Amino acids are important nitrogen-containing compounds and organic carbon components that exist widely in the atmosphere. The formation of atmospheric aerosols is affected by their interactions with amides. The dimers formed by glutamic acid (Glu) or protonated glutamic acid (Glu+) with three kinds of amide molecules (formamide FA, acetamide AA, urea U) and the hydrated clusters formed by Glu or Glu+, U molecules along with one to six water molecules were systematically studied at the M06-2X/6-311++G(3df,3pd) level. U is predicted to form a more stable structure with Glu/Glu+ than FA and AA by thermodynamics. If the concentration ratio of FA to U is less than 104, U will play a critical role in NPF. The degree of hydration in Glu+-mU-nW is higher than that of Glu-mU-nW (m = 0, 1; n = 0-6) clusters. Notably, Glu contributes more to the Rayleigh scattering properties than glutaric acid and sulfuric acid, and thus may lead to the destruction of atmospheric visibility. This study is helpful to better understand the properties of organic aerosols containing amino acids or amides.

Synthesis of RNA nucleobases from formamide is one of the recurring topics of prebiotic chemistry research. Earlier reports suggest that thymine, the substitute for uracil in DNA, may also be synthesized from formamide in the presence of catalysts enabling conversion of formamide to formaldehyde. In the current paper, we show that to a lesser extent conversion of uracil to thymine may occur even in the absence of catalysts. This is enabled by the presence of formic acid in the reaction mixture that forms as the hydrolysis product of formamide. Under the reaction conditions of our study, the disproportionation of formic acid may produce formaldehyde that hydroxymethylates uracil in the first step of the conversion process. The experiments are supplemented by quantum chemical modeling of the reaction pathway, supporting the plausibility of the mechanism suggested by Saladino and coworkers.

The intermediate metabolites and redox status imbalance were supported as the two major points for N,N-dimethylformamide (DMF)-induced hepatotoxicity. However, the potential mechanism has not yet been concerned. By applying two inhibitors, this study tried to seek the major role in DMF-induced toxicity on HL7702 cell. We observed that DMF induced cell apoptosis through mitochondrial-dependent and p53 pathway. Inhibition reactive oxygen species by catalase remarkably attenuated the mitochondrial transmembrane potential (MMP), apoptotic proteins, and apoptosis. On the contrary, it reduced the biodegradation rate of DMF by coincubation with CYP2E1 antagonist (DDC) partially reduced late apoptosis. However, the change in MMP, the ratio of Bax to Bcl-xl, and cleaved-caspase 9 was not attenuated by DDC. The pathway in DDC coincubation groups was related to the p53 rather than the mitochondrial pathway. Restoring the redox balance during biodegradation is much more effective than attenuating the metabolite rate of DMF. This study may provide a suitable prevention method to occupational workers.

Using the dispersion-corrected DFT calculations, different adsorption modes of formamide molecule are studied over the pristine and Al-doped boron nitride nanosheets (BNNS). It is found that the interaction between the Al atom and its neighboring N atoms in the Al-doped BNNS is very strong, which would hinder the dispersion and clustering of the Al atoms over the BNNS surface. Unlike the pristine nanosheet, the electronic properties of Al-doped BNNS are very sensitive to the formamide adsorption. The adsorption energies of formamide over the Al-doped sheet are in the range of -0.93 to -1.85 eV, which indicates the quite strong interaction of this molecule with the surface. Moreover, the dehydrogenation of formamide over the Al-doped BNNS is examined. According to our results, the N-H bond scission of formamide is more energetically favorable than the C-H one.

Widespread contamination of N,N-dimethylformamide (DMF) has been identified in the environment of leather industries and their surrounding residential areas. Few studies have assessed the dose-response relationships between internal exposure biomarkers and liver injury in DMF exposed populations. We assessed urinary N-methylformamide (NMF) and N-acetyl-S-(N-methylcarbamoyl) cysteine (AMCC) and blood N-methylcarbmoylated hemoglobin (NMHb) levels in 698 Chinese DMF-exposed workers and 188 nonDMF- exposed workers using ultraperformance liquid-chromatography tandem mass-spectrometry. Liver injury was defined as having abnormal serum activities of any of the 3 liver enzymes, including alanine aminotransferase, aspartate aminotransferase, and γ-glutamyl transpeptidase. Higher liver injury rates were identified in DMF-exposed workers versus nonDMF-exposed workers (9.17% vs 4.26%, P = .029) and in male versus female workers (11.4% vs 3.2%, P < .001). Positive correlations between environmental exposure categories and internal biomarker levels were identified with all 3 biomarkers undetectable in nonDMF-exposed workers. Lower confidence limit of benchmark dose (BMDL) was estimated using the benchmark dose (BMD) method. Within all study subjects, BMDLs of 14.0 mg/l for NMF, 155 mg/l for AMCC, and 93.3 nmol/g for NMHb were estimated based on dose-response relationships between internal levels and liver injury rates. Among male workers, BMDLs of 10.9 mg/l for NMF, 119 mg/l for AMCC, and 97.0 nmol/g for NMHb were estimated. In conclusion, NMF, AMCC, and NMHb are specific and reliable biomarkers and correlate well with DMF-induced hepatotoxicity. NMF correlates the best with liver injury, while NMHb may be the most stable indicator. Males have a greater risk of liver injury than females upon DMF exposure.

The procedure of the directed synthesis of N-vinylpyrrolidone-N-vinylformamide (VP-VFA) copolymers with grafted iminodiacetate (IDA) chelating units is presented. The methods for labelling resulting conjugates with indium-113m were developed. The metal-copolymer conjugates were characterized by different physicochemical methods, including IR and NMR, viscometry, light scattering, and exclusion high-performance liquid chromatography. Parameters of radiochemical synthesis of the conjugates labelled with indium-113m were optimized. It was shown that the VP-VFA-IDA copolymer firmly binds indium-113m both in the acid and alkaline solutions, with pH of the reaction mixture having almost no effect on the complexation. VP-VFA-IDA-In conjugates were found to be unstable in histidine challenge reaction.

OBJECTIVE: There are still concerns regarding occupational exposure to hepatotoxic DMF. This study was designed to evaluate possible liver damaging effects of DMF under current workplace conditions in synthetic fibres industries.
METHODS: Among other laboratory parameters, liver function parameters (alkaline phosphatase (ALP), aspartate aminotransferase, alanine aminotransferase and gamma-glutamyltransferase), the mean corpuscular erythrocyte volume (MCV) and carbohydrate-deficient transferrin (CDT) of the workforce of two companies present at the days of study were investigated. Internal exposure to DMF was assessed via three different biomarkers [sum of N-methylformamide and N-hydroxymethyl-N-methylformamide, N-acetyl-S-(N-carbamoyl)cysteine (AMCC) and 3-methyl-5-isopropylhydantoin (MIH)]. Alcohol consumption was assessed by means of direct ethanol metabolites (ethylglucuronide and ethylsulfate).
RESULTS: None of the tested liver enzyme activities showed a positive association with any of the three exposure markers, nor did CDT and MCV. CDT was negatively associated with AMCC and the ALP activity negatively with all three exposure markers. Changes in liver function are seen mainly in conjunction with ethanol consumption but also with increasing body weight and age. MCV was associated with smoking. Almost half of the workers stated to experience alcohol flush reaction.
CONCLUSIONS: The present study indicates that long-term exposure to DMF, which was specified by median urinary AMCC levels of 4.84 mg/g creatinine and DMF haemoglobin adduct levels of 60.5 nmol/MIH/g globin, respectively, does not result in any adverse liver effects. In contrast, these DMF exposure levels still elicit certain alcohol intolerance reactions.

The preparation of solar-cell-grade Cu2 ZnSnS4 (CZTS) thin films from ligand-capped small-grained CZTS particles remains hindered by problems of phase segregation, composition non-uniformity, and in particular carbon-layer formation. Herein, through a systematic comparative study of annealed films of CZTS nanocrystals prepared using conventional oleylamine and those prepared using formamide, these problems are found to be mainly attributable to the influence of the ligands, and mechanisms are proposed. Importantly, the origin of the carbon layer in oleylamine-capped CZTS films is revealed to be the reaction between oleylamine and sulfur. This carbon layer has a very poor electrical conductivity, which can be the reason for the limited performance of such films. Fortunately, these problems can almost all be avoided by replacing oleylamine with formamide to form CZTS films.

In complementarity with X-ray scattering and as extension of our previous publication, neutron scattering measurements are combined to DFT calculation to investigate the structural features of N-methylformamide-water mixtures (NMF-water) for three water molar fractions x w = 0.5 , 0.66 and x w = 0.75 . The recorded data at atmospheric pressure and room temperature are analyzed to yield the structure factor, the molecular form factor and the pair correlation function. Neutron investigations corroborate the X-ray ones and clearly show that liquid order in solutions is well accounted for by a tetramer. In this cluster, an NMF molecule is connected to three water molecules by one N-D···O and two O-D···O hydrogen bonds.

The human immunodeficiency virus type 1 protease (HIV-1 PR) is a major target for the design of anti-AIDS (acquired immune deficiency syndrome) drugs. Some C2-symmetric inhibitors have been designed for the C2-symmetric binding pocket of HIV-1PR. The crystallographic structures reveal that the binding modes are not C2-symmetric for C2-symmetric inhibitors binding to PR. In this work, four molecular dynamics (MD) simulations were performed to investigate the binding modes between four C2-symmetric inhibitors (6 AD, 6AG, 6FD and 6FG) and PR, as well as the stabilities of these inhibitors in the binding pocket. Analysis of the hydrophobic surface of the binding pocket shows that it is necessary to add a polar group to the P1 (benzyl) and P2 (phenyl) groups of the inhibitor 6AD. Analysis of the hydrogen bonds formed between inhibitors and residues (Asp25/Asp25\', Ile50/Ile50\') indicates that the steric structures of the inhibitors are not suitable for the binding pocket. The two increased polar groups of trifluoromethyl and formamido meet the needs of the binding pocket for polar molecules. The inhibitor with both these groups (6FG) has stronger stability than the other three inhibitors, which have only one (6AG and 6FD) or none (6AD) of these groups. The ranking of binding free energies calculated by molecular mechanics-generalized born surface area (MM-GBSA) method agrees well with the experimental data. It is expected that this study will provide theoretical guidance for the design of anti-AIDS drugs targeting HIV-1PR.