More Like this

1. Unnatural Lysines with Reduced Sidechain N ‐Basicity: Synthesis of N ‐trifluoroethyl Substituted Lysine and Homologs

   https://doi.org/10.1002/slct.202203132  

   Jameson, Brian; Glaser, Rainer (December 2022, ChemistrySelect)

   Abstract The syntheses are reported of N^ϵ‐(2,2,2‐trifluoroethyl)‐D,L‐lysine (^tFK) and N^ζ‐(2,2,2‐trifluoroethyl)‐D,L‐homolysine (^tFK₊₁) from amino alcohols HO−(CH₂)_n−NH₂. The syntheses involve reductive amination, Appel bromination, and the stereoselective bond formation between C_α of the amino acid and the fluorinated alkyl chain in the Schöllkopf bislactim amino acid synthesis. The methyl esters of the fluorinated amino acids are the relevant substrates for oligopeptide synthesis. With theR‐Schöllkopf reagent, we stereoselectively generated methyl N^ϵ‐boc‐N^ϵ‐(2,2,2‐trifluoroethyl)‐L‐lysinate and methyl N^ζ‐boc‐N^ζ‐(2,2,2‐trifluoroethyl)‐L‐homolysinate. Products and intermediates were characterized by ¹H NMR, ¹³C NMR, COSY, HSQC, and LCMS. A variety of N‐functionality may be introduced by reacting hemiacetals with different appendages. This fluorine modification reduces the sidechain N‐basicity by combined ‐I effect of the three fluorines. This effect increases the [amine]/[ammonium ion] ratio of the sidechain amine in lysine to facilitate carbamylation at lower pH conditions. 

   more » « less
2. Amination of polypropylene‐ g ‐(maleic anhydride) using reactive extrusion

   https://doi.org/10.1002/app.56085  

   Kay, Ian_P; Goddard, Julie_M (August 2024, Journal of Applied Polymer Science)

   Abstract We report synthesis of a radical scavenging aminated thermoplastic polymer through reactive extrusion of polyethyleneimine (PEI) with a polypropylene and polypropylene‐graft‐maleic anhydride (PP‐g‐MA) meltblend. The reaction was confirmed using acid orange 7 (AO7) amine density assay, toluidine blue O (TBO) carboxylic acid density assay, Fourier transform infrared spectroscopy (FTIR), and a migration assay. FTIR spectra revealed a reduction of the asymmetric stretching of the maleic anhydride (MA) carbonyl group at 1777 cm⁻¹and the emergence of the maleimide carbonyl peak at 1702 cm⁻¹. AO7 supported surface orientation of grafted amine groups by introduction of 7.22 nmol cm⁻²primary amines, corresponding to the reduction of surface carboxylic acids quantified by TBO from 12.46 nmol cm⁻²to 0.43 nmol cm⁻². After incubation (40°C, 10 days) in ethanol, acetic acid, and water, < 0.1 mg cm⁻²PEI migrated from the materials, supporting the covalent nature of the grafting. Antioxidant activity was demonstrated exhibiting 5.90 and 4.31 nmol Trolox_eqcm⁻²in aqueous and organic environments, respectively. Results indicate a successful condensation reaction during reactive extrusion, producing an aminated thermoplastic polymer with antioxidant activity for target applications such as food packaging, wastewater treatment, carbon capture, and others. 

   more » « less
3. Morphologies of Galaxies at z ≳ 9 Uncovered by JWST/NIRCam Imaging: Cosmic Size Evolution and an Identification of an Extremely Compact Bright Galaxy at z ∼ 12

   https://doi.org/10.3847/1538-4357/acd44a  

   Ono, Yoshiaki; Harikane, Yuichi; Ouchi, Masami; Yajima, Hidenobu; Abe, Makito; Isobe, Yuki; Shibuya, Takatoshi; Wise, John H.; Zhang, Yechi; Nakajima, Kimihiko; et al (July 2023, The Astrophysical Journal)

   Abstract We present morphologies of galaxies atz≳ 9 resolved by JWST/NIRCam 2–5μm imaging. Our sample consists of 22 galaxy candidates identified by stringent dropout and photo-zcriteria in GLASS, CEERS, SMACS J0723, and Stephan’s Quintet flanking fields, one of which has been spectroscopically identified atz= 11.44. We perform surface brightness (SB) profile fitting with GALFIT for six bright galaxies with a signal-to-noise ratio = 10–40 on an individual basis and for stacked faint galaxies with secure point-spread functions (PSFs) of the NIRCam real data, carefully evaluating systematics by Monte Carlo simulations. We compare our results with those of previous JWST studies, and confirm that the effective radiir_eof our measurements are consistent with those of previous measurements atz∼ 9. We obtainr_e≃ 200–300 pc with the exponential-like profiles, Sérsic indexes ofn≃ 1–1.5, for galaxies atz∼ 12–16, indicating that the relation ofr_e∝ (1 +z)^sfor $s=-{1.22}_{-0.16}^{+0.17}$explains cosmic evolution overz∼ 0–16 for $\sim L_{z=3}^{*}$galaxies. One bright (M_UV= −21 mag) galaxy atz∼ 12, GL-z12-1, has an extremely compact profile withr_e= 39 ± 11 pc that is surely extended over the PSF. Even in the case that the GL-z12-1 SB is fit by active galactic nuclei + galaxy composite profiles, the best-fit galaxy component is again compact, $r_{\mathrm{e}}={48}_{-15}^{+38}$pc, which is significantly (>5σ) smaller than the typicalr_evalue atz∼ 12. Compared with numerical simulations, we find that such a compact galaxy naturally forms atz≳ 10, and that frequent mergers at the early epoch produce more extended galaxies following ther_e∝ (1 +z)^srelation. 

   more » « less
4. NMR Study of CO ₂ Capture by Butylamine and Oligopeptide KDDE in Aqueous Solution: Capture Efficiency and Gibbs Free Energy of the Capture Reaction as a Function of pH**

   https://doi.org/10.1002/cphc.202300053  

   Yang, Kaidi; Schell, Joseph; Gallazzi, Fabio; Wycoff, Wei; Glaser, Rainer (April 2023, ChemPhysChem)

   Abstract We have been interested in the development of rubisco‐based biomimetic systems for reversible CO₂capture from air. Our design of the chemical CO₂capture and release (CCR) system is informed by the understanding of the binding of the activator CO₂(^ACO₂) in rubisco (ribulose‐1,5‐bisphosphate carboxylase/oxygenase). The active site consists of the tetrapeptide sequence Lys‐Asp‐Asp‐Glu (or KDDE) and the Lys sidechain amine is responsible for the CO₂capture reaction. We are studying the structural chemistry and the thermodynamics of CO₂capture based on the tetrapeptide CH₃CO−KDDE−NH₂(“KDDE”) in aqueous solution to develop rubisco mimetic CCR systems. Here, we report the results of¹H NMR and¹³C NMR analyses of CO₂capture by butylamine and by KDDE. The carbamylation of butylamine was studied to develop the NMR method and with the protocol established, we were able to quantify the oligopeptide carbamylation at much lower concentration. We performed a pH profile in the multi equilibrium system and measured amine species and carbamic acid/carbamate species by the integration of¹H NMR signals as a function of pH in the range 8≤pH≤11. The determination of ΔG₁(R) for the reaction R−NH₂+CO₂R−NH−COOH requires the solution of a multi‐equilibrium equation system, which accounts for the dissociation constantsK₂andK₃controlling carbonate and bicarbonate concentrations, the acid dissociation constantK₄of the conjugated acid of the amine, and the acid dissociation constantK₅of the alkylcarbamic acid. We show how the multi‐equilibrium equation system can be solved with the measurements of the daughter/parent ratioX, the knowledge of the pH values, and the initial concentrations [HCO₃⁻]₀and [R‐NH₂]₀. For the reaction energies of the carbamylations of butylamine and KDDE, our best values are ΔG₁(Bu)=−1.57 kcal/mol and ΔG₁(KDDE)=−1.17 kcal/mol. Both CO₂capture reactions are modestly exergonic and thereby ensure reversibility in an energy‐efficient manner. These results validate the hypothesis that KDDE‐type oligopeptides may serve as reversible CCR systems in aqueous solution and guide designs for their improvement. 

   more » « less
5. Decoupling Electron‐ and Phase‐Transfer Processes to Enhance Electrochemical Nitrate‐to‐Ammonia Conversion by Blending Hydrophobic PTFE Nanoparticles within the Electrocatalyst Layer

   https://doi.org/10.1002/aenm.202203891  

   Gao, Jianan; Ma, Qingquan; Young, Joshua; Crittenden, John C.; Zhang, Wen (March 2023, Advanced Energy Materials)

   Abstract Electrochemical upcycling of nitrate into ammonia at ambient conditions offers a sustainable synthesis pathway that can complement the current industrial NH₃production from the Haber–Bosch process. One of the key rate‐limiting steps is the effective desorption of gaseous or interfacial bubble products, mainly NH₃with some minor side products of nitrogen and hydrogen, from the electrode surfaces to sustain available sites for the NO₃⁻reduction reaction. To facilitate the gaseous product desorption from the catalytic sites, hydrophobic polytetrafluoroethylene (PTFE) nanoparticles are blended within a CuO catalyst layer, which is shown to eliminate the undesirable accumulation and blockage of electrode surfaces and largely decouples the electron‐ and phase‐transfer processes. The NH₃partial current density normalized by the electrochemically active surface area (ECSA) increases by nearly a factor of 17.8 from 11.4 ± 0.1 to 203.3 ± 1.8 mA cm⁻²_ECSA. The DFT and ab‐initio molecular dynamics simulations suggest that the hydrophobic PTFE nanoparticles may serve as segregated islands to enhance the spillover and transport the gaseous products from electrocatalysts to the PTFE. Thus, a higher ammonia transfer is achieved for the mixed PTFE/CuO electrocatalyst. This new and simple strategy is expected to act as inspiration for future electrochemical gas‐evolving electrode design. 

   more » « less