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Ozonation is widely used in wastewater reclamation treatment trains, either for micropollutant control or as a disinfectant and preoxidant in certain reuse processes. We recently found that ozonation of secondary effluent produces nitromethane, which can be efficiently transformed to genotoxic halonitromethanes by chlorination. In this work, the fate of nitromethane through water reuse treatment trains was characterized by analyzing samples from five reuse operations employing ozone. Nitromethane was poorly (50%) rejected by reserve osmosis (RO), not removed by, and in some cases, increased by ultraviolet/advanced oxidation processes (UV/AOP). Sufficient nitromethane remained after advanced treatment that when chlorine was added to mimic secondary disinfection, halonitromethane formation was consistently observed. In contrast, biological activated carbon removed most (75%) nitromethane. Bench-scale experiments were conducted to verify low removal by RO in clean systems and with wastewater effluent and to quantify the kinetics of direct and indirect photolysis of nitromethane in UV/AOP. An explanation for increasing nitromethane concentration during AOP is proposed. These results indicate that nitromethane presents a unique hazard to direct potable reuse systems, due to its ubiquitous formation during wastewater ozonation, poor removal by RO and UV/AOP, and facile conversion into genotoxic halonitromethanes upon chlorine addition.

Scatter plot analyses for 14,169 phenylethanes of the substructure C

Geometries of nitromethane homodimers have been revisited using

The direct reductive N-arylation of nitromethane by organophosphorus-catalyzed reductive C–N coupling with arylboronic acid derivatives is reported. This method operates by the action of a small ring organophosphorus-based catalyst (1,2,2,3,4,4-hexamethylphosphetane P-oxide) together with a mild terminal reductant hydrosilane to drive the selective installation of the methylamino group to (hetero)aromatic boronic acids and esters. This method also provides for a unified synthetic approach to isotopically-labeled N-methylanilines from various stable isotopologues of nitromethane (i.e. CD(3)NO(2), CH(3)(15)NO(2) and (13)CH(3)NO(2)), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.

Two proposition 65 no-significant-risk level (NSRL)-type values were derived for 2-nitropropane (2-NP), in the absence of a Californian published NSRL. In addition, a safety assessment was performed based on estimated typical consumer inhalation and dermal exposure to 2-NP during indoor application of paint from a spray can containing the solvent 1-nitropropane. For the NSRL derivation, benchmark dose (BMD) modeling was performed using hepatocellular carcinoma incidence data from 2-NP single exposure inhalation studies in Sprague-Dawley rats. Several BMD models provided an acceptable fit for the male rat hepatocellular carcinoma incidence data (gamma, log-probit, log-logistic and multistage); therefore, the mean of the BMD lower limits from each model were used as the point of departure to derive the inhalation cancer potency. The oral human cancer potency was derived from the inhalation human cancer potency based on the ratio of the uptake factors for inhalation vs. oral routes. The derived inhalation and oral NSRLs are 67 μg/day and 32 μg/day, respectively. For the inhalation and dermal exposure assessment, three key factors were analyzed: the 2-NP residual concentration in the spray paint product, the mass of spray paint used and the frequency of use. Based on the screening exposure assessment, potential consumer inhalation and dermal exposure to 2-NP from indoor application of paint from a spray can does not exceed our proposed NSRLs, and a warning label is therefore not required for spray can products containing the solvent 1-nitropropane where 2-NP is a minor contaminant.

A rod-shaped, Gram-negative staining strain, FBM22

To investigate the efficacy of Fig fruit powder and olive on hepatic, renal and splenic injury induced by 2-nitropropane (2-NP) in mice, especially if they were used in combination.A total of 40 adult BALB/c male mice weighting 25-30 g/each. Mice were categorized into five groups (8 each). Group 1 as negative control. Group 2 as positive control group intraperitoneally injected with 2-NP (100 mg/kg b. w.) 3 times/weekly for eight weeks. Group 3 injected with 2-NP and were orally supplemented with Fig (300 mg/kg). Group 4 injected with 2-NP and were orally supplemented with olive (100 mg/kg). Group 5 injected with 2-NP and were orally supplemented with mixture of Fig and olive (3:1 respectively).Histopathological observation of liver in mice treated with 2-NP showed cellular degeneration, pyknosis, and congestion of the portal vein. In kidney there were disorganization of the cortical tissues, cellular necrosis and plenty of inflammatory lymphocytic aggregation. Significant elevations in liver function parameters (alanine aminotransferase and aspartate aminotransferase), mRNA expression levels of tumor necrosis factor-α, nicotinamide adenine dinucleotide phosphate oxidase and cyclooxygenase were detected as anti-inflammatory markers and 5-lipoxygenase, interleukin-1α and interleukin-6 as inflammatory biomarkers for liver and spleen, also significant elevations was detected in lipid peroxidation levels. The levels of antioxidants, glutathione, glutathione peroxidase, catalase and superoxide dismutase were significantly decreased.our findings indicated that Fig fruit powder and olive protected against hepatic, renal and splenic injury induced with 2-NP in mice, especially if they were used in combination.

A novel N,N-dibenzyl diaminomethylenemalononitrile organocatalyst efficiently promoted asymmetric Henry reactions of trifluoromethyl enones with nitromethane, affording corresponding highly functionalized products in high yields with excellent enantioselectivities (up to 90% ee). This study is the first to report the successful example of the asymmetric 1,2-additions of nitromethane to trifluoromethyl enones.

Route design and proof of concept synthesis was conducted on a synthetically challenging atropisomeric KRAS

Adding amines to liquid nitromethane (NM) is known to lower the threshold for the shock-to-detonation transition because amines catalyze proton transfer reactions that are the initial steps in the energy release process. We studied NM with 1 wt % ethylenediamine (NM/EDA) with 4 ns input shocks using time and space resolved diagnostics: photon Doppler velocimetry (PDV), optical pyrometry, and nanosecond video imaging. The 4 ns shocks are fast enough to time-resolve the reaction kinetics and the shock-to-detonation transition. We find that it is possible to shock ignite the NM/EDA without producing a detonation, so there is more to amine sensitization of the shock-to-detonation process than simply lowering the barrier to initial reactions. We find that although 1 wt % EDA has little effect on the ambient properties of NM, it dramatically alters the Hugoniot. The shock speed in NM/EDA is reduced, indicating that shocked NM/EDA is significantly more compressible than NM. Higher compressibility is associated with greater adiabatic heating, so EDA both lowers the barrier to proton transfer reactions and increases shock energy absorption. To explain the enhanced compressibility, we propose that shocking NM/EDA produces a reactive flow that has a much higher ionic strength than in NM. The sudden transformation from a molecular liquid to an ionic liquid with stronger intermolecular interactions is responsible for enhanced compressibility and shock heating.

Adding aluminum hydride (AlH3) into energetic materials (EMs) can improve their combustion and energy performance effectively. However, the potential mechanism of AlH3 on EMs is still unclear. Based on the ReaxFF-lg method, the thermal decomposition of nitromethane/nano-aluminum hydride (NM/nano-AlH3) composites were studied. The addition of AlH3 reduces the energy barrier and increases the energy release during the decomposition of NM, accelerates the decomposition of NM. The main way of AlH3 oxidation involves the capture of O atoms from NM. The results show that AlH3 content and passivated layer affect the oxidation and hydrogen release of AlH3. The explosion of small particle size AlH3 leads to rapid oxidation and hydrogen release. The oxidation of large particle size AlH3 is dominated by the inward and outward diffusion of O and Al atoms. The products of NM/nano-AlH3 composites are H2O, CO2, N2 gases, and Al clusters. This work is expected to guide the application of AlH3 in EMs.

Nitroalkanes are organic aliphatic hydrocarbon compounds with a nitro moiety that are commonly used as solvents or intermediates to synthesize a variety of organic compounds due to their inherent reactivity. In June 2020, a harmonized classification and labeling (CLH) proposal was submitted to the European Chemicals Agency (ECHA) for the following harmonized carcinogenicity, mutagenicity, and reproductive toxicity ("CMR") classifications for nitromethane (NM), nitroethane (NE), and 1-nitropropane (1-NP): NM Carc. 1B and Repr. 1B; NE Repr. 1B; and 1-NP Repr. 2. In this assessment, a weight of evidence (WoE) evaluation of studies on animal carcinogenicity and reproductive and developmental toxicity, genotoxicity, and mode of action for these three nitroalkanes was performed to critically assess the relevance of the proposed CMR classifications. Overall, the WoE indicates that NM, NE, and 1-NP are not carcinogenic, genotoxic, nor selective reproductive or developmental toxicants. Based on our analysis, classifying NM, NE, and 1-NP as Category 2 reproductive toxicants is most appropriate. Furthermore, not classifying NE and 1-NP with respect to their carcinogenicity is appropriate based on the available studies for this endpoint coupled with negative results in genotoxicity studies, metabolism data, and in silico predictions. We determined that the classification for NM of Carc. 1B is not appropriate, based on the fact that rat mammary and harderian tumors are likely not relevant to humans and lung and liver tumors reported in mice were equivocal in their dose-response and statistical significance.

BACKGROUND Studies suggest that patch testing with formaldehyde releasers (FRs) gives significant additional information to formaldehyde 1% aq. and should be considered for addition to the European baseline series (EBS). It is not known if this is also true for formaldehyde 2% aq. OBJECTIVES To determine the frequency of sensitization to formaldehyde 2% aq. and co-reactivity with FRs. To establish whether there is justification for including FRs in the EBS. MATERIALS AND METHODS A 4-year, multi-center retrospective analysis of patients with positive patch test reactions to formaldehyde 2% aq. and five FRs. RESULTS A maximum of 15 067 patients were tested to formaldehyde 2% aq. and at least one FR. The percentage of isolated reactions to FR, without co-reactivity to, formaldehyde 2% aq. for each FR were: 46.8% for quarternium-15 1% pet.; 67.4% imidazolidinyl urea 2% pet.; 64% diazolidinyl urea 2% pet.; 83.3% 1,3-dimethylol-5, 5-dimethyl hydantoin (DMDM) hydantoin 2% pet. and 96.3% 2-bromo-2-nitropropane-1,3-diol 0.5% pet. This demonstrates that co-reactivity varies between FRs and formaldehyde, from being virtually non-existent in 2-bromo-2-nitropropane-1,3-diol 0.5% pet. (Cohen's kappa: 0, 95% confidence interval [CI] -0.02 to 0.02)], to only weak concordance for quaternium-15 [Cohen's kappa: 0.22, 95%CI 0.16 to 0.28)], where Cohen's kappa value of 1 would indicate full concordance. CONCLUSIONS Formaldehyde 2% aq. is an inadequate screen for contact allergy to the formaldehyde releasers, which should be considered for inclusion in any series dependant on the frequency of reactions to and relevance of each individual allergen.

A calix-shaped polyoxometalate, [V12O32]4&minus, (V12), stabilizes an anion moiety in its central cavity. This molecule-sized container has the potential to control the reactivity of an anion. The highly-reactive cyanate is smoothly trapped by V12 to form [V12O32(CN)]5&minus, In the CH3NO2 solution, cyanate abstracts protons from CH3NO2, and the resultant CH2NO2&minus, is stabilized in V12 to form [V12O32(CH2NO2)]5&minus, (V12(CH2NO2)). A crystallographic analysis revealed the double-bond characteristic short bond distance of 1.248 &Aring, between the carbon and nitrogen atoms in the nitromethane anion in V12. 1H and 13C NMR studies showed that the nitromethane anion in V12 must not be exchanged with the nitromethane solvent. Thus, the V12 container restrains the reactivity of anionic species.

Nitromethane is a known toxicant and suspected human carcinogen. Exposure to nitromethane in a representative sample of the civilian, noninstitutionalized population in the United States ≥12 years old was assessed using 2007-2012 National Health and Nutritional Examination Survey (NHANES) data. Nitromethane was detected in all 8000 human blood samples collected, of which 6730 were used for analyses reported here. Sample-weighted median blood nitromethane was higher among exclusive combusted tobacco users (exclusive smokers; 774 ng/L) than nonusers of tobacco products (625 ng/L). In stratified sample-weighted regression analysis, smoking 0.5 pack of cigarettes per day was associated with a statistically significant increase in blood nitromethane by 150 ng/L, and secondhand smoke exposure (serum cotinine0.05 ng/mL and10 ng/mL) was statistically significant with a 31.1 ng/L increase in blood nitromethane. Certain dietary sources were associated with small but statistically significant increases in blood nitromethane. At median consumption levels, blood nitromethane was associated with an increase of 7.55 ng/L (meat/poultry), 9.32 ng/L (grain products), and 14.5 ng/L (vegetables). This is the first assessment of the magnitude and relative source apportionment of nitromethane exposure in the U.S. population.

Diesel engines are playing a vital responsibility in the field of automobile, agriculture, construction, and power generation. In the present world, much research is going on in the field of renewable energy to replace conventional sources of energy. But it is not very easy to replace diesel engines with other sources due to the better power output and reliability. The emissions from CI engines are very harmful for human health and for the environment. The major emissions are smoke and NOx which need to be controlled in an effective manner. In this work, direct injection variable compression ratio CI engine was used in experimental investigations for determining the combustion characteristics for D–MXEE–NM blends at different compression ratios. By performance analysis and exhaust emission of engine at peak load, D–MXEE5–NM2.5 (diesel 92.5%, 2–methoxyethyl ether 5%, and nitromethane 2.5%) blend was identified as best blend among all tested fuel blends and pure diesel at normal compression ratio (17.5). Further, all considered fuels with different CR values at peak load were ranked by Entropy–VIKOR method. From the analysis, D–MXEE5–NM2.5 at CR 19.5 was found as best fuel blend (ranked first) among all fuel blends and different compression ratios considered with same experimental conditions. By comparison of best fuel blend D–MXEE5–NM2.5 (at advanced compression ratio 19.5) with diesel (at standard CR 17.5), emission decline (HC 66.66%, CO 70.00%, and smoke 16.09%) and performance improvement (decrement in BSFC 7.07% and increment in BTE 4.41%) were obtained significantly at peak load. However, negligible increment in NOx (3.58%) was observed.

Potable reuse of wastewater is expanding, and ozonation for water reuse is becoming more common, either as a preoxidant before membranes or as part of ozone/biological activated carbon (O

Nitroalkane oxidase (NAO) and nitronate monooxygenase (NMO) are two different types of nitroalkane oxidizing flavoenzymes identified in nature. A previous study suggested that the hypothetical protein PA4202 from Pseudomonas aeruginosa PAO1 is NMO and utilizes only anionic nitronates. However, the structural similarity between the PA4202 protein and Streptomyces ansochromogenes NAO has motivated investigation for what features of the two enzymes differentiate between the NAO and NMO activities. Herein, we report the crystal structure of PA4202 in a ternary complex with a neutral nitroethane (NE) and flavin mononucleotide (FMN) cofactor to elucidate the substrate recognition mechanism using a site-directed mutagenesis. The ternary complex structure indicates that the NE is bound with an orientation, which is poised for the proton transfer to H183 (which is the essential first catalytic step with nitroalkanes), and subsequent reactions with FMN. Moreover, a kinetic study reveals that the catalytic reactions of the wild type and H183 mutants PA4202s with nitroalkane substrates may yield the products of hydrogen peroxide and nitrite that are specified to NAO, although they show a low catalytic efficiency. Our results provide the first structure-based molecular insight into the substrate binding property of the hypothetical protein PA4202, including the interactions with neutral nitroalkanes as the substrate.

A continuous-flow synthesis of β-nitroolefins by using heterogeneous base catalysts has been developed. Although the use of an excess amount of nitro-donor such as nitromethane is required in conventional methods, nearly equimolar amounts of nitro-donors and carbonyl compounds are sufficient for high-yielding production of nitroolefins. Catalysts for this flow protocol are inexpensive and abundant, and high durability and high productivity were also realized by using an appropriate second support.

Halonitromethanes (HNMs) as one typical class of nitrogenous disinfection byproducts have been widely found in drinking water. In vitro test found HNMs could induce higher cytotoxicity and genotoxicity than trihalomethanes and haloacetic acids. However, data on toxic effect from in vivo experiment is limited. In this study, bromonitromethane (BNM), bromochloronitromethane (BCNM) and trichloronitromethane (TCNM) were chosen as target HNMs, and exposed to mice for 30 d. Hepatic toxicity and serum metabolic profiles were determined to reveal toxic effects and mechanisms of the three HNMs. Results showed the three HNMs significantly decreased relative liver weight, indicating liver is one of the target organs. Further, the three HNMs exposure damaged hepatic antioxidant defense system, and increased oxidative DNA damage. Nuclear magnetic resonance based metabolomics analysis found amino acid metabolism and carbohydrate metabolism were disturbed by HNMs exposure. Some metabolites in these metabolisms are related to oxidative stress and damage. Combined with above results, BNM had the highest toxicity, followed by BCNM and TCNM, indicating bromo-HNMs had higher toxicity than chloro-HNMs. Induction of oxidative stress is one of the toxicity mechanisms of HNMs. This study firstly provides the insight into in vivo toxicity of HNMs and their underlying mechanisms based on metabolomics methods, which is very useful for their health risk assessment in drinking water.

The aliphatic nitroalkene ( E )-1-nitropentadec-1-ene ( NPD ), reported in early seventies in soldiers of the termite genus Prorhinotermes , was the first documented nitro compound produced by insects. Yet, its biosynthetic origin has long remained unknown. Here, we investigated in detail the biosynthesis of NPD in P. simplex soldiers. First, we track the dynamics in major metabolic pathways during soldier ontogeny, with emphasis on likely NPD precursors and intermediates. Second, we propose a hypothesis of NPD formation and verify its individual steps using in vivo incubations of putative precursors and intermediates. Third, we use a de novo assembled RNA-Seq profiles of workers and soldiers to identify putative enzymes underlying NPD formation. And fourth, we describe the caste- and age-specific expression dynamics of candidate initial genes of the proposed biosynthetic pathway. Our observations provide a strong support to the following biosynthetic scenario of NPD formation, representing an analogy of the sphingolipid pathway starting with the condensation of tetradecanoic acid with l -serine and leading to the formation of a C 16 sphinganine. The C 16 sphinganine is then oxidized at the terminal carbon to give rise to 2-amino-3-hydroxyhexadecanoic acid, further oxidized to 2-amino-3-oxohexadecanoic acid. Subsequent decarboxylation yields 1-aminopentadecan-2-one, which then proceeds through six-electron oxidation of the amino moiety to give rise to 1-nitropentadecan-2-one. Keto group reduction and hydroxyl moiety elimination lead to NPD . The proposed biosynthetic sequence has been constructed from age-related quantitative dynamics of individual intermediates and confirmed by the detection of labeled products downstream of the administered labeled intermediates. Comparative RNA-Seq analyses followed by qRT-PCR validation identified orthologs of serine palmitoyltransferase and 3-ketodihydrosphingosine reductase genes as highly expressed in the NPD production site, i.e. the frontal gland of soldiers. A dramatic onset of expression of the two genes in the first days of soldier's life coincides with the start of NPD biosynthesis, giving further support to the proposed biosynthetic hypothesis.

Breast and prostate cancers are frequently treated with chemotherapy. Several novel chemicals are being reported for this purpose, particularly synthetic and natural benzophenones. This work reports the synthesis of substituted 2-hydroxybenzophenones through 1,4-conjugate addition/intramolecular cycloaddition/dehydration of nitromethane on key intermediate chromones. Structures were extensively studied by means of 2D NMR spectroscopy and single-crystal XRD. Their cytotoxicity was evaluated in vitro in two breast cancer cell lines (MDA-MB-231 and T47-D) and one prostate cancer cell line (PC3). The most potent compound exhibited good cytotoxic effects against the three cancer cell lines (IC50 values ranging from 12.09 to 26.49 μm) and induced cell-cycle retardation only on prostate cancer cells, which suggested that it might exert cell-type-specific effects.

The current article was designed to assess the role of chitosan nanoparticles (CNPs) in the management of hepatic injury induced by the hepatocarcinogen 2-nitropropane (2-NP). Rats were divided into three groups. The first group served as a control, the second group was injected with 2-NP, while the third group was treated with CNPs 1 h before 2-NP injection every other day for 4 weeks. The 2-NP injection upregulated serum AST and ALT activities, as well as hepatic TNF- α, IL-6, and MDA levels and the expression of vascular endothelial growth factor (VEGF) and caspase-3, whereas GSH contents and SOD activity were decreased. Immunohistochemistry investigations revealed that the hepatic protein expression of collagen I, inducible nitric oxide synthetase, proliferating cell nuclear antigen, cluster of differentiation, and p53 were upregulated. hematoxylin and eosin (H&E) and Masson’s trichrome stains supported the previous parameters, and CNPs ameliorated most of the previous biochemical parameters. CNPs achieved promising results in the limitation of 2-NP hepatotoxicity.

Nitromethane (CH 3 NO 2 ) is an important organic chemical raw material with a wide variety of applications as well as one of the most common pollutants. Therefore it is pretty important to establish a simple and sensitive detection method for CH 3 NO 2 . In our study, a novel amperometric biosensor for nitromethane (CH 3 NO 2 ) based on immobilization of electrochemically-reduced graphene oxide (rGO), chitosan (CS) and hemoglobin (Hb) on a glassy carbon electrode (GCE) was constructed. Scanning electron microscopy, infrared spectroscopy and electrochemical methods were used to characterize the Hb-CS/rGO-CS composite film. The effects of scan rate and pH of phosphate buffer on the biosensor have been studied in detail and optimized. Due to the graphene and chitosan nanocomposite, the developed biosensor demonstrating direct electrochemistry with faster electron-transfer rate (6.48 s −1 ) and excellent catalytic activity towards CH 3 NO 2 . Under optimal conditions, the proposed biosensor exhibited fast amperometric response ( 3 NO 2 with a wide linear range of 5 μM~1.46 mM ( R =0.999) and a low detection limit of 1.5 μM ( S / N =3). In addition, the biosensor had high selectivity, reproducibility and stability, providing the possibility for monitoring CH 3 NO 2 in complex real samples.

Sphingolipids have been considered for many years only as structural components of membranes. It is now acknowledged that they are also involved in controlling cellular processes such as proliferation.The present work was designed to find the anticancer activity of the crab Dromia dehanni hemolymph in in-vivo and in vitro with special reference to the anticancer compound sphingolipids isolation and characterization. The active fraction of the purified hemolymph was subjected to NMR and ESI-MS/MS analysis. The ESI-MS/MS spectrum exhibited intense signals for sodiated molecular ions [M + Na]+ of sphingomyelins (SM) identified as N-2-O-Acetyl-12 pentadecenoyl sphingosine phosphorylcholine, N-9-eicosenoyl- sphinganine phosphocholine and the corresponding dehydro sphingomyelin, N-9-eicosenoyl- dehydro- sphinganine phosphocholine along with the ions at m/z 147, 184 characteristic of phosphocholine. The present study revealed D. dehaani might be a great source for the novel anti-cancer compounds which can be used for human benefits.

Methanogenic substrate loss is reported to be a major bottleneck in microbial fuel cell (MFC), which significantly reduces the power production capacity and coulombic efficiency (CE) of this system. Nitroethane is found to be a potent inhibitor of hydrogenotrophic methanogens in rumen fermentation process. Influence of nitroethane pre-treated sewage sludge inoculum on suppressing the methanogenic activity and enhancing the electrogenesis in MFC was evaluated. MFC inoculated with nitroethane pre-treated anodic inoculum demonstrated a maximum operating voltage of 541 mV, with CE and maximum volumetric power density of 39.85% and 20.5 W/m3, respectively. Linear sweep voltammetry indicated a higher electron discharge on the anode surface due to enhancement of electrogenic activity while suppressing methanogenic activity. A 63% reduction in specific methanogenic activity was observed in anaerobic sludge pre-treated with nitroethane, emphasizing the significance of this pre-treatment for suppressing methanogenesis and its utility for enhancing electricity generation in MFC.

The continuous rise in cost of fossil fuels and environmental pollution has attracted research in the area of clean alternative fuels for improving the performance and emission of internal combustion engines. In the present work, methanol and nitromethane were treated as a biofuel and investigations have been made to evaluate the feasibility of replacing diesel with a suitable diesel-methanol-nitromethane blend. For this, experimental investigations were carried out on a VCR diesel engine using diesel-methanol-nitromethane blends to determine the most favorable blending ratio and engine operating parameters for enhancing performance and reduce emissions. The best results of performance and emissions were observed with D-M5-NM2.5 blend (diesel 92.5%, methanol 5%, nitromethane 2.5%) at standard engine parameters. The improvement in engine performance (13% increment in BTE and 19.5% decrement in BSFC) and reduction in emission (smoke 26.47%, NOx 21.66%, and CO 14.28%) was found using D-M5-NM2.5 blend as compared to pure diesel at full load condition; however, HC emission was slightly increased by 10.71%. To find out the best suitable value of CR for D-M5-NM2.5 blend, experiments were further performed on different compression ratios by which higher compression ratio of 19.5 was found better under similar operating conditions. By increasing CR from 18.5 (standard) to 19.5, improvement in engine performance (BTE increased 3.8% and BSFC decreased 3.4%) and reduction in emission (smoke 10%, CO 16.67%, and HC 61.29%) were observed using D-M5-NM2.5 blend; however, NOx was found to be on slightly higher side with tolerable increment of 6.38%.

Chloropicrin formation has been associated with ozonation followed by chlorination, but the reaction pathway and precursors have been poorly characterized. Experiments with methylamine demonstrated that ozonation converts methylamine to nitromethane at ∼100% yield. Subsequent chlorination converts nitromethane to chloropicrin at ∼50% yield under the conditions evaluated. Similarly high yields from other primary amines were limited to those with functional groups on the β-carbon (e.g., the carboxylic acid in glycine) that facilitate carbon-carbon bond cleavage to release nitromethyl anion. Secondary amines featuring these reactive primary amines as functional groups (e.g., secondary N-methylamines) formed chloropicrin at high yields, likely by facile dealkylation to release the primary nitro compound. Chloropicrin yields from tertiary amines were low. Natural water experiments, including derivatization to transform primary and secondary amines to less reactive carbamate functional groups, indicated that primary and secondary amines were the dominant chloropicrin precursors during ozonation/chlorination. Ozonation followed by chlorination of the primary amine side chain of lysine demonstrated low yields (∼0.2%) of chloropicrin, but high yields (∼17%) of dichloronitrolysine, a halonitroalkane structural analogue to chloropicrin. However, chloropicrin yields increased and dichloronitrolysine yields decreased in the absence of hydroxyl radical scavengers, suggesting that future research should characterize the potential occurrence of such halonitroalkane analogues relative to natural radical scavenger (e.g., carbonate) concentrations.

In this paper, heart-cutting two-dimensional GC/MS (GC-GC/MS) method in combination with a simple sample collection procedure was developed for the determination of 6 nitroalkanes in mainstream cigarette smoke. The method could remove large amounts of impurities on-line in the first polar column by heart-cuts and separate from the left interferences in a second mid-polar column. And the target compounds could be focused at the inlet of the second column by cryo-concentration. Compared to conventional GC/MS, GC-GC/MS achieved a lower noise level and sensitivity at least an order of magnitude higher. Furthermore, the GC-GC/MS method could avoid the false negative and false positive results that appeared in the compared conventional GC/MS analysis. By trapping the vapor phase of 20 cigarettes smoke, the LODs and LOQs of the nitroalkanes were 1.3 to 9.8 and 4.3 to 32.6ng/cigarette, respectively, and all linear correlation efficiencies were larger than 0.999. The validation results also indicate that the method has high accuracy (spiked recoveries between 84% and 102%) and good repeatability (RSD between 7.2% and 9.4%). The developed method was applied to analyze 1 Kentucky reference cigarette (3R4F) and 10 Chinese commercial brands of cigarettes. The research results indicated that nitromethane, nitroethane, 2-nitropropane and 1-nitro-n-pentane were detected in mainstream cigarette smoke, but 1-nitro-n-butane and 2-nitropropane, which were reported by one previous study, were not detected in all cigarette samples.

Catalytic conditions for the α-arylation of aryl nitromethanes have been discovered using parallel microscale experimentation, despite two prior reports of the lack of reactivity of these aryl nitromethane precursors. The method efficiently provides a variety of substituted, isolable diaryl nitromethanes. In addition, it is possible to sequentially append two different aryl groups to nitromethane. Mild oxidation conditions were identified to afford the corresponding benzophenones via the Nef reaction, and reduction conditions were optimized to afford several diaryl methylamines.

In this work, a highly reproducible standard gas generating vial is proposed. The vial is comprised of a silicon diffusion pump oil spiked with an appropriate calibration compound, such as modified McReynolds probes (benzene, 2-pentanone, pyridine, 1-nitropropane, 1-pentanol, and n-octane), and then mixed with polystyrene/divinylbenzene (PS/DVB) particles. The concentrations of these compounds in gaseous headspace were found to substantially decrease in comparison to previously developed hydrocarbon pump oil based vials; hence, the amount of standard loaded onto SPME fibers was at most, half that of the previous vial design. Depletion for all compounds after 208 successive extractions was shown to be less than 3.5%. Smaller quantities of standards being used resulted in a vial that depleted slower while remaining statistically repeatable over a wider number of runs. Indeed, it was found that depletion could be largely predicted by using a mass balance theoretical model. This behavior allowed a further increase in the number of loadings that could be performed repeatedly. At a 95% level of confidence, the ANOVA test demonstrated that the prepared vials were statistically identical, with no significant intra- or inter-batch differences. In addition, it was found that vials stored under different conditions (e.g. under light exposure, room temperature, and within a refrigerator) were stable over 10 weeks. Silicon based vials proved to be ideal for performing instrument quality control and loading of internal standards onto fibers, both of which are of great importance when performing on-site analysis using portable GC-MS instrumentation and high throughput determinations in laboratory.

The utility of the repeated-dose liver micronucleus (RDLMN) assay in the detection of a genotoxic hepatocarcinogen was evaluated. In this paper, a rat hepatocarcinogen, 2-nitropropane (2-NP), was administered orally to young adult rats for 14 and 28 days without a partial hepatectomy or a mitogen, and the micronucleus induction in liver was examined using a simple method to isolate hepatocytes. In addition, a bone marrow micronucleus assay was conducted concomitantly. The frequency of micronucleated hepatocytes induced by 2-NP increased significantly in both the 14- and 28-day repeated-dose studies, while the bone marrow micronucleus assays were negative in each study. These results indicate that the RDLMN assay is useful for detecting a genotoxic hepatocarcinogen that is negative in bone marrow micronucleus assays and is a suitable in vivo genotoxicity test method for integration into a repeated-dose general toxicity study.

The promiscuity of de novo designed enzymes provides a privileged platform for diverse abiological reactions. In this work, we report the first example of a nitroolefin synthase that catalyzes the Henry condensation between aromatic aldehydes and nitromethane. Significant catalytic activity was discovered in the computationally designed and evolved carboligase RA95.5-8, and mutations around the active site were shown to improve the reaction rate, demonstrating the potential to optimize the enzyme by directed evolution. This novel nitroolefin synthase could participate in complex biological cascades, whereby the highly tunable chemoselectivity could afford useful synthetic building blocks.

An efficient and mechanistically different method for the electrosynthesis of enaminone directly from methyl ketones, amines and nitromethane was developed. This transition-metal-free method proceeded at room temperature to give a wide array of enaminones in one step, utilizing nitromethane as the carbon source.

The deterioration of water quality, especially organic pollution in Tai Lake and the Qiantang River, have recently received attention in China. The objectives of this study were to evaluate the formation of halonitromethanes (HNMs) using multiple regression models for chlorination and chloramination and to identify the key factors that influence the formation of HNMs in Tai Lake and the Qiantang River. The results showed that the total formation of HNMs (T-HNMs) during chlorination and chloramination could be described using the following models: (1) [Formula: see text] =(10)(5.267)(DON)(6.645)(Br(-))(0.737)(DOC)(-)(5.537)(Cl2)(0.333)(t)(0.165) (R(2)=0.974, p0.01, n=33), and (2) T-HNMNH2Cl=(10)(-)(2.481)(Cl2)(0.451)(NO2(-))(0.382)(Br(-))(0.630)(t)(0.640)(Temp)(0.581) (R(2)=0.961, p0.05, n=33), respectively. The key factors that influenced the T-HNM yields during chlorination were dissolved organic nitrogen (DON), bromide and dissolved organic carbon (DOC). The nitrite and bromide concentrations and the reaction time mainly affected the T-HNM yields during chloramination. Additional analysis indicated that the bromine incorporation factors (BIFs) for trihalogenated HNMs generally decreased as the chlorine/chloramine dose, temperature and reaction time decreased and increased as the bromide concentration increased.

Aim: Nitromethane, found in fuels used for short distance racing, model cars, and model airplanes, produces a falsely elevated serum creatinine with standard creatinine analysis via the Jaffe method. Erroneous creatinine elevation often triggers extensive testing, leads to inaccurate diagnoses, and delayed or inappropriate medical interventions. Multiple reports in the literature identify “enzymatic assays“ as an alternative method to detect the true value of creatinine, but this ambiguity does not help providers translate what type of enzymatic assay testing can be done in real time to determine if there is indeed false elevation.Methods: We report seven cases of ingested nitromethane where creatinine was determined via Beckman Coulter® analyser using the Jaffe method, Vitros® analyser, or i-Stat® point-of-care testing. Nitromethane was detected and semi-quantified using a common clinical toxic alcohol analysis method, and quantified by headspace-gas chromatography-mass spectrometry.Results: When...

Enzyme catalytic promiscuity is the ability of a single enzyme active site to catalyze several chemical transformations, among them those which are different from natural. We have attempted to use this feature of enzymes in the nucleophilic addition of nitromethane to aldimines (the aza-Henry reaction) whose chemically catalyzed version leads to synthetically useful β-nitroamines. We succeded in obtaining for the first time the desired products in the yields up to 81%. The most efficient proved lipase TL (from Pseudomonas stutzeri) and oxynitrilase from Arabidopsis thaliana. However, all the reactions investigated were non-stereoselective.

A novel one-pot strategy for the synthesis of 3-trifluoromethylquinoxalines from N-aryl enamines and nitromethane was developed. The tandem reaction is achieved through nitrosation of alkenes, tautomerization and cyclization, which can be applicable to a wide range of enamines with excellent functional group tolerance and afford quinoxalines in moderate to good yields.

Nitromethane interferes with Jaffé measurements of creatinine, potentially mimicking acute kidney injury.We determined the proportional contribution of nitromethane in blood samples to creatinine measured by the Jaffé colorimetric and the point-of-care (POC) reactions and determined whether the difference can reliably estimate the concentration of nitromethane. Additionally, we determined whether the presence of nitromethane interferes with anion/osmolal gaps and ascertained the stability of nitromethane in serum after 7 days.Nitromethane was added to whole blood from four healthy volunteers to achieve concentrations of 0, 0.25, 0.5, 1, and 2 mmol/L. The following tests were performed: creatinine (Jaffé and POC), electrolytes (associated with Jaffé and POC), osmolality and nitromethane concentration (gas chromatography [GC]). Remaining samples were refrigerated and reanalyzed using GC at 7 days. Anion and osmolal gaps were calculated. Proportional recovery and degradation of nitromethane were measured using GC. Data were analyzed for agreement with single-factor ANOVA (p = 0.05).Mean creatinine for POC and Jaff methods were 0.93 vs. 0.76 mg/dL, respectively. Jaff creatinine concentrations increased linearly with increasing nitromethane concentrations (R(2) = 1, p = 0.01): measured creatinine (mg/dL) = 7.1*nitromethane (mmol/L) = 0.79. POC creatinine remained unchanged across the range of nitromethane concentrations (p = 0.99). Anion and osmolal gaps also remained unchanged. Nitromethane was reliably identified in all sample concentrations using GC on Day 0. Detection of 0.25 mmol/L nitromethane was not consistently recovered on Day 7. Nitromethane degradation was most pronounced at 2 mmol/L concentrations (81% recovery).Nitromethane alters apparent concentration of creatinine using the Jaffé reaction in a linear fashion but not when using the POC reaction. Measured difference between Jaffé and POC creatinine may identify the presence and estimate concentration of nitromethane. Presence of nitromethane did not alter the anion or osmolal gap; thus it would not potentially interfere with the diagnosis of co-exposure to a toxic alcohol.

Quantum calculations at the DFT-D3/def2-TZVPD level of theory have been used to examine complexes between O2YBr (Y═N, P, and As) molecules and several Lewis bases, that is, NH3, H2O, and HF. The interactions of the lone pair of the ammonia, water, and hydrogen fluoride with the σ-hole and π-hole of O2YBr molecules have been considered. In general, the complexes where the Lewis base lone pair interacts with the π-hole are more favorable than those with σ-hole. The nature of the interactions has been characterized with the Bader theory of atoms in molecules (AIM). We have also studied the ability of trifluoronitromethane and nitromethane to interact with anions using their π-hole along with an analysis the Cambridge Structural Database. We have found a large number of hits that provide strong experimental support for ability of the nitryl (-NO2) group to interact with anions and Lewis bases. In some X-ray structures, the π-hole interaction is crucial in the crystal packing and has a strong influence in the solid state architecture of the complexes. Finally, due to the relevance in atmospheric chemistry, we have studied noncovalent σ/π-hole complexes of nitryl bromide with ozone.