Stereoselective Analysis of Methadone and EDDP in Laboring Women and Neonates in Plasma and Dried Blood Spots and Association with Neonatal Abstinence Syndrome.

OBJECTIVE: This pilot study evaluated the relationship between maternal and neonatal R- and S-methadone and R- and S-2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine (EDDP) exposure and the severity of neonatal abstinence syndrome (NAS). The use of dried blood spots (DBS) as an alternative for plasma in assessing methadone and EDDP was also assessed. STUDY DESIGN: Women receiving methadone for medication assisted treatment of opioid use disorder during pregnancy were eligible for recruitment. Plasma and DBS samples were collected from mothers during labor, from cord blood, and from newborns during genetic screen. R-/S-methadone and EDDP were measured by high-performance liquid chromatography tandem mass spectrometry (HPLC/MS/MS). Associations between methadone exposure, neonatal morphine requirements, and severity of NAS were examined. RESULTS: Twenty women and infants completed the study. Maternal methadone dose at delivery was 112 mg/day (range = 60-180 mg/day). Sixteen neonates experienced NAS requiring morphine; three also required phenobarbital. Higher cord blood concentrations of R-methadone, R- and S-EDDP were associated with higher maximum doses of morphine (p < 0.05). CONCLUSION: Maternal methadone and cord blood concentration at delivery are variable and may be potential markers of neonatal abstinence syndrome.

Thermal Decomposition and Hypergolic Reaction of a Dicyanoborohydride Ionic Liquid.

In this study, in situ infrared spectroscopy techniques and thermogravimetric analysis coupled with mass spectrometry (TGA-MS) are employed to characterize the reactivity of the ionic liquid, 1-butyl-3-methylimidazolium dicyanoborohydride (BMIM+DCBH-), in comparison to the well-characterized 1-butyl-3-methylimidazolium dicyanamide (BMIM+DCA-) ionic liquid. TGA measurements determined the enthalpy of vaporization (ΔHvap) to be 112.7 ± 12.3 kJ/mol at 298 K. A rapid scan Fourier transform infrared spectrometer was used to obtain vibrational information useful in tracking the appearance and disappearance of species in the hypergolic reactions of BMIM+DCBH- and BMIM+DCA- with white fuming nitric acid (WFNA) and in the thermal decomposition of these energetic ionic liquids. Attenuated total reflectance measurements recorded the infrared spectra of the reactant sample (BMIM+DCBH-) and the liquid reaction products after reacting with WFNA. Computational chemistry efforts, aided by the experimental results, were used to propose key reaction pathways leading to the hypergolic ignition of BMIM+DCBH- + WFNA. Experimental results indicate that the hypergolic reaction of BMIM+DCBH- with WFNA generates both common and unique intermediates as compared to previous BMIM+DCA- + WFNA investigations: nitrous oxide was generated during both hypergolic reactions indicating that it may play a crucial role in the hypergolic ignition process, NO2 was generated in significantly higher concentrations for BMIM+DCBH- than for BMIM+DCA-, CO2 was only generated for BMIM+DCA-, and HCN was only generated during thermal decomposition and hypergolic ignition of BMIM+DCBH-.

A perspective on biomass-derived biofuels: From catalyst design principles to fuel properties.

The hazards to health and the environment associated with the transportation sector include smog, particulate matter, and greenhouse gas emissions. Conversion of lignocellulosic biomass into biofuels has the potential to provide significant amounts of infrastructure-compatible liquid transportation fuels that reduce those hazardous materials. However, the development of these technologies is inefficient, due to: (i) the lack of a priori fuel property consideration, (ii) poor shared vocabulary between process chemists and fuel engineers, and (iii) modern and future engines operating outside the range of traditional autoignition metrics such as octane or cetane numbers. In this perspective, we describe an approach where we follow a "fuel-property first" design methodology with a sequence of (i) identifying the desirable fuel properties for modern engines, (ii) defining molecules capable of delivering those properties, and (iii) designing catalysts and processes that can produce those molecules from a candidate feedstock in a specific conversion process. Computational techniques need to be leveraged to minimize expenses and experimental efforts on low-promise options. This concept is illustrated with current research information available for biomass conversion to fuels via catalytic fast pyrolysis and hydrotreating; outstanding challenges and research tools necessary for a successful outcome are presented.