the overall cell electrochemical performances. During the discharge, in all cases, an increase of the anodic potential towards more positive values was observed, while the cathodic potential remained almost constant. Thus, the final failure of the cells was mainly due to the degradation of the anodic interface. This indicates the possibility to further increase the cell capacity by adopting suitable mitigation strategies of anodic parasitic reaction or different electrolyte design, with the final aim to realize efficient, cheap, and eco-friendly aluminum-air cells.
The processes involved in the photoionization of sodium‐doped clusters are complex, not fully understood for many systems and still strongly debated, especially because of the discrepancy between ...experimental results and predicted cluster structures. We have performed a study on sodium doped formic acid clusters based on UV photoionization spectroscopy and DFT/TDDFT calculations. Apart from the monomer, all the predicted structures show vertical ionization potential values higher than those obtained by the photoionization measurements. We have calculated the absorption spectra and found many Rydberg‐like states near the adiabatic ionization potentials and, crucially, in the UV range where the clusters appearance energies fall. This finding supports the hypothesis of adiabatic contributions in the measured ionization potentials for these clusters.
Low ionization threshold: Why can a cluster be photoionized although its ionization potential is much higher than the ionizing energy?
Abstract The adjuvants approved in human vaccine with recombinant/purified antigens induce weak cellular immune response and so the development of new adjuvant strategies is critical. CpG-ODN has ...successfully been used as an adjuvant (phase I–III clinical trials) but its bioavailability needs to be improved. We investigated the adjuvant ability of CpG-ODN formulated with a liquid crystal nanostructure of 6-O-ascorbyl palmitate (Coa-ASC16). Mice immunized with OVA/CpG-ODN/Coa-ASC16 elicited a potent specific IgG1, IgG2a, Th1 and Th17 cellular response without systemic adverse effects. These responses were superior to those induced by OVA/CpG-ODN (solution of OVA with CpG-ODN) and to those induced by the formulation OVA/CpG-ODN/Al(OH)3 . Immunization with OVA/CpG-ODN/Coa-ASC16 resulted in a long-lasting cell-mediated immune response (at least 6.5 months). Furthermore, Coa-ASC16 alone allows a controlled release of CpG-ODN in vitro and induces local inflammatory response, independent of TLR4 signaling, characterized by an influx of neutrophils and Ly6Chigh monocytes and pro-inflammatory cytokines. Remarkably, the adjuvant capacity of CpG-ODN co-injected with Coa-ASC16 (OVA/CpG-ODN plus Coa-ASC16) was similar to the adjuvant activity of OVA/CpG-ODN, supporting the requirement for whole formulation to help CpG-ODN adjuvanticity. These results show the potential of this formulation, opening a new avenue for the development of better vaccines.
Abstract
Background
The European Renal Association – European Dialysis and Transplant Association (ERA-EDTA) Registry collects data on kidney replacement therapy (KRT) via national and regional renal ...registries in Europe and countries bordering the Mediterranean Sea. This article summarizes the 2018 ERA-EDTA Registry Annual Report, and describes the epidemiology of KRT for kidney failure in 34 countries.
Methods
Individual patient data on patients undergoing KRT in 2018 were provided by 34 national or regional renal registries and aggregated data by 17 registries. The incidence and prevalence of KRT, the kidney transplantation activity and the survival probabilities of these patients were calculated.
Results
In 2018, the ERA-EDTA Registry covered a general population of 636 million people. Overall, the incidence of KRT for kidney failure was 129 per million population (p.m.p.), 62% of patients were men, 51% were ≥65 years of age and 20% had diabetes mellitus as cause of kidney failure. Treatment modality at the onset of KRT was haemodialysis (HD) for 84%, peritoneal dialysis (PD) for 11% and pre-emptive kidney transplantation for 5% of patients. On 31 December 2018, the prevalence of KRT was 897 p.m.p., with 57% of patients on HD, 5% on PD and 38% living with a kidney transplant. The transplant rate in 2018 was 35 p.m.p.: 68% received a kidney from a deceased donor, 30% from a living donor and for 2% the donor source was unknown. For patients commencing dialysis during 2009–13, the unadjusted 5-year survival probability was 42.6%. For patients receiving a kidney transplant within this period, the unadjusted 5-year survival probability was 86.6% for recipients of deceased donor grafts and 93.9% for recipients of living donor grafts.
Equilibrium geometries and thermodynamic potentials of the neutral and ionised species of the
$ \hbox {Na}\cdots (\hbox {H}_{2}\hbox {O})_{{n}} $
Na
⋯
(
H
2
O
)
n
(
$ {n}=1,..,8 $
n
=
1
,
.
.
,
8
) ...mixed clusters were computed at MN15/def2-TZVPD level of density functional theory (DFT). The vertical and adiabatic ionisation energies and enthalpies were computed and their cluster size dependence was discussed. Laser-induced ionisation involves electronic excitation through Rydberg-type excited states, which have been characterised using the TDDFT method, including the ωB2PLYP double-hybrid exchange-correlation functional. Ab initio molecular dynamics calculations were performed on a time scale of 20 picoseconds. Fluctuations of the charge and the sodium-oxygen atomic distances predict that, the
$ 3\hbox {s}^{1} $
3
s
1
electron of the sodium atom are transferred from the delocalised Rydberg orbitals to the Rydberg orbitals around the water molecules and the sodium atom becomes positively charged with around 0.6e after the first
$ 10\,\hbox {ps} $
10
ps
. On the other hand, some of the water molecules can move away up to 5 Å from the sodium with a significant negative charge on them. It has been shown that non-radiative relaxation cannot be excluded, they can mostly occur for cases
$ n \geqslant 4 $
n
⩾
4
. The results confirm that the adiabatic photo-ionisation can occur on the basis of cluster disintegration.
Inherited platelet disorders are a heterogeneous group of rare diseases, caused by inherited defects in platelet production and/or function. Their genetic diagnosis would benefit clinical care, ...prognosis and preventative treatments. Until recently, this diagnosis has usually been performed
Sanger sequencing of a limited number of candidate genes. High-throughput sequencing is revolutionizing the genetic diagnosis of diseases, including bleeding disorders. We have designed a novel high-throughput sequencing platform to investigate the unknown molecular pathology in a cohort of 82 patients with inherited platelet disorders. Thirty-four (41.5%) patients presented with a phenotype strongly indicative of a particular type of platelet disorder. The other patients had clinical bleeding indicative of platelet dysfunction, but with no identifiable features. The high-throughput sequencing test enabled a molecular diagnosis in 70% of these patients. This sensitivity increased to 90% among patients suspected of having a defined platelet disorder. We found 57 different candidate variants in 28 genes, of which 70% had not previously been described. Following consensus guidelines, we qualified 68.4% and 26.3% of the candidate variants as being pathogenic and likely pathogenic, respectively. In addition to establishing definitive diagnoses of well-known inherited platelet disorders, high-throughput sequencing also identified rarer disorders such as sitosterolemia, filamin and actinin deficiencies, and G protein-coupled receptor defects. This included disease-causing variants in
(n=2) and
(n=3). Our study reinforces the feasibility of introducing high-throughput sequencing technology into the mainstream laboratory for the genetic diagnostic practice in inherited platelet disorders.
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