Stretchable unidirectional liquid-transporting membrane with antibacterial and biocompatible features based on chitosan derivative and composite nanofibers.

Unidirectional liquid transport is critical in achieving high-performance moisture-management fabrics for medical care. However, realizing unidirectional liquid transport while simultaneously satisfying other requirements, such as antibacterial function, adhesiveness, low cytotoxicity, and adequate mechanical strength remains a challenge. In this study, Janus nanofibrous membranes exhibiting both unidirectional liquid transport and antibacterial activity were fabricated via electrospinning and a mild crosslinking procedure. This membrane provides continuous and spontaneous unidirectional water transport with a high one-way transport value (R) of 1483%. The membrane achieved antibacterial rates of 99.2% and 98.7% against E. coli and S. aureus, respectively, without leaching antibacterial agents. In addition, it has high elasticity and self-adhesive properties, which facilitates its use in a range of applications. The design of this versatile Janus nanofibrous membrane provides a new strategy for developing novel moisture-wicking systems, particularly in the field of medical dressings.

Tailoring Surface Properties of Electrodes for Synchronous Enhanced Extracellular Electron Transfer and Enriched Exoelectrogens in Microbial Fuel Cells.

An extracellular electron transfer (EET) process between an electroactive biofilm and an electrode is a crucial step for the performance of microbial fuel cells (MFCs), which is highly related to the enrichment of exoelectrogens and the electrocatalytic activity of the electrode. Herein, an efficient N- and Fe-abundant carbon cloth (CC) electrode with the comodification of iron porphyrin (FePor) and polyquaternium-7 (PQ) was synthesized using a facile solvent evaporation and immersion method and developed as an anode (named FePor-PQ) in MFCs. The surface structural characterizations confirmed the successful introduction of N and Fe atoms, whereas FePor-PQ achieved the N content of 9.59 at %, which may offer various active sites for EET. The introduction of PQ contributed to improving the surface hydrophilicity, providing the composite electrode good biocompatibility for bacterial attachment and colonization as well as substrate diffusion. Based on the advantages, the MFC with the FePor-PQ anode produced a maximum power density of 2165.7 mW m-2, strikingly higher than those of CC (1124.0 mW m-2), PQ (1668.8 mW m-2), and FePor (1978.9 mW m-2). Furthermore, with the EET mediated by the binding of flavins and c-type cytochromes on the outer membrane was enhanced prominently, the typical exoelectrogen Geobacter was enriched up to 55.84% in the FePor-PQ anode biofilm. This work reveals a synergistic effect from heteroatom coating and surface properties tailoring to boost both the EET efficiency and exoelectrogen enrichment for enhancing MFC performance, which also provides valuable insights for designing electrodes in other bio-electrochemical systems.

Intranasal immunization with O-2'-Hydroxypropyl trimethyl ammonium chloride chitosan nanoparticles loaded with Newcastle disease virus DNA vaccine enhances mucosal immune response in chickens.

BACKGROUND: There has been a great interest in developing strategies for enhancing antigen delivery to the mucosal immune system as well as identifying mucosal active immunostimulating agents. To elevate the potential of O-2'-Hydroxypropyl trimethyl ammonium chloride chitosan (O-2'-HACC) as an adjuvant and mucosal immune delivery carrier for DNA vaccine, we prepared the O-2'-HACC loaded with Newcastle disease virus (NDV) F gene plasmid DNA and C3d6 molecular adjuvant (O-2'-HACC/pFDNA microparticles). RESULTS: The O-2'-HACC/pFDNA exhibited a regular spherical morphology with a particle size of 202.3 ± 0.52 nm, a zeta potential of 50.8 ± 8.21 mV, encapsulation efficiency of 90.74 ± 1.10%, and a loading capacity of 49.84 ± 1.20%. The plasmid DNA could be sustainably released from the O-2'-HACC/pFDNA after an initial burst release. Intranasal vaccination of chickens immunized with O-2'-HACC/pFDNA not only induced higher anti-NDV IgG and sIgA antibody titers but also significantly promoted lymphocyte proliferation and produced higher levels of IL-2, IL-4, IFN-γ, CD4+, and CD8 + T lymphocytes compared with the NDV commercial live attenuated vaccine. Intranasal delivery of the O-2'-HACC/pFDNA enhanced humoral, cellular, and mucosal immune responses and protected chickens from the infection of highly virulent NDV compared with the intramuscular delivery. CONCLUSIONS: Collectively, our findings indicated that the O-2'-HACC could be used as a vaccine adjuvant and delivery system for mucosal immunity and have an immense application promise.

Structural assessment of the bioplastic (poly-3-hydroxybutyrate) produced by Bacillus flexus Azu-A2 through cheese whey valorization.

The demand for the production of biodegradable plastics has significantly increased. Bioplastics have become an essential alternative to the threats of the daily consumable plastics, sourced from fossil fuels, to the environment. Polyhydroxyalkonates (PHAs) are a ubiquitous group of bioderived and biodegradable plastics, however their production is limited by the costs associated mainly with the carbon sources. Herein, this study aims to reduce the PHAs production cost by using a by-product from the dairy industry, i.e., cheese whey (CW), as a sole carbon source. The developed process recruits an aquatic isolate, Bacillus flexus Azu-A2, and is optimized via studying various parameters using the shaking flasks technique. The results showed that the maximum PHA production (0.95 g L-1) and PHA content (20.96%, w/w), were obtained after incubation period 72 h at 45 °C, 100 rpm agitation rate, 50% CWS concentration, pH 8.5, and 1.0 g L-1 ammonium chloride. Physiochemically, Fourier transform infrared spectroscopy (FTIR), gas chromatography-mass spectroscopy (GC-MS), nuclear magnetic resonance (NMR), and energy-dispersive X-ray (EDX) techniques, emphasized the type of the extracted PHA as polyhydroxybutyrate (PHB). The thermal properties of PHB were measured using differential scanning calorimetry (DSC), recording melting transition temperature (Tm) at 170.96 °C. Furthermore, a scanning electron microscope (SEM) visualized a homogenous microporous structure for the thin PHB biofilm. In essence, this study highlights the ability of Bacillus flexus Azu-A2 to produce a good yield of highly purified PHB at reduced production cost from dairy CW. Consequently, the current study paves the way for an improved whey management strategy.

Fabrication of gelatin microspheres containing ammonium hydrogen carbonate for the tunable release of herbicide.

The major challenge in utilizing pesticides lies in identifying the precise application that would improve the efficiency of these pesticides and decline their environmental and health hazards at the same time. Such application requires the development of specific formulations that enable controlled, stimuli-responsive release of the pesticides. Gelatin is a relatively cheap material characterized by temperature-sensitivity and abundant amino acid groups, which makes it suitable for the storage and controlled release of pesticides. In this study, gelatin microspheres were prepared by emulsion and cross-linking, then they were loaded with 2,4-dichlorophenoxyacetic acid sodium (2,4-D Na) as a model herbicide. To achieve temperature-tunable release of 2,4-D Na from the microspheres, NH4HCO3 was added to the formulations at different concentrations. The prepared formulations were characterized by SEM, FTIR, and size distribution analyzes, and their drug loading capacities were determined. Based on bioassay experiments, the 2,4-D Na-NH4HCO3-loaded gelatin microspheres can effectively control the spread of dicotyledonous weeds. Therefore, the strategy proposed herein can be used to develop novel, effective herbicide formulations.

Novel Approach for the Synthesis of Chlorophosphazene Cycles with a Defined Size via Controlled Cyclization of Linear Oligodichlorophosphazenes [Cl(PCl2=N)n-PCl3]+[PCl6].

Despite a significant number of investigations in the field of phosphazene chemistry, the formation mechanism of this class of cyclic compounds is still poorly studied. At the same time, a thorough understanding of this process is necessary, both for the direct production of phosphazene rings of a given size and for the controlled cyclization reaction when it is secondary and undesirable. We synthesized a series of short linear phosphazene oligomers with the general formula Cl[PCl2=N]n-PCl3+PCl6- and studied their tendency to form cyclic structures under the influence of elevated temperatures or in the presence of nitrogen-containing agents, such as hexamethyldisilazane (HMDS) or ammonium chloride. It was established that linear oligophosphazenes are inert when heated in the absence of the mentioned cyclization agents, and the formation of cyclic products occurs only when these agents are involved in the process. The ability to obtain the desired size phosphazene cycle from corresponding linear chains is shown for the first time. Known obstacles, such as side interaction with the PCl6- counterion and a tendency of longer chains to undergo crosslinking elongation instead of cyclization are still relevant, and ways to overcome them are being discussed.

Cation-amino acid interactions: Implications for protein destabilization.

The mechanism for protein stabilization or destabilization has long been an open quest. In the present study, we have studied the interactions between amino acids and guanidinium (Gdm+)/ammonium (NH4+) ions by using low field nuclear magnetic resonance (LF-NMR), where Gdm+ and NH4+ are denaturant and stabilizer for proteins, respectively. It shows that Gdm+ favors to bind to the thiol group or the hydroxyl group on the side chain but weakly interacts with the α-carboxyl group. In contrast, NH4+ prefers to bind to the α-carboxyl group but slightly interacts with the thiol group or the hydroxyl group on the side chain of amino acids. 1HNMR reveals the hydrogen bonding between NH4+ and the α-carboxyl group, which is not involved in the interactions between Gdm+ and cysteine. Our study demonstrates that the strong interactions between the denaturant and the sulfur atom or the disulfide bond promote the direct binding of the denaturant toward proteins, leading to the destabilization.

Combination of solvent extraction with deep eutectic solvent based dispersive liquid-liquid microextraction for the analysis of aflatoxin M1 in cheese samples using response surface methodology optimization.

A new extraction procedure based on combination of a solvent extraction and deep eutectic solvent based dispersive liquid-liquid microextraction has been introduced for the extraction of aflatoxin M1 from cheese samples. In this method, acetonitrile, deionized water, and n-hexane are added onto the sample and vortexed. Owning to different affinities of the substances in cheese toward the mentioned solvents, an efficient and selective extraction of the analyte is done in the acetonitrile phase. After centrifugation, the acetonitrile phase is removed and mixed with a new hydrophobic deep eutectic solvent prepared from N,N-diethanol ammonium chloride and carvacrol as an extraction solvent. The mixture is injected into deionized water, and a cloudy solution is obtained. Eventually, an aliquot of the organic phase is injected into high-performance liquid chromatography-fluorescence detection. After optimizing the effective parameters with the response surface methodology and a quadratic model, limits of detection and quantification were 0.74 and 2.56 ng/kg, respectively. The obtained extraction recovery and enrichment factor were 94% and 94, respectively. Also, intra- (n = 6) and interday (n = 4) precisions were less than or equal to 8.6% at a concentration of 5 ng/kg. The suggested method was applied to determine aflatoxin M1 in different cheese samples.

Design, synthesis, and biological evaluation of benzo[d]imidazole-2-carboxamides as new anti-TB agents.

Tuberculosis is the leading cause of death globally among infectious diseases. Due to the development of resistance of Mycobacterium tuberculosis to currently used anti-TB medicines and the TB-HIV synergism the urgent need to develop novel anti-mycobacterial agents has been realized. The drug-to-target path has been the successful strategy for new anti-TB drug development. All the six drug candidates that have shown promise during the clinical trials and some of these being approved for treatment against MDR TB are the results of phenotype screening of small molecule compound libraries. In search of compounds belonging to novel pharmacophoric class that could be subjected to whole cell assay to generate new anti-TB leads the benzo[d]imidazole-2-carboxamide moiety has been designed as a novel anti-TB scaffold. The design was based on the identification of the benzimidazole ring as a prominent substructure of the FDA approved drugs, the structural analysis of reported anti-TB benzimidazoles, and the presence of the C-2 carboxamido functionality in novel bioisoteric anti-TB benzothiazoles. Twenty seven final compounds have been prepared via NH4Cl-catalyzed amidation of ethyl benzo[d]imidazole-2-carboxylates, as the required intermediates, obtained through a green "all water" one-pot synthetic route following a tandem N-arylation-reduction-cyclocondensation procedure. All of the synthesised target compounds were assessed for anti-TB potential using H37Rv ATCC27294 strain. Thirteen compounds were found with better MIC (0.78-6.25 µg/mL) than the standard drugs and being non-cytotoxic nature (<50% inhibition against RAW 264.7 cell lines at 50 µg/mL). The compound 8e exhibited best anti-TB activity (MIC: 2.15 µM and selectivity index: > 60) and a few others e.g., 8a, 8f, 8k and 8o are the next best anti-TB hits (MIC: 1.56 µg/mL). The determination and analysis of various physiochemical parameters revealed favorable druglike properties of the active compounds. The compounds 8a-l and 8o, with MIC values of ≤ 6.25 µg/mL, have high LipE values (10.66-11.77) that are higher than that of the suggested value of > 6 derived from empirical evidence for quality drug candidates and highlight their therapeutic potential. The highest LipE value of 11.77 of the best active compound 8e with the MIC of 0.78 µg/mL indicates its better absorption and clearance as a probable clinical candidate for anti-TB drug discovery. These findings highlight the discovery of benzimidazole-2-carboxamides for further development as new anti-TB agents.

Synthesis and Aggregation Behavior of Jellyfish-Shaped Triazine Hexamer Quaternary Ammonium Chloride Surfactant.

A novel jellyfish-shaped triazine hexamer quaternary ammonium chloride surfactant (TH12QC) was synthesized, which consisted of one triazine spacer group and six long flexible hydrophobic chains. The molecular structure and aggregation behavior of TH12QC was investigated by nuclear magnetic resonance (NMR), surface tension, electrical conductivity, dynamic light scattering (DLS), transmission electron microscope (TEM), etc. The results show that the jellyfish-shaped TH12QC has better surface activity and lower surface tension than traditional ionic and Gemini surfactants in aqueous solution. There are two inflection points in the curve of conductivity versus concentration of the TH12QC aqueous solution, which correspond to the critical aggregation concentration (CAC) and the critical micelle concentration (CMC) respectively. The existence of CAC indicates that there is a pre-aggregation process before TH12QC forms micelles. The results of DLS and TEM show that network pre-aggregation, spherical aggregation and dense spherical aggregation were observed in different concentration of TH12QC aqueous solution, and the electrostatic equilibrium of the system subtly depends on the concentration of the solution. In addition, intramolecular and intermolecular hydrogen bonding is also an important factor. This study provides a method for studying the aggregation behavior and morphology of oligomeric surfactants with rigid spacer groups.

Cation Specific Effects on the Domain-Domain Interaction of Heterogeneous Dimeric Protein Revealed by FRET Analysis.

Specific monovalent cation effects on the domain-domain interaction of heterogeneous dimeric protein were investigated using green fluorescent protein (GFP)-glutathione-s-transferase (GST) fusion protein as a model protein. Conjugating N-terminal of GST domain with a fluorescence probe Cyanine3, complementary increase and decrease of fluorescence intensities of Cyanine3 and GFP were recognized on the exclusive excitation of GFP and further the fluorescence decay of GFP was remarkably accelerated to show that an excellent Förster type of resonance excitation energy transfer (FRET) pair was constructed between GFP- and GST-domain. The spectral overlap integral and critical distance of the FRET pair were estimated to be 5.96×1013 M-1cm3 and 62.5 Å, respectively. The FRET rate and efficiency evaluated by fluorescence lifetime of the energy donor, GFP, were influenced by the monovalent cations included in the buffer solution to suggest that the domain-domain interactions of GFP-GST fusion protein would be susceptible to cation species and their concentrations. The order affecting the domain-domain interaction was estimated to be Li+>NH4+ >Na+>K+>Cs+, almost corresponding to the reverse Hofmeister series.

Water Soluble Coumarin Quaternary Ammonium Chlorides: Synthesis and Biological Evaluation.

In the present study, coumarin-bearing three pyridinium and three tetra-alkyl ammonium salts were synthesized. The compounds were fully characterized by 1 H- and 13 C-NMR, LC/MS and IR spectroscopic methods and elemental analyses. The cytotoxic properties of all compounds were tested against human liver cancer (HepG2), human colorectal cancer (Caco-2) and non-cancer mouse fibroblast (L-929) cell lines. Some compounds performed comparable cytotoxicity with standard drug cisplatin. Antibacterial properties of the compounds were tested against Gram-negative Escherichia coli and Gram-positive Bacillus subtilis bacteria, but the compounds did not have any antibacterial effect against both bacteria. Enzyme inhibitory properties of all compounds were tested on the activities of human carbonic anhydrase I and II, and xanthine oxidase. All compounds inhibited both enzymes more effectively than standard drugs, acetazolamide and allopurinol, respectively. The biological evaluation results showed that ionic and water soluble coumarin derivatives are promising structures for further investigations especially on enzyme inhibition field.

Microwave assisted copolymerization of sodium alginate and dimethyl diallyl ammonium chloride as flocculant for dye removal.

Flocculant made from natural polymers has the advantages of abundant source, affordable cost and environmental friendliness. In this work, a binary flocculant (sodium alginate-dimethyl diallyl ammonium chloride, SAD) was successfully prepared using microwave assisted free radical copolymerization technique. Based on the flocculation properties of yellow 7GL dye, the synthetic process was optimized with the amount of initiator was 0.8 wt% (equal molar ratio of ammonium peroxydisulfate and sodium bisulfite as complex initiator), sodium alginate: dimethyl diallyl ammonium chloride = 1:1 (molar ratio), and the microwave irradiation time was 18 min at the power of 280 W. The experimental results show that the color removal ratio was 73.5% at the SAD dosage of 425 mg/L for the 100 mg/L yellow 7GL simulated wastewater. The SAD also maintained excellent decolorization ratios under a wide range of flocculant dosage and environmental pH. The flocculation mechanism might be the combination of charge neutralization and bridging effect. The prepared SAD flocculant has the virtues of simple synthesis process, ecofriendliness and high decolorization ratio, which make it broad application prospect in the treatment of dye wastewater.

Synthesis of New 3-Arylaminophthalides and 3-Indolyl-phthalides using Ammonium Chloride, Evaluation of their Anti-Mycobacterial Potential and Docking Study.

OBJECTIVE: The study aims at the derivatization of "Phthalides" and synthesizes 3- arylaminophthalides & 3-indolyl-phthalides compounds, and evaluates their anti-tubercular and antioxidant activities. The study has also intended to employ the in silico methods for the identification of possible drug targets in Mycobacterium and evaluate the binding affinities of synthesized compounds. METHODS: This report briefly explains the synthesis of phthalide derivatives using ammonium chloride. The synthesized compounds were characterized using spectral analysis. Resazurin Microtiter Assay (REMA) plate method was used to demonstrate the anti-mycobacterial activity of the synthesized compounds. An in-silico pharmacophore probing approach was used for target identification in Mycobacterium. The structural level interaction between the identified putative drug target and synthesized phthalides was studied using Lamarckian genetic algorithm-based software. RESULTS AND DISCUSSION: In the present study, we report an effective, environmentally benign scheme for the synthesis of phthalide derivatives. Compounds 5c and 5d from the current series appear to possess good anti-mycobacterial activity. dCTP: deaminasedUTPase was identified as a putative drug target in Mycobacterium. The docking results clearly showed the interactive involvement of conserved residues of dCTP with the synthesized phthalide compounds. CONCLUSION: On the eve of evolving anti-TB drug resistance, the data on anti-tubercular and allied activities of the compounds in the present study demonstrates the enormous significance of these newly synthesized derivatives as possible candidate leads in the development of novel anti-tubercular agents. The docking results from the current report provide a structural rationale for the promising anti-tubercular activity demonstrated by 3-arylaminophthalides and 3-indolyl-phthalides compounds.

The responses of cadmium phytotoxicity in rice and the microbial community in contaminated paddy soils for the application of different long-term N fertilizers.

An eight-year field trial was conducted to investigate the effects of four different N fertilization treatments of urea (CO(NH2)2, the control), ammonium sulfate ((NH4)2SO4), ammonium chloride (NH4Cl), and ammonium hydrogen phosphate [(NH4)2HPO4]) on cadmium (Cd) phytotoxicity in rice and soil microbial communities in a Cd-contaminated paddy of southern China. The results demonstrate that the different N treatments exerted different effects: the application of (NH4)2HPO4 and (NH4)2SO4 significantly increased rice grain yield and decreased soil-extractable Cd content when compared with those of the control, while NH4Cl had a converse effect. Expression of genes related to Cd uptake (IRT and NRAPM genes) and transport (HMA genes) by roots may be responsible for Cd phytotoxicity in rice grown in the different N fertilization treatments. Our results further demonstrate that N fertilization had stronger effects on soil bacterial communities than fungal communities. The bacterial and fungal keystone species were identified by phylogenetic molecular ecological network (pMEN) analysis and mainly fell into the categories of Gammaproteobacteria, Acidobacteria and Actinobacteria for the bacterial species and Ascomycota for the fungal species; all of these keystone species were highly enriched in the (NH4)2HPO4 treatment. Soil pH and soil available-Cd content emerged as the major determinants of microbial network connectors. These results could provide effective fertilizing strategies for alleviating Cd phytotoxicity in rice and enhance the understanding of its underlying microbial mechanisms.

Analytical quality by design development of an ecologically acceptable enantioselective HPLC method for timolol maleate enantiomeric purity testing on ovomucoid chiral stationary phase.

Official method in Ph. Eur. for evaluation of timolol enantiomeric purity is normal-phase high performance liquid chromatography (NP-HPLC) method. Compared to other HPLC modes, NP is depicted as quite expensive with high consumption of organic solvents which leads to chronic exposure of analysts to toxic and carcinogenic effects. In order to overcome above-mentioned drawbacks, the aim of this study was to develop new method with better eco-friendly features. This was enabled by using protein type Chiral Stationary Phase (CSP) in reversed-phase mode that required up to 10 % (v/v) of organic solvent. Therefore, an enantioselective HPLC method was developed and validated for quantification of (S)-timolol and its chiral impurity, (R)-isomer. Optimized separation conditions on ovomucoid column were set using Analytical Quality by Design (AQbD) approach in method development. Optimization step was performed following the Box-Behnken experimental plan and the influence of three critical method parameters (CMPs) towards enantioseparation of the above-mentioned peak pair was examined. CMPs included variation of acetonitrile content in the mobile phase (5-10 %, v/v), pH value of the aqueous phase (6.0-7.0) and ammonium chloride concentration in the aqueous part of the mobile phase (10-30 mmol L-1). The most relevant critical method attributes (CMAs) in this case were the separation criterion between studied critical pair and retention factor of the second eluting peak, (S)-timolol. Qualitative Design Space (DS) was defined by Monte Carlo simulations providing adequate assurance of method's qualitative robustness (π = 95 %). The selected working point situated in the middle of the DS was characterized by following combination of CMPs: acetonitrile content in the mobile phase 7 % (v/v), pH value of the aqueous phase 6.8 and concentration of ammonium chloride in aqueous phase 14 mmol L-1. In the next step, the quantitative robustness was tested by Plackett-Burman experimental design. The validation studies confirmed adequacy of the proposed method for its intended purpose. Finally, Analytical Eco-Scale metric tool was applied to confirm that developed method represents excellent green analytical method compared to the official one.

Fabrication of an N-doped mesoporous bio-carbon electrocatalyst efficient in Zn-air batteries by an in situ gas-foaming strategy.

A nitrogen doped bio-carbon catalyst with high specific surface area and a hierarchical interconnected porous structure was fabricated by an in situ gas-foaming strategy from sodium alginate and ammonium chloride. The optimized catalyst displays a fabulous ORR activity, providing a facile approach for the mass production of metal-free bio-carbon catalysts in fuel cells and metal-air batteries.

Correlations of Ion Composition and Power Efficiency in a Reverse Electrodialysis Heat Engine.

The main objective of this study is to explore the influence of ion composition on the trans-membrane potential across the ion exchange membrane (IEM), and thus offers a reference for the deep insight of "reverse electrodialysis heat engine" running in the composite systems. In comparison to the natural system (river water | seawater), the performance of the reverse electrodialysis (RED) stack was examined using NaHCO3, Na2CO3, and NH4Cl as the supporting electrolyte in the corresponding compartment. The effect of flow rates and the concentration ratio in the high salt concentration compartment (HCC)/low salt concentration compartment (LCC) on energy generation was investigated in terms of the open-circuit voltage (OCV) and power density per membrane area. It was found that the new system (0.49 M NaCl + 0.01 M NaHCO3|0.01 M NaHCO3) output a relatively stable power density (0.174 W·m-2), with the open-circuit voltage 2.95 V under the low flow rate of 0.22 cm/s. Meanwhile, the simulated natural system (0.5 M NaCl|0.01 M NaCl) output the power density 0.168 W·m-2, with the open-circuit voltage 2.86 V under the low flow rate of 0.22 cm/s. The findings in this work further confirm the excellent potential of RED for the recovery of salinity gradient energy (SGP) that is reserved in artificially-induced systems (wastewaters).

Development of an ammonium chloride-enhanced thermal-assisted-ESI LC-HRMS method for the characterization of chlorinated paraffins.

Simultaneous quantification of short-, medium-, and long-chain chlorinated paraffins (CPs) in environmental matrices is challenging and has received much attention from environmental chemists. In this study, ammonium-chloride-enhanced liquid chromatography coupled with high-resolution mass spectrometry (LC-HRMS) was developed for the first time to quantify CPs in sediments and aqueous samples. Three ionization sources, including atmospheric pressure chemical ionization (APCI), electrospray ionization (ESI), and thermal-assisted-ESI, were employed to examine the performance of ammonium chloride as the chloride ion supply reagent in comparison with traditional chloride ion supply reagent, dichloromethane. Ammonium chloride can be easily used with reversed-phase liquid chromatography (LC), whereas dichloromethane is not compatible with aqueous LC mobile phase. Furthermore, other anion-supply reagents, such as ammonium formate, ammonium acetate, and ammonium bromide, were also tested. It was concluded that the adducts of the CPs with the anions were reversible and could partially dissociate into deprotonated CP ions. The yield of deprotonated CP ions was associated with the gas-phase basicity of the deprotonated CP ions and the corresponding anions. Furthermore, collision-induced dissociation curves were drawn to quantify the stability of anionic CP adducts. The ammonium-chloride-enhanced LC-HRMS was further employed for identifying CPs in sediment samples and coupled with an online SPE method for detecting CPs in aqueous samples. This study may significantly contribute to the qualification and quantification of CPs in environmental matrices.

Simultaneous determination of nitrate and nitrite in vegetables by poly(vinylimidazole-co-ethylene dimethacrylate) monolithic capillary liquid chromatography with UV detection.

Simultaneous determination of nitrate (NO3‾) and nitrite (NO2‾) in vegetables was performed on a poly(1-vinylimidazole-co-ethylene dimethacrylate) (VIM-EDMA) monolithic column by capillary liquid chromatography (LC) with UV detection. Good linearity (0.5-100 µg mL-1 i.e. 12.5 -2500 µg g-1 in vegetables) was obtained with coefficient of determination > 0.996. Limits of detection (signal-to-noise ratio: S/N= 3) were estimated at 0.06 and 0.05 µg mL-1, which corresponded to 1.50 and 1.25 µg g-1 for NO2‾ and NO3‾, respectively, in vegetables. The limits of quantification (S/N= 10) were estimated at 0.17 and 0.16 µg mL-1 (4.25 and 4.00 µg g-1 in vegetables) for NO2‾ and NO3‾, respectively. Although the detection limits were relatively higher than other LC-UV techniques, this proposed method offered satisfactory sensitivity for complying the Acceptable Daily Intake (ADI) levels set by EU to monitor the occurrence of NO2‾ and NO3‾in vegetables. The intra-day/inter-day precision (0.14-3.35%/0.06-6.93%) and accuracy (90.33-103.32%/96.00-101.26%) were also examined for method validation. No obvious carry-over and decline of separation efficiency were observed for more than 200 analyses of real samples. The occurrence of NO2‾ and NO3‾in various vegetable samples was investigated to demonstrate the potential of utilizing the developed polymeric monolith-based capillary LC-UV method for food safety application.