Diagnostic Protocols for Evaluating the Degradation Mechanisms in Gel-Polymer Lithium Batteries.

Gel polymer electrolytes (GPEs) present a promising alternative to standard liquid electrolytes (LE) for Lithium-ion Batteries (LIBs) and Lithium Metal Batteries bridging the advantages of both liquid and solid polymer electrolytes. However, their cycle life still lags behind that of standard LIBs, and their degradation mechanisms remain poorly understood. A significant challenge is the need for specific diagnostic protocols to systematically study the degradation mechanisms of GPE-based cells. Challenges include the separation of cell components and effective washing, as well as the study of the solid electrolyte interfaces, all complicated by the semi-solid nature of GPEs. This paper provides a brief review of existing literature and proposes a comprehensive set of diagnostic tools for dismantling and evaluating the degradation of GPE-based LIBs. Finally, these methods and recommendations are applied to LiNi0.5Mn1.5O4 (LNMO)-graphite cells, revealing electrolyte oxidation as a major source of cell degradation.

Quality-dependent performance of hydrophobic ZIF-67 upon high-pressure water intrusion-extrusion process.

Zeolitic imidazolate framework (ZIF) microporous materials have already been employed in many fields of energetic and environmental interest since the last decade. The commercial scale production of some of these materials makes them more accessible for their implementation in industrial processes; however, their massive synthesis may entail modifications to the preparation protocols, which may result in a loss in the optimization of this process and a drop in the material's quality. This fact may have implications for the performance of these materials during their lifetime, especially when they are used in applications such as energy dissipation, in which they are subjected to several operating cycles under high pressures. This study focuses on ZIF-67, a material that has demonstrated in the past its ability to dissipate energy through the water intrusion-extrusion process under high pressure. Two ZIF-67 samples were synthesized using different protocols, and 2 batches of different qualities (labelled as high quality (HQ) and low quality (LQ)) were obtained and analysed by water porosimetry to study their performance in the intrusion-extrusion process. Unexpectedly, minor structural differences, which are typically neglected especially under production conditions, had a dramatic effect on their performance. The results presented in this study reiterate the importance of quality control with respect to reproducibility of experimental results. In a broader perspective, they are critical to the technology transfer from academia to industry.

Evaluation of Electronic-Ionic Transport Properties of a Mg/Zr-Modified LiNi0.5Mn1.5O4 Cathode for Li-Ion Batteries.

There is an enormous drive for moving toward cathode material research in LIBs due to the proposal of zero-emission electric vehicles together with the restriction of cathode materials in design. LiNi0.5Mn1.5O4 (LNMO) attracts great research interests as high-voltage Co-free cathodes in LIBs. However, a more extensive study is required for LNMO due to its poor electrochemical performance, especially at high temperature, because of the instability of the LNMO interface. Herein, we design structural modifications using Mg and Zr to alleviate the above-mentioned drawbacks by limiting Mn dissolution and tailoring interstitial sites (which are shown by structural and electrochemical characterizations). This strategy enhances the cycle life up to 1000 cycles at both 25 and 50 °C. In addition, a thorough characterization by impedance spectroscopy is applied to give an insight into the electronic and ionic transport properties and the intricate phase transitions occurring upon oxidation and reduction.

The impact after 20 years of an early detection program for severe retinopathy of prematurity in a Latin American city.

Purpose: To evaluate the effects of long-standing early detection program in the incidence and trends of severe retinopathy of prematurity (ROP) in Cali, Colombia. Methods: This was a retrospective cohort study of infants included in an ROP prevention, early detection, and prompt treatment program, from January 01, 2002, to December 31, 2021 (20 years). Infants with gestational age (GA) <37 weeks or birth weight (BW) <2000 g and those with known ROP risk factors were screened. The incidence of severe ROP was calculated, and the average annual percent change (AAPC) was estimated through a joinpoint model. Results: 16,580 infants were screened, with an average GA and BW of 31.4 ± 2.8 weeks and 1526.5 ± 56.7 g, respectively. The incidence of severe ROP was 2.69% (446 cases, 95% confidence interval [95%CI]: 2.45%; 2.95%), with an average annual decrease of - 14% (AAPC, 95%CI: -16.3%; -11.6%) from 13.6% in 2002 to 0.7% in 2021. In infants with GA <32 weeks, the incidence was 5.21%. A significant reduction in the risk of ROP was observed with increasing GA and BW (P < 0.05). Among the cases with severe ROP, 6.5% (29/446) had a GA ≥32 weeks with a maximum of 37 weeks; only 0.4% (2/446) of the detected infants had a BW >2000 g. Conclusion: Awareness and screening as part of the early detection program to prevent ROP has shown a significant decline in the incidence of severe ROP over time. Screening infants with GA <32 weeks or BW <2000 g and preterm infants (<37 weeks) with risk factors may be a feasible decision for resource optimization.

Feasibility of Multifunctional Cellulose-Based Polysalt as a Polymer Matrix for Li Metal Polymer Batteries.

Li metal secondary batteries known for their high energy and power density are the much-awaited energy storage systems owing to the high specific capacity of Li metal. However, due to the instability of Li metal with common Li-ion battery electrolytes, a combination with a polymer electrolyte seems to be an effective strategy to alleviate the safety issues of employing Li metal and provide design conformity to the system. Current trends show improvements in different aspects, such as improving ionic conductivity, single-ion conductivity, mechanical stability, and electrochemical stability. A combination of all these properties has been a bottleneck for the development of polymer electrolytes for safe and efficient operation of all solid-state batteries. Herein, a multifunctional polysalt has been synthesized from green and sustainable materials, namely, ethyl cellulose, plasticized with adiponitrile, that contributes to meeting the critical properties enabling high compatibility with Li metal and a quasi-single-ion-conducting property while simultaneously acting as a matrix/filler for efficient operation of the cells. This multifunctional polymer matrix inhibits further decomposition of nitrile-based plasticizers on Li metal anodes with the formation of a favorable Li metal anode interface, thus enabling the utilization of high-voltage stable nitrile-based plasticizers (4.2 V) to be implemented as an electrolyte component for realization of high-voltage Li metal anode polymer batteries.

A Registry Study of 240 Patients with X-Linked Agammaglobulinemia Living in the USA.

PURPOSE: To understand the natural history and clinical outcomes for patients with X-linked agammaglobulinemia (XLA) in the United States utilizing the United States Immunodeficiency Network (USIDNET) patient registry. METHODS: The USIDNET registry was queried for data from XLA patients collected from 1981 to 2019. Data fields included demographics, clinical features before and after diagnosis of XLA, family history, genetic mutation in Bruton's tyrosine kinase (BTK), laboratory findings, treatment modalities, and mortality. RESULTS: Data compiled through the USIDNET registry on 240 patients were analyzed. Patient year of birth ranged from 1945 to 2017. Living status was available for 178 patients; 158/178 (88.8%) were alive. Race was reported for 204 patients as follows: White, 148 (72.5%); Black/African American, 23 (11.2%); Hispanic, 20 (9.8%); Asian or Pacific Islander, 6 (2.9%), and other or more than one race, 7 (3.4%). The median age at last entry, age at disease onset, age at diagnosis, and length of time with XLA diagnosis was 15 [range (r) = 1-52 years], 0.8 [r = birth-22.3 years], 2 [r = birth-29 years], and 10 [r = 1-56 years] years respectively. One hundred and forty-one patients (58.7%) were < 18 years of age. Two hundred and twenty-one (92%) patients were receiving IgG replacement (IgGR), 58 (24%) were on prophylactic antibiotics, and 19 (7.9%) were on immunomodulatory drugs. Eighty-six (35.9%) patients had undergone surgical procedures, two had undergone hematopoietic cell transplantation, and two required liver transplantation. The respiratory tract was the most affected organ system (51.2% of patients) followed by gastrointestinal (40%), neurological (35.4%), and musculoskeletal (28.3%). Infections were common both before and after diagnosis, despite IgGR therapy. Bacteremia/sepsis and meningitis were reported more frequently before XLA diagnosis while encephalitis was more commonly reported after diagnosis. Twenty patients had died (11.2%). The median age of death was 21 years (range = 3-56.7 years). Neurologic condition was the most common underlying co-morbidity for those XLA patients who died. CONCLUSIONS: Current therapies for XLA patients reduce early mortality, but patients continue to experience complications that impact organ function. With improved life expectancy, more efforts will be required to improve post-diagnosis organ dysfunction and quality of life. Neurologic manifestations are an important co-morbidity associated with mortality and not yet clearly fully understood.

High-Temperature Thermal Reactivity and Interface Evolution of the NMC-LATP-Carbon Composite Cathode.

Temperature-assisted densification methods are typically used in oxide-based solid-state batteries to suppress resistive interfaces. However, chemical reactivity among the different cathode components (which include a catholyte, the conducting additive, and the electroactive material) still represents a major challenge and processing parameters need thus to be carefully selected. In this study, we evaluate the impact of temperature and heating atmosphere in the LiNi0.6Mn0.2Co0.2O2 (NMC), Li1+xAlxTi2-xP3O12 (LATP), and Ketjenblack (KB) system. A rationale of the chemical reactions between components is proposed from the combination of bulk and surface techniques and overall involves a cation redistribution in the NMC cathode material that is accompanied by the loss of lithium and oxygen from the lattice enhanced by LATP and KB, which act as lithium and oxygen sinks. The final result is the formation of several degradation products, starting at the surface, that lead to a rapid capacity decay above 400 °C. Both the reaction mechanism and threshold temperature depend on the heating atmosphere, with the air atmosphere being more favorable compared to oxygen or any other inert gases.

Turning Molecular Springs into Nano-Shock Absorbers: The Effect of Macroscopic Morphology and Crystal Size on the Dynamic Hysteresis of Water Intrusion-Extrusion into-from Hydrophobic Nanopores.

Controlling the pressure at which liquids intrude (wet) and extrude (dry) a nanopore is of paramount importance for a broad range of applications, such as energy conversion, catalysis, chromatography, separation, ionic channels, and many more. To tune these characteristics, one typically acts on the chemical nature of the system or pore size. In this work, we propose an alternative route for controlling both intrusion and extrusion pressures via proper arrangement of the grains of the nanoporous material. To prove the concept, dynamic intrusion-extrusion cycles for powdered and monolithic ZIF-8 metal-organic framework were conducted by means of water porosimetry and in operando neutron scattering. We report a drastic increase in intrusion-extrusion dynamic hysteresis when going from a fine powder to a dense monolith configuration, transforming an intermediate performance of the ZIF-8 + water system (poor molecular spring) into a desirable shock-absorber with more than 1 order of magnitude enhancement of dissipated energy per cycle. The obtained results are supported by MD simulations and pave the way for an alternative methodology of tuning intrusion-extrusion pressure using a macroscopic arrangement of nanoporous material.

X-Linked Agammaglobulinemia: Infection Frequency and Infection-Related Mortality in the USIDNET Registry.

X-linked agammaglobulinemia (XLA) is a primary immunodeficiency disorder caused by mutations in the Bruton tyrosine kinase (BTK) gene leading to B lymphocyte deficiency and susceptibility to infection. A potential benefit of earlier diagnosis and treatment initiation on morbidity and mortality in XLA is incompletely understood. In the USIDNET Registry, we describe infection frequency and infection-related mortality in patients with XLA and their relationship to age of diagnosis and treatment initiation. Among the 231 XLA patients enrolled in the Registry, respiratory infections (N = 203, 88%) were the most commonly reported. Among those deceased (N = 20) where cause of death was known (N = 17), mortality was attributed to infection in most (N = 12, 71%). Chronic lung disease, often a consequence of repeated lower respiratory tract infection (LRTI), was also a frequent complication associated with mortality (N = 9, 53%). Age of diagnosis in years was lower for those without LRTI compared to those with (median 1.5 [IQR 0.5-3.3] vs. median 3.0 [IQR 1.0-5.0], p = 0.0026) and among living patients compared to deceased (median 1.8 [IQR 0.5-5.0] vs. median 2.7 [IQR 1.6-6.0], p = 0.04). Age at treatment initiation in years was lower among those without LRTIs compared to those with (median 1.0 [IQR 0.4-2.4] vs. median 2.8 [IQR 1.0-5.4], p = 0.0006). For every year increase in age at start of therapy, the odds of experiencing a LRTI was 1.216 (OR 1.216, 95% CI 1.048-1.411, p = 0.01). Given the expected finding of reduced LRTIs and mortality among those with earlier age at diagnosis, our study findings support inclusion of XLA in newborn screening programs.

Morphological Evolution and Solid-Electrolyte Interphase Formation on LiNi0.6Mn0.2Co0.2O2 Cathodes Using Highly Concentrated Ionic Liquid Electrolytes.

Employing high-voltage Ni-rich cathodes in Li metal batteries (LMBs) requires stabilization of the electrode/electrolyte interfaces at both electrodes. A stable solid-electrolyte interphase (SEI) and suppression of active material pulverization remain the greatest challenges to achieving efficient long-term cycling. Herein, studies of NMC622 (1 mAh cm-2) cathodes were performed using highly concentrated N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide (C3mpyrFSI) 50 mol % lithium bis(fluorosulfonyl)imide (LiFSI) ionic liquid electrolyte (ILE). The resulting SEI formed at the cathode enabled promising cycling performance (98.13% capacity retention after 100 cycles), and a low degree of ion mixing and lattice expansion was observed, even at an elevated temperature of 50 °C. Fitting of acquired impedance spectra indicated that the SEI resistivity (RSEI) had a low and stable contribution to the internal resistivity of the system, whereas active material pulverization and secondary grain isolation significantly increased the charge transfer resistance (RCT) throughout cycling.

Ten Years of Newborn Screening for Severe Combined Immunodeficiency (SCID) in Massachusetts.

BACKGROUND: Massachusetts began newborn screening (NBS) for severe combined immunodeficiency (SCID) using measurement of T-cell receptor excision circles (TRECs) from dried blood spots. OBJECTIVE: We describe developments and outcomes from the first 10 years of this program (February 1, 2009, to January 31, 2019). METHODS: TREC values, diagnostic, and outcome data from all patients screened for SCID were evaluated. RESULTS: NBS of 720,038 infants prompted immunologic evaluation of 237 (0.03%). Of 237, 9 were diagnosed with SCID/leaky SCID (4% of referrals vs 0.001% general population). Another 7 were diagnosed with other combined immunodeficiencies, and 3 with athymia. SCID/leaky SCID incidence was approximately 1 in 80,000, whereas approximately 1 in 51,000 had severe T-cell lymphopenia for which definitive treatment was indicated. All patients with SCID/leaky SCID underwent hematopoietic cell transplant or gene therapy with 100% survival. One patient with athymia underwent successful thymus transplant. No known cases of SCID were missed. Compared with outcomes from the 10 years before SCID NBS, survival trended higher (9 of 9 vs 4 of 7), likely due to a lower rate of infection before treatment. CONCLUSIONS: Our data support a single NBS testing-and-referral algorithm for all gestational ages. Despite lower median TREC values in premature infants, the majority for all ages are well above the TREC cutoff and the algorithm, which selects urgent (undetectable TREC) and repeatedly abnormal TREC values, minimizes referral. We also found that low naïve T-cell percentage is associated with a higher risk of SCID/CID, demonstrating the utility of memory/naïve T-cell phenotyping as part of follow-up flow cytometry.

Infections in Infants with SCID: Isolation, Infection Screening, and Prophylaxis in PIDTC Centers.

PURPOSE: The Primary Immune Deficiency Treatment Consortium (PIDTC) enrolled children with severe combined immunodeficiency (SCID) in a prospective natural history study of hematopoietic stem cell transplant (HSCT) outcomes over the last decade. Despite newborn screening (NBS) for SCID, infections occurred prior to HSCT. This study's objectives were to define the types and timing of infection prior to HSCT in patients diagnosed via NBS or by family history (FH) and to understand the breadth of strategies employed at PIDTC centers for infection prevention. METHODS: We analyzed retrospective data on infections and pre-transplant management in patients with SCID diagnosed by NBS and/or FH and treated with HSCT between 2010 and 2014. PIDTC centers were surveyed in 2018 to understand their practices and protocols for pre-HSCT management. RESULTS: Infections were more common in patients diagnosed via NBS (55%) versus those diagnosed via FH (19%) (p = 0.012). Outpatient versus inpatient management did not impact infections (47% vs 35%, respectively; p = 0.423). There was no consensus among PIDTC survey respondents as to the best setting (inpatient vs outpatient) for pre-HSCT management. While isolation practices varied, immunoglobulin replacement and antimicrobial prophylaxis were more uniformly implemented. CONCLUSION: Infants with SCID diagnosed due to FH had lower rates of infection and proceeded to HSCT more quickly than did those diagnosed via NBS. Pre-HSCT management practices were highly variable between centers, although uses of prophylaxis and immunoglobulin support were more consistent. This study demonstrates a critical need for development of evidence-based guidelines for the pre-HSCT management of infants with SCID following an abnormal NBS. TRIAL REGISTRATION: NCT01186913.

Vaccines in Patients with Primary Immune Deficiency.

Evaluation of antibodies produced after immunization is central to immune deficiency diagnosis. This includes assessment of responses to routine immunizations as well as to vaccines administered specifically for diagnosis. Here, we present the basic concepts of the humoral immune response and their relevance for vaccine composition and diagnosis of immune deficiency. Current vaccines are discussed, including nonviable protein and glycoprotein vaccines, pure polysaccharide vaccines, polysaccharide-protein conjugate vaccines, and live agent vaccines. Diagnostic and therapeutic applications of vaccine antibody measurement are discussed in depth. Important adverse effects of vaccines are also presented.

Personalized therapy for common variable immunodeficiency.

Background: Common variable immunodeficiency (CVID) represents a clinical descriptive diagnosis that was defined in the 1970s. Despite the vast increase in knowledge with regard to immune function and genetics, the pathophysiology of this disorder remains poorly understood in the majority of patients (75%); however, recent advances have led to a much clearer understanding of this heterogeneous group of disorders in the remaining 25%. These advances, along with developments in immune modulatory and reconstitution therapies, now permit sophisticated and specific targeting of therapies for individual patients. Methods: A literature review and author experience. Results: For > 50 years, immune globulin therapy has been applied to patients with CVID. There are several options open to patients, including a diversity of products and modes of administration. Stem cell therapy is increasingly applicable in patients with severe immune dysregulation. In some disorders (e.g., lipopolysaccharide-responsive and beige-like anchor protein, and cytotoxic T lymphocyte antigen 4 deficiencies), knowledge of the genetic basis and molecular pathophysiology permit targeted therapy by using small-molecule immune modulators and biologics. Conclusion: In the near future, it is likely that further advances in understanding the pathophysiology of CVID, together with ongoing development of biologics and small-molecule immune modulators will lead to additional targeted therapies for these patients.

Stable and Unstable Diglyme-Based Electrolytes for Batteries with Sodium or Graphite as Electrode.

We study the stability of several diglyme-based electrolytes in sodium|sodium and sodium|graphite cells. The electrolyte behavior for different conductive salts [sodium trifluoromethanesulfonate (NaOTf), NaPF6, NaClO4, bis(fluorosulfonyl)imide (NaFSI), and sodium bis(trifluoromethanesulfonyl)imide (NaTFSI)] is compared and, in some cases, considerable differences are identified. Side reactions are studied with a variety of methods, including X-ray diffraction, scanning electron microscopy, transmission electron microscopy, online electrochemical mass spectrometry, and in situ electrochemical dilatometry. For Na|Na symmetric cells as well as for Na|graphite cells, we find that NaOTf and NaPF6 are the preferred salts followed by NaClO4 and NaFSI, as the latter two lead to more side reactions and increasing impedance. NaTFSI shows the worst performance leading to poor Coulombic efficiency and cycle life. In this case, excessive side reactions lead also to a strong increase in electrode thickness during cycling. In a qualitative order, the suitability of the conductive salts can be ranked as follows: NaOTf ≥ NaPF6 > NaClO4 > NaFSI ≫ NaTFSI. Our results also explain two recent, seemingly conflicting findings on the degree of solid electrolyte interphase formation on graphite electrodes in sodium-ion batteries [ Maibach , J. ; ACS Appl. Mater. Interfaces 2017 , 9 , 12373 - 12381 ; Goktas , M. ; Adv. Energy Mater. 2018 , 8 , 1702724 ]. The contradictory findings are due to the different conductive salts used in both studies.