PVP/aprepitant microcapsules produced by supercritical antisolvent process.

The supercritical antisolvent (SAS) process was a green alternative to improve the low bioavailability of insoluble drugs. However, it is difficult for SAS process to industrialize with limited production capacity. A coaxial annular nozzle was used to prepare the microcapsules of aprepitant (APR) and polyvinylpyrrolidone (PVP) by SAS with N, N-Dimethylformamide (DMF) as solvent. Meanwhile, the effects of polymer/drug ratio, operating pressure, operating temperature and overall concentration on particles morphology, mean particle diameter and size distribution were analyzed. Microcapsules with mean diameters ranging from 2.04 µm and 9.84 µm were successfully produced. The morphology, particle size, thermal behavior, crystallinity, drug content, drug dissolution and residual amount of DMF of samples were analyzed. The results revealed that the APR drug dissolution of the microcapsules by SAS process was faster than the unprocessed APR. Furthermore, the drug powder collected every hour is in the kilogram level, verifying the possibility to scale up the production of pharmaceuticals employing the SAS process from an industrial point of view.

NLRP3 inflammasome activation triggers severe inflammatory liver injury in N, N-dimethylformamide-exposed mice.

N,N-dimethylformamide (DMF) is a widely utilized chemical solvent with various industrial applications. Previous studies have indicated that the liver is the most susceptible target to DMF exposure, whereas the underlying mechanisms remain to be elucidated. This study aimed to investigate the role of NLRP3 inflammasome in DMF-induced liver injury in mice by using two NLRP3 inflammasome inhibitors, Nlrp3-/- mice, Nfe2l2-/- mice, and a macrophage-depleting agent. RNA sequencing revealed that endoplasmic reticulum (ER) stress and NLRP3 inflammasome-associated pathways were activated in the mouse liver after acute DMF exposure, which was validated by Western blotting. Interestingly, DMF-induced liver injury was effectively suppressed by two inflammasome inhibitors, MCC950 and Dapansutrile. In addition, knockout of Nlrp3 markedly attenuated DMF-induced liver injury without affecting the metabolism of DMF. Furthermore, silencing Nfe2l2 aggravated the liver injury and the NLRP3 inflammasome activation in mouse liver. Finally, the depletion of hepatic macrophages by clodronate liposomes significantly reduced the liver damage caused by DMF. These results suggest that NLRP3 inflammasome activation is the upstream molecular event in the development of acute liver injury induced by DMF.

Dimethylformamide dimethyl acetal reagent for in situ chiral analyses of organic molecules on Titan with the Dragonfly mass spectrometer space instrument (Dragonfly mission).

Thanks to the Cassini-Huygens space mission between 2004 and 2017, a lot was learned about Titan, the biggest satellite of Saturn, and its intriguing atmosphere, surface, and organic chemistry complexity. However, key questions about the potential for the atmosphere and surface chemistry to produce organic molecules of direct interest for prebiotic chemistry and life did not find an answer. Due to Titan potential as a habitable world, NASA selected the Dragonfly space mission to be launched in 2027 to Titan's surface and explore the Shangri-La surface region for minimum 3 years. One of the main goals of this mission will be to understand the past and actual abundant prebiotic chemistry on Titan, especially using the Dragonfly Mass Spectrometer (DraMS). Two recently used sample pre-treatments for Gas Chromatography - Mass Spectrometry (GC-MS mode of DraMS) analyses are planned prior analysis to extract refractory organic molecules of interest for prebiotic chemistry and astrobiology. The dimethylformamide dimethylacetal (DMF-DMA) derivatization reaction offers undoubtedly an opportunity to detect biosignatures by volatilizing refractory biological or prebiotic molecules and conserving the chiral carbons' conformation while an enantiomeric excess indicates a chemical feature induced primarily by life (and may be aided on the primitive systems by light polarization). The goal of this study is to investigate the ageing of DMF-DMA in DraMS (and likely MOMA) capsules prior to in situ analysis on Titan (or Mars). The main results highlighted by our work on DMF-DMA are first its satisfactory stability for space requirements through time (no significant degradation over a year of storage and less than 30 % of lost under thermal stress) to a wide range of temperature (0 °C to 250 °C), or the presence of water and oxidants during the derivatization reaction (between 0 and 10 % of DMF-DMA degradation). Moreover, this reagent derivatized very well amines and carboxylic acids in high or trace amounts (ppt to hundreds of ppm), conserving their molecular conformation during the heat at 145 °C for 3 min (0 to 4% in the enantiomeric form change).

The proliferation of antibiotic resistance genes (ARGs) and microbial communities in industrial wastewater treatment plant treating N,N-dimethylformamide (DMF) by AAO process.

The excessive use of antibiotics has resulted in the contamination of the environment with antibiotic resistance genes (ARGs), posing a significant threat to public health. Wastewater treatment plants (WWTPs) are known to be reservoirs of ARGs and considered to be hotspots for horizontal gene transfer (HGT) between bacterial communities. However, most studies focused on the distribution and dissemination of ARGs in hospital and urban WWTPs, and little is known about their fate in industrial WWTPs. In this study, collected the 15 wastewater samples containing N,N-dimethylformamide (DMF) from five stages of the anaerobic anoxic aerobic (AAO) process in an industrial WWTPs. The findings revealed a stepwise decrease in DMF and chemical oxygen demand (COD) content with the progression of treatment. However, the number and abundances of ARGs increase in the effluents of biological treatments. Furthermore, the residues of DMF and the treatment process altered the structure of the bacterial community. The correlation analysis indicated that the shift in bacterial community structures might be the main driver for the dynamics change of ARGs. Interestingly, observed that the AAO process may acted as a microbial source and increased the total abundance of ARGs instead of attenuating it. Additionally, found that non-pathogenic bacteria had higher ARGs abundance than pathogenic bacteria in effluents. The study provides insights into the microbial community structure and the mechanisms that drive the variation in ARGs abundance in industrial WWTPs.

Ultrathin organic solvent nanofiltration membrane with polydopamine-HKUST-1 interlayer for organic solvent separation.

Polydopamine (PDA) and metal-organic skeleton HKUST-1 were co-deposited on the base membrane of hexamethylenediamine (HDA)-crosslinked polyetherimide (PEI) ultrafiltration membrane as the interlayer, and high-throughput organic solvent nanofiltration membrane (OSN) was prepared by interfacial polymerization and solvent activation reaction. The polyamide (PA) layer surface roughness from 28.4 nm in PA/PEI to 78.3 nm in PA/PDA-HKUST-10.6/PEI membrane, reduced the thickness of the separation layer from 79 to 14 nm, and significantly improved the hydrophilic, thermal and mechanical properties. The flux of the PA/PDA-HKUST-10.6/PEI membrane in a 0.1 g/L Congo Red (CR) ethanol solution at 0.6 MPa test pressure reached 21.8 L/(m2·hr) and the rejection of CR was 92.8%. Solvent adsorption test, N, N-dimethylformamide (DMF) immersion experiment, and long-term operation test in ethanol showed that the membranes had high solvent tolerance. The solvent flux test demonstrated that, under the test pressure of 0.6 MPa, the flux of different solvents ranked as follows: methanol (56.9 L/(m2·hr)) > DMF (39.6 L/(m2·hr)) > ethanol (31.2 L/(m2·hr)) > IPA (4.5 L/(m2·hr)) > N-hexane (1.9 L/(m2·hr)). The ability of the membranes to retain dyes in IPA/water dyes solution was also evaluated. The flux of the membrane was 30.4 L/(m2·hr) and the rejection of CR was 91.6% when the IPA concentration reached 50%. This OSN membrane-making strategy is economical, environment-friendly and efficient, and has a great application prospect in organic solvent separation systems.

Impact analysis of hydraulic residence time and dissolved oxygen on performance efficiency and microbial community in N, N-dimethylformamide wastewater treated by an AnSBR-ASBR.

Suitable operating parameters are one of the key factors to efficient and stable biological wastewater treatment of N, N-dimethylformamide (DMF) wastewater. In this study, an improved AnSBR-ASBR reactor (anaerobic sequencing batch reactor, AnSBR, and aerobic SBR, ASBR, run in series) was used to investigated the effects of operating conditions such as hydraulic residence time (HRT), AnSBR stirring speed and ASBR dissolved oxygen (DO) for DMF wastewater treatment. When HRT decreased from 24 h to 12 h, the average removal rates of COD by the AnSBR were 34.59% and 39.54%, respectively. Meanwhile, the removal rate of NH4+-N by ASBR decreased from 88.38% to 62.81%. The DMF removal rate reached the best at 18 h and the expression of dehydrogenase was the highest in the AnSBR. The abundance of Megasphaera, the dominant sugar-degrading bacteria in the AnSBR, continued to decline due to the decrease of HRT. The relative abundance of Methanobacterium gradually increased to 80.2% with the decrease of HRT and that hydrotrophic methanogenesis dominated the methanogenic process. The HRT decrease promoted butyrate and pyruvate metabolism in anaerobic sludge, but the proportion of glycolysis and methane metabolism decreased. The AnSBR-ASBR reactor had the best operation performance when HRT was 18 h, AnSBR speed was 220 r/min, and ASBR DO content was 3-4 mg/L. This study provided an effective reference for the reasonable selection of operating parameters in the treatment of DMF-containing wastewater by the AnSBR-ASBR.

N,N-Dimethyl Formamide European Restriction Demands Solvent Substitution in Research and Development.

As of December 2023, the use of common solvent N,N-dimethyl formamide (DMF) will be restricted in the European Union because of its reproductive health hazard. Industrial facilities must comply with stricter exposure limits, and researchers are recommended to find alternative solvents. Here we explain the restrictions on DMF, which disciplines are affected, and how to substitute DMF to keep research and development commercially relevant.

DMF mineralization and substrate specificity mechanism of Aminobacter ciceronei DMFA1.

N,N-dimethylformamide (DMF) is widely used in various industries, but its direct release into water poses high risks to human beings. Although a lot of DMF-degrading bacteria has been isolated, limited studies focus on the degradation preference among DMF and its analogues. In this study, an efficient DMF mineralization bacterium designated Aminobacter ciceronei DMFA1 was isolated from marine sediment. When exposed to a 0.2% DMF (∼1900 mg/L), strain DMFA1 exhibited a degradation efficiency of 100% within 4 days. The observed growth using formamide as the sole carbon source implied the possible DMF degradation pathway of strain DMFA1. Meanwhile,the strain DMFA1 possesses a broad-spectrum substrate degradation, which could effectively degraded 0.2% N,N-dimethylacetamide (DMAC) and N-methylformamide (NMF). Genomic analysis further confirmed the supposed pathway through annotating the genes encoding N, N-dimethylformamidase (DMFase), formamidase, and formate dehydrogenase. The existence of sole DMFase indicating its substrate specificity controlled the preference of DMAc of strain DMFA1. By integrating multiple sequence alignment, homology modeling and molecular docking, the preference of the DMFase in strain DMFA1 towards DMAc are related to: 1) Mutations in key active site residues; 2) the absence of small subunit; and 3) no energy barrier for substrates entering the active site.

[Development of 2,4,6-trinitrophenol examination methods to evaluate the features of its distribution in warm-blooded animals]. / Razrabotka metodik issledovaniya 2,4,6-trinitrofenola dlya otsenki kharaktera ego raspredeleniya v organizme teplokrovnykh zhivotnykh.

THE OBJECTIVE: Is to study a 2, 4, 6-trinitrophenol (2.4,6-TNP) distribution in warm-blooded animals using physical chemical analysis methods after intragastric injection of toxicant. The methods of thin-layer chromatography, spectrophotometry and high-efficient liquid chromatography were used in the study process. Four-months-old rats of the Wistar line (males) were considered as a model of warm-blooded organisms. The investigated substance in amount of three-times LD50 was intragastrically injected in the aqueous-suspension state. 2.4,6-TNP was isolated by a mixture of acetone-acetonitrile (1:1) in a double (by 0.5 of hour) infusing mode from the bioactive matrix of experimental animals, sustaining the mass ratio of isolated agent to bioactive matrix equaled to 2:1. Purification and preliminary identification of analyte were conducted on «Sorbfil¼ plates (mobile phase - acetone - chloroform (7:3)), confirming identification - by absorption in dimethylformamide medium and by retention time in column (64×2 mm) of «Separon C-18¼ sorbent during elution by acetonitrile-water (2:8) mixture. The evaluation of 2, 4, 6-trinitrophenol quantitative content by optical density of dimethylformamide solution of analyte at 379 nm was carried out. The analyte in unchanged form was found in blood, parenchymatous and hollow organs, their contents and blood of experimental animals. The highest content of 2.4,6-TNP (mg/100 gr) was revealed in gastric content (149.88±22.70), gastric tissue (97.89±4.86), blood (15.91±0.90) and muscles (10.87±1.91).

Genomic profiling and characteristics of a C1 degrading heterotrophic fresh-water bacterium Paracoccus sp. strain DMF.

Paracoccus species are metabolically versatile gram-negative, aerobic facultative methylotrophic bacteria showing enormous promise for environmental and bioremediation studies. Here we report, the complete genome analysis of Paracoccus sp. strain DMF (P. DMF) that was isolated from a domestic wastewater treatment plant in Kanpur, India (26.4287 °N, 80.3891 °E) based on its ability to degrade a recalcitrant organic solvent N, N-dimethylformamide (DMF). The results reveal a genome size of 4,202,269 base pairs (bp) with a G + C content of 67.9%. The assembled genome comprises 4141 coding sequences (CDS), 46 RNA sequences, and 2 CRISPRs. Interestingly, catabolic operons related to the conventional marine-based methylated amines (MAs) degradation pathway were functionally annotated within the genome of an obligated aerobic heterotroph that is P. DMF. The genomic data-based characterization presented here for the novel heterotroph P. DMF aims to improve the understanding of the phenotypic gene products, enzymes, and pathways involved with greater emphasis on facultative methylotrophic motility-based latent pathogenicity.

Insight into the metabolic pathways of Paracoccus sp. strain DMF: a non-marine halotolerant methylotroph capable of degrading aliphatic amines/amides.

Paracoccus sp. strain DMF (P. DMF from henceforth) is a gram-negative heterotroph known to tolerate and utilize high concentrations of N,N-dimethylformamide (DMF). The work presented here elaborates on the metabolic pathways involved in the degradation of C1 compounds, many of which are well-known pollutants and toxic to the environment. Investigations on microbial growth and detection of metabolic intermediates corroborate the outcome of the functional genome analysis. Several classes of C1 compounds, such as methanol, methylated amines, aliphatic amides, and naturally occurring quaternary amines like glycine betaine, were tested as growth substrates. The detailed growth and kinetic parameter analyses reveal that P. DMF can efficiently aerobically degrade trimethylamine (TMA) and grow on quaternary amines such as glycine betaine. The results show that the mechanism for halotolerant adaptation in the presence of glycine betaine is dissimilar from those observed for conventional trehalose-mediated halotolerance in heterotrophic bacteria. In addition, a close genomic survey revealed the presence of a Co(I)-based substrate-specific corrinoid methyltransferase operon, referred to as mtgBC. This demethylation system has been associated with glycine betaine catabolism in anaerobic methanogens and is unknown in denitrifying aerobic heterotrophs. This report on an anoxic-specific demethylation system in an aerobic heterotroph is unique. Our finding exposes the metabolic potential for the degradation of a variety of C1 compounds by P. DMF, making it a novel organism of choice for remediating a wide range of possible environmental contaminants.

Allyl methyl disulfide (AMDS) prevents N,N-dimethyl formamide-induced liver damage by suppressing oxidative stress and NLRP3 inflammasome activation.

N,N-dimethylformamide (DMF), a widely consumed industrial solvent with persistent characteristics, can induce occupational liver damage and pose threats to the general population due to the enormous DMF-containing industrial efflux and emission from indoor facilities. This study was performed to explore the roles of allyl methyl disulfide (AMDS) in liver damage induced by DMF and the underlying mechanisms. AMDS was found to effectively suppress the elevation in the liver weight/body weight ratio and serum aminotransferase activities, and reduce the mortality of mice induced by DMF. In addition, AMDS abrogated DMF-elicited increases in malondialdehyde (MDA) and 4-hydroxynonenal (4-HNE) levels and decreases in glutathione (GSH) levels in mouse livers. The increase in macrophage number, mRNA expression of M1 macrophage biomarkers, and protein expression of key components in the NF-κB pathway and NLRP3 inflammasome induced by DMF exposure were all suppressed by AMDS in mouse livers. Furthermore, AMDS inhibited DMF-induced cell damage and NF-κB activation in cocultured AML12 hepatocytes and J774A.1 macrophages. However, AMDS per se did not significantly affect the protein level and activity of CYP2E1. Collectively, these results demonstrate that AMDS effectively ameliorates DMF-induced acute liver damage possibly by suppressing oxidative stress and inactivating the NF-κB pathway and NLRP3 inflammasome.

Effect of isolation protocols and cryoprotectants on freezing of stallion epididymal spermatozoa.

BACKGROUND: The recovery of spermatozoa from the cauda epididymis may be the only option to obtain genetic material from elite stallions that had undergone castration or sudden death due to colic or severe injury. OBJECTIVE: To evaluate two different protocols for retrieval of stallion epididymal spermatozoa and to evaluate different cryoprotectants on the freezability of the epididymal spermatozoa. MATERIALS AND METHODS: Six epididymides from three stallions were collected immediately after routine castration under general anesthesia. In the first experiment, each epididymis (of two testes) of the same stallion were processed using different methods for retrieval of the epididymal spermatozoa and were pooled and cryopreserved either using 5% glycerol or 5% dimethyl formamide (DMF) as cryoprotectant. The semen quality parameters viz., progressive motility, HOST, viability and acrosome integrity were evaluated at the fresh, pre-freeze and post-thaw stages. RESULTS: Retrograde method of flushing of epididymis yielded significantly (p < 0.05) higher concentration of the stallion sperm than that of the floating method. The qualitative semen parameters i.e., viability, plasma membrane integrity and acrosome integrity were found to be significantly restored using 5% DMF as cryoprotectant in comparison to when 5% glycerol was used. CONCLUSION: Retrograde flushing method of epididymis yielded significantly higher sperm concentration to that of the floating method, and 5% DMF as cryoprotectant provided acceptable freezability of stallion epididymal spermatozoa. DOI: 10.54680/fr23310110312.

Phase-Dependent Dual Discrimination of MoSe2/MoO3 Composites Toward N,N-Dimethylformamide and Triethylamine at Room Temperature.

Herein, we present, a chemiresistive-type gas sensor composed of two-dimensional 1T-2H phase MoSe2 and MoO3. Mixed phase MoSe2 and MoSe2/MoO3 composites were synthesized via a facile hydrothermal method. The structure analysis using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy revealed the formation of different phases of MoSe2 at different temperatures. With increase in synthesis temperature from 180 to 200 °C, the relative percentage of 1T and 2H-MoSe2 phases changed from 80 to 48%. On the other hand, at 220 °C, 2H-MoSe2 was obtained as a major component. The gas sensing properties of individual MoSe2 and composites were investigated at room temperature toward various analytes. The obtained results revealed that composites possess improved sensing features as compared with individual MoSe2 or MoO3. Data also revealed that the composite with dominating 1T-phase exhibits relatively higher response (10%, at 10 ppm) for dimethylformamide (DMF) compared to triethylamine (TEA) (3%, at 10 ppm). In contrast, the composite with larger 2H-phase exhibited affinity toward TEA and had a relative response of about 2%. Therefore, selectivity of a sensor device can be tuned by an appropriately designed MoSe2/MoO3 composite. These results signify the importance of MoO3-based composites with dual-phase MoSe2 for successfully discriminating between DMF and TEA at room-temperature.

Single-chemical and mixture effects of multiple volatile organic compounds exposure on liver injury and risk of non-alcoholic fatty liver disease in a representative general adult population.

Evidence on liver injury and non-alcoholic fatty liver disease (NAFLD) from volatile organic compounds (VOCs) exposure is insufficient. A cross-sectional study including 3011 US adults from the National Health and Nutrition Examination Survey was conducted to explore the associations of urinary exposure biomarkers (EBs) for 13 VOCs (toluene, xylene, ethylbenzene, styrene, acrylamide, N,N-dimethylformamide, acrolein, crotonaldehyde, 1,3-butadiene, acrylonitrile, cyanide, propylene oxide, and 1-bromopropane) with liver injury biomarkers and the risk of NAFLD by performing single-chemical (survey weight regression) and mixture (Bayesian kernel machine regression [BKMR] and weighted quantile sum [WQS]) analyses. We found significant positive associations of EBs for toluene and 1-bromopropane with alanine aminotransferase (ALT), EBs for toluene, crotonaldehyde, and 1,3-butadiene with asparate aminotransferase (AST), EBs for 1,3-butadiene and cyanide with alkaline phosphatase (ALP), EBs for xylene and cyanide with hepamet fibrosis score (HFS), EBs for the total 13 VOCs (except propylene oxide) with United States fatty liver index (USFLI), and EBs for xylene, N,N-dimethylformamide, acrolein, crotonaldehyde, and acrylonitrile with NALFD; and significant inverse associations of EBs for ethylbenzene, styrene, acrylamide, acrolein, crotonaldehyde, 1,3-butadiene, acrylonitrile, cyanide, and propylene oxide with total bilirubin, EBs for ethylbenzene, styrene, acrylamide, acrolein, 1,3-butadiene, acrylonitrile, and cyanide with albumin (ALB), EBs for ethylbenzene, styrene, acrylamide, N,N-dimethylformamide, acrolein, crotonaldehyde, 1,3-butadiene, acrylonitrile, cyanide, and propylene oxide with total protein (TP), and EB for 1-bromopropane with AST/ALT (all P-FDR<0.05). In BKMR and WQS, the mixture of VOC-EBs was significantly positively associated with ALT, AST, ALP, HFS, USFLI, and the risk of NAFLD, while significantly inversely associated with TBIL, ALB, TP, and AST/ALT. VOCs exposure was associated with liver injury and increased risk of NAFLD in US adults. These findings highlight that great attention should be paid to the potential risk of liver health damage from VOCs exposure.

Low-dimensional compounds containing bioactive ligands. XXII. First crystal structure, cytotoxic activity and DNA and HSA binding of a zirconium(IV) complex with 8-hydroxyquinoline-2-carboxylic acid.

A new zirconium(IV) complex, diaquabis(8-hydroxyquinoline-2-carboxylato-κ3N,O2,O8)zirconium(IV) dimethylformamide disolvate, [Zr(C10H5NO3)2(H2O)2]·2C3H7NO or [Zr(QCa)2(H2O)2]·2DMF (1) (HQCaH is 8-hydroxyquinoline-2-carboxylic acid and DMF is dimethylformamide), was prepared and characterized by elemental analysis, IR spectroscopy and single-crystal X-ray structure analysis. Complex 1 is a mononuclear complex in which the ZrIV atoms sit on the twofold axis and they are octacoordinated by two N and six O atoms of two tridentate anionic QCa2- ligands, and two aqua ligands. Outside the coordination sphere are two DMF molecules bound to the complex unit by hydrogen bonds. The structure and stability of complex 1 in dimethyl sulfoxide were verified by NMR spectroscopy. The cytotoxic properties of 1 and HQCaH were studied in vitro against eight cancer cell lines, and their selectivity was tested on the BJ-5ta noncancerous cell line. Both the complex and HQCaH exhibited low activity, with IC50 > 200 µM. DNA and human serum albumin (HSA) binding studies showed that 1 binds to calf thymus (CT) DNA via intercalation and is able to bind to the tryptophan binding site of HSA (Trp-214).

Biosynthesis of poly(3-hydroxybutyrate) by N,N-dimethylformamide degrading strain Paracoccus sp. PXZ: A strategy for resource utilization of pollutants.

N,N-dimethylformamide is a toxic chemical solvent, which widely exists in industrial wastewater. Nevertheless, the relevant methods merely achieved non-hazardous treatment of N,N-dimethylformamide. In this study, one efficient N,N-dimethylformamide degrading strain was isolated and developed for pollutant removal coupling with poly(3-hydroxybutyrate) (PHB) accumulation. The functional host was characterized as Paracoccus sp. PXZ, which could consume N,N-dimethylformamide as the nutrient substrate for cell reproduction. Whole-genome sequencing analysis confirmed that PXZ simultaneously possesses the essential genes for poly(3-hydroxybutyrate) synthesis. Subsequently, the approaches of nutrient supplementation and various physicochemical variables to strengthen poly(3-hydroxybutyrate) production were investigated. The optimal biopolymer concentration was 2.74 g·L-1 with a poly(3-hydroxybutyrate) proportion of 61%, showing a yield of 0.29 g-PHB·g-1-fructose. Furthermore, N,N-dimethylformamide served as the special nitrogen matter that could realize a similar poly(3-hydroxybutyrate) accumulation. This study provided a fermentation technology coupling with N,N-dimethylformamide degradation, offering a new strategy for resource utilization of specific pollutants and wastewater treatment.

Fluorescence intensity and fluorescence lifetime measurements of various carbon dots as a function of pH.

Measurement and monitoring of pH are essential in both the industry and academia. It is therefore important to continue developing novel, low-cost pH sensors that provide increased accuracy over long periods of time. Particularly promising are sensors based on materials that show pH-dependent fluorescence intensity (FI) and lifetime (FL). Carbon dots (CDs) are emerging as promising candidates because of their low cost, ease of manufacturing, low toxicity, and negligible photobleaching. However, little has been done to quantify the FI and FL values of CDs. Here we report the characterisation of the pH-dependent FI and FL of four novel solvothermal synthesised CDs. The fifth CD is used as a reference sample and was synthesised following a published synthesis. The precursors for the CDs include disperse blue 1 dye, phloroglucinol, m-phenylenediamine (m-PD), N, and N-dimethylformamide (DMF). The average diameter size of the CDs ranges from 1.5 to 15 nm. An excitation wavelength of 452 nm with a bandwidth of 45 nm was used to quantify the fluorescence in the pH range 5-9. Three CDs show a decreasing trend in FI with pH, while two CDs show an increasing trend. None of the CDs shows strong FL dependence. The FL changes around 0.5 ± 0.2 ns across the tested pH range. We suggest that the differences in the fluorescence trends can be attributed to the precursors chosen for synthesising the CDs.

Influence of pH and salts on DMF-DMA derivatization for future Space Applications.

For gas chromatography - mass spectrometry (GC-MS) analyses performed in situ, pH and salts (e.g., chlorides, sulfates) may enhance or inhibit the detection of targeted molecules of interest for astrobiology (e.g. amino acids, fatty acids, nucleobases). Obviously, salts influence the ionic strength of the solutions, the pH value, and the salting effect. But the presence of salts may also produce complexes or mask ions in the sample (masking effect on hydroxide ion, ammonia, etc.). For future space missions, wet chemistry will be conducted before GC-MS analyses to detect the full organic content of a sample. The defined organic targets for space GC-MS instrument requirements are generally strongly polar or refractory organic compounds, such as amino acids playing a role in the protein production and metabolism regulations for life on Earth, nucleobases essential for DNA and RNA formation and mutation, and fatty acids that composed most of the eukaryote and prokaryote membranes on Earth and resist to environmental stress long enough to still be observed on Mars or ocean worlds in geological well-preserved records. The wet-chemistry chemical treatment consists of reacting an organic reagent with the sample to extract and volatilize polar or refractory organic molecules (i.e. dimethylformamide dimethyl acetal (DMF-DMA) in this study). DMF-DMA derivatizes functional groups with labile H in organics, without modifying their chiral conformation. The influence of pH and salt concentration of extraterrestrial materials on the DMF-DMA derivatization remains understudied. In this research, we studied the influence of different salts and pHs on the derivatization of organic molecules of astrobiological interest with DMF-DMA, such as amino acids, carboxylic acids, and nucleobases. Results show that salts and pH influence the derivatization yield, and that their effect depend on the nature of the organics and the salts studied. Second, monovalent salts lead to a higher or similar organic recovery compared to divalent salts regardless of pH below 8. However, a pH above 8 inhibits the DMF-DMA derivatization influencing the carboxylic acid function to become an anionic group without labile H. Overall, considering the negative effect of the salts on the detection of organic molecules, future space missions may have to consider a desalting step prior to derivatization and GC-MS analyses.

Cobalt-Catalyzed Chemoselective Reduction of N-Heteroaryl Ketones with N,N-Dimethylformamide as a Hydride Source.

A method for chemoselective reduction of 2-pyridyl ketones and related N-heteroaryl compounds catalyzed by cobalt stearate using DMF as a hydride source is developed. The ketone substrate is activated by chelation with cobalt, which makes the present method highly chemoselective. A possible reaction mechanism is proposed on the basis of control experiments.