Creation of a 3D Goethite-Spongin Composite Using an Extreme Biomimetics Approach.

The structural biopolymer spongin in the form of a 3D scaffold resembles in shape and size numerous species of industrially useful marine keratosan demosponges. Due to the large-scale aquaculture of these sponges worldwide, it represents a unique renewable source of biological material, which has already been successfully applied in biomedicine and bioinspired materials science. In the present study, spongin from the demosponge Hippospongia communis was used as a microporous template for the development of a new 3D composite containing goethite [α-FeO(OH)]. For this purpose, an extreme biomimetic technique using iron powder, crystalline iodine, and fibrous spongin was applied under laboratory conditions for the first time. The product was characterized using SEM and digital light microscopy, infrared and Raman spectroscopy, XRD, thermogravimetry (TG/DTG), and confocal micro X-ray fluorescence spectroscopy (CMXRF). A potential application of the obtained goethite-spongin composite in the electrochemical sensing of dopamine (DA) in human urine samples was investigated, with satisfactory recoveries (96% to 116%) being obtained.

Spongin as a Unique 3D Template for the Development of Functional Iron-Based Composites Using Biomimetic Approach In Vitro.

Marine sponges of the subclass Keratosa originated on our planet about 900 million years ago and represent evolutionarily ancient and hierarchically structured biological materials. One of them, proteinaceous spongin, is responsible for the formation of 3D structured fibrous skeletons and remains enigmatic with complex chemistry. The objective of this study was to investigate the interaction of spongin with iron ions in a marine environment due to biocorrosion, leading to the occurrence of lepidocrocite. For this purpose, a biomimetic approach for the development of a new lepidocrocite-containing 3D spongin scaffold under laboratory conditions at 24 °C using artificial seawater and iron is described for the first time. This method helps to obtain a new composite as "Iron-Spongin", which was characterized by infrared spectroscopy and thermogravimetry. Furthermore, sophisticated techniques such as X-ray fluorescence, microscope technique, and X-Ray diffraction were used to determine the structure. This research proposed a corresponding mechanism of lepidocrocite formation, which may be connected with the spongin amino acids functional groups. Moreover, the potential application of the biocomposite as an electrochemical dopamine sensor is proposed. The conducted research not only shows the mechanism or sensor properties of "Iron-spongin" but also opens the door to other applications of these multifunctional materials.

On the Mechanical Properties of Microfibre-Based 3D Chitinous Scaffolds from Selected Verongiida Sponges.

Skeletal constructs of diverse marine sponges remain to be a sustainable source of biocompatible porous biopolymer-based 3D scaffolds for tissue engineering and technology, especially structures isolated from cultivated demosponges, which belong to the Verongiida order, due to the renewability of their chitinous, fibre-containing architecture focused attention. These chitinous scaffolds have already shown excellent and promising results in biomimetics and tissue engineering with respect to their broad diversity of cells. However, the mechanical features of these constructs have been poorly studied before. For the first time, the elastic moduli characterising the chitinous samples have been determined. Moreover, nanoindentation of the selected bromotyrosine-containing as well as pigment-free chitinous scaffolds isolated from selected verongiids was used in the study for comparative purposes. It was shown that the removal of bromotyrosines from chitin scaffolds results in a reduced elastic modulus; however, their hardness was relatively unaffected.

The Loss of Structural Integrity of 3D Chitin Scaffolds from Aplysina aerophoba Marine Demosponge after Treatment with LiOH.

Aminopolysaccharide chitin is one of the main structural biopolymers in sponges that is responsible for the mechanical stability of their unique 3D-structured microfibrous and porous skeletons. Chitin in representatives of exclusively marine Verongiida demosponges exists in the form of biocomposite-based scaffolds chemically bounded with biominerals, lipids, proteins, and bromotyrosines. Treatment with alkalis remains one of the classical approaches to isolate pure chitin from the sponge skeleton. For the first time, we carried out extraction of multilayered, tube-like chitin from skeletons of cultivated Aplysina aerophoba demosponge using 1% LiOH solution at 65 °C following sonication. Surprisingly, this approach leads not only to the isolation of chitinous scaffolds but also to their dissolution and the formation of amorphous-like matter. Simultaneously, isofistularin-containing extracts have been obtained. Due to the absence of any changes between the chitin standard derived from arthropods and the sponge-derived chitin treated with LiOH under the same experimental conditions, we suggest that bromotyrosines in A. aerophoba sponge represent the target for lithium ion activity with respect to the formation of LiBr. This compound, however, is a well-recognized solubilizing reagent of diverse biopolymers including cellulose and chitosan. We propose a possible dissolution mechanism of this very special kind of sponge chitin.

Effect of Wax Additives and Silanization of Diatom Surfaces on Thermomechanical Properties of Polylactide Composites.

In the present study, tests were conducted on high-filled composite samples on a polylactide matrix, modified with diatomaceous earth, three types of silanes, and natural and synthetic wax. The obtained samples were characterized in terms of the effect of modifications on mechanical properties (tensile strength, flexural strength, and impact resistance) or processing properties, e.g., melt flow rate (MFR). The study showed that the modification had a favorable effect on the processing properties of the composites, associated with up to an eight-fold increase in flow rate index compared with the reference sample, especially for samples treated with methyltrimethoxysilane (MTMOS), and up to a ten-fold increase under low shear-rate flow conditions. The effect of the addition of waxes of different origins (synthetic and natural) was also determined, and it was shown that beeswax tended to reduce the flow rate of the composites regardless of the silane used. The addition of synthetic wax to composites increased the tendency to agglomerate diatomaceous earth, while natural wax had a positive effect on filler dispersion.

Synthesis of Magnetic Molecularly Imprinted Polymer Sorbents for Isolation of Parabens from Breast Milk.

Magnetic molecularly imprinted polymers (MMIPs) are an invaluable asset in the development of many methods in analytical chemistry, particularly sample preparation. Novel adsorbents based on MMIPs are characterized by high selectivity towards a specific analyte due to the presence of a specific cavity on their polymer surface, enabling the lock-key model interactions to occur. In addition, the magnetic core provides superparamagnetic properties that allow rapid separation of the sorbent from the sample solution. Such a combination of imprinted polymers with a magnetic core has an innovative influence on the development of separation techniques. Hence, the present study describes the synthesis of MMIPs with 17ß-estradiol used as a template molecule in the production of imprinted polymers. The as-prepared sorbent was used for a sorption/desorption study of five parabens from breast milk samples. The obtained results were characterized by sorption efficiency exceeding 92%, which shows the high affinity of the analytes to the functional groups on the sorbent. The final determination of the selected analytes was done with high-performance liquid chromatography using a fluorometric detector. The determined linearity ranges for selected parabens were characterized by high determination coefficients (r2 from 0.9992 to 0.9999), and the calculated limit of detection (LOD) and limit of quantification (LOQ) for the identified compounds were low (LOD from 1.1-2.7 ng mL-1; LOQ from 3.6-8.1 ng mL-1), which makes their quantitative analysis in real samples feasible.

Carbon dots as rapid assays for detection of mercury(II) ions based on turn-off mode and breast milk.

In this research, nitrogen co-doped carbon dots were synthesized by solid thermal method with citric acid used as the precursor of carbon, and melamine as nitrogen source. Such carbon dots show high quantum yield of 44%. Furthermore, the native fluorescence of CDs can be reduced by mercury(II), while other metals had no significant influence on fluorescence intensity. During the study, the optimal parameters were selected, such as pH or time for incubation with analyte. Under the optimal conditions, quenching effect caused by mercury ions was evaluated. It was observed that with increasing mercury concentration, the fluorescence of the carbon dots decreased proportionally. The response was characterized by linearity within the range from 2 to 14 µM. Moreover, the limit of detection was 0.44 µM. It was the first time that human milk was used as a real sample to test the applicability of carbon dots. The study results demonstrated good recovery in the 74-111% range (RSD < 6%) As a novel carbon material, CDs show promise for broader applications in analyzing complicated biological samples.

QuEChERS extraction coupled to GC-MS for a fast determination of polychlorinated biphenyls in breast milk from Polish women.

Polychlorinated biphenyls (PCBs) in breast milk has been determined. Therefore, it was necessary to develop and adapt an analytical method to analyze PCB compounds. The whole procedure was applied to 31 breast milk samples, which were collected from Polish mothers. The QuEChERS method was optimized as a fast and cheap sample preparation method. The procedure allowed us to obtain recovery values between 96.46% and 119.98% with acceptable relative standard deviations (3.36-12.71%). Gas chromatography with mass spectrometry (GC-MS) was used for final determination. The method was validated using parameters such as linearity, limit of detection and quantification, intra-day precision, and reproducibility. The mean concentration of ∑iPCBs in this study was 30.94 ng/g of lipid. Assigned daily intake of PCBs was lower than the tolerable daily intake, which shows that the analyzed milk is safe to the infants. However, the monitoring of PCBs in milk is still important, and the QuEChERS method with GC-MS can be an effective tool for tracking organic impurities in breast milk.

The impact of environmental pollution on the quality of mother's milk.

Breastfeeding is a gold standard of neonate nutrition because human milk contains a lot of essential compounds crucial for proper development of a child. However, milk is also a biofluid which can contain environmental pollution, which can have effects on immune system and consequently on the various body organs. Polychlorinated biphenyls are organic pollutants which have been detected in human milk. They have lipophilic properties, so they can penetrate to fatty milk and ultimately to neonate digestive track. Another problem of interest is the presence in milk of heavy metals-arsenic, lead, cadmium, and mercury-as these compounds can lead to disorders in production of cytokines, which are important immunomodulators. The toxicants cause stimulation or suppression of this compounds. This can lead to health problems in children as allergy, disorders in the endocrine system, end even neurodevelopment delay and disorder. Consequently, correlations between pollutants and bioactive components in milk should be investigated. This article provides an overview of environmental pollutants found in human milk as well as of the consequences of cytokine disorder correlated with presence of heavy metals. Graphical abstract.