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BackgroundProviders and patients have called for improved understanding of the health care requirements of adults with sickle cell disease (SCD) and have identified the need for a systematic, reliable and valid method to document the patient-reported outcomes (PRO) of adult SCD care. To address this need, the Adult Sickle Cell Quality of Life Measurement System (ASCQ-Me) was designed to complement the Patient Reported Outcome Measurement Information System (PROMIS®). Here we describe methods and results of the psychometric evaluation of ASCQ-Me item banks (IBs).MethodsAt seven geographically-disbursed clinics within the US, 556 patients responded to questions generated to assess cognitive, emotional, physical and social impacts of SCD. We evaluated the construct validity of the hypothesized domains using exploratory factor analysis (EFA), parallel analysis (PA), and bi-factor analysis (Item Response Theory Graded Response Model, IRT-GRM). We used IRT-GRM and the Wald method to identify bias in responses across gender and age. We used IRT and Cronbach’s alpha coefficient to evaluate the reliability of the IBs and then tested the ability of summary scores based on IRT calibrations to discriminate among tertiles of respondents defined by SCD severity.ResultsOf the original 140 questions tested, we eliminated 48 that either did not form clean factors or provided biased measurement across subgroups defined by age and gender. Via EFA and PA, we identified three subfactors within physical impact: sleep, pain and stiffness impacts. Analysis of the resulting six item sets (sleep, pain, stiffness, cognitive, emotional and social impacts of SCD) supported their essential unidimensionality. With the exception of the cognitive impact IB, these item sets also were highly reliable across a broad range of values and highly significantly related to SCD disease severity.ConclusionASCQ-Me pain, sleep, stiffness, emotional and social SCD impact IBs demonstrated exceptional measurement properties using modern and classical psychometric methods of evaluation. Further development of the cognitive impact IB is required to improve its sensitivity to differences in SCD disease severity. Future research will evaluate the sensitivity of the ASCQ-Me IBs to change in SCD disease severity over time due to health interventions.

Lattice Mg2+ in a tailored solid solution spinel, MgCrMnO4, is electrochemically utilized at high Mn-redox potentials in a nonaqueous electrolyte. Complementary evidence from experimental and theoretical analyses supports bulk Mg2+ (de)­intercalation throughout the designed oxide frame where strong electrostatic interaction between Mg2+ and O2– exists. Mg/Mn antisite inversion in the spinel is lowered to ∼10% via postannealing at 350 °C to further improve Mg2+ mobility. Spinel lattice is preserved upon removal of Mg2+ without any phase transformations, denoting structural stability at the charged state at a high potential ∼3.0 V (vs Mg/Mg2+). Clear remagnesiation upon first discharge, harvesting up to ∼180 Wh/kg at 60 °C is shown. In the remagnesiated state, insertion of Mg2+ into interstitial sites in the spinel is detected, possibly resulting in partial reversibility which needs to be addressed for structural stability. The observations constitute a first clear path to the development of a practical high voltage Mg-ion cathode using a spinel oxide.

Chicago, IL; Sacramento, CA; Silver Spring, MD; and Durham, NC, capturing a sociodemographically diverse sample with specific attention to ensuring inclusion of Hispanic, African-American, and elderly participants. Of 1774 people recruited, 75% participated: 961 took part in a deliberative method and 377 participants comprised the RMO control group. To assess effectiveness of the deliberative methods overall and of individual methods, we evaluated whether mean pre-post changes on a knowledge and attitude survey were statistically different from the RMO control using ANCOVA. In addition, we calculated mean scores capturing participant views of the impact and value of deliberation. Participating in deliberation increased participants' knowledge of evidence and comparative effectiveness research and shifted participants' attitudes regarding the role of evidence in decision-making. When comparing each deliberative method to the RMO control group, all four deliberative methods resulted in statistically significant change on at least one knowledge or attitude measure. These findings were underscored by self-reports that the experience affected participants' opinions. Public deliberation offers unique potential for those seeking informed input on complex, values-laden topics affecting broad public constituencies.

BackgroundSickle Cell Disease (SCD) causes profound suffering and decrements in daily functioning. Demand is growing for valid and reliable measures to systematically document these effects, particularly in adults. The Adult Sickle Cell Quality of Life Measurement System, ASCQ-Me℠, was developed for this purpose. ASCQ-Me℠ is one of four measurement systems housed within the Person–Centered Assessment Resource (PCAR), funded by the National Institutes of Health, to support clinical research. To help users select the best of these measures for adults with SCD, we evaluated and compared two PCAR systems: one designed to be “universally applicable” (the Patient-Reported Outcome Measurement Information System, PROMIS®) and one designed specifically for SCD (ASCQ-Me℠).MethodsRespondents to PROMIS and ASCQ-Me questions were 490 adults with SCD from seven geographically-disbursed clinics within the US. Data were collected for six ASCQ-Me measures (Emotional Impact, Sleep Impact, Social Impact, Stiffness Impact, Pain Impact, SCD Pain Episode Frequency and Severity) and ten PROMIS measures (Pain Impact, Pain Behavior, Physical Functioning, Anxiety, Depression, Fatigue, Satisfaction with Discretionary Social Activities, Satisfaction with Social Roles, Sleep Disturbance, and Sleep-Related Impairment). Statistical analyses, including analysis of variance and multiple linear regression, were conducted to determine the sensitivity of measures to SCD severity. SCD severity was assessed via a checklist of associated treatments and conditions.ResultsFor those with the most severe SCD, PROMIS scores showed worse health compared to the general population for nine of ten health domains: the magnitude of the difference ranged 0.5 to 1.1 standard deviation units. The PROMIS domains most severely affected were Physical Functioning and Pain (Impact and Behavior). Significant differences by tertile of the SCD-MHC were shown for most PROMIS short forms and all ASCQ-Me short and fixed forms. In most models, ASCQ-Me measures explained statistically significant unique variance in SCD-MHC scores complementary to that explained by corresponding PROMIS measures.ConclusionsStudy results supported the validity of both PROMIS and ASCQ-Me measures for use in adults with SCD. Compared to comparable PROMIS scores, most ASCQ-Me scores were better predictors of SCD disease severity, as measured by a medical history checklist. The clinical implications of these results require further investigation.

The development of group 15 Lewis acids is an area of active investigation that has led to numerous advances in anion sensing and catalysis. While phosphorus has drawn considerable attention, emerging research shows that organoantimony(III) reagents may also act as potent Lewis acids. Comparison of the properties of SbPh , Sb(C F ) , and SbAr with those of their tetrachlorocatecholate analogues SbPh Cat, Sb(C F ) Cat, and SbAr Cat (Cat=o-O C Cl , Ar =3,5-(CF ) C H ) demonstrates that the Lewis acidity of electron deficient organoantimony(III) reagents can be readily enhanced by oxidation to the +V state-as verified by binding studies, organic reaction catalysis, and computational studies. The results are rationalized by explaining that oxidation of the antimony center leads to a lowering of the accepting σ* orbital and a deeper carving of the associated σ-hole.

A promising high-voltage spinel oxide cathode material MgCrMnO4 with 18% Mg/Mn inversion was synthesized successfully. A new custom operando battery device was designed to study the cation migration mechanisms of the MgCrMnO4 cathode using 0.1 M Mg(TPFA)2 electrolyte dissolved in triglyme and activated carbon as the anode. For the first time in multivalent batteries, high quality operando diffraction data enabled the accurate quantification of cation contents in the host structure. Besides the exceptional reversibility of 12% Mg 2+ insertion in Mg1-xCrMnO4 (x1), a partially reversible insertion of excess Mg 2+ during over-discharging was also observed. Moreover, the insertion/extraction reaction was experimentally shown to be accompanied by a series of cation re-distributions in the spinel framework, which were further supported by density functional theory calculations. The inverted Mn is believed to be directly involved in the cation migrations, which would cause voltage hysteresis and irreversible structural evolution after over-discharging. Tuning the Mg/Mn inversion rate could provide a direct path to further optimize spinel oxide cathodes for Mg-ion batteries, and more generally, the operando techniques developed in this work should play a key role in understanding the complex mechanisms involved in multivalent ion insertion systems.

Developing next-generation battery chemistries that move beyond traditional Li-ion systems is critical to enabling transformative advances in electrified transportation and grid-level energy storage. In this work, we provide the first evidence for common descriptors for improved reversibility of metal plating/ stripping in nonaqueous electrolytes for multivalent ion batteries. Focusing first on the specific role of chloride (Cl − ) in promoting electrochemical reversibility in multivalent systems, rotating disk (RDE) and ring-disk electrode (RRDE) investigations were performed utilizing a variety of divalent cations (Mg 2+ , Zn 2+ , and Cu 2+ ) and the bis-(trifluoromethane sulfonyl) imide (TFSI − ) anion. By introducing varying concentrations of Cl − , a cooperative effect is observed between TFSI − and Cl − that yields the more reversible behavior of mixed electrolytes relative to electrolytes containing only TFSI − . This effect is shown to be general for Mg, Zn, and Cu electrodeposition, and mechanistic understanding of the role of Cl − in improving reversibility of TFSI-based electrolytes is obtained through the combination of R(R)DE experimental results and density functional theory (DFT) evaluation of the redox activity and thermodynamic stability of various TFSI-and Cl-based solution complexes of metal ions. The cooperative anion effect is further generalized to other mixed-anion systems, where systematic variations in anion association strength predicted from DFT (i.e., Cl − > OTf − ≈ TFSI − > BF 4 − > PF 6 − ) yield corresponding trends in redox potentials and improvements of ≥200 mV in the reversibility of metal deposition/dissolution. These results identify anion association strength as a common descriptor for the reversibility of divalent metal anodes and suggest a set of general design principles for developing new electrolytes with improved activity and stability.