Gas chromatography mass spectrometer determination of dimethylamine impurity in N,N-dimethylformamide solvent by derivatization of N,N-dimethylbenzamide with benzoyl chloride agent.

This study describes the development of a reliable and linear analytical method for precisely determining dimethylamine impurity in N,N-dimethylformamide solvent utilizing a benzoyl chloride derivatization reagent and a gas chromatography mass spectrometer. Benzoyl chloride was used to derivatize dimethylamine. At normal temperature, benzoyl chloride combined with dimethylamine, producing N,N-dimethylbenzamide. This method separated N,N-dimethylbenzamide using Rtx-5 amine (30 m × 0.32 mm × 1.50 µm) as the stationary phase, helium as the carrier gas, argon as the collision gas, and methanol as the diluent. The column flow rate was 2 mL/min. The retention time of N,N-dimethylbenzamide was determined to be 8.5 min. Precision, linearity, and accuracy were tested using ICH Q2 (R2) and USP<1225> guidelines. The percentage coefficient of variation (CV) for N,N-dimethylbenzamide in the system suitability parameter was 1.1%. The correlation coefficient of N,N-dimethylbenzamide was found to be >0.99. In the method precision parameter, the % CV for N,N-dimethylbenzamide was found to be 1.9%, whereas the % CV for N,N-dimethylbenzamide was 1.2% in intermediate precision. The percentage recovery of N,N-dimethylbenzamide was determined to be between 80% and 98%.

Competitive Uptake of Dimethylamine and Trimethylamine against Ammonia on Acidic Particles in Marine Atmospheres.

Alkaline gases such as NH3 and amines play important roles in neutralizing acidic particles in the atmosphere. Here, two common gaseous amines (dimethylamine (DMA) and trimethylamine (TMA)), NH3, and their corresponding ions in PM2.5 were measured semicontinuously using an ambient ion monitor-ion chromatography (AIM-IC) system in marine air during a round-trip cruise of approximately 4000 km along the coastline of eastern China. The concentrations of particulate DMA, detected as DMAH+, varied from <4 to 100 ng m-3 and generally decreased with increasing atmospheric NH3 concentrations. Combining observations with thermodynamic equilibrium calculations using the extended aerosol inorganics model (E-AIM) indicated that the competitive uptake of DMA against NH3 on acidic aerosols generally followed thermodynamic equilibria and appeared to be sensitive to DMA/NH3 molar ratios, resulting in molar ratios of DMAH+ to DMA + DMAH+ of 0.31 ± 0.16 (average ± standard deviation) at atmospheric NH3 concentrations over 1.8 µg m-3 (with a corresponding DMA/NH3 ratio of (1.8 ± 1.0) × 10-3), 0.80 ± 0.15 at atmospheric NH3 concentrations below 0.3 µg m-3 (with a corresponding DMA/NH3 ratio of (1.3 ± 0.6) × 10-2), and 0.56 ± 0.19 in the remaining cases. Particulate TMA concentrations, detected as TMAH+, ranged from <2 to 21 ng m-3 and decreased with increasing concentrations of atmospheric NH3. However, TMAH+ was depleted concurrently with the formation of NH4NO3 under low concentrations of atmospheric NH3, contradictory to the calculated increase in the equilibrated concentration of TMAH+ by the E-AIM.

Fast and Robust Quantification of Detergent Micellization Thermodynamics from Isothermal Titration Calorimetry.

Detergents are widely used in modern in vitro biochemistry and biophysics, in particular to aid the characterization of integral membrane proteins. An important characteristic of these chemicals in aqueous solutions is the concentration above which their molecular monomers self-associate to form micelles, termed the critical micellar concentration (CMC). Micelles are supramolecular assemblies arranged with the hydrophobic portions oriented inward and the hydrophilic head groups positioned outward to interact with the aqueous solvent. Knowledge of the CMC is not only of practical relevance but also of theoretical interest because it provides thermodynamic insights. Isothermal titration calorimetry (ITC) is a powerful method to determine CMCs, as it furnishes additional information on the enthalpy and entropy of micellization. Here we describe our extension of previous methods to determine CMCs and other thermodynamic parameters from ITC demicellization curves. The new algorithm, incorporated into the stand-alone software package D/STAIN, analyzes ITC demicellization curves by taking advantage of state-of-the-art thermogram-integration techniques and automatically providing rigorous confidence intervals on the refined parameters. As a demonstration of the software's capabilities, we undertook ITC experiments to determine the respective CMCs of n-octyl ß-d-glucopyranoside (OG), n-dodecyl ß-d-maltopyranoside (DDM), and lauryldimethylamine N-oxide (LDAO). Motivated by the fact that in vitro membrane protein studies often require additives such as precipitants (e.g., polyethylene glycol (PEG)), we also carried out ITC demicellization studies in the presence of PEG3350, finding in all cases that PEG had significant effects on the thermodynamics of detergent micellization.

Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric acid vapor and different stabilizing species, including ammonia and dimethylamine, as well as oxidation products of pinanediol, a surrogate for organic vapors formed from monoterpenes. A striking resemblance is revealed between the mass spectra from the chamber experiments with oxidized organics and ambient data obtained during new particle formation events at the Hyytiälä boreal forest research station. We observe that large oxidized organic compounds, arising from the oxidation of monoterpenes, cluster directly with single sulfuric acid molecules and then form growing clusters of one to three sulfuric acid molecules plus one to four oxidized organics. Most of these organic compounds retain 10 carbon atoms, and some of them are remarkably highly oxidized (oxygen-to-carbon ratios up to 1.2). The average degree of oxygenation of the organic compounds decreases while the clusters are growing. Our measurements therefore connect oxidized organics directly, and in detail, with the very first steps of new particle formation and their growth between 1 and 2 nm in a controlled environment. Thus, they confirm that oxidized organics are involved in both the formation and growth of particles under ambient conditions.

Development of an SPME-GC-MS method for the specific quantification of dimethylamine and trimethylamine: use of a new ratio for the freshness monitoring of cod fillets.

BACKGROUND: Fish is a highly perishable food, so it is important to be able to estimate its freshness to ensure optimum quality for consumers. The present study describes the development of an SPME-GC-MS technique capable of quantifying both trimethylamine (TMA) and dimethylamine (DMA), components of what has been defined as partial volatile basic nitrogen (PVB-N). This method was used, together with other reference methods, to monitor the storage of cod fillets (Gadus morhua) conserved under melting ice. RESULTS: Careful optimisation enabled definition of the best parameters for extracting and separating targeted amines and an internal standard. The study of cod spoilage by sensory analysis and TVB-N assay led to the conclusion that the shelf-life of cod fillet was between 6 and 7 days. Throughout the study, TMA and DMA were specifically quantified by SPME-GC-MS; the first was found to be highly correlated with the values returned by steam distillation assays. Neither TMA-N nor DMA-N were able to successfully characterise the decrease in early freshness, unlike dimethylamine/trimethylamine ratio (DTR), whose evolution is closely related to the results of sensory analysis until the stage where fillets need to be rejected. CONCLUSION: DTR was proposed as a reliable indicator for the early decrease of freshness until fish rejection. © 2015 Society of Chemical Industry.

The presence of aliphatic and aromatic amines in reservoir and canal water as precursors to disinfection by-products.

This research aimed at determining the dimethylamine (DMA), diethylamine (DEA), dibutylamine (DBA), and aromatic aniline (AN) in reservoir and canal water in the U-Tapao River Basin, Songkhla, Thailand. The trihalomethane formation potential (THMFP) and N-nitrosodimethylamine formation potential (NDMA-FP) of the reservoir and canal water were analyzed. Water samples from two reservoirs and raw water from water treatment plants at upstream, midstream, and downstream locations of the canal were collected twice. The analysis of the DMA, DEA, DBA, and AN were conducted using gas chromatography and spectrofluorometry techniques. The DMA, DEA, and DBA levels in the reservoir and canal waters ranged from not detectable (ND) to 10 µg/L and from ND to 21.2 µg/L, respectively. AN was detected from 123 to 129 ng/L and from 112 to 177 ng/L in the reservoir and canal waters, respectively. The DMA, DEA, DBA, and AN exhibited two fluorescent peaks at 230nmEx/345nmEm and 280 nmEx/355nmEm. These two peaks corresponded to the peak positions of tryptophan. Detection limits of DMA, DEA, and DBA for fluorescent analysis were 500 µg/L whereas that of AN and tryptophan were 10 and 0.5 µg/L, respectively. The NDMA-FP measured in all the water samples was lower than the detection limit of 237 ng/L. THMFP ranged from 175 to 248 µg/L and 214 to 429 µg/L was detected in the reservoir and canal waters, respectively. The THMFP/dissolved organic carbon (DOC) of the reservoir and canal waters were comparable within the ranges of 73 to 131 µg THMFP/mg DOC.

Role of Chlorine Dioxide in N-Nitrosodimethylamine Formation from Oxidation of Model Amines.

N-Nitrosodimethylamine (NDMA) is an emerging disinfection byproduct, and we show that use of chlorine dioxide (ClO2) has the potential to increase NDMA formation in waters containing precursors with hydrazine moieties. NDMA formation was measured after oxidation of 13 amines by monochloramine and ClO2 and pretreatment with ClO2 followed by postmonochloramination. Daminozide, a plant growth regulator, was found to yield 5.01 ± 0.96% NDMA upon reaction with ClO2, although no NDMA was recorded during chloramination. The reaction rate was estimated to be ∼0.0085 s(-1), and on the basis of our identification by mass spectrometry of the intermediates, the reaction likely proceeds via the hydrolytic release of unsymmetrical dimethylhydrazine (UDMH), with the hydrazine structure a key intermediate in NDMA formation. The presence of UDMH was confirmed by gas chromatography-mass spectrometry analysis. For 10 of the 13 compounds, ClO2 preoxidation reduced NDMA yields compared with monochloramination alone, which is explained by our measured release of dimethylamine. This work shows potential preoxidation strategies to control NDMA formation may not impact all organic precursors uniformly, so differences might be source specific depending upon the occurrence of different precursors in source waters. For example, daminozide is a plant regulator, so drinking water that is heavily influenced by upstream agricultural runoff could be at risk.

Single-particle speciation of alkylamines in ambient aerosol at five European sites.

Alkylamines are associated with both natural and anthropogenic sources and have been detected in ambient aerosol in a variety of environments. However, little is known about the ubiquity or relative abundance of these species in Europe. In this work, ambient single-particle mass spectra collected at five sampling sites across Europe have been analysed for their alkylamine content. The aerosol time-of-flight mass spectrometer (ATOFMS) data used were collected in Ireland (Cork), France (Paris, Dunkirk and Corsica) and Switzerland (Zurich) between 2008 and 2013. Each dataset was queried for mass spectral marker ions associated with the following ambient alkylamines: dimethylamine (DMA), trimethylamine (TMA), diethylamine (DEA), triethylamine (TEA), dipropylamine (DPA) and tripropylamine (TPA). The fraction of ambient particles that contained detectable alkylamines ranged from 1 to 17 % depending on location, with the highest fractions observed in Paris and Zurich in the winter months. The lowest fractions were observed at coastal sites, where the influence of animal husbandry-related alkylamine emissions is also expected to be lowest. TMA was the most ubiquitous particle phase alkylamine detected and was observed at all locations. Alkylamines were found to be internally mixed with both sulphate and nitrate for each dataset, suggesting that aminium salt formation may be important at all sites investigated. Interestingly, in Corsica, all alkylamine particles detected were also found to be internally mixed with methanesulphonic acid (MSA), indicating that aminium methanesulphonate salts may represent a component of marine ambient aerosol in the summer months. Internal mixing of alkylamines with sea salt was not observed, however. Alkylamine-containing particle composition was found to be reasonably homogeneous at each location, with the exception of the Corsica and Dunkirk sites, where two and four distinct mixing states were observed, respectively.

Branching ratios in reactions of OH radicals with methylamine, dimethylamine, and ethylamine.

The branching ratios for the reaction of the OH radical with the primary and secondary alkylamines: methylamine (MA), dimethylamine (DMA), and ethylamine (EA), have been determined using the technique of pulsed laser photolysis-laser-induced fluorescence. Titration of the carbon-centered radical, formed following the initial OH abstraction, with oxygen to give HO2 and an imine, followed by conversion of HO2 to OH by reaction with NO, resulted in biexponential OH decay traces on a millisecond time scale. Analysis of the biexponential curves gave the HO2 yield, which equaled the branching ratio for abstraction at αC-H position, r(αC-H). The technique was validated by reproducing known branching ratios for OH abstraction for methanol and ethanol. For the amines studied in this work (all at 298 K): r(αC-H,MA) = 0.76 ± 0.08, r(αC-H,DMA) = 0.59 ± 0.07, and r(αC-H,EA) = 0.49 ± 0.06 where the errors are a combination in quadrature of statistical errors at the 2σ level and an estimated 10% systematic error. The branching ratios r(αC-H) for OH reacting with (CH3)2NH and CH3CH2NH2 are in agreement with those obtained for the OD reaction with (CH3)2ND (d-DMA) and CH3CH2ND2 (d-EA): r(αC-H,d-DMA) = 0.71 ± 0.12 and r(αC-H,d-EA) = 0.54 ± 0.07. A master equation analysis (using the MESMER package) based on potential energy surfaces from G4 theory was used to demonstrate that the experimental determinations are unaffected by formation of stabilized peroxy radicals and to estimate atmospheric pressure yields. The branching ratio for imine formation through the reaction of O2 with α carbon-centered radicals at 1 atm of N2 are estimated as r(CH2NH2) = 0.79 ± 0.15, r(CH2NHCH3) = 0.72 ± 0.19, and r(CH3CHNH2) = 0.50 ± 0.18. The implications of this work on the potential formation of nitrosamines and nitramines are briefly discussed.

Dissipation and residues of 2,4-D: -dimethylammonium in wheat and soil.

The environmental behavior of 720 g/L 2,4-D: -dimethylammonium AS under wheat field conditions was studied in detail. The dissipation behaviors of 2,4-D: -dimethylammonium in wheat and soil were fitted to first-order kinetic equation (C = C (0) e (-lambdat )). But different experimental points and years have different initial deposits and half-lives (T (1/2)). After applying 720 g/L 2,4-D: -dimethylammonium AS at recommended dosage and 1.5-fold recommended dosage during 3-4 leaf stage, the residues of 2,4-D: -dimethylammonium in wheat plant, wheat grain and soil were all lower than 0.02 mg/kg. The obtained results suggested that, it is safety for application at the recommended dosage during 3-4 leaf stage to control weeds in wheat field.

A faster and simpler UPLC-MS/MS method for the simultaneous determination of trimethylamine N-oxide, trimethylamine and dimethylamine in different types of biological samples.

Gut microbiota-dependent metabolites trimethylamine N-oxide (TMAO), trimethylamine (TMA) and dimethylamine (DMA) from dietary methylamines have recently gained much attention due to their high association with chronic kidney disease risk. Hence a simpler and faster performance liquid chromatography-tandem mass spectrometry method was developed and validated. The quantitative analysis was achieved within 6 min by using Agilent 6460C UPLC-MS/MS with 10% methyl alcohol isocratic elution and was more simple, convenient and rapid than that of previously reported methods. Furthermore, method verification results showed that the method correlation coefficient was 0.99978293, 0.99997514 and 0.98784721, and the detection limit was 0.121, 8.063 and 0.797 µg L-1, and the precision of the retention time and peak area of analytes was less than 0.331 and 3.280, respectively. The method was applied to simultaneously determine TMAO, TMA and DMA in the urine and serum from mice treated with normal, high l-carnitine, or high choline diet. Quantitative recoveries of TMAO, TMA and DMA were in the range of 94.2%-101.0%, and the RSD values were lower than 5.17%. The proposed UPLC-MS/MS-based assay should be of value for further evaluating TMAO as a risk marker and for examining the effect of dietary factors on TMAO metabolism.

Automated on-line in-tube solid-phase microextraction-assisted derivatization coupled to liquid chromatography for quantifying residual dimethylamine in cationic polymers.

A method for the analysis of dimethylamine (DMA) by automated in-tube solid-phase microextraction (IT-SPME)-supported chemical derivatization coupled with high-performance liquid chromatography was developed. Extraction, derivatization and desorption were studied by using a capillary coated with 95% polydimethylsiloxane and 5% polydiphenylsiloxane. Solution derivatization and automated IT-SPME derivatization using 9-fluorenylmethyl chloroformate (FMOC) were compared. The proposed procedure provided adequate linearity, accuracy and precision in the 0.2-2.0 microg/mL concentration interval, and the limit of detection (LOD) was 50 ng/mL. The main advantages of the proposed procedure are: (i) no off-line sample manipulation, (ii) rapidity, as the total analysis time is about 10 min, (iii) specificity for the samples assayed, (iv) minimal consumption of FMOC reagent and (v) minimal residues. Therefore, the proposed method is an environmental-friendly and cost-effective alternative for the control of residual DMA in polymeric cationic surfactants used like flocculants in water treatment.

Dimethylamine and diet.

Forty-six different foods eaten by six healthy male volunteers were investigated as potential sources of the aliphatic secondary amine, dimethylamine. None that were representatives from the fruit and vegetable, meat, dairy and grain produce categories afforded any measurable elevation in urinary dimethylamine output following ingestion. All of the statistically significant increases occurred after consumption of fish and seafoods. However, within this category a wide variation was observed. The highest values were obtained for coley, squid and whiting with cod, haddock, sardine, skate and swordfish also producing substantial increases. Freshwater trout, plaice and prawns gave no discernable effect. It seems that not all fish and seafoods may be treated equally with regards to human dimethylamine exposure and that the situation is more complicated than at first appears.

Groundwater derived arsenic in high carbonate wetland soils: sources, sinks, and mobility.

Wetlands and organic soils have been recognized as important sinks for arsenic in the environment, yet sources and immobilization mechanisms of As are often unclear. To begin rectifying this deficiency, we investigated As retention and binding mechanisms at a degraded, minerotrophic wetland site in contact with groundwater rich in As and Fe. Arsenic occurred in high dissolved concentrations of up to 467 microg L(-1) in the groundwater, but dropped to values below 10 microg L(-1) towards the surface. The solid phase As content instead was high in the topsoil with up to 3400 mg kg(-1) and decreased with depth to 15 mg kg(-1). A similar pattern was observed with respect to Fe. Amorphous and crystalline iron precipitates were the main sorbents for arsenic in the soil horizons according to results from wet chemical sequential extractions. Arsenic was apparently not associated with inorganic carbon phases, but a substantial portion of up to 31% of As(tot) could be mobilized by dispersion of soil organic matter. Ratios of dissolved As(III)/As(V) decreased from the deeper As(III) dominated groundwater to the As(V) dominated soil porewaters, where As was apparently immobilized in its oxidized form. Concentrations of the organic species DMA and MMA were negligible. According to the results of simple one-dimensional estimates the vertical arsenic transport from the source in the groundwater to the topsoil was slow given an extrapolation of current conditions. These results suggest that As accumulation started before the beginning of drainage in the now degraded peatland soils and the degradation and mass loss of organic matter under oxic conditions caused the very high As concentrations found in the topsoil horizon today.

Biodegradability and ecotoxicity of amine oxide based surfactants.

The aerobic and anaerobic biodegradability as well as the aquatic toxicity of two fatty amine oxides and one fatty amido amine oxide were investigated. Aerobic biodegradation was evaluated using the CO(2) headspace test (ISO 14593) and biodegradation under anaerobic conditions was assessed employing a standardised batch test. The three amine oxide based surfactants tested were readily biodegradable under aerobic conditions but only the alkyl amido amine oxide was found to be easily biodegradable under anaerobic conditions. Toxicity to Photobacterium phosphoreum and Daphnia magna was evaluated. Bacteria (EC(50) from 0.11 to 11 mg l(-1)) proved to be more sensitive to the toxic effects of the amine oxide based surfactants than crustacea (IC(50) from 6.8 to 45 mg l(-1)). The fatty amido amine oxide showed the lowest aquatic toxicity.

A novel liquid chromatography-mass spectrometric method for the simultaneous determination of trimethylamine, dimethylamine and methylamine in fishery products.

A novel multianalyte method has been developed to determine the concentration of trimethylamine (TMA), dimethylamine (DMA) and methylamine (MA) in fish. The optimal points of the key parameters (pH 8, 60 °C and 60 min of reaction time) were determined for the reaction with tert-butyl bromoacetate. An HILIC column was used to elute all the compounds in only 12 min and selective quantitation of the compounds was achieved. The methodology was validated in trout, hake and Atlantic horse mackerel and was used to study the shelf life of fish under refrigeration. A good correlation with the picrate method was obtained and the proposed methodology has been proved to be robust, specific and sensible with a limit of detection of 0.08 mg N-TMA kg(-1) in freshwater fish and 1 mg N-TMA kg(-1) in marine fish. In addition, TMA has been proved to be a good spoilage indicator also in freshwater fish.

Endotoxin adsorbent using dimethylamine ligands.

Various adsorbents have been investigated for removing endotoxin from protein solutions. It is believed that electrostatic interaction and hydrophobic intermolecular interaction are the main interactions in adsorption of endotoxin. In this work, a series of novel molecular recognition adsorbents for removal of endotoxin with dimethylamine ligand were prepared by coupling ligands on polymethyl methacrylate. We found that its adsorption capacity of endotoxin increased almost 8 times in the presence of a hydroxyl group at beta-site of ligand. The computer simulation showed that the hydroxyl group at beta-site could form H bond with endotoxin, as a result an octatomic ring was formed. The spacer in adsorbent and the long alkyl chain in endotoxin were located at the same side of the octatomic ring. In this situation, electrostatic interaction, H bond, cooperative effect of octatomic ring and hydrophobic intermolecular interaction effected simultaneously. The combination of endotoxin with adsorbent was tight and adsorption capacity was effectually increased.

Determination of the number of detergent molecules associated with the reaction center protein isolated from the photosynthetic bacterium Rhodopseudomonas viridis. Effects of the amphiphilic molecule 1,2,3-heptanetriol.

Detergent-free reaction center (RC) proteins from the photosynthetic bacterium Rhodopseudomonas viridis were obtained using Bio-Beads SM-2. With these RCs, the amount of detergent molecules associated with the protein was measured by determining the detergent concentration at which re-solubilization occurred as a function of the RC concentration. For N,N-dimethyl dodecylamine-N-oxide (LDAO), Triton X-100 and beta-octylglucoside 260 +/- 30,105 +/- 10 and 360 +/- 100 detergent molecules were necessary to dissolve the protein, respectively. With this technique we have studied the effect of the amphiphilic molecule 1,2,3-heptanetriol, which is essential in the crystallization process of these RCs. Addition of 5% 1,2,3-heptanetriol reduces the value for LDAO to 120 +/- 20 LDAO/RC, supporting the notion that crystallization of the RCs is promoted by increasing the number of protein-protein contacts.

Trimethylamine: the substance mainly responsible for the fishy odor often associated with bacterial vaginosis.

The vaginal discharge of women with bacterial vaginosis often has a prominent fishy odor. Intensification of this fishy odor by the addition of strong base to the vaginal discharge suggests that it could be due to trimethylamine, the substance responsible for the characteristic odor of spoiling fish. Samples were collected from 11 women with a vaginal discharge having a fishy odor and from 10 women with no detectable odor. Gas chromatographic analysis of headspace samples of alkalinized vaginal discharges indicated the presence of trimethylamine in all 11 samples with the fishy odor but not in the other samples. The chemical identity of trimethylamine was confirmed by gas chromatography-mass spectrometry of headspace samples from two vaginal discharge samples. It is concluded that trimethylamine is the primary cause of the fishy odor associated with bacterial vaginosis.