An ICP-MS, ESI-MS and molecular modelling investigation of homogeneous gallium affinity tagging (HMAT) of phosphopeptides

Protein phosphorylation and de-phosphorylation, provide one of the most common signalling pathways within cells, being involved in regulating cellular processes, mediating enzyme inhibition, protein-protein recognition and protein degradation. Compared with normal proteomics, phosphoproteomics poses some additional challenges requiring more initial separation and additional sensitivity to detect and quantify potentially ultra-low abundance species. In this work, the selective detection of phosphopeptides is described based on the incorporation of a metal tag, gallium-N,N-biscarboxymethyl lysine (Ga-LysNTA), in solution before separation and detection by liquid chromatography coupled to inductively coupled plasma mass spectrometry (LC-ICP-MS). Experimental and theoretical characterisation of the resulting Ga-phosphopeptide complex is presented based on linear ion trap electrospray ionisation mass spectrometry (ESI-MS), Fourier transform mass spectrometry (FT-MS) and molecular modelling data. Linear ion trap electrospray ionisation mass spectrometry (ESI-MS) was employed to study the interaction of the gallium tag with platelet derived growth factor beta receptor (β-PDGF), a small phosphopeptide. In addition high resolution Fourier transform mass spectrometry (FT-MS) was used for accurate mass determination and multistage tandem mass spectrometry of the gallium-β-PDGF complex identified the fragmentation pathway. Finally, molecular modelling was used to investigate the energetically favoured structures of both the Ga-LysNTA material and the β-PDGF-Ga-LysNTA complex

Aroma-loaded microcapsules with antibacterial activity for eco-friendly textile application: synthesis, characterization, release, and green grafting

Fragrant and antimicrobial properties were conferred to cotton fabrics following microencapsulation using green materials. Limonene and vanillin microcapsules were produced by complex coacervation using chitosan/gum Arabic as shell materials and tannic acid as hardening agent. The effect of two emulsifiers; Span 85 and polyglycerol polyricinoleate (PGPR), on the encapsulation efficiency (EE%), microcapsule’s size and morphology, and cumulative release profiles was studied. The mean diameter of the produced microcapsules ranged between 10.4 and 39.0 μm, whereas EE% was found to be between 90.4% and 100%. The use of Span 85 resulted in mononuclear morphology while PGPR gave rise to polynuclear structures, regardless of the core material (vanillin or limonene). The obtained microcapsules demonstrated a sustained release pattern; namely the total cumulative release of the active agents after 7 days at 37 ± 1 °C was 75%, 52% and 19.4% for the polynuclear limonene microcapsules, the mononuclear limonene microcapsules and the polynuclear vanillin microcapsules, respectively. Grafting of the produced microcapsules onto cotton fabrics through na esterification reaction using citric acid as a nontoxic cross-linker followed by thermofixation and curing, was confirmed by SEM and FTIR spectroscopy. Standard antibacterial assays conducted on both microcapsules alone and impregnated onto the fabrics indicated a sustained antibacterial activity.info:eu-repo/semantics/publishedVersio

Oxaliplatin complexes with carnosine and its derivatives: in vitro cytotoxicity, mass spectrometric and computational studies with a focus on complex fragmentation

The complexation of the Pt-based anti-cancer drug oxaliplatin (OxPt) with biological ligands other than DNA is believed to be a major cellular sink for the drug reducing its therapeutic potential and acting as a potential cause of toxicity. In this paper, an in vitro study on hepatocellular carcinoma HepG2 cells suggests that the naturally abundant cytoplasmic dipeptide ligand β-alanyl-L-histidine dipeptide (carnosine) may inhibit the cytotoxic action of OxPt most likely through the formation of complexes that are less cytotoxic than OxPt alone. Evidence is provided to suggest that pre-exposure of HepG2 cells to elevated levels of carnosine appears to have a lasting effect on reducing the cytotoxicity of OxPt even after the removal of the carnosine. This effect, however, is shown to be under kinetic control as its magnitude was shown not to vary significantly with the level of carnosine exposure within the concentration range used in this study. Various mass spectrometry techniques employing electrospray ionization and chip nanospray were employed to study the interaction of oxaliplatin with carnosine as well as two of its derivatives being β-alanyl-N-methylhistidine (anserine) and N-Acetylcarnosine (NAC). Evidence of complexation between OxPt and each of the three ligands examined is presented. Most species observed were unambiguously assigned and compared to their theoretical isotopic patterns. Common fragmentation products due to the collisionally-activated protonated complexes of each of the ligands examined with OxPt, [M + OxPt + H]+ where M= carnosine, anserine or NAC were reported. Density functional calculations at B3LYP/LANL2DZ were used to obtain structural information and relative free energies of different isomers of the observed precursor [Carnosine + OxPt + H]+ both in the gas phase and in solution as well as to probe its fragmentation, highlighting plausible fragmentation mechanisms that account for all the experimental results.Data are presented to show several binding modes between electron rich sites such as N and O centers of carnosine and the Pt metal of OxPt. Calculations were also employed to obtain proton affinities and free energies of key reactions. The proton affinities of carnosine, Anserine and NAC at 298 K were calculated to be 254.4, 255.9 and 250.2 kcal mol-1 respectively. To the best of our knowledge the proton affinities of anserine and N-acetyl-carnosine are the first reported values in the literature

Determination of Pt-DNA adducts and the sub-cellular distribution of Pt in human cancer cell lines and the leukocytes of cancer patients, following mono- or combination treatments, by inductively-coupled plasma mass spectrometry

Determination of Pt-DNA adducts and the sub-cellular distribution of Pt in human cancer cell lines and the leukocytes of cancer patients, following mono- or combination treatments, by inductively-coupled plasma mass spectrometr

GAPS-megacities: A new global platform for investigating persistent organic pollutants and chemicals of emerging concern in urban air

A pilot study was initiated in 2018 under the Global Atmospheric Passive Sampling (GAPS) Network named GAPS-Megacities. This study included 20 megacities/major cities across the globe with the goal of better understanding and comparing ambient air levels of persistent organic pollutants and other chemicals of emerging concern, to which humans residing in large cities are exposed. The first results from the initial period of sampling are reported for 19 cities for several classes of flame retardants (FRs) including organophosphate esters (OPEs), polybrominated diphenyl ethers (PBDEs), and halogenated flame retardants (HFRs) including new flame retardants (NFRs), tetrabromobisphenol A (TBBPA) and hexabromocyclododecane (HBCDD). The two cities, New York (USA) and London (UK) stood out with ∼3.5 to 30 times higher total FR concentrations as compared to other major cities, with total concentrations of OPEs of 15,100 and 14,100 pg/m3, respectively. Atmospheric concentrations of OPEs significantly dominated the FR profile at all sites, with total concentrations in air that were 2-5 orders of magnitude higher compared to other targeted chemical classes. A moderately strong and significant correlation (r = 0.625, p < 0.001) was observed for Gross Domestic Product index of the cities with total OPEs levels. Although large differences in FR levels were observed between some cities, when averaged across the five United Nations regions, the FR classes were more evenly distributed and varied by less than a factor of five. Results for Toronto, which is a "reference city" for this study, agreed well with a more in-depth investigation of the level of FRs over different seasons and across eight sites representing different urban source sectors (e.g. traffic, industrial, residential and background). Future sampling periods under this project will investigate trace metals and other contaminant classes, linkages to toxicology, non-targeted analysis, and eventually temporal trends. The study provides a unique urban platform for evaluating global exposome.Fil: Saini, Amandeep. Environment and Climate Change; CanadáFil: Harner, Tom. Environment and Climate Change; CanadáFil: Chinnadhurai, Sita. Environment and Climate Change; CanadáFil: Schuster, Jasmin K.. Environment and Climate Change; CanadáFil: Yates, Alan. Environment and Climate Change; CanadáFil: Sweetman, Andrew. Lancaster Environment Centre; Reino UnidoFil: Aristizabal Zuluaga, Beatriz H.. Universidad Nacional de Colombia; ColombiaFil: Jiménez, Begoña. Consejo Superior de Investigaciones Científicas; EspañaFil: Manzano, Carlos A.. Universidad de Chile; ChileFil: Gaga, Eftade O.. Eskisehir Technical University; TurquíaFil: Stevenson, Gavin. National Measurement Institute; AustraliaFil: Falandysz, Jerzy. Uniwersytet Gdanski; PoloniaFil: Ma, Jianmin. Peking University; ChinaFil: Miglioranza, Karina Silvia Beatriz. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Marinas y Costeras. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Marinas y Costeras; ArgentinaFil: Kannan, Kurunthachalam. Nyu Grossman School Of Medicine; Estados UnidosFil: Tominaga, Maria. Sao Paulo State Environmental Company; BrasilFil: Jariyasopit, Narumol. No especifíca;Fil: Rojas, Nestor Y.. Universidad Nacional de Colombia; ColombiaFil: Amador-Muñoz, Omar. Universidad Nacional Autónoma de México; MéxicoFil: Sinha, Ravindra. Patna University; IndiaFil: Alani, Rose. University of Lagos; NigeriaFil: Suresh, R.. No especifíca;Fil: Nishino, Takahiro. Tokyo Metropolitan Research Institute for Environmental Protection; JapónFil: Shoeib, Tamer. American University In Cairo; Egipt

Spectrophotometric Determination of Choline in Pharmaceutical Formulations via Host-Guest Complextaion with a Biomimetic Calixarene Receptor.

Choline is a quaternary ammonium bioactive compound that is used as a dietary supplement. Direct determination of choline in pharmaceutical formulations is a challenging analytical task. The strong UV absorbance of p-sulfonatocalix[4]arene (SC4) and its outstanding complexation properties towards quaternary ammonium compounds have been utilized to develop a method to detect and quantify choline in aqueous solution. This method has been applied to a commercial pharmaceutical choline formulation showing results with no statistically significant difference from those obtained by the official U.S. Pharmacopeial method. The method was validated according to ICH guidelines and the limit of detection for choline was calculated to be 7.2 × 10−6 mol L−1 (1.30 μg mL−1). The host-guest complexation between SC4 and choline were investigated using UV and 1H NMR spectroscopy and DFT calculations. The peak amplitude of the host-guest complexes formed were found to be linearly proportional to the concentration of the choline and L-carnitine analytes in the ranges of 1.0 × 10−5 to 1.6 × 10−4 mol L−1 and 1.0 × 10−5 to 1.8 × 10−4 mol L−1 respectively. The reaction stoichiometry between either choline or L-carnitine with SC4 in the formed complexes were determined to be 1:1 while the stability constants for the complexes formed were estimated to be 8.3 × 104 M−1 and 2.8 × 104 M−1 in the case of choline and L-carnitine, respectively. Both 1H NMR spectroscopy and DFT calculations suggest the complexation between choline and SC4 involves the insertion of the trimethylammonium group of choline into the cavity of SC4 in agreement with previously published X-ray data. The spectrophotometric method presented here should not be limited to the determination of choline. The linear relationship between the peak amplitude of the host-guest complex formed between SC4 and L-carnitine presented here suggests the applicability of the method for the detection of other small molecular species possessing a quaternary ammonium group

Evaluating the effects of the preoxidation of H2O2, NaClO, and KMnO4 and reflocculation on the dewaterability of sewage sludge.

The preoxidation effects of H2O2, NaClO, and KMnO4 on the dewaterability of sewage sludge were compared by analyzing the changes in specific resistance to filtration (SRF), filter cake moisture content (FCMC), extracellular polymeric substance (EPS) fractions and components, and floc properties. The three oxidants varied in oxidation efficiency and exhibited distinctive mechanisms. NaClO not only destroyed sludge flocs and EPSs but also effectively caused cell lysis, resulting in release of a considerable amount of organic matters and subsequently significant deterioration of dewatering performance. The oxidation of H2O2 and KMnO4 was relatively mild and occurred mainly on the outer layers of the sludge flocs and cell-bound EPSs. By contrast, the SRF and FCMC of the sludge conditioned with a low dose of KMnO4 were slightly improved, and a fraction of soluble EPS was compressed because of the coagulation effect of the oxidation product MnO2. The pH of the sludge conditioned with H2O2 and KMnO4 showed no considerable change. Meanwhile, NaClO evidently increased the alkalinity of the sludge because of the hydrolysis effect. After the pH of the NaClO-treated sludge was readjusted to 7.0, the partial protonation efficiency slightly alleviated the deterioration of sludge dewatering performance. The preoxidized sludge was then subjected to reflocculation treatment using FeCl3, polyacrylamide, and a cationic starch-based flocculant, respectively. The combined treatment of preoxidation and reflocculation showed a high dewatering efficiency owing to their synergistic effect

Concentrations of Several Phthalates Contaminants in Egyptian Bottled Water: Effects of Storage Conditions and Estimate of Human Exposure.

The occurrence and concentrations of six common phthalates were investigated for the first time in bottled water locally produced in the Egyptian market. The compounds investigated were dimethyl phthalate (DMP), diethyl phthalate (DEP), dibutyl phthalate (DBP), n-butyl benzyl phthalate (BBP), diethyl hexyl phthalate (DEHP), and Di-n-octyl phthalate (D-n-OP). A set of 108 bottled water samples from six different commercial brands of water bottled in transparent polyethylene terephthalate (PET) plastic bottles with high density polyethylene (HDPE) plastic caps were investigated. Water samples were analyzed immediately after purchasing (~ 2 weeks after production), after being stored at room temperature (25 ± 5 °C), in a refrigerator (4 ± 1 °C) and outdoor under sun exposure (daylight temperature of 40 ± 5 °C). Samples were stored up to six months depending on the tested condition. Among the target compounds, only DEHP and DBP were detected in the samples analyzed immediately after purchasing with a detection frequency of 50 and 58% and mean concentrations of 0.104 and 0.082 μg l− 1 respectively. Significant positive correlation was obtained between the storage time, temperature and the concentration of phthalate compounds detected in the bottled water, indicating possible migration from the PET plastic material as the source. The estimated contribution of bottled water consumption to the tolerable daily intake (TDI) levels of the two most abundant phthalates observed here for adults and toddlers did not exceed 0.16 and 0.72% for DBP while these values were 0.04 and 0.16% for DEHP respectively. These estimated daily intake values from PET bottled water consumption were far below their respective TDI values and therefore should constitute no adverse health effects