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1.
Arch Microbiol ; 204(8): 529, 2022 Jul 28.
Artículo en Inglés | MEDLINE | ID: mdl-35900598

RESUMEN

A rod-shaped, Gram-negative staining strain, FBM22T, was isolated from a microbial fermentation bed substrate from a pig farm. Its colonies appeared yellow and were 0.5-1.2 mm in diameter. Cells were 0.3-0.5 µm wide, 0.5-0.83 µm long. Optimal growth occurred at 30 °C and pH 7.0-8.0; NaCl was not required for growth. The strain performed denitrification and nitrate reduction functions. And it could produce catalase. FBM22-1T utilized the following organic substrates for growth: tyrosine, glutamic acid, D-glucose, and galactose. The novel isolate could degrade 2-nitropropane as carbon and nitrogen source. The dominant respiratory quinone was Q-10. The major polar lipids were diphosphatidylglycerol, phosphatidylcholine and phosphatidylethanolamine. C18:1 ω7c, C16:1 ω7c and/ or C16:1 ω6c, and C14:0 2-OH were the major (≥ 8%) fatty acids. The G+C content was 56.8 mol%. FBM22T was found to be a member of the genus Sphingopyxis in the family Sphingomonadaceae of the class Alphaproteobacteria. It had the highest sequence similarity with the type strains Sphingopyxis terrae subsp. ummariensis UI2T (96.47%) and Sphingopyxis terrae subsp. terrae NBRC 15098T (96.40%). Furthermore, FBM22T had 18.7% and 18.4% relatedness (based on digital DNA-DNA hybridization) with its two relatives (S. terrae subsp. ummariensis UI2T and S. terrae subsp. terrae NBRC 15098T). The morphological, physiological, and genotypic differences identified in this study support the classification of FBM22T as a novel species within the genus Sphingopyxis, for which the name Sphingopyxis yananensis sp. nov. is proposed. The type strain is FBM22T (= KCTC 82290T = CCTC AB2020286T).


Asunto(s)
Sphingomonadaceae , Animales , Técnicas de Tipificación Bacteriana , ADN Bacteriano/genética , Ácidos Grasos/análisis , Fermentación , Nitroparafinas , Fosfolípidos/química , Filogenia , Propano/análogos & derivados , ARN Ribosómico 16S/genética , Análisis de Secuencia de ADN , Porcinos
2.
Contact Dermatitis ; 87(5): 439-446, 2022 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-35736503

RESUMEN

BACKGROUND: The European baseline series (EBS) of contact allergens is subject to change. An allergen is considered for inclusion when routine patch testing of patients with suspected contact dermatitis results in ≥0.5% prevalence rate. OBJECTIVES: We aimed to determine the frequency of sensitizations to 30 EBS allergens and 10 locally added allergens. Additionally, we assessed the strength and evolution of reactions to all tested allergens and co-reactivity of additional allergens. METHODS: Patch testing with our baseline series of 40 allergens was done in 748 consecutive adults. Tests were applied to the upper back and removed by patients after 48 h. Readings were done on Day 3 (D3) and D6 or D7 (D6/7). Positive reactions fulfilled the criteria of at least one plus (+) reaction. A retrospective analysis was done. RESULTS: Eight allergens not listed in the EBS had ≥0.5% prevalence rate (i.e., cocamidopropyl betaine, thiomersal, disperse blue mix 106/124, 2-bromo-2-nitropropane-1,3-diol, diazolidinyl urea, propylene glycol, Compositae mix II and dexamethasone-21-phosphate), and 16.6% of positive reactions would have been missed without D6/7 readings. CONCLUSION: We propose further studies to evaluate whether cocamidopropyl betaine, disperse blue mix 106/124, 2-bromo-2-nitropropane-1,3-diol, diazolidinyl urea and Compositae mix II need to be added to the EBS.


Asunto(s)
Alérgenos , Dermatitis Alérgica por Contacto , Adulto , Alérgenos/efectos adversos , Betaína/análogos & derivados , Dermatitis Alérgica por Contacto/diagnóstico , Dermatitis Alérgica por Contacto/epidemiología , Dermatitis Alérgica por Contacto/etiología , Dexametasona , Humanos , Nitroparafinas , Pruebas del Parche/métodos , Fosfatos , Propano/análogos & derivados , Glicoles de Propileno , Estudios Retrospectivos , Timerosal , Urea/análogos & derivados
3.
J Org Chem ; 87(12): 7798-7805, 2022 06 17.
Artículo en Inglés | MEDLINE | ID: mdl-35657289

RESUMEN

Scatter plot analyses for 14,169 phenylethanes of the substructure Cß-CαH2-Ph with three open coordination positions at Cß and 150,568 phenylethanes of Cß-CαHX-Ph with an additional open coordination position X at Cα have been performed, based on searches in the Cambridge Structural Database. The correlation of rotation angle ψ = Cß-Cα-Ci-Co with a pyramidalization angle θ = Co-Co'-Ci-Cα in a 360° rotation about the bond Cα-Ci reveals a sinusoidal pattern with three maxima and minima, whereas the correlation of rotation angle ψ with bond angle ω = Cß-Cα-Ci and bond length d = Cß-Cα results in sinusoidal patterns with two maxima and minima. A total of 3993 nitro derivatives of the substructure Cß-CαHX-NO2 confirm the results and show that atoms Ci/Co/Co' in the phenyl compounds can be replaced by atoms N/O/O' without any change in the two- and threefold patterns. In 15,295 methyl acetates of the substructure Cß-CαHX-C'(═O)OMe, pyramidalization of the group CαC'(═O)OMe results in a chiral flat tetrahedron with four different corners. (Rθ)/(Sθ) selectivity in the configuration of the tetrahedron is induced by the bonds Cα-Cß, Cα-H, and Cα-X, emanating from the tetrahedral center Cα. It is surprising that bonds as different as Cα-Cß, Cα-H, and Cα-X (X = H, C, N, O, S, etc.) give almost the same induction intensities.


Asunto(s)
Etano , Etano/análogos & derivados , Etano/química , Nitroparafinas
4.
J Phys Chem A ; 126(22): 3511-3520, 2022 Jun 09.
Artículo en Inglés | MEDLINE | ID: mdl-35608948

RESUMEN

Geometries of nitromethane homodimers have been revisited using ab initio and density functional methodologies, following their formation within cryogenic matrices, confirmed using infrared spectroscopy. In contrast to the claim that the intermolecular interactions are due to dispersion forces or very weak hydrogen bonds, in the present work, concrete evidence for the prevalence of O═N...O pnicogen bonding has been presented. The pnicogen bonds have been found to be primarily responsible for the characteristic geometry of a homodimer. The formation of a nitromethane dimer with pnicogen bonding stabilization is evidenced using matrix isolation infrared spectroscopy with Ne and Ar matrices and computations. The interactions within homodimers have been characterized using quantum theory of atoms in molecules, natural bond orbital, energy decomposition, electrostatic potential mapping, and noncovalent interaction analyses. The larger intermolecular separations in liquid nitromethane indicated by previous molecular dynamics-based studies alongside the supposed invariance of infrared spectra in the gas phase and liquid phase could have led to the assumption of a lack of intermolecular interactions. However, the prevalence of hydrogen and pnicogen bonds across these larger than usual separations is affirmed by the geometries presented here.


Asunto(s)
Nitroparafinas , Teoría Cuántica , Enlace de Hidrógeno , Metano/análogos & derivados , Espectrofotometría Infrarroja
5.
Yakugaku Zasshi ; 142(2): 139-144, 2022.
Artículo en Japonés | MEDLINE | ID: mdl-35110450

RESUMEN

Deuterium (2H, D) is a stable isotope of hydrogen (1H). Deuterium-incorporated (labelled) compounds are widely utilized in various scientific fields such as mechanistic studies of organic reactions, elucidation of drug metabolism, application as tracers for microanalysis. Recently, development of heavy drugs and molecular imaging using techniques such as neutron scattering and Raman spectroscopy are spotlighted. We have developed various deuterium-incorporated compounds using D2O as an inexpensive deuterium source to construct novel functional materials. The use of platinum group metals on carbon as catalysts could result in the multi-deuteration of compounds in the mixed solvents of 2-propanol and D2O, and site-selectively deuterated compounds can be synthesized by organocatalytic methods. In this review, the latter deuteration methods using organocatalysts and their applications are summarized. Terminal alkynes smoothly underwent deuterium incorporation by using triethylamine as an organic base or a solid resin possessing the tertiary amine moiety in the same molecule to give mono-deuterated alkynes. These compounds were partially reduced over our prepared specific palladium catalyst under atmospheric D2 gas to produce tri-deuterated alkenes. Achiral or chiral di-deuterated ß-nitro alcohols were also prepared by the organic-base-catalyzed deuteration of nitromethane, followed by nitroaldol reactions in a one pot manner. The mono-deuteration of aromatic aldehyde could be effectively catalyzed by N-heterocyclic carbene. Furthermore, the α-deuteration of aliphatic aldehydes using a basic resin catalyst and the subsequent Knoevenagel condensation with malononitrile could provide γ-deuterium-incorporated α,ß-unsaturated nitrile derivatives. The deuterated compounds thus obtained can be important synthetic precursors to construct the deuterium-incorporated target functional materials.


Asunto(s)
Alquenos/síntesis química , Alquinos/química , Alquinos/síntesis química , Química Orgánica/métodos , Deuterio/química , Desarrollo de Medicamentos/métodos , Etilaminas/química , 2-Propanol/química , Aminas/síntesis química , Carbono/química , Catálisis , Gases , Metano/análogos & derivados , Metano/química , Imagen Molecular/métodos , Nitrilos/síntesis química , Nitrilos/química , Nitroparafinas/química , Paladio/química , Platino (Metal)/química , Solventes
6.
J Org Chem ; 87(4): 2075-2086, 2022 02 18.
Artículo en Inglés | MEDLINE | ID: mdl-34652911

RESUMEN

Route design and proof of concept synthesis was conducted on a synthetically challenging atropisomeric KRASG12C inhibitor to support clinical API manufacture. Improvements to the synthesis of a chiral piperazine fragment gave reduced step count and streamlined protecting group strategy via the formation and methanol ring opening of an N-carboxy-anhydride (NCA). The complex atropisomeric nitroquinoline was accessed via an early stage salt-resolution followed by a formal two-part nitromethane-carbonylation, avoiding a high temperature Gould-Jacobs cyclization that previously led to atropisomer racemization. The substrate scope of the formal nitromethane-carbonylation strategy was further explored for a range of ortho-substituted bromo/iodo unprotected anilines.


Asunto(s)
Proteínas Proto-Oncogénicas p21(ras) , Metano/análogos & derivados , Nitroparafinas
7.
Chem Asian J ; 17(4): e202101299, 2022 Feb 14.
Artículo en Inglés | MEDLINE | ID: mdl-34927372

RESUMEN

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.


Asunto(s)
Nitroparafinas , Catálisis , Metano/análogos & derivados , Estructura Molecular , Estereoisomerismo
8.
J Tradit Chin Med ; 41(6): 891-899, 2021 12.
Artículo en Inglés | MEDLINE | ID: mdl-34939385

RESUMEN

OBJECTIVE: 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. METHODS: 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). RESULTS: 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. CONCLUSION: 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.


Asunto(s)
Enfermedad Hepática Inducida por Sustancias y Drogas , Ficus , Olea , Alanina Transaminasa/metabolismo , Animales , Antiinflamatorios/farmacología , Antioxidantes/farmacología , Aspartato Aminotransferasas/metabolismo , Enfermedad Hepática Inducida por Sustancias y Drogas/metabolismo , Ficus/metabolismo , Hígado/metabolismo , Masculino , Ratones , Nitroparafinas , Olea/metabolismo , Estrés Oxidativo , Propano/análogos & derivados , Superóxido Dismutasa/metabolismo
9.
J Mol Graph Model ; 108: 107987, 2021 11.
Artículo en Inglés | MEDLINE | ID: mdl-34303180

RESUMEN

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.


Asunto(s)
Metano , Nitroparafinas , Hidrógeno , Metano/análogos & derivados , Tamaño de la Partícula
10.
J Phys Chem B ; 125(29): 8185-8192, 2021 07 29.
Artículo en Inglés | MEDLINE | ID: mdl-34270252

RESUMEN

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.


Asunto(s)
Metano , Nitroparafinas , Etilenodiaminas , Cinética , Metano/análogos & derivados
12.
Sci Prog ; 104(2): 368504211011839, 2021.
Artículo en Inglés | MEDLINE | ID: mdl-33940981

RESUMEN

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.


Asunto(s)
Quitosano , Nanopartículas , Animales , Antígenos CD/metabolismo , Antígenos de Diferenciación Mielomonocítica/metabolismo , Quitosano/metabolismo , Quitosano/farmacología , Quitosano/uso terapéutico , Hígado , Nanopartículas/uso terapéutico , Nanopartículas/toxicidad , Nitroparafinas , Antígeno Nuclear de Célula en Proliferación/genética , Antígeno Nuclear de Célula en Proliferación/metabolismo , Propano/análogos & derivados , Ratas , Factor de Necrosis Tumoral alfa/metabolismo , Proteína p53 Supresora de Tumor/genética , Proteína p53 Supresora de Tumor/metabolismo , Factor A de Crecimiento Endotelial Vascular/genética , Factor A de Crecimiento Endotelial Vascular/metabolismo
13.
Environ Sci Technol ; 55(9): 6281-6289, 2021 05 04.
Artículo en Inglés | MEDLINE | ID: mdl-33881830

RESUMEN

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.


Asunto(s)
Ozono , Contaminantes Químicos del Agua , Purificación del Agua , Metano/análogos & derivados , Nitroparafinas , Aguas Residuales , Agua
14.
J Appl Toxicol ; 41(12): 1910-1936, 2021 12.
Artículo en Inglés | MEDLINE | ID: mdl-33847381

RESUMEN

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.


Asunto(s)
Etano/análogos & derivados , Metano/análogos & derivados , Nitroparafinas/toxicidad , Propano/análogos & derivados , Reproducción/efectos de los fármacos , Animales , Pruebas de Carcinogenicidad , Etano/toxicidad , Humanos , Metano/toxicidad , Ratones , Pruebas de Mutagenicidad , Propano/toxicidad , Ratas
15.
Contact Dermatitis ; 84(2): 95-102, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-32876992

RESUMEN

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.


Asunto(s)
Dermatitis Alérgica por Contacto/diagnóstico , Formaldehído/administración & dosificación , Formaldehído/efectos adversos , Pruebas del Parche/métodos , Alérgenos/administración & dosificación , Alérgenos/efectos adversos , Dermatitis Alérgica por Contacto/etiología , Humanos , Nitroparafinas/administración & dosificación , Nitroparafinas/efectos adversos , Propano/administración & dosificación , Propano/efectos adversos , Propano/análogos & derivados , Urea/administración & dosificación , Urea/efectos adversos , Urea/análogos & derivados
16.
Environ Sci Pollut Res Int ; 28(4): 3960-3971, 2021 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-33170464

RESUMEN

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.


Asunto(s)
Gasolina , Óxidos de Nitrógeno , Biocombustibles , Monóxido de Carbono/análisis , Éter , Éteres , Humanos , Metano/análogos & derivados , Óxidos de Nitrógeno/análisis , Nitroparafinas , Reproducibilidad de los Resultados , Emisiones de Vehículos
17.
Molecules ; 25(23)2020 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-33271966

RESUMEN

A calix-shaped polyoxometalate, [V12O32]4- (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-. In the CH3NO2 solution, cyanate abstracts protons from CH3NO2, and the resultant CH2NO2- is stabilized in V12 to form [V12O32(CH2NO2)]5- (V12(CH2NO2)). A crystallographic analysis revealed the double-bond characteristic short bond distance of 1.248 Å 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.


Asunto(s)
Aniones/química , Aniones/aislamiento & purificación , Compuestos Inorgánicos/química , Metano/análogos & derivados , Nitroparafinas/química , Solventes/química , Calixarenos/química , Metano/química , Modelos Moleculares , Estructura Molecular
18.
J Am Chem Soc ; 142(38): 16205-16210, 2020 09 23.
Artículo en Inglés | MEDLINE | ID: mdl-32886500

RESUMEN

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., CD3NO2, CH315NO2, and 13CH3NO2), revealing this easy-to-handle compound as a versatile precursor for the direct installation of the methylamino group.


Asunto(s)
Aminas/síntesis química , Ácidos Borónicos/química , Ésteres/química , Metano/análogos & derivados , Nitroparafinas/química , Compuestos Organofosforados/química , Aminación , Aminas/química , Catálisis , Metano/química , Estructura Molecular , Oxidación-Reducción
19.
J Appl Toxicol ; 40(5): 691-705, 2020 05.
Artículo en Inglés | MEDLINE | ID: mdl-32030785

RESUMEN

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.


Asunto(s)
Nitroparafinas/toxicidad , Propano/análogos & derivados , Solventes/toxicidad , Administración por Inhalación , Administración Oral , Animales , Humanos , Masculino , Rociadores Nasales , Nitroparafinas/administración & dosificación , Vaporizadores Orales , Propano/administración & dosificación , Propano/toxicidad , Ratas Sprague-Dawley , Medición de Riesgo , Solventes/administración & dosificación , Toxicocinética
20.
Environ Sci Technol ; 54(4): 2182-2191, 2020 02 18.
Artículo en Inglés | MEDLINE | ID: mdl-32020793

RESUMEN

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 (O3/BAC) systems. However, previous research has demonstrated that ozone drastically increases the formation potential of genotoxic halonitromethanes (HNMs), including during O3/BAC. Chloropicrin, the most common HNM, is synthesized by chlorinating nitromethane, suggesting that nitromethane may be the immediate precursor of chloropicrin, although nitromethane is unlikely to occur naturally in wastewater. We hypothesized that wastewater ozonation forms nitromethane, which would be the key intermediate toward HNMs. Ozonation of wastewater effluent was shown to form abundant nitromethane, which explained the majority (in one case, all) of subsequent chloropicrin formation. Next, we investigated a suspected category of nitromethane precursor: stimulant drugs, such as ephedrine and methamphetamine, and certain antidepressants. These drugs all feature N-methylamine functional groups, and certain N-alkylamines have been shown to produce primary nitroalkanes upon ozonation. Ozonation of N-methylamine drugs ubiquitously formed nitromethane, typically at >50% yield. Subsequent chlorination converted nitromethane to chloropicrin. The reaction mechanism was investigated to understand the variation in nitromethane yield between different precursors. These results suggest that nitromethane fate during reuse and nitromethane control should be investigated.


Asunto(s)
Ozono , Contaminantes Químicos del Agua , Purificación del Agua , Metano/análogos & derivados , Metilaminas , Nitroparafinas , Aguas Residuales
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