Optimization of Cyanocobalamin (Vitamin B12) Sorption onto Mesoporous Superparamagnetic Iron Oxide Nanoparticles.

The techniques used to detect and quantify cyanocobalamin (vitamin B12) vary considerably in terms of detection sensitivity, from the most sensitive, based on radioisotopes and mass spectrometry (MS) with limits of detection (LOD) in fg mL-1, to fluorescence (FL) and surface plasmon resonance (SPR) biosensors with LOD values in the range of a few µg mL-1. For accurate quantification of an analyte present at trace levels in complex biological matrices, a selective separation and enrichment step is required to overcome matrix interferences and ensure sufficient detection sensitivity. In this study, iron oxide magnetic nanoparticles (IONPs) were used for the extraction and initial preconcentration of cyanocobalamin (vitamin B12). In the dependence of the magnetization on the H-field (hysteresis loop), no coercivity and remanence values were found at 300 K, indicating the superparamagnetic properties of the tested IONPs. Perfluorinated acids were used as amphiphilic agents to allow the sorption of cyanocobalamin onto the IONPs. FT-IR/ATR spectroscopy was used to confirm the sorption of cyanocobalamin on the IONPs. The influence of the addition of a homologous series of perfluorinated acids such as trifluoroacetic acid (TFAA), heptafluorobutyric acid (HFBA), and trichloroacetic acid (TCAA) to the extraction mixture was tested considering their type, mass, and time required for effective sorption. The adsorption kinetics and isotherm, described by the Freundlich and Langmuir equations, were analyzed. The maximum adsorption capacity (qm) exceeded 6 mg g-1 and was 8.9 mg g-1 and 7.7 mg g-1 for HFBA and TCAA, respectively, as the most efficient additives. After the desorption process using aqueous KH2PO4 solution, the sample was finally analyzed spectrophotometrically and chromatographically. The IONP-based method was successfully applied for the isolation of cyanocobalamin from human urine samples. The results showed that the developed approach is simple, cheap, accurate, and efficient for the determination of traces of cyanocobalamin in biological matrices.

Consequences of Disturbing Manganese Homeostasis.

Manganese (Mn) is an essential trace element with unique functions in the body; it acts as a cofactor for many enzymes involved in energy metabolism, the endogenous antioxidant enzyme systems, neurotransmitter production, and the regulation of reproductive hormones. However, overexposure to Mn is toxic, particularly to the central nervous system (CNS) due to it causing the progressive destruction of nerve cells. Exposure to manganese is widespread and occurs by inhalation, ingestion, or dermal contact. Associations have been observed between Mn accumulation and neurodegenerative diseases such as manganism, Alzheimer's disease, Parkinson's disease, Huntington's disease, and amyotrophic lateral sclerosis. People with genetic diseases associated with a mutation in the gene associated with impaired Mn excretion, kidney disease, iron deficiency, or a vegetarian diet are at particular risk of excessive exposure to Mn. This review has collected data on the current knowledge of the source of Mn exposure, the experimental data supporting the dispersive accumulation of Mn in the brain, the controversies surrounding the reference values of biomarkers related to Mn status in different matrices, and the competitiveness of Mn with other metals, such as iron (Fe), magnesium (Mg), zinc (Zn), copper (Cu), lead (Pb), calcium (Ca). The disturbed homeostasis of Mn in the body has been connected with susceptibility to neurodegenerative diseases, fertility, and infectious diseases. The current evidence on the involvement of Mn in metabolic diseases, such as type 2 diabetes mellitus/insulin resistance, osteoporosis, obesity, atherosclerosis, and non-alcoholic fatty liver disease, was collected and discussed.

Linking Metallic Micronutrients and Toxic Xenobiotics to Atherosclerosis and Fatty Liver Disease-Postmortem ICP-MS Analysis of Selected Human Tissues.

Dyslipidaemia is a disorder of the lipid metabolism, caused mainly by poor eating habits. The most severe consequence of an inappropriate diet is the development of atherosclerosis and hepatic steatosis. It is generally believed that a change in nutrition, and increased physical activity can eliminate these health problems. The contemporary research and therapies used to treat dyslipidemia mainly focus on lowering the triglyceride and cholesterol levels. However, disturbances in trace element homeostasis or the accumulation of toxic elements can also affect physiological processes, and be involved in the development of metabolically mediated diseases. The present study aimed to determine the mineral profiles of liver and brain tissues collected at autopsy (n = 39) in groups of people with hepatic steatosis (n = 5), atherosclerosis (n = 9), hepatic steatosis, and atherosclerosis (n = 16), and others without the selected disorders (n = 9). Concentrations of 51 elements were analysed via inductively coupled plasma mass spectrometry (ICP-MS) after the initial wet mineralisation of the samples with nitric acid. The results obtained allow us to conclude that the hepatic steatosis group suffers from a deficiency of important trace elements, such as copper, zinc, and molybdenum (p < 0.05), whereas the group with atherosclerosis is characterised by elevated levels of cadmium in the liver tissue (p = 0.01). Analysing the mean values of the element concentrations measured in 11 brain areas, statistically significant higher levels of calcium and copper (p < 0.001) were found in the atherosclerosis group, compared to the hepatic steatosis group, confirming the involvement of these elements in the pathogenesis of atherosclerosis. In addition, an accumulation of cadmium, lead, titanium, and strontium in the brain tissue was observed in the atherosclerosis group. While the accumulation of individual elements differs in different parts of the brain, the differences in the cadmium content (p < 0.05) between the study groups apply to the whole brain, except for the nucleus accumbens septi area, where a statistically significant titanium accumulation occurs in the atherosclerosis and steatosis groups, compared to the others (p < 0.05). In addition, the disruption of elemental homeostasis in the brain of a single case with bipolar disorder, and a case with hip replacement was observed. Our results confirm the involvement of chemical elements in the pathogenesis of selected metabolic diseases, and the need for further studies in larger populations.

Assessment of the Concentration of 51 Elements in the Liver and in Various Parts of the Human Brain-Profiling of the Mineral Status.

The anthropogenic environment and diet introduce many metals into the human body, both essential and toxic. Absorption leads to systemic exposure and accumulation in body fluids and tissues. Both excess and deficiency of trace elements are health hazards. The primary aim of the present study was to evaluate the concentration of 51 elements in liver samples and 11 selected brain regions obtained at post-mortem examination from a population of adults living in south-eastern Poland (n = 15). A total of 180 analyses were performed by inductively coupled plasma mass spectrometry in two independent replicates. The collected data show very high individual variability in the content of the investigated elements. Macroelements such as sodium, magnesium, phosphorus, potassium, calcium, iron, and zinc occurred in the highest concentrations and with the greatest statistically significant variations. Although the elemental content of the brain and liver differed significantly, the strongest positive correlation between liver and polus frontalis was observed for the essential element selenium (0.9338) and the strongest negative one for manganese (-0.4316) and lanthanum (-0.5110). The brain areas studied have different requirements for phosphorus, manganese, iron, and molybdenum. In addition, males had a significantly (p < 0.05) higher brain content of lanthanides and actinides than females. The results of this study show that the inhabitants of south-eastern Poland are exposed to a fairly uniform accumulation of aluminum and vanadium in the brain, which have the highest affinity to the thalamus dorsalis. This result proves that there is environmental exposure to these elements.

Nutritional Supplements for Skin Health-A Review of What Should Be Chosen and Why.

Supplementation of micronutrients is considered to be crucial in the reinforcement of the skin's barrier. In this paper, 14 nutritional compounds commonly used in food or pharmaceutic industries were analyzed in terms of influencing skin conditions. The major objective of this paper was to provide a narrative review of the available literature regarding several chosen compounds that are currently widely recommended as supplements that aim to maintain proper and healthy skin conditions. We conducted a review of the literature from PubMed, Scopus, and Web of Science until September 2023 without any other restrictions regarding the year of the publication. Ultimately, we reviewed 238 articles, including them in this review. Each of the reviewed compounds, including vitamin A, vitamin C, vitamin D, vitamin E, curcumin, chlorella, Omega-3, biotin,Ppolypodium leucotomos, Simmondsia chinesis, gamma oryzanol, olive leaf extract, spirulina, and astaxanthin, was observed to present some possible effects with promising benefits for a skin condition, i.e., photoprotective radiation. Adding them to the diet or daily routine might have a positive influence on some skin inflammatory diseases such as atopic dermatitis or psoriasis. Further, UV radiation protection facilitated by some supplements and their impact on human cells might be helpful during chemotherapy or in preventing melanoma development. Further research is needed because of the lack of clear consensus regarding the doses of the described compounds that could provide desirable effects on the skin.

Multi-Elemental Analysis of Human Optic Chiasm-A New Perspective to Reveal the Pathomechanism of Nerve Fibers' Degeneration.

The effect of metals on the functioning of the human eye is multifactorial and includes enzyme activity modulation, trace metal metabolic pathways changes, and cytotoxic activity. Functional dysfunctions appear mostly as a result of the accumulation of toxic xenobiotic metals or disturbances of micronutrients' homeostasis. So far, the affinity of selected metals to eye tissues, i.e., the cornea, choroid, lens, and anterior chamber fluid, has been most studied. However, it is known that many eye symptoms are related to damage to the optic nerve. In order to fill this gap, the aim of the study is to perform a multi-element analysis of tissue collected postmortem from optic chiasm and optic nerves. A total of 178 samples from 107 subjects were tested. The concentrations of 51 elements were quantified by inductively coupled plasma mass spectrometry (ICP-MS) after the wet-mineralization step. In terms of elemental composition, the optic chiasm is dominated by two trace elements, i.e., iron (Fe) and zinc (Zn), besides macro-elements Ca, K, Na, P, and Mg. The subjects formed a homogeneous cluster (over 70% subjects) with the highest accumulation of aluminum (Al). The remaining two departing clusters were characterized by an increased content of most of the elements, including toxic elements such as bismuth (Bi), uranium (U), lead (Pb), chromium (Cr), and cadmium (Cd). Changes in elemental composition with age were analyzed statistically for the selected groups, i.e., females, males, and subjects with alcohol use disorder (AUD) and without AUD. A tendency of women to lose Se, Cu, Zn, Fe with age was observed, and a disturbed Ca/Mg, Na/K ratio in subjects with AUD. Although the observed trends were not statistically significant, they shed new light on the risks and possible pathologies associated with metal neurotoxicity in the visual tract.

Chronic Alcohol Abuse Alters Hepatic Trace Element Concentrations-Metallomic Study of Hepatic Elemental Composition by Means of ICP-OES.

Trace element accumulation varies in different human tissues. Distribution of several elements was found to be disrupted in the case of excessive alcohol consumption, causing negative effects and exacerbation of pathological processes in the liver. In this study, we analyzed the levels and interactions between seven trace elements including calcium (Ca), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), potassium (K), and magnesium (Mg), manganese (Mn), sodium (Na), zinc (Zn), and selenium (Se) in individuals with alcohol-use disorder (AUD) and patients without AUD (control group). The liver samples were collected during autopsy from 39 individuals with AUD and 45 control subjects. Elemental composition inductively coupled plasma optical emission spectrometry (ICP-OES) after wet mineralization by nitric acid was applied for the evaluation of the samples. Positive correlations dominated in the AUD group, mainly in relation to Mg, which strongly positively correlated with Ca, Mn, Fe; K correlated with Mn and Zn, and Cu positively correlated with K and Zn. The strongest positive correlation in the AUD group was observed for the Mg-Mn pair (r = 0.87). Significant statistical differences (p < 0.05) between the groups concerned the average concentration of Co, Cu, Mn, and Mg, which were lower in the AUD group, and Fe, the level of which was significantly higher in the AUD group compared to the control group. Evaluation of the chronic alcohol consumption effect on the accumulation of trace elements in the liver allows a better understanding of the pathological processes taking place in this organ.

Helicobacter pylori Infection and Extragastric Diseases-A Focus on the Central Nervous System.

Helicobacter pylori (H. pylori) is most known to cause a wide spectrum of gastrointestinal impairments; however, an increasing number of studies indicates that H. pylori infection might be involved in numerous extragastric diseases such as neurological, dermatological, hematologic, ocular, cardiovascular, metabolic, hepatobiliary, or even allergic diseases. In this review, we focused on the nervous system and aimed to summarize the findings regarding H. pylori infection and its involvement in the induction/progression of neurological disorders. Neurological impairments induced by H. pylori infection are primarily due to impairments in the gut-brain axis (GBA) and to an altered gut microbiota facilitated by H. pylori colonization. Currently, regarding a potential relationship between Helicobacter infection and neurological disorders, most of the studies are mainly focused on H. pylori.

Autism spectrum disorder: Trace elements imbalances and the pathogenesis and severity of autistic symptoms.

The identification of biomarkers as diagnostic tools and predictors of response to treatment of neurological developmental disorders (NDD) such as schizophrenia (SZ), attention deficit hyperactivity disorder (ADHD), or autism spectrum disorder (ASD), still remains an important challenge for clinical medicine. Metallomic profiles of ASD patients cover, besides essential elements such as cobalt, chromium, copper, iron, manganese, molybdenum, zinc, selenium, also toxic metals burden of: aluminum, arsenic, mercury, lead, beryllium, nickel, cadmium. Performed studies indicate that children with ASD present a reduced ability of eliminating toxic metals, which leads to these metals' accumulation and aggravation of autistic symptoms. Extensive metallomic studies allow a better understanding of the importance of trace elements as environmental factors in the pathogenesis of ASD. Even though a mineral imbalance is a fact in ASD, we are still expecting relevant tests and the elaboration of reference levels of trace elements as potential biomarkers useful in diagnosis, prevention, and treatment of ASD.

Green Synthesis of Silver Nanoparticles Using Natural Extracts with Proven Antioxidant Activity.

Natural extracts are a rich source of biomolecules that are useful not only as antioxidant drugs or diet supplements but also as complex reagents for the biogenic synthesis of metallic nanoparticles. The natural product components can act as strong reducing and capping substrates guaranteeing the stability of formed NPs. The current work demonstrates the suitability of extracts of Camellia sinensis, Ilex paraguariensis, Salvia officinalis, Tilia cordata, Levisticum officinale, Aegopodium podagraria, Urtica dioica, Capsicum baccatum, Viscum album, and marine algae Porphyra Yezoensis for green synthesis of AgNPs. The antioxidant power of methanolic extracts was estimated at the beginning according to their free radical scavenging activity by the DPPH method and reducing power activity by CUPRAC and SNPAC (silver nanoparticle antioxidant capacity) assays. The results obtained by the CUPRAC and SNAPC methods exhibited excellent agreement (R2~0.9). The synthesized AgNPs were characterized by UV-vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), dynamic light scattering (DLS) particle size, and zeta potential. The UV-vis absorption spectra showed a peak at 423 nm confirming the presence of AgNPs. The shapes of extract-mediated AgNPs were mainly spherical, spheroid, rod-shaped, agglomerated crystalline structures. The NPs exhibited a high negative zeta potential value in the range from -49.8 mV to -56.1 mV, proving the existence of electrostatic stabilization. FTIR measurements indicated peaks corresponding to different functional groups such as carboxylic acids, alcohol, phenol, esters, ethers, aldehydes, alkanes, and proteins, which were involved in the synthesis and stabilization of AgNPs. Among the examined extracts, green tea showed the highest activity in all antioxidant tests and enabled the synthesis of the smallest nanoparticles, namely 62.51, 61.19, and 53.55 nm, depending on storage times of 30 min, 24 h, and 72 h, respectively. In turn, the Capsicum baccatum extract was distinguished by the lowest zeta potential, decreasing with storage time from -66.0 up to -88.6 mM.

The [DPPH●/DPPH-H]-HPLC-DAD Method on Tracking the Antioxidant Activity of Pure Antioxidants and Goutweed (Aegopodium podagraria L.) Hydroalcoholic Extracts.

The 2,2-diphenyl-1-picrylhydrazyl (DPPH)-reverse phase (RP)-HPLC-diode array detector (DAD) method was tested on standard antioxidants (AOs), i.e., reduced glutathione (GSH), ascorbic acid (vitamin C), and alcoholic extracts of A. podagraria L. An elaborated HPLC procedure enabled the simultaneous measurement of the redox couple DPPH-R (2,2-diphenyl-1-picrylhydrazyl radical)/DPPH-H (2,2-diphenyl-1-picrylhydrazine). Both forms were fully separated (Rs = 2.30, α = 1.65) on a Zorbax Eclipse XDB-C18 column eluted with methanol-water (80:20, v/v) and detected at different wavelengths in the range of 200-600 nm. The absorbance increases of the DPPH-H as well as the DPPH-R peak inhibition were measured at different wavelengths in visible and UV ranges. The chromatographic method was optimized, according to reaction time (slow, fast kinetics), the linearity range of DPPH radical depending on the detection conditions as well as the kind of the investigated antioxidants (reference chemicals and the ground elder prepared from fresh and dry plants). The scavenging capacity was expressed by the use of percentage of peak inhibition and the IC50 parameters. The evaluated extracts displayed antioxidant activity, higher than 20% inhibition against 350 µM DPPH free radical. The results show that extract prepared from dry plants in the ultrasonic bath exhibits the highest antioxidant potential (IC50 = 64.74 ± 0.22 µL/mL).

Ionic Liquids Toxicity-Benefits and Threats.

Ionic liquids (ILs) are solvents with salt structures. Typically, they contain organic cations (ammonium, imidazolium, pyridinium, piperidinium or pyrrolidinium), and halogen, fluorinated or organic anions. While ILs are considered to be environmentally-friendly compounds, only a few reasons support this claim. This is because of high thermal stability, and negligible pressure at room temperature which makes them non-volatile, therefore preventing the release of ILs into the atmosphere. The expansion of the range of applications of ILs in many chemical industry fields has led to a growing threat of contamination of the aquatic and terrestrial environments by these compounds. As the possibility of the release of ILs into the environment s grow systematically, there is an increasing and urgent obligation to determine their toxic and antimicrobial influence on the environment. Many bioassays were carried out to evaluate the (eco)toxicity and biodegradability of ILs. Most of them have questioned their "green" features as ILs turned out to be toxic towards organisms from varied trophic levels. Therefore, there is a need for a new biodegradable, less toxic "greener" ILs. This review presents the potential risks to the environment linked to the application of ILs. These are the following: cytotoxicity evaluated by the use of human cells, toxicity manifesting in aqueous and terrestrial environments. The studies proving the relation between structures versus toxicity for ILs with special emphasis on directions suitable for designing safer ILs synthesized from renewable sources are also presented. The representants of a new generation of easily biodegradable ILs derivatives of amino acids, sugars, choline, and bicyclic monoterpene moiety are collected. Some benefits of using ILs in medicine, agriculture, and the bio-processing industry are also presented.