Chemometric evaluation of inorganic and organic parameters found in Rosaceae plants proposed as food supplements.

This study discusses the organic and inorganic composition of young inflorescence tissues of seven medical plants from the Prunus, Malus, and Chaenomeles families. These plants contain bioactive compounds with antioxidant and cytotoxic properties, and the study determined 29 elements, including essential and potentially harmful ones, established correlations with inorganic and organic compounds, as well as antioxidative and cytotoxic effects. The elemental patterns show that the plants contribute beneficial essential elements to the human diet. The levels of toxic elements in the plants are within safe limits set by the World Health Organization for medicinal herbs. The results confirmed genus- and species-specific uptake and accumulation. Positive correlations between d-block metals and alkaline earth metals in the inflorescences were found alongside statistically significant differences between analyte categories regarding macro-, micro- and trace elements and bioactive compounds. These correlations need to be considered when giving dietary recommendations or advice for uses as home-remedies.

Deep reinforcement learning classification of sparkling wines based on ICP-MS and DOSY NMR spectra.

An approach that combines NMR spectroscopy and inductively coupled plasma mass spectrometry (ICP-MS) and advanced tensor decomposition algorithms with state-of-the-art deep learning procedures was applied for the classification of Croatian continental sparkling wines by their geographical origin. It has been demonstrated that complex high-dimensional NMR or ICP-MS data cannot be classified by higher-order tensor decomposition alone. Extension of the procedure by deep reinforcement learning resulted in an exquisite neural network predictive model for the classification of sparkling wines according to their geographical origin. A network trained on half of the sample set was able to classify even 94% of all samples. The model can particularly be useful in cases where the number of samples is limited and when simpler statistical methods fail to produce reliable data. The model can further be exploited for the identification and differentiation of sparkling wines including a high potential for authenticity or quality control.

Evaluation of two-phase sample transport upon ablation of gelatin as a proxy for soft biological matrices using nanosecond laser ablation - inductively coupled plasma - mass spectrometry.

BACKGROUND: Recent papers on LA-ICP-MS have reported that certain elements are transported in particulate form, others in gaseous form and still others in a combination of both upon ablation of C-based materials. These two phases display different transport behaviour characteristics, potentially causing smearing in elemental maps, and could be processed differently in the ICP which raises concerns as to accuracy of quantification and emphasizes the need for matrix-matching of external standards. This work aims at a better understanding of two-phase sample transport by evaluating the peak profile changes observed upon varying parameters such as laser energy density and wavelength. RESULTS: It is demonstrated that upon ablation of gelatin, elements are transported predominantly in particulate phase, but already at low laser energy density, a significant fraction of some elements is transported in the gaseous phase, which is even more expressed at higher energy density. This behaviour is element-specific since the ratio of the signal intensity for the analyte element transported in gas phase to the total signal intensity was 0 % for 23Na, 43 % for 66Zn and as high as 95 % for 13C using a 193 nm laser. The results also suggest an effect of the laser wavelength, as all elements show either the same or higher amount of gas phase formation upon ablating with 213 nm versus 193 nm. It was even established that elements that fully occur in particulate form upon ablation using 193 nm laser radiation are partly converted into gaseous phase when using 213 nm. SIGNIFICANCE: This work provides a thorough investigation of the underexposed phenomenon of two-phase sample transport upon ablation of biological samples upon via LA-ICP-MS. It is shown that for some elements a fraction of the ablated material is converted and transported in the gas phase, which can lead to significant smearing effects. As such, it is important to evaluate element-specific peak profiles on beforehand and, if necessary, adapt instrument settings and slow down data acquisition.

Novel Zinc/Silver Ions-Loaded Alginate/Chitosan Microparticles Antifungal Activity against Botrytis cinerea.

Addressing the growing need for environmentally friendly fungicides in agriculture, this study explored the potential of biopolymer microparticles loaded with metal ions as a novel approach to combat fungal pathogens. Novel alginate microspheres and chitosan/alginate microcapsules loaded with zinc or with zinc and silver ions were prepared and characterized (microparticle size, morphology, topography, encapsulation efficiency, loading capacity, and swelling behavior). Investigation of molecular interactions in microparticles using FTIR-ATR spectroscopy exhibited complex interactions between all constituents. Fitting to the simple Korsmeyer-Peppas empirical model revealed the rate-controlling mechanism of metal ions release from microparticles is Fickian diffusion. Lower values of the release constant k imply a slower release rate of Zn2+ or Ag+ ions from microcapsules compared to that of microspheres. The antimicrobial potential of the new formulations against the fungus Botrytis cinerea was evaluated. When subjected to tests against the fungus, microspheres exhibited superior antifungal activity especially those loaded with both zinc and silver ions, reducing fungal growth up to 98.9% and altering the hyphal structures. Due to the slower release of metal ions, the microcapsule formulations seem suitable for plant protection throughout the growing season. The results showed the potential of these novel microparticles as powerful fungicides in agriculture.

Cation Adsorption in TiO2 Nanotubes: Implication for Water Decontamination.

TiO2 nanotubes constitute very promising nanomaterials for water decontamination by the removal of cations. We combined a range of experimental techniques from structural analyses to measurements of the properties of aqueous suspensions of nanotubes, with (i) continuous solvent modeling and (ii) quantum DFT-based simulations to assess the adsorption of Cs+ on TiO2 nanotubes and to predict the separation of metal ions. The methodology is set to be operable under realistic conditions, which, in this case, include the presence of CO2 that needs to be treated as a substantial contaminant, both in experiments and in models. The mesoscopic model, based on the Poisson-Boltzmann equation and surface adsorption equilibrium, predicts that H+ ions are the charge-determining species, while Cs+ ions are in the diffuse layer of the outer surface with a significant contribution only at high concentrations and high pH. The effect of the size of nanotubes in terms of the polydispersity and the distribution of the inner and outer radii is shown to be a third-order effect that is very small when the nanotube layer is not very thick (ranging from 1 to 2 nm). Besides, DFT-based molecular dynamics simulations demonstrate that, for protonation, the one-site and successive association assumption is correct, while, for Cs+ adsorption, the size of the cation is important and the adsorption sites should be carefully defined.

Preliminary Study of Pepper Types Based on Multielement Content Combined with Chemometrics.

Different types of pepper (Piper nigrum L.) and cayenne pepper (Capsicum annuum L.) are widely used spices that exhibit therapeutic properties in addition to nutritional properties. In order to characterize these foods in further detail, the content of macro- (Ca, K, Mg, Na) and microelements (Ag, Al, As, Ba, Be, Bi, Cd, Co, Cr, Cu, Fe, Ga, Li, Mn, Mo, Ni, Pb, Rb, Se, Sr, Te, Tl, V and Zn) of four pepper types was determined via inductively coupled plasma mass spectrometry (ICP-MS) after microwave-assisted digestion using nitric acid and hydrogen peroxide. The obtained results were then evaluated using chemometric methods. The content of macroelements and microelements lies in the expected ranges for such spices but differs significantly between different types. The content of macro- and microelements is characteristic for pepper types originating from different plant species, but also based on further processing. Whilst green and black pepper are similar to each other, clearly diverse patterns are obtained for white pepper (different processing method) and cayenne pepper (different plant species).

Multielement Determination in Turmeric (Curcuma longa L.) Using Different Digestion Methods.

The antioxidant, anti-inflammatory and antiseptic properties of turmeric (Curcuma longa L.) derive from its rich nutritional composition making it interesting for medicinal uses, besides being used as spice in cooking. To complete the picture on the composition of turmeric, not only the organic compounds need to be known, but also the elemental composition covering essential and potentially toxic elements. The samples were digested in a microwave assisted digestion system using different reagent mixtures. The best digestion mixture was semi-concentrated nitric acid combined with hydrogen peroxide. After optimization of the sample preparation method, the contents of Ag, Al, As, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Ga, K, Li, Mg, Mn, Mo, Na, Ni, Pb, Rb, Se, Sr, Te, Tl, V and Zn in curcuma were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES), as well as by inductively coupled plasma mass spectrometry (ICP-MS). Even if the general composition found is in line with the scarce data in literature, clear differences can be seen between the analyzed samples, considering provenience, production procedures, and harvesting year as potential influencing factors. Whereas all samples contained less As and Pb than regulated by WHO, one limit exceeding was found for Cd.

Influence of Soil Salinity on Selected Element Contents in Different Brassica Species.

Climate changes in coastal regions cause increased soil salinity, a well-known type of environmental stress for a high number of agricultural crop species, including Brassicaceae, whose growth and development, and consequently the crop quality and yield, are affected by salinity stress. The aim of the present study is to investigate the effect of salt stress on micro- and macro-element homeostasis in different Brassica crops. Kale (Brassica oleracea var. acephala), white cabbage (B. oleracea var. capitata) and Chinese cabbage (B. rapa ssp. pekinensis) were grown hydroponically and treated with 200 mmol/L sodium chloride for 24 h to mimic short-term salt stress. The contents of Al, Ca, K, Mg, Na, B, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn were determined in the roots and leaves of the salt-treated plants and corresponding controls by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry. While Al, Ca, K, Mg and Na were determined in the mg/g range, the contents of the other elements were found at the µg/g level. A statistical analysis of the obtained data showed that the applied salt treatment significantly influenced the single-element contents in different plant parts. The major elements Ca, K and Mg were mainly unaffected in the more-salt-tolerant kale and white cabbage under salinity stress, while K and Mg were significantly decreased in the more-sensitive Chinese cabbage. The levels of micro-elements were found to be species/variety specific. In general, potentially toxic elements were accumulated in the roots of salt-treated plants to a higher extent than in the corresponding controls.

First Extensive Polyphenolic Profile of Erodium cicutarium with Novel Insights to Elemental Composition and Antioxidant Activity.

Erodium cicutarium is known for its total polyphenolic content, but this work reveals the first highly detailed profile of E. cicutarium, obtained with UHPLC-LTQ OrbiTrap MS4 and UHPLC-QqQ-MS/MS techniques. A total of 85 phenolic compounds were identified and 17 constituents were quantified. Overall, 25 new compounds were found, which have not yet been reported for the Erodium genera, or the family Geraniaceae. Along with methanolic extracts, the so far poorly investigated water extracts exhibited in vitro antioxidant activity according to all performed assays, including the ferric reducing/antioxidant power assay (FRAP), 2,2-diphenyl-1-picrylhydrazyl assay (DPPH), 2,2'-azinobis(3-ethylbenzthiazoline-6-sulfonic acid) assay (ABTS) and cupric ion reducing antioxidant capacity assay (CUPRAC). Elemental composition analysis performed with inductively coupled plasma atomic emission spectrometry (ICP-AES) and, additionally, hydride generation atomic absorption spectrometry (HydrEA-ETAAS) showed six most abundant elements to be decreasing as follows: Mg>Ca>K>S>P>Na, and gave first data regarding inorganic arsenic content (109.3-248.4 ng g-1 ). These results suggest E. cicutarium to be a valuable source of various phenolic compounds with substantial potential for further bioactivity testing.

Characterization of nZVI nanoparticles functionalized by EDTA and dipicolinic acid: a comparative study of metal ion removal from aqueous solutions.

The simultaneous adsorption of metal ions on bare and functionalized zero-valent iron nanoparticles (nZVI) from aqueous solution was tested using inductively coupled plasma optical emission spectrometry (ICP-OES). The nanomaterials were synthetized using borohydride reduction of iron salt followed by addition of EDTA and pyridine-2,6-dicarboxylic acid (dipicolinic acid, PDCA) in different molar ratios. Functionalized materials were characterized by FT-IR, XRD and SEM-EDS methods. The ligand attachment on the particles was confirmed by FT-IR spectroscopy. The formation of a magnetite and feroxyhyte shell on the core of functionalized nanoparticles was confirmed by the XRD study. Transformation of chain-like structures into clusters of nanospheres with smaller diameter size was observed from SEM study of EDTA-nVZI particles. The average diameter of bare nZVI particles comprised 115 nm, while EDTA functionalization resulted in an average diameter of 22 and 35 nm. The PDCA-nZVI particles obtained with the molar ratio of Fe : PDCA = 1 : 1 retain the chain-like structure with enlargement of the average particle diameter to 267 nm. SEM study of PDCA-nZVI particles that were produced using the ratio Fe : PDCA = 2 : 1 have demonstrated the unique property of elongation into ellipsoidal forms of reduced dimensions (a = 61 nm; b = 28 nm). The simultaneous metal ion removal from aqueous solution was the most efficient in the case of bare nZVI particles (91-97%). EDTA functionalization was found to be highly selective for Cu and Cr removal (95%), while PDCA functionalization shows selective adsorption of Cu, Cr and V in an aqueous medium (93%). Iron nanoparticles functionalized with PDCA in both of the used ratios showed more efficient metal ion adsorption in the case when smaller ellipsoidal particles were formed.

Elemental profiling of Noah's Ark shell (Arca noae, Linnaeus, 1758) by plasma optical spectrometry and chemometric tools.

Determination of metal content in biominerals provides essential information with respect to relations between biomineralization processes and environmental status. Mussels are species that have a great potential as bio-marker species and therefore, they are in the focus of numerous biomineralization and ecological studies. In this study, elemental profile of mussel shell of Noah's Ark (Arca noe, Linnaeus, 1758), which inhabit eastern Adriatic Sea was obtained by determination of seventeen elements content using inductively coupled plasma optical emission spectrometry (ICP-OES). Shell samples were collected from marine protected area and from marine shipping route in eastern Adriatic Sea. The accuracy of applied analytical procedure based on microwave decomposition of shell samples was tested by use of reference materials of limestone and by matrix-matched standards. By aid of chemometric methods, the elemental profile along with variability of elements content of shell was obtained. The impact of different environment on elements content was established by use of multivariate statistical PCA method. Discernment between two groups of samples was manifested. Among results of main, minor and trace elements content, the last one which denoted to Cd, Co, Cu, Pb, and Mn was expressed as principal distinctive feature of shell samples collected from different sampling sites. Elemental profiling of mussel shell Noah's Ark provides novel insight in species status as well as in environmental status on the observed locations.

Tin content determination in canned fruits and vegetables by hydride generation inductively coupled plasma optical emission spectrometry.

Tin content in samples of canned fruits and vegetables was determined by hydride generation inductively coupled plasma atomic emission spectrometry (HG-ICP-OES), and it was compared with results obtained by standard method of flame atomic absorption spectrometry (AAS). Selected tin emission lines intensity was measured in prepared samples after addition of tartaric acid and followed by hydride generation with sodium borohydride solution. The most favorable line at 189.991 nm showed the best detection limit (1.9 µg L(-1)) and limit of quantification (6.4 µg kg(-1)). Good linearity and sensitivity were established from time resolved analysis and calibration tests. Analytical accuracy of 98-102% was obtained by recovery study of spiked samples. Method of standard addition was applied for tin determination in samples from fully protected tinplate. Tin presence at low-concentration range was successfully determined. It was shown that tenth times less concentrations of Sn were present in protected cans than in nonprotected or partially protected tinplate.