Functionalization of bacterial microcompartment shell interior with cysteine containing peptides enhances the iron and cobalt loading capacity.

Bacterial microcompartments (BMCs) are prokaryotic organelles involved in several biochemical processes in bacterial cells. These cellular substructures consist of an icosahedral shell and an encapsulated enzymatic core. The outer shells of BMCs have been proposed as an attractive platform for the creation of novel nanomaterials, nanocages, and nanoreactors. In this study, we present a method for functionalizing recombinant GRM2-type BMC shell lumens with short cysteine-containing sequences and demonstrate that the iron and cobalt loading capacity of such modified shells is markedly increased. These results also imply that a passive flow of cobalt and iron atoms across the BMC shell could be possible.

Multi-Element Profile Characterization of Monofloral and Polyfloral Honey from Latvia.

Honey is of scientific interest mainly due to its health-promoting and antibacterial properties, which are also associated with its floral origins. However, the methods for confirming honey floral origins are quite limited and require improvements. One method suggested in the search for a multi-method approach to evaluating the floral origins of Latvian honey is inductively coupled plasma mass spectrometry (ICP-MS). This study investigated the multi-element profile of 83 honey samples of well-specified floral origins. The main findings included using Ba, Ca, Cs, Fe, and Rb as indicator elements for heather honey. The chemometric evaluation supported the use of ICP-MS for distinguishing heather honey from other types of honey. The Latvian polyfloral honey multi-element profile was defined and compared to honey samples with other geographical origins. Additionally, the multi-element profiles of buckwheat, clover, and polyfloral honey proteins were investigated to clarify whether the majority of elements were bound with proteins or not. Preliminary results indicated that Ca, K, Mg, Mn, Na, and Sr were mainly found in non-protein-bound forms, while the majority of Al, Cu, Ni, and Zn were in the form of large chemical structures (>10 kDa).

Distribution of Minor and Major Metallic Elements in Residential Indoor Dust: A Case Study in Latvia.

The coronavirus disease 2019 (COVID-19) pandemic has not only brought considerable and permanent changes to economies and healthcare systems, but it has also greatly changed the habits of almost the entire society. During the lockdowns, people were forced to stay in their dwellings, which served as a catalyst for the initiation of a survey on the estimation of the metallic element content in residential indoor dust in different parts of Latvia. This article presents the study results obtained through the analysis of collected dust samples from 46 dwellings, both in the capital of Latvia, Riga, and in smaller cities. Two methods were employed for indoor dust collection: vacuum sampling and manual sampling with a brush and plastic spatula. After microwave-assisted acid extraction, the samples were analyzed using inductively coupled plasma mass spectrometry (ICP-MS) in terms of the major (Na, K, Ca, Mg, Al and Fe) and minor (Mn, Ni, Co, Pb, Cr, As, Ba, Li, Be, B, V, Cu, Zn, Se, Rb, Sr, Cd, La, Ce and Bi) elements. For the data analysis, principal component analysis was performed. Among the measured metals, the highest values were determined for the macro and most abundant elements (Na > K > Ca > Fe > Mg > Al). The concentration ranges of the persistently detected elements were as follows: Pb, 0.27-1200 mg kg-1; Cd, 0.01-6.37 mg kg-1; Ni, 0.07-513 mg kg-1; As, 0.01-69.2 mg kg-1; Cu, 5.71-1900 mg kg-1; Zn, 53.6-21,100 mg kg-1; and Cr, 4.93-412 mg kg-1. The critical limit values of metallic elements in soil defined by the legislation of the Republic of Latvia (indicating the level at or above which the functional characteristics of soil are disrupted, or pollution poses a direct threat to human health or the environment) were exceeded in the following numbers of dwellings: Pb = 4, Ni = 2, As = 1, Cu = 16, Cr = 1 and Zn = 28.

Antimicrobial and Antibiofilm Properties of Latvian Honey against Causative Agents of Wound Infections.

Honey is widely used in traditional medicine and modern wound healing biomaterial research as a broad-spectrum antimicrobial, anti-inflammatory and antioxidant agent. The study's objectives were to evaluate the antibacterial activity and polyphenolic profiles of 40 monofloral honey samples collected from beekeepers in the territory of Latvia. The antimicrobial and antifungal activity of Latvian honey samples were compared with commercial Manuka honey and the honey analogue sugar solutions-carbohydrate mixture and tested against Escherichia coli, Pseudomonas aeruginosa, Staphylococcus aureus, clinical isolates Extended-Spectrum Beta-Lactamases produced Escherichia coli, Methicillin-resistant Staphylococcus aureus and Candida albicans. Antimicrobial activity was evaluated with the well-diffusion method (80% honey solution w/v) and microdilution method. The honey samples with the highest antimicrobial potential were tested to prevent biofilm development and activity against a preformed biofilm. The principal component analysis of the antimicrobial properties of honey samples vs. polyphenolic profile was performed. Eleven honey samples exhibited antibacterial activity to all investigated bacteria. The antibacterial effect of the samples was most significant on the Gram-positive bacteria compared to the studied Gram-negative bacteria. Latvian honey presents promising potential for use in wound healing biomaterials, opening the possibility of achieving long-term antibacterial effects.

Procyanidins from Cranberry Press Residues-Extraction Optimization, Purification and Characterization.

Procyanidins are a polyphenolic group that can be found in a variety of foods such as chocolate, tea, cranberries and others. Type A procyanidins can be found in a handful of sources and one of the richest sources are American cranberries. These compounds possess antioxidative, anticancer and anti-inflammatory activities and are most widely used as prevention for urinary tract infections. Cranberries are utilized for jam and juice production, and the latter produces industrial food waste press residues. Press residues contain free and bound procyanidins which can be extracted for use as nutraceuticals. In this study, the extraction of cranberry press residues has been optimized using RSM and the resulting extracts have been purified and fractionated. The obtained procyanidin fractions have been investigated for their antioxidative potential and analyzed using LC-ESI-FTICR-HRMS to determine individual procyanidins. The optimization showed that the optimal extraction can be conducted using acetone in a concentration of 53% without the addition of an acidifying agent. Strong correlation was observed for procyanidin contents and their antioxidative activity using DPPH, ABTS and FRAP methods. The purified fractions contained 78 individual (65 Type A) procyanidins with the degree of polymerization of up to 9.

Combined Thermomechanical-Biological Treatment for Corn By-Product Valorization into Added-Value Food (Feed) Material.

The aim of this study was to apply the combined thermomechanical-biological treatment for corn processing by-product (CPBP) valorization to added-value food and feed material. The mechanical-thermal pre-treatment was performed by applying the extrusion technique. Extruded CPBPs (14, 16, and 18% moisture) were further biodegraded with Lactiplantibacillus plantarum-LUHS122 (Lpl), Liquorilactobacillus uvarum-LUHS245 (Lu), Lacticaseibacillus casei-LUHS210 (Lc), and Lacticaseibacillus paracasei-LUHS244 (Lpa). Acidity parameters, microbial characteristics, sugars concentration, amino and fatty acids profile, biogenic amines (BA), and antibacterial and antifungal properties of CPBP were analyzed. Fermented CPBP had a reduced count of mould/yeast. A significantly lower (p ≤ 0.05) count of total enterobacteria was found in most of the extruded-fermented CPBP. Fermentation of extruded CPBP (moisture of 16 and 18%) increased valine and methionine content. Cadaverine and spermidine were not found after treatment of CPBP, and the lowest content of BA was found in the extruded-fermented (Lpa, moisture 18%) CPBP. Applied treatment had a significant effect on most of the fatty acids. CPBP fermented with Lpl, Lu, and Lpa displayed inhibition properties against 3 of the 10 tested pathogenic/opportunistic bacterial strains. Extruded-fermented (Lu, Lc, and Lpa moisture of 14 and 18%) CPBP showed antifungal activity against Rhizopus. Extruded-fermented (14% moisture, Lpl) CPBP inhibited Rhizopus and Aspergillus fumigatus. In conclusion, combined treatment can improve certain parameters and properties of CPBP in order to produce safer and more nutritious ingredients for food and feed industries.

Identification and Evaluation of Hazardous Pyrolysates in Bio-Based Rigid Polyurethane-Polyisocyanurate Foam Smoke.

In this study, rigid polyurethane (PU) and polyisocyanurate (PIR) foam samples made from renewable material (tall oil fatty acid) based polyols were analyzed by pyrolysis gas chromatography mass spectrometry (Py-GC/MS) to obtain information about the full relative smoke content, with a focus on substance identification by their functional groups and hazardousness. The relative content of gaseous products produced during the thermal degradation was evaluated between the two samples, differenced by their assigned isocyanate (NCO) index value-150 and 300. The main thermal degradation components of the rigid PU-PIR foam were found to originate from the decomposition of isocyanate, primarily forming 4,4'-methylenedianiline, 3,3'-diaminodiphenylmethane, N-methylaniline, aniline, 4-benzylaniline and phenyl isocyanate. Hazard analysis revealed that the most common hazards were the hazards related to health: H315 (36%), H319 (28%), H335 (25%), and H302 (23%). The chemical compound with the highest relative content value-4,4'-methylenedianiline (45.3% for PU and 52.4% for PIR)-was identified to be a suspected carcinogen and mutagen. The focus of the study was identifying and evaluating the relative quantities of the produced gaseous products, examine their hazardousness, and provide information on the released thermal degradation products to form a renewable-source based rigid PU and PIR foam.

Dataset of trace elements concentrations in snow samples collected in Jelgava City (Latvia) in December 2020.

The data set provided in this article consist of two repeated data sets of chemical elements concentrations in snow samples. The snow samples were collected in Jelgava city at December 15th with 5 day exposition time. Snow samples were collected in 59 monitoring points in Jelgava city and in one sample in rural area monitoring point as control. The collected snow samples were melted, acidified with HNO3 and analysed with ICP-MS. The samples were analysed Aluminium (Al), Silicon (Si), Chrome (Cr), Manganese (Mn), Iron (Fe), Nickel (Ni), Copper (Cu), Zinc (Zn), Arsenic (As), Molybdenum (Mo), Cadmium (Cd), Barium (Ba), Tungsten (W), Lead (Pb). The collected data are with fundamental scientific value and can be applied only for local data analysis. Data set is useful for local city air quality research work and for evaluation not only local urban impact but in future evaluate city green infrastructure impact on air quality and evaluation of air pollution mitigation measures efficiency.

Determination of Floral Origin Markers of Latvian Honey by Using IRMS, UHPLC-HRMS, and 1H-NMR.

The economic significance of honey production is crucial; therefore, modern and efficient methods of authentication are needed. During the last decade, various data processing methods and a combination of several instrumental methods have been increasingly used in food analysis. In this study, the chemical composition of monofloral buckwheat (Fagopyrum esculentum), clover (Trifolium repens), heather (Calluna vulgaris), linden (Tilia cordata), rapeseed (Brassica napus), willow (Salix cinerea), and polyfloral honey samples of Latvian origin were investigated using several instrumental analysis methods. The data from light stable isotope ratio mass spectrometry (IRMS), ultra-high performance liquid chromatography coupled with high-resolution mass spectrometry (UHPLC-HRMS), and nuclear magnetic resonance (NMR) analysis methods were used in combination with multivariate analysis to characterize honey samples originating from Latvia. Results were processed using the principal component analysis (PCA) to study the potential possibilities of evaluating the differences between honey of different floral origins. The results indicate the possibility of strong differentiation of heather and buckwheat honeys, and minor differentiation of linden honey from polyfloral honey types. The main indicators include depleted δ15N values for heather honey protein, elevated concentration levels of rutin for buckwheat honey, and qualitative presence of specific biomarkers within NMR for linden honey.

Variations in the concentrations of macro- and trace elements in two grasses and in the rhizosphere soil during a day.

The aim of the research was to study short-term variations in concentrations of 17 elements in two widely distributed natural plant species (couch grass and plantain) and in the rhizosphere soil of the plants. The plant and soil samples were collected in a field from a small site over a daytime. In the course of the day, the variations of the total amounts of C, N, and H in the rhizosphere soil were rather marked and different for the soils taken from roots of plantain and couch grass. The concentrations of some other elements in the rhizosphere soil of the plants varied in a similar way. The short-term variations of element concentrations in roots and leaves of the plants were also rather large. In many cases, a decrease of element concentration in roots correlated with an increase of its concentration in leaves. Although couch grass and plantain were collected simultaneously and from the same site, mean concentrations of many elements in the two plant species were statistically significantly different. This may be result of the fact that the plants belong to different clades. The differences between concentrations of most part of elements in roots and leaves of the plants were also statistically significant. The concentrations of many trace elements were higher in roots than in leaves, while the concentrations of essential plant nutrients were often higher in leaves compared to roots. The distribution of elements between different plant parts were not the same in couch grass and plantain.

Geochemical (soil) and phylogenetic (plant taxa) factors affecting accumulation of macro- and trace elements in three natural plant species.

A field study was carried out to estimate the variations in the concentrations of macro- and trace elements in the rhizosphere soil and in roots and leaves of three widely distributed plant species-couch grass, plantain, and yarrow collected simultaneously from two sites characterized by different soil parameters. Main attention was paid to environmental (soil characteristics) and phylogenetic (plant species) factors that can influence on the concentrations of different elements in the plants and in soils. Both the factors cannot be considered as independent, although their contribution to the plant elemental composition may be different. There were statistically significant differences between concentrations of C, N, and H and 13 macro- and trace elements in the soils collected from the two sites. The concentrations of many chemical elements in the rhizosphere soil of the three plant species collected from the same site were often different. The differences in the characteristics of the soils at the sites resulted in differences between the concentrations of several elements in the plants growing at the sites. However, this was only one of the reasons of significant difference between the concentrations of macro- and trace elements in the same plant species collected from the sites. Couch grass, plantain, and yarrow had different reactions on the soil characteristics. The elemental composition of each plant species was unique although they grew at the same place and were collected simultaneously. Among the plants, yarrow was more tolerant to varying environmental conditions than plantain and couch grass.

Structural analysis of Borrelia burgdorferi periplasmic lipoprotein BB0365 involved in Lyme disease infection.

The periplasmic lipoprotein BB0365 of the Lyme disease agent Borrelia burgdorferi is expressed throughout mammalian infection and is essential for all phases of Lyme disease infection; its function, however, remains unknown. In the current study, our structural analysis of BB0365 revealed the same structural fold as that found in the NqrC and RnfG subunits of the NADH:quinone and ferredoxin:NAD+ sodium-translocating oxidoreductase complexes, which points to a potential role for BB0365 as a component of the sodium pump. Additionally, BB0365 coordinated Zn2+ by the His51, His55, His140 residues, and the Zn2+ -binding site indicates that BB0365 could act as a potential metalloenzyme; therefore, this structure narrows down the potential functions of BB0365, an essential protein for B. burgdorferi to cause Lyme disease.

Development and optimization of gas chromatography coupled to high resolution mass spectrometry based method for the sensitive determination of Dechlorane plus and related norbornene-based flame retardants in food of animal origin.

An analytical method has been developed for the trace determination of 10 dechlorane-related compounds (DRCs) in food products by gas chromatography - high resolution mass spectrometry (GC-HRMS). The highest sensitivity of this instrumental analysis method was achieved by selection of the GC column type, optimization of the heated zones within the instrument, and adjusting the electron impact energy. The efficiency of solid phase extraction as clean-up procedure was also optimized. Two different types of cartridges - neutral silica gel and Florisil®, as well as seven organic solvents or their mixtures - n-hexane, cyclohexane, acetone, toluene, n-hexane/ethyl acetate, n-hexane/acetone, and n-hexane/dichloromethane - were evaluated. The analytical method was characterized as selective, precise, accurate, and linear over the concentration ranges from 1.00 to 100 pg µL-1 for DRCs. Ultra-trace level sensitivity was achieved with the instrumental limits of quantification (i-LOQs) varying from ∼0.01 pg to âˆ¼ 1 pg and method limits of quantification (m-LOQs) by the analysis of 10 g of sample varying from ∼0.04 to âˆ¼ 5 pg g-1. The developed method was successfully applied for the analysis of food samples and the analyses revealed the presence of majority of selected DRCs, with the Dechlorane Plus (DP) isomers occurring to a greater extent, pointing to the highest levels in cod liver and other fish products.

The application of headspace gas chromatography coupled to tandem quadrupole mass spectrometry for the analysis of furan in baby food samples.

Selective methodology employing a tandem quadrupole mass spectrometer coupled to a gas chromatograph with headspace autosampler (HS-GC-MS/MS) was elaborated in this study. Application of the elaborated procedure resulted in a limit of detection of 0.021µgkg(-1) and a limit of quantification of 0.071µgkg(-1). The mean recoveries during in-house validation ranged from 89% to 109%, and coefficients of variation for repeatability ranged from 4% to 11%. The proposed analytical method was applied for monitoring the furan content of 30 commercial baby food samples available on the Latvian retail market. The level of furan found in these samples varied from 0.45 to 81.9µgkg(-1), indicating that infants whose sole diet comprises baby food sold in jars and cans are exposed constantly to furan. Samples containing vegetables and meat had higher levels of furan than those containing only fruits.

Cribra orbitalia as a potential indicator of childhood stress: Evidence from paleopathology, stable C, N, and O isotopes, and trace element concentrations in children from a 17th-18th century cemetery in Jekabpils, Latvia.

Cribra orbitalia (CO), or porotic hyperostosis (PH) of the orbital roof, is one of the most common pathological conditions found in archaeological subadult skeletal remains. Reaching frequencies higher than 50% in many prehistoric samples, CO has been generally attributed to a variety of factors including malnutrition (e.g., megaloblastic anemia) and parasitism. In this study, we tested the relationship between CO, trace element concentrations, and stable isotope values (δ13C, δ15N, δ18O) in subadult skeletons from a 17th to 18th century cemetery in the historic town of Jekabpils, Latvia. A total of 28 subadults were examined, seven of which (25%) showed evidence of CO. Bioarchaeological evidence indicated high mortality for children in this cemetery: half of the burials were subadults under the age of 14, while a third were under the age of four. Life expectancy at birth was estimated to have been only 21.6 years. Trace element concentrations measured by Inductively Coupled Plasma - Mass Spectrometry (ICP-MS) showed no relationship between presence or absence of CO and levels of manganese, zinc, strontium, barium, copper, cadmium, or lead in the bones (p>0.05). However, a significant correlation (p<0.05) was found between the presence of CO and decreased levels of iron. The correlations between CO and decreased levels of copper and lead approached significance (p=0.056 for both elements). Individuals with CO furthermore displayed significantly lower δ15N isotope values, suggesting greater consumption of lower trophic level food resources than those unaffected by CO; δ13C and δ18O values, in contrast, showed no significant differences. These results suggest that the prevalence of CO may be related to dietary deficiencies. In this case, low iron levels may also signify a diet low in other key vitamins (e.g., B9 and B12), which are known to cause megaloblastic anemia.

Efficacy of Ozonation Treatments of Smoked Fish for Reducing Its Benzo[a]pyrene Concentration and Toxicity.

Ozone is widely used in food processing, for example, to decompose mycotoxins or pesticide residues, to extend the shelf life of products, and for sanitation. The objective of this study was to assess the possibility of expanding the application of ozone for oxidative degradation of polycyclic aromatic hydrocarbons (PAHs). The evaluation was conducted by ozonation of a benzo[a]pyrene (BaP) standard solution and smoked fish (sprats) contaminated with PAHs. The effect of ozonation was immediate in the BaP solution; 89% of this toxic compound was decomposed after only 1 min of treatment. However, the impact of ozonation on the smoked sprats was less pronounced, even after prolonged treatment. The final reduction in benzo[b]fluoranthene and BaP concentrations in smoked sprats contaminated with PAHs was 34 and 46%, respectively, after 60 min of ozonation, but no significant decrease of benzo[a]anthracene and chrysene concentrations was observed. To evaluate the safety of ozonation, the toxicity of the ozone-treated BaP standard solution was investigated. In vitro toxicity was evaluated using human hepatocellular carcinoma and mouse embryonic fibroblast cell lines as models. The cytotoxicity of the BaP standard solution significantly increased after ozonation, indicating a pronounced negative effect in terms of food safety.

Application of LA-ICP-MS as a rapid tool for analysis of elemental impurities in active pharmaceutical ingredients.

The control of inorganic contaminants in active pharmaceutical ingredients has a significant role in the quality control of drug products. The concentration limits for metal residues in drug products have been defined by various regulatory guidelines. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is a powerful and fast analytical technique for multi-elemental analysis. A disadvantage in using LA-ICP-MS method is the lack of matrix reference materials for validation and calibration purposes. This article focuses on the handling strategy of laboratory-made matrix calibration standards for the quantification of elemental impurities in an active pharmaceutical ingredient by LA-ICP-MS.

Research review trends of food analysis in Latvia: major and trace element content.

The current paper involves overview of several studies concerning quantitative major and trace element analysis of different food samples, such as products of plant origin, e.g., locally grown vegetables (carrots, onions, potatoes) and products of animal origin derived with or without processing (cottage cheese, eggs, honey). Food samples were collected over the territory of Latvia in the time period 2009-2012. Sample pre-treatment was chosen according to the product specifics but mostly wet mineralization with concentrated nitric acid was applied. Analysis of major elements (e.g., Ca, Fe, K, Mg, Na) and trace elements (e.g., As, Cd, Co, Cr, Cu, Ni, Pb, Se, Zn) was performed by appropriate quantitative analytical technique: atomic absorption spectrometry, inductively coupled plasma mass spectrometry or total reflection X-ray fluorescence spectrometry. Not only the influence of environmental factors (e.g., geographical or seasonal impact) was detected in element dissemination in food, also botanical origin (if applicable) and applied agricultural praxis, product processing and storage specifics were found to be important. Possible food contamination by potentially toxic elements can be associated mostly with the consequences of anthropogenic activities. The studies revealed the significance of food research in the context of environmental science.

Arsenic removal using natural biomaterial-based sorbents.

Arsenic contamination of water is a major problem worldwide. A possible solution can be approached through developing new sorbents based on cost-effective and environmentally friendly natural biomaterials. We have developed new sorbents based on biomaterial impregnation with iron oxyhydroxide. In this study, raw peat material, iron-modified peat, iron-modified biomass (shingles, straw, sands, cane and moss) as well as iron humate were used for the removal of arsenate from contaminated water. The highest sorption capacity was observed in iron-modified peat, and kinetic studies indicated that the amount of arsenic sorbed on this material exceeds 90 % in 5 h. Arsenate sorption on iron-modified peat is characterised by the pseudo-second-order mechanism. The results of arsenic sorption in the presence of competing substances indicated that sulphate, nitrate, chloride and tartrate anions have practically no influence on As(V) sorption onto Fe-modified peat, whereas the presence of phosphate ions and humic acid significantly lowers the arsenic removal efficiency.

Crystal structure of human gamma-butyrobetaine hydroxylase.

Gamma-butyrobetaine hydroxylase (GBBH) is a 2-ketoglutarate-dependent dioxygenase that catalyzes the biosynthesis of l-carnitine by hydroxylation of gamma-butyrobetaine (GBB). l-carnitine is required for the transport of long-chain fatty acids into mitochondria for generating metabolic energy. The only known synthetic inhibitor of GBBH is mildronate (3-(2,2,2-trimethylhydrazinium) propionate dihydrate), which is a non-hydroxylatable analog of GBB. To aid in the discovery of novel GBBH inhibitors by rational drug design, we have solved the three-dimensional structure of recombinant human GBBH at 2.0A resolution. The GBBH monomer consists of a catalytic double-stranded beta-helix (DBSH) domain, which is found in all 2KG oxygenases, and a smaller N-terminal domain. Extensive interactions between two monomers confirm earlier observations that GBBH is dimeric in its biological state. Although many 2KG oxygenases are multimeric, the dimerization interface of GBBH is very different from that of related enzymes. The N-terminal domain of GBBH has a similar fold to the DUF971 superfamily, which consists of several short bacterial proteins with unknown function. The N-terminal domain has a bound Zn ion, which is coordinated by three cysteines and one histidine. Although several other 2KG oxygenases with known structures have more than one domain, none of them resemble the N-terminal domain of GBBH. The N-terminal domain may facilitate dimer formation, but its precise biological role remains to be discovered. The active site of the catalytic domain of GBBH is similar to that of other 2KG oxygenases, and Fe(II)-binding residues form a conserved His-X-Asp-X(n)-His triad, which is found in all related enzymes.