AgII -Mediated Electrocatalytic Ambient CH4 Functionalization Inspired by HSAB Theory.

Although most class (b) transition metals have been studied in regard to CH4 activation, divalent silver (AgII ), possibly owing to its reactive nature, is the only class (b) high-valent transition metal center that is not yet reported to exhibit reactivities towards CH4 activation. We now report that electrochemically generated AgII metalloradical readily functionalizes CH4 into methyl bisulfate (CH3 OSO3 H) at ambient conditions in 98 % H2 SO4 . Mechanistic investigation experimentally unveils a low activation energy of 13.1 kcal mol-1 , a high pseudo-first-order rate constant of CH4 activation up to 2.8×103  h-1 at room temperature and a CH4 pressure of 85 psi, and two competing reaction pathways preferable towards CH4 activation over solvent oxidation. Reaction kinetic data suggest a Faradaic efficiency exceeding 99 % beyond 180 psi CH4 at room temperature for potential chemical production from widely distributed natural gas resources with minimal infrastructure reliance.

Prenatal aneuploidy screening in a low-risk Hispanic population: price elasticity and cost-effectiveness.

BACKGROUND: In October 2015, the Massachusetts Medicaid program temporarily stopped reimbursement for procedures in which the International Classification of Diseases, Tenth Edition, code for serum aneuploidy screening used by certain communities was stipulated. This change led to a substantial number of patients who went without aneuploidy screening for approximately 3 years. OBJECTIVE: This study aimed to determine the change in use and cost-effectiveness of prenatal aneuploidy serum screening in a low-risk Hispanic Medicaid population in Massachusetts. STUDY DESIGN: We conducted a retrospective chart review of Spanish-speaking pregnant patients younger than 35 years of age who underwent aneuploidy serum screening at a Massachusetts community health center. The study compared the aneuploidy serum screening rates for the periods before and after May 2016 when the Massachusetts Medicaid program, MassHealth, temporarily discontinued reimbursement for the screening. Based on these rates, we developed a Markov cohort simulation model to assess the economic value of reimbursed aneuploidy screening vs nonreimbursed or limited screening. Clinical outcomes included trisomy 21, live births, and therapeutic abortions for a trisomy 21 diagnosis. Economic outcomes included discounted quality-adjusted life years and lifetime medical costs, net health benefit, and incremental cost-effectiveness ratios. RESULTS: Before the MassHealth policy change, 69% (55/80) of pregnant individuals selected quad or sequential screens in comparison with only 9% (10/112) who selected screens after the policy change. Traditional aneuploidy serum screening in a low-risk (aged <35 years) Hispanic population was considered to be cost-saving (ie, led to lower incremental costs and higher incremental benefits when compared with nonreimbursed or limited screening). CONCLUSION: From a United States healthcare payer perspective, aneuploidy serum screening for Hispanic pregnant individuals under 35 years of age is economically advantageous when compared with limited screening.

Ambient methane functionalization initiated by electrochemical oxidation of a vanadium (V)-oxo dimer.

The abundant yet widely distributed methane resources require efficient conversion of methane into liquid chemicals, whereas an ambient selective process with minimal infrastructure support remains to be demonstrated. Here we report selective electrochemical oxidation of CH4 to methyl bisulfate (CH3OSO3H) at ambient pressure and room temperature with a molecular catalyst of vanadium (V)-oxo dimer. This water-tolerant, earth-abundant catalyst possesses a low activation energy (10.8 kcal mol‒1) and a high turnover frequency (483 and 1336 hr-1 at 1-bar and 3-bar pure CH4, respectively). The catalytic system electrochemically converts natural gas mixture into liquid products under ambient conditions over 240 h with a Faradaic efficiency of 90% and turnover numbers exceeding 100,000. This tentatively proposed mechanism is applicable to other d0 early transition metal species and represents a new scalable approach that helps mitigate the flaring or direct emission of natural gas at remote locations.

Repercusiones urológicas de la malformación anorrectal alta / Urological repercussions of high anorectal anomaly

Se revisaron los casos de 64 pacientes con diagnóstico de malformación anorrectal alta con el fin de identifiar la incidencia y los tipos de malformaciones urológicas que acompañan, así como su diagnóstico y tratamiento, ademas de las repercusiones en el curso clínico de los mismos. Se encontró que 42 por ciento presentaban una o más de estas malformaciones, y que destacaban el reflujo vesicoureteral (55 por ciento), la vejiga neurogénica (25.9 por ciento) y la agenesia renal (18.5 por ciento). El diagnóstico oportuno fue realizado en menos de mitad en 60 por ciento de los casos. Fueron cinco en promedio las operaciones por paciente para su reconstrución. Cinco pacientes desarrollaron insuficiencia renal crónica. Se concluye que las malformaciones urológicas acompañantes representan una causa significativa de morbimortalidad. Se recomiendan la realización de ultrasonido renal y uretrocistograma en forma oportuna y la atención de estos pacientes en un centro especializado.