Green and efficient extraction of phenolic compounds from Neem leaves using deep eutectic solvents based ultrasonic-assisted extraction.

Deep eutectic solvent (DES) combined with ultrasonic-assisted extraction was employed as an environmentally friendly technique for extracting antioxidant phenolic compounds from Neem leaves in place of organic solvents. Choline chloride-Ethylene glycol (1:2) with 40% V/V water content (DES-1) was investigated as a potential total phenolic content extractant (38.2 ± 1.2 mg GAE/g DW, where GAE: gallic acid equivalent, DW: dry weight). The optimal operational parameters assessed using single-factor experiments to maximize the total phenolic compounds content were as follows: extraction time of 30 min, 40% V/V water content, liquid-solid ratio of 15:1, and room temperature. Additionally, the in-vitro antioxidant experiments (2,2-diphenyl-1- picrylhydrazyl radical scavenging assay and ferric reducing antioxidant power assay) demonstrated the DES-1-based extract of Neem leaves as a potent antioxidant agent, compared to traditional solvents. Moreover, microscopic morphological analysis supported the effectiveness of DES-1 for the noticeable alteration in the fiber surface structure of Neem leaves after extraction which benefited in the release of polyphenols from these leaves. Eventually, the mass analysis of the extract disclosed the presence of eleven polyphenols in the extract. The Green Analytical Procedure Index revealed the greenness of the extraction method.

Nontarget analysis of Murchison soluble organic matter by high-field NMR spectroscopy and FTICR mass spectrometry.

High-field NMR spectra of Murchison meteorite methanolic extracts revealed primarily aliphatic extraterrestrial organic matter (EOM) with near statistical branching of commonly C(3-5) units separated by heteroatoms and aromatic units. The ratios of CCH, OCH and C(sp2)H units were 89 : 8 : 3, whereas carbon-based aliphatic chain termination was in the order methyl > -COOH > -CH(CH3)COOH. Aliphatic methine carbon was abundant, but its weak NMR signatures were primarily deduced from JRES (J-resolved) NMR spectra. Carbon NMR spectra were dominated by methylene and methyl carbon; strong apodization revealed methine carbon, of which about 20% was aromatic. Extrapolation provided 5-7% aromatic carbon present in Murchison soluble EOM. Compositional heterogeneity in Murchison methanolic extracts was visible in NMR and Fourier transform ion cyclotron (FTICR) mass spectra obtained from a few cubic millimeters of solid Murchison meteorite; increasing sample size enhanced uniformity of NMR spectra. Intrinsic chemical diversity and pH-dependent chemical shift variance contributed to the disparity of NMR spectra. FTICR mass spectra provided distinct clustering of CHO/CHOS and CHNO/CHNOS molecular series and confirmed the prevalence of aliphatic/alicyclic (73%) over single aromatic (21%) and polyaromatic (6%) molecular compositions, suggesting extensive aliphatic substitution of aromatic units as proposed by NMR. Murchison soluble EOM molecules feature a center with enhanced aromatic and heteroatom content, which provides rather diffuse and weak NMR signatures resulting from a huge overall chemical diversity. The periphery of Murchison EOM molecules comprises flexible branched aliphatic chains and aliphatic carboxylic acids. These project on narrow ranges of chemical shift, facilitating observation in one-dimensional and two-dimensional NMR spectra. The conformational entropy provided by these flexible surface moieties facilitates the solubility of EOM.

Kendrick-analogous network visualisation of ion cyclotron resonance Fourier transform mass spectra: improved options for the assignment of elemental compositions and the classification of organic molecular complexity.

Here, we propose a novel computational and visual approach for the analysis of high field Fourier transform ion cyclotron resonance mass spectra (FTICR/MS) based on successive and multiple atomic and Kendrick analogous mass difference analyses. Compositional networks based on elemental compositions and functional networks based on selected functional groups equivalents enable improved assignment options of elemental composition and classification of organic complexity with tunable validation windows. The approach is demonstrated through the analysis of a 12T FTICR mass spectrum of an intricate water soluble extract of a secondary organic aerosol with a previously established abundance in CHNOS molecules.

Comparison of humic substances isolated from thermal water and surface water by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry.

Characterization of humic substances isolated from thermal water and surface water was carried out by elemental analysis and electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. Atomic ratios derived from elemental analysis represented compositional differences of humic substances. Hydrogen-to-carbon and oxygen-to-carbon atomic ratios were also calculated from molecular formulae determined by ultra high-resolution mass spectrometry. The van Krevelen diagram was used to illustrate the bias between the atomic ratios from elemental analysis and mass spectrometry.

Natural organic matter and the event horizon of mass spectrometry.

Soils, sediments, freshwaters, and marine waters contain natural organic matter (NOM), an exceedingly complex mixture of organic compounds that collectively exhibit a nearly continuous range of properties (size-reactivity continuum). NOM is composed mainly of carbon, hydrogen, and oxygen, with minor contributions from heteroatoms such as nitrogen, sulfur, and phosphorus. Suwannee River fulvic acid (SuwFA) is a fraction of NOM that is relatively depleted in heteroatoms. Ultrahigh resolution Fourier transform ion cyclotron (FTICR) mass spectra of SuwFA reveal several thousand molecular formulas, corresponding in turn to several hundred thousand distinct chemical environments of carbon even without accountancy of isomers. The mass difference deltam among adjoining C,H,O-molecules between and within clusters of nominal mass is inversely related to molecular dissimilarity: any decrease of deltam imposes an ever growing mandatory difference in molecular composition. Molecular formulas that are expected for likely biochemical precursor molecules are notably absent from these spectra, indicating that SuwFA is the product of diagenetic reactions that have altered the major components of biomass beyond the point of recognition. The degree of complexity of SuwFA can be brought into sharp focus through comparison with the theoretical limits of chemical complexity, as constrained and quantized by the fundamentals of chemical binding. The theoretical C,H,O-compositional space denotes the isomer-filtered complement of the entire, very vast space of molecular structures composed solely of carbon, hydrogen, and oxygen. The molecular formulas within SuwFA occupy a sizable proportion of the theoretical C,H,O-compositional space. A 100 percent coverage of the theoretically feasible C,H,O-compositional space by SuwFA molecules is attained throughout a sizable range of mass and H/C and O/C elemental ratios. The substantial differences between (and complementarity of) the SuwFA molecular formulas that are observed using six different modes of ionization (APCI, APPI, and ESI in positive and negative modus) imply considerable selectivity of the ionization process and suggest that the observed mass spectra represent simplified projections of still more complex mixtures.

Photolysis pathway of imazapic in aqueous solution: ultrahigh resolution mass spectrometry analysis of intermediates.

Direct degradation of imazapic, an herbicide of the imidazoline family, has been investigated in aqueous solution at different concentrations, pH values, and temperatures. The efficiency of the photodegradation process has been evaluated through degradation rate constants that could be fitted best with pseudo-first-order kinetics ( Ct = C0 e(- kt )). Ultrahigh resolution mass spectrometry (FTICR/MS) was used in electrospray ionization mode as a tool to study the photolysis process on a molecular level, whereas UV-vis and high-performance liquid chromatography/mass spectrometry analysis were used to follow, by time, the evolution of the intermediates. Taking advantage of the high resolving power of FTICR/MS to perform precise formula assignments taking account of the natural abundance of isotopes, we herein propose and demonstrate an approach using 2D-derived van Krevelen visualization (O/C, H/C, m/z) to confirm the formation of imazapic intermediates. Such an approach allows a qualitative analysis of intermediates and elucidates the plausible reaction pathways of the photolysis process. More than eight photoproducts were separated and identified as a phototransformation of the imidazole ring. A mechanistical pathway was proposed.

Characterization of imazamox degradation by-products by using liquid chromatography mass spectrometry and high-resolution Fourier transform ion cyclotron resonance mass spectrometry.

The photodecomposition of imazamox, a herbicide of the imidazolinone family, was investigated in pure water. The main photoproducts from the photolysis were followed over time by liquid chromatography mass spectrometry and structures were proposed from exact mass determinations obtained by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry. The method comprised exact mass determination with better than 0.2 ppm mass accuracy and a corresponding structural visualization taking care of respective isotopes with an adapted van Krevelen diagram that enabled a systematic approach to the characterisation of the elementary composition of each photoproduct. By taking advantage of the high resolving power of FT-ICR MS to make precise formula assignments, the derived 2D van Krevelen diagram (O/C; H/C; m/z) enabled one to structurally differentiate the formed photoproducts and to propose a degradation pathway for imazamox.

The role of humic substances in chromium sorption onto natural organic matter (peat).

To elucidate mechanisms of Cr3+ sorption onto the unaltered solid natural organic matter, the comparative studies of this ion binding from a solution at pH 4.0 onto three selected particle size fractions: 2000-1000 microm, 630-200 microm and 63-20 microm of markedly different HS content and structure, separated by a wet sieving from an overall sample of peat (Brushwood Peat Humus) were carried out. Comparable patterns of COOH groups and CEC(t) confirmed that for cation exchange capacity were responsible mainly cations connected with COO- functional groups. It was though found that aliphatic acids in the solid state did not take part in Cr3+ binding, thus the finest studied fraction 63-20 microm of the highest contents of functional groups showed the lowest sorption capacity for Cr3+, while similar patterns of sorbed Cr3+, soluble HS content and base CEC(0) indicated that these parameters were directly interrelated. The base ion exchange processes determined by CEC(0) (with Ca2+ as a predominant exchangeable cation) appeared to be not the major mechanisms responsible for Cr3+ sorption. For this metal, strong binding to insoluble large molecular weight organic pool two- to threefold prevailed over the ion exchange processes. Very low acid desorption indicated generally low mobility of Cr3+ -organic compounds.

Direct analysis of selected N-acyl-L-homoserine lactones by gas chromatography/mass spectrometry.

A rapid, simple and selective method involving direct separation by gas chromatography (GC) with electron ionization mass spectrometry (EI-MS) was employed to determine some N-acylhomoserine lactones (AHLs). Using GC/EI-MS, simultaneous separation and characterization of AHLs were possible without prior derivatization. Informative fragmentation patterns were obtained to identify the structures of N-acyl chains of AHLs. Electron ionization resulted in a common fragmentation pattern with the most abundant ion at m/z 143 and other minor peaks at m/z 71, 57, and 43. The presence of AHLs in extracts of Burkholderia cepacia strains was achieved in selected ion monitoring mode by using the prominent fragment at m/z 143.

Utilization and transformation of aquatic humic substances by autochthonous microorganisms.

Aquatic humic substances (HS) from a bog lake water, a riverwater, and a groundwater were isolated after enrichment on XAD 8 columns and added to a Czapek-Dox nutrient broth which was used either in full strength or without glucose and/or NaNO3. The individual flasks were inoculated with natural microbial populations of corresponding water samples or with a Pseudomonas fluorescens strain isolated from groundwater. The presence of HS resulted in an increase of bacterial numbers in nearly all cultures incubated for 3 weeks at 25 degrees C on a shaker. HS reisolated from cultures without glucose or NaNO3 showed no or only minor quantitative differences as compared to those from sterile controls. In full strength nutrient broth up to 27% of HS were utilized. Data obtained by spectroscopic methods (UV/vis/FTIR) and elemental analysis indicated a decrease in particle size and a loss in aromaticity and aliphatic carbon in HS reisolated from the microbial cultures. Simultaneously an increase in the N content of HS was observed, which probably originated from some constituents of microbial biomass such as proteins and amino sugars. The NMR data also documented that significant transformations of HS occurred in the individual microbial cultures. After incubation, increased amounts of aromatic acids were detected in some liquid media and residual HS by GC/MS or capillary electrophoresis. 1H NMR spectroscopy was less effective in indicating structural differences in the HS than 13C NMR but revealed considerable detail of the microbial degradation of riverine HS, when limited sample was available. The newly developed NMR increment analysis provided substantial detail of aromatic structures in a microbially altered HS. The microbial degradation of HS strongly depended on the composition of the HS, the species selection of the microorganisms, and to a lesser extent on the culture conditions. For any series of identical inoculum and HS, full broth media initiated the most extensive alteration of HS.