Chitin, an insoluble linear polymer of β-1,4-N-acetyl-d-glucosamine (GlcNAc; A), can be converted to chitosan, a soluble heteropolymer of GlcNAc and d-glucosamine (GlcN; D) residues, by partial deacetylation. In nature, deacetylation of chitin is catalyzed by enzymes called chitin deacetylases (CDA) and it has been proposed that CDAs could be used to produce chitosan. In this work, we show that CDAs can remove up to approximately 10% of N-acetyl groups from two different (α and β) chitin nanofibers, but cannot produce chitosan.

The OH-initiated photo-oxidation of piperazine and 1-nitropiperazine as well as the photolysis of 1-nitrosopiperazine were investigated in a large atmospheric simulation chamber. The rate coefficient for the reaction of piperazine with OH radicals was determined by the relative rate method to be k_{OH-piperazine} = (2.8 ± 0.6) × 10^–10 cm³ molecule^–1 s^–1 at 307 ± 2 K and 1014 ± 2 hPa. Product studies showed the piperazine + OH reaction to proceed both via C–H and N–H abstraction, resulting in the formation of 1,2,3,6-tetrahydropyrazine as the major product and in 1-nitropiperazine and 1-nitrosopiperazine as minor products. The branching in the piperazinyl radical reactions with NO, NO₂, and O₂ was obtained from 1-nitrosopiperazine photolysis experiments and employed analyses of the 1-nitropiperazine and 1-nitrosopiperazine temporal profiles observed during piperazine photo-oxidation. The derived initial branching between N–H and C–H abstraction by OH radicals, k_N–H/(k_N–H + k_C–H), was 0.18 ± 0.04. All experiments were accompanied by substantial aerosol formation that was initiated by the reaction of piperazine with nitric acid. Both primary and secondary photo-oxidation products including 1-nitropiperazine and 1,4-dinitropiperazine were detected in the aerosol particles formed. Corroborating atmospheric photo-oxidation schemes for piperazine and 1-nitropiperazine were derived from M06-2X/aug-cc-pVTZ quantum chemistry calculations and master equation modeling of the pivotal reaction steps. The atmospheric chemistry of piperazine is evaluated, and a validated chemical mechanism for implementation in dispersion models is presented.

The OH-initiated degradation of 2-amino-2-methyl-1-propanol [CH₃C(NH₂)(CH₃)CH₂OH, AMP] was investigated in a large atmospheric simulation chamber, employing time-resolved online high-resolution proton-transfer reaction-time-of-flight mass spectrometry (PTR-ToF-MS) and chemical analysis of aerosol online PTR-ToF-MS (CHARON-PTR-ToF-MS) instrumentation, and by theoretical calculations based on M06-2X/aug-cc-pVTZ quantum chemistry results and master equation modeling of the pivotal reaction steps. The quantum chemistry calculations reproduce the experimental rate coefficient of the AMP + OH reaction, aligning k(T) = 5.2 × 10^–12 × exp (505/T) cm³ molecule^–1 s^–1 to the experimental value k_exp,300K = 2.8 × 10^–11 cm³ molecule^–1 s^–1. The theoretical calculations predict that the AMP + OH reaction proceeds via hydrogen abstraction from the −CH₃ groups (5–10%), −CH₂– group, (>70%) and −NH₂ group (5–20%), whereas hydrogen abstraction from the −OH group can be disregarded under atmospheric conditions. A detailed mechanism for atmospheric AMP degradation was obtained as part of the theoretical study. The photo-oxidation experiments show 2-amino-2-methylpropanal [CH₃C(NH₂)(CH₃)CHO] as the major gas-phase product and propan-2-imine [(CH₃)₂C═NH], 2-iminopropanol [(CH₃)(CH₂OH)C═NH], acetamide [CH₃C(O)NH₂], formaldehyde (CH₂O), and nitramine 2-methyl-2-(nitroamino)-1-propanol [AMPNO₂, CH₃C(CH₃)(NHNO₂)CH₂OH] as minor primary products; there is no experimental evidence of nitrosamine formation. The branching in the initial H abstraction by OH radicals was derived in analyses of the temporal gas-phase product profiles to be BCH₃/BCH₂/BNH₂ = 6:70:24. Secondary photo-oxidation products and products resulting from particle and surface processing of the primary gas-phase products were also observed and quantified. All the photo-oxidation experiments were accompanied by extensive particle formation that was initiated by the reaction of AMP with nitric acid and that mainly consisted of this salt. Minor amounts of the gas-phase photo-oxidation products, including AMPNO₂, were detected in the particles by CHARON-PTR-ToF-MS and GC×GC-NCD. Volatility measurements of laboratory-generated AMP nitrate nanoparticles gave Δ_vapH = 80 ± 16 kJ mol^–1 and an estimated vapor pressure of (1.3 ± 0.3) × 10^–5 Pa at 298 K. The atmospheric chemistry of AMP is evaluated and a validated chemistry model for implementation in dispersion models is presented.

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k_CH2NN+O3 = (3.2 ± 0.4) × 10⁻¹⁷ and k_CH2NN+OH = (1.68 ± 0.12) × 10⁻¹⁰ cm³ molecule⁻¹ s⁻¹ at 295 ± 3 K and 1013 ± 30 hPa, whereas the CH₂NN + NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed. GRAPHICAL ABSTRACT