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1. Supercritical Fluid Nanospray Mass Spectrometry

   https://doi.org/10.1021/jasms.2c00134  

   Mostafa, Mahmoud Elhusseiny; Grinias, James P.; Edwards, James L. (September 2022, Journal of the American Society for Mass Spectrometry)

   Supercritical fluids are typically electrosprayed using an organic solvent makeup flow to facilitate continuous electrical connection and enhancement of electrospray stability. This results in sample dilution, loss in sensitivity, and potential phase separation. Premixing the supercritical fluid with organic solvent has shown substantial benefits to electrospray efficiency and increased analyte charge state. Presented here is a nanospray mass spectrometry system for supercritical fluids (nSF-MS). This split flow system used small i.d. capillaries, heated interface, inline frit, and submicron emitter tips to electrospray quaternary alkyl amines solvated in supercritical CO2 with a 10% methanol modifier. Analyte signal response was evaluated as a function of total system flow rate (0.5–1.5 mL/min) that is split to nanospray a supercritical fluid with linear flow rates between 0.07 and 0.42 cm/sec and pressure ranges (15–25 MPa). The nSF system showed mass-sensitive detection based on increased signal intensity for increasing capillary i.d. and analyte injection volume. These effects indicate efficient solvent evaporation for the analysis of quaternary amines. Carrier additives generally decreased signal intensity. Comparison of the nSF-MS system to the conventional SF makeup flow ESI showed 10-fold signal intensity enhancement across all the capillary i.d.s. The nSF-MS system likely achieves rapid solvent evaporation of the SF at the emitter point. The developed system combined the benefits of the nanoemitters, sCO2, and the low modifier percentage which gave rise to enhancement in MS detection sensitivity. 

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2. NanoSF-MS

   Mahmoud Elhusseiny Mostafa, James P. (September 2022, Journal of the American Society for Mass Spectrometry)

   Supercritical fluids are typically electrosprayed using an organic solvent makeup flow to facilitate continuous electrical connection and enhancement of electrospray stability. This results in sample dilution, loss in sensitivity, and potential phase separation. Premixing the supercritical fluid with organic solvent has shown substantial benefits to electrospray efficiency and increased analyte charge state. Presented here is a nanospray mass spectrometry system for supercritical fluids (nSF-MS). This split flow system used small i.d. capillaries, heated interface, inline frit, and submicron emitter tips to electrospray quaternary alkyl amines solvated in supercritical CO2 with a 10% methanol modifier. Analyte signal response was evaluated as a function of total system flow rate (0.5–1.5 mL/min) that is split to nanospray a supercritical fluid with linear flow rates between 0.07 and 0.42 cm/sec and pressure ranges (15–25 MPa). The nSF system showed mass-sensitive detection based on increased signal intensity for increasing capillary i.d. and analyte injection volume. These effects indicate efficient solvent evaporation for the analysis of quaternary amines. Carrier additives generally decreased signal intensity. Comparison of the nSF-MS system to the conventional SF makeup flow ESI showed 10-fold signal intensity enhancement across all the capillary i.d.s. The nSF-MS system likely achieves rapid solvent evaporation of the SF at the emitter point. The developed system combined the benefits of the nanoemitters, sCO2, and the low modifier percentage which gave rise to enhancement in MS detection sensitivity. 

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3. Novel ionization reagent for the measurement of gas‐phase ammonia and amines using a stand‐alone atmospheric pressure gas chromatography (APGC) source

   https://doi.org/10.1002/rcm.8561  

   Perraud, Véronique; Li, Xiaoxiao; Smith, James_N; Finlayson‐Pitts, Barbara_J (February 2020, Rapid Communications in Mass Spectrometry)

   Abstract RationaleContaminants present in ambient air or in sampling lines can interfere with the target analysis through overlapping peaks or causing a high background. This study presents a positive outcome from the unexpected presence ofN‐methyl‐2‐pyrrolidone, released from a PALL HEPA filter, in the analysis of atmospherically relevant gas‐phase amines using chemical ionization mass spectrometry. MethodsGas‐phase measurements were performed using a triple quadrupole mass spectrometer equipped with a modified atmospheric pressure gas chromatography (APGC) source which allows sampling of the headspace above pure amine standards. Gas‐phaseN‐methyl‐2‐pyrrolidone (NMP) emitted from a PALL HEPA filter located in the inlet stream served as the ionizing agent. ResultsThis study demonstrates that some alkylamines efficiently form a [NMP + amine+H]⁺cluster with NMP upon chemical ionization at atmospheric pressure. The extent of cluster formation depends largely on the proton affinity of the amine compared with that of NMP. Aromatic amines (aniline, pyridine) and diamines (putrescine) were shown not to form cluster ions with NMP. ConclusionsThe use of NMP as an ionizing agent with stand‐alone APGC provided high sensitivity for ammonia and the smaller amines. The main advantages, in addition to sensitivity, are direct sampling into the APGC source and avoiding uptake on sampling lines which can be a significant problem with ammonia and amines. 

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4. Scope and Mechanistic Probe into Asymmetric Synthesis of α-Trisubstituted-α-Tertiary Amines by Rhodium Catalysis

   https://doi.org/10.1021/jacs.3c04211  

   Arachchi, Madhawee K.; Schaugaard, Richard N.; Schlegel, H. Bernhard; Nguyen, Hien M. (September 2023, Journal of the American Chemical Society)

   Asymmetric reactions that convert racemic mixtures into enantioenriched amines are of significant importance due to the prevalence of amines in pharmaceuticals, with about 60% of drug candidates containing tertiary amines. Although transition metal catalyzed allylic substitution processes have been developed to provide access to enantioenriched α-disubstituted allylic amines, enantioselective synthesis of sterically demanding α-tertiary amines with a tetrasubstituted carbon stereocenter remains a major challenge. Herein, we report a chiral diene-ligated rhodium catalyzed asymmetric substitution of racemic tertiary allylic trichloroacetimidates with aliphatic secondary amines to afford α-trisubstituted-α-tertiary amines. Mechanistic investigation is conducted using synergistic experimental and computational studies. Density functional theory calculations show that the chiral diene-ligated rhodium promotes the ionization of tertiary allylic substrates to form both anti and syn π-allyl intermediates. The anti π-allyl pathway proceeds through a higher energy than the syn π-allyl pathway. The rate of conversion of the less reactive π-allyl intermediate to the more reactive isomer via π−σ−π interconversion was faster than the rate of nucleophilic attack onto the more reactive intermediate. These data imply that the Curtin−Hammett conditions are met in the amination reaction, leading to dynamic kinetic asymmetric transformation. Computational studies also show that hydrogen bonding interactions between β-oxygen of allylic substrate and amine-NH greatly assist the delivery of amine nucleophile onto more hindered internal carbon of the π-allyl intermediate. The synthetic utility of the current methodology is showcased by efficient preparation of α-trisubstituted-α-tertiary amines featuring pharmaceutically relevant secondary amine cores with good yields and excellent selectivities (branched−linear >99:1, up to 99% enantiomeric excess). 

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5. LES Simulation of turbulent supercritical CO2 heat transfer in microchannels

   Nabil, M.; Rattner, A.S. (March 2018, 6th International Supercritical CO2 Power Cycles Symposium)

   Although supercritical CO2 (sCO2) heat transfer has been employed in industrial process since the 1960s, the underlying transport phenomenon in high-flux microscale geometries, as could be employed in concentrating solar receivers, is poorly understood. To date, nearly all experimental studies and simulations of supercritical convective heat transfer have focused on large diameter vertical channel and tube bundle flows, which may differ dramatically from microscale supercritical convection. Computational studies have primarily employed Reynolds averaged (RANS) turbulence modeling approaches, which may not capture effects from the sharply varying property trends of supercritical fluids. In this study, large eddy simulation (LES) turbulence modeling techniques are employed to study heat transfer characteristics of sCO2 in microscale heat exchangers. The simulation geometry consists of a microchannel of 750×737 μm cross-section and 5 mm length, heated from all four sides. Simulation cases are evaluated at reduced pressure P_r = 1.1, mass flux G = 1000 kg/m^2-s, heat flux q'' = 1.7 − 8.9 W/cm^2 , and varying inlet temperature: 20 − 100℃. Computational results reveal thermal transport mechanisms specific to microscale sCO2 flows. Results have been compared with available supercritical convection correlations to identify the most applicable heat transfer models for engineering of microchannel sCO2 heat exchangers. 

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