Green composites based on volcanic red algae Cyanidiales, cellulose, and coffee waste biomass modified with magnetic nanoparticles for the removal of methylene blue.

In this paper, green nanocomposites based on biomass and superparamagnetic nanoparticles were synthesized and used as adsorbents to remove methylene blue (MB) from water with magnetic separation. The adsorbents were synthesized through the wet co-precipitation technique, in which iron-oxide nanoparticles coated the cores based on coffee, cellulose, and red volcanic algae waste. The procedure resulted in materials that could be easily separated from aqueous solutions with magnets. The morphology and chemical composition of the nanocomposites were characterized by SEM, FT-IR, and XPS methods. The adsorption studies of MB removal with UV-vis spectrometry showed that the adsorption performance of the prepared materials strongly depended on their morphology and the type of the organic adsorbent. The adsorption studies presented the highest effectiveness in neutral pH with only a slight effect on ionic strength. The MB removal undergoes pseudo-second kinetics for all adsorbents. The maximal adsorption capacity for the coffee@Fe3O4-2, cellulose@Fe3O4-1, and algae@Fe3O4-1 is 38.23 mg g-1, 41.61 mg g-1, and 48.41 mg g-1, respectively. The mechanism of MB adsorption follows the Langmuir model using coffee@Fe3O4 and cellulose@Fe3O4, while for algae@Fe3O4 the process fits to the Redlich-Peterson model. The removal efficiency analysis based on UV-vis adsorption spectra revealed that the adsorption effectiveness of the nanocomposites increased as follows: coffee@Fe3O4-2 > cellulose@Fe3O4-1 > algae@Fe3O4-1, demonstrating an MB removal efficiency of up to 90%.

The Proposal and Necessity of the Numerical Description of Nano- and Microplastics' Surfaces (Plastisphere).

The constantly growing amount of synthetic materials < 5 mm, called microplastics (MPs), is fragmented in the environment. Thus, their surface, Plastisphere, is substantially increasing forming an entirely new ecological niche. It has already been extensively studied by microbiologists observing the biofilm and by material scientists interested in the weathering of polymer materials. This paper aims to construct a bridge between the physical and chemical description of the Plastisphere and its microbiological and ecological significance. Various algorithms, based on the analysis of pictures obtained by scanning electron microscopy (SEM), are proposed to describe in detail the morphology of naturally weathered polymers. In particular, one can study the size and distribution of fibres in a standard filter, search the synthetic debris for mapping, estimate the grain size distribution, quantitatively characterize the different patterns of degradation for polymer spheres and ghost nets, or calculate the number of pores per surface. The description and visualization of a texture, as well as the classification of different morphologies present on a surface, are indispensable for the comprehensive characterization of weathered polymers found inside animals (e.g., fishes). All these approaches are presented as case studies and discussed within this work.

Tracking of Glycans Structure and Metallomics Profiles in BRAF Mutated Melanoma Cells Treated with Vemurafenib.

Nearly half of patients with advanced and metastatic melanomas harbor a BRAF mutation. Vemurafenib (VEM), a BRAF inhibitor, is used to treat such patients, however, responses to VEM are very short-lived due to intrinsic, adaptive and/or acquired resistance. In this context, we present the action of the B-Raf serine-threonine protein kinase inhibitor (vemurafenib) on the glycans structure and metallomics profiles in melanoma cells without (MeWo) and with (G-361) BRAF mutations. The studies were performed using α1-acid glycoprotein (AGP), a well-known acute-phase protein, and concanavalin A (Con A), which served as the model receptor. The detection of changes in the structure of glycans can be successfully carried out based on the frequency shifts and the charge transfer resistance after interaction of AGP with Con A in different VEM treatments using QCM-D and EIS measurements. These changes were also proved based on the cell ultrastructure examined by TEM and SEM. The LA-ICP-MS studies provided details on the metallomics profile in melanoma cells treated with and without VEM. The studies evidence that vemurafenib modifies the glycans structures and metallomics profile in melanoma cells harboring BRAF mutation that can be further implied in the resistance phenomenon. Therefore, our data opens a new avenue for further studies in the short-term addressing novel targets that hopefully can be used to improve the therapeutic regiment in advanced melanoma patients. The innovating potential of this study is fully credible and has a real impact on the global patient society suffering from advanced and metastatic melanomas.

Enhancement of mechanical properties of vertically aligned carbon nanotube arrays due to N+ ion irradiation.

In this work we apply N+ ion irradiation on vertically aligned carbon nanotube (VACNT) arrays in order to increase the number of connections and joints in the CNT network. The ions energy was 50 keV and fluence 5 × 1017 ions cm-2. The film was 160 µm thick. SEM images revealed the ion irradiation altered the carbon bonding and created a sponge-like, brittle structure at the surface of the film, with the ion irradiation damage region extending ∼4 µm in depth. TEM images showed the brittle structure consists of amorphous carbon forming between nanotubes. The significant enhancement of mechanical properties of the irradiated sample studied by the cyclic nanoindentation with a flat punch indenter was observed. Irradiation on the VACNT film made the structure stiffer, resulted in a higher percentage recovery, and reduced the energy dissipation under compression. The results are encouraging for further studies which will lead to create a class of materials-ion-irradiated VACNT films-which after further research may find application in storage or harvesting energy at the micro/nanoscale.

The marine nano- and microplastics characterisation by SEM-EDX: The potential of the method in comparison with various physical and chemical approaches.

The marine microplastic (MMs) is an interdisciplinary problem. The polymer debris are ubiquitous (soil, hydrosphere, atmosphere) and the majority ends, transported by the freshwaters, in the global ocean system: from pelagial waters, surface gyres and benthos up to the animals at different trophic levels. Their quantitative, qualitative and eco-toxicological analyses, based on analytical, physical and chemical methods, are still a challenge due to the complex matrices, materials weathering, limited concentration, and size. Moreover, further fragmentation due to the waves and UV radiation leads to the constant increase of their surface. The aim of this article is to present the advantages, drawbacks and future perspectives of using SEM-EDX method in the analyses of marine polymer debris from macro to the nanoscale. Theoretical issues are presented in comparison to the commonly used approaches. The practical aspects will be discussed based on case studies. Examples of the results, high-resolution SEM pictures are included.

Physical and chemical changes in Alhydrogel™ damaged by freezing.

Accidental freezing of aluminum-based vaccines occurs during their storage and transportation, in both developed and developing countries. Freezing damages the freeze-sensitive aluminum adjuvanted vaccines, through separation of lattice between aluminum adjuvant and antigen, leading to formation of aluminum aggregates, and loss of potency. In this study, we examined Alhydrogel™ ([AlO(OH)]xnH2O, aluminum hydroxide, hydrated for adsorption) stored under recommended conditions, and exposed to freezing temperature until solid-frozen. The main purpose of our research was to determine the destruction areas of the solid-frozen Alhydrogel™ using selected methods of scanning electron microscopy, energy dispersive X-ray spectroscopy, Raman spectroscopy, Fourier-transform infrared spectroscopy and transmission electron microscopy working in diffraction mode. The Zeta potential evaluation, measurements of albumin adsorption power, thermogravimetric analysis and estimation of the mass loss after drying indicated significant structural (physical) and chemical differences between the freeze-damaged and non-frozen vaccine adjuvant. The presented results are important to better understand the type and nature of damages occurring in freeze-damaged aluminum-based vaccines. These results can be used in future studies to improve the temperature stability of aluminum adjuvanted vaccines.

Tannic Acid-Modified Silver and Gold Nanoparticles as Novel Stimulators of Dendritic Cells Activation.

Silver nanoparticles (AgNPs) are promising new antimicrobial agents against a wide range of skin and mucosal pathogens. However, their interaction with the immune system is currently not fully understood. Dendritic cells (DCs) are crucial during development of T cell-specific responses against bacterial and viral pathogens. We have previously shown that tannic acid-modified silver nanoparticles (TA-AgNPs) consist of a promising microbicide against HSV-2. The aim of this study was to compare the ability of TA-AgNPs or TA-AuNPs of similar sizes (TA-Ag/AuNPs) to induce DCs maturation and activation in the presence of HSV-2 antigens when used at non-toxic doses. First, we used JAWS II DC line to test toxicity, ultrastructure as well as activation markers (MHC I and II, CD40, CD80, CD86, PD-L1) and cytokine production in the presence of TA-Ag/AuNPs. Preparations of HSV-2 treated with nanoparticles (TA-Ag/AuNPs-HSV-2) were further used to investigate HSV-2 antigen uptake, activation markers, TLR9 expression, and cytokine production. Additionally, we accessed proliferation and activation of HSV-2-specific T cells by DCs treated with TA-AgNP/AuNPs-HSV-2. We found that both TA-AgNPs and TA-AuNPs were efficiently internalized by DCs and induced activated ultrastructure. Although TA-AgNPs were more toxic than TA-AuNPs in corresponding sizes, they were also more potent stimulators of DCs maturation and TLR9 expression. TA-Ag/AuNPs-HSV-2 helped to overcome inhibition of DCs maturation by live or inactivated virus through up-regulation of MHC II and CD86 and down-regulation of CD80 expression. Down-regulation of CD40 expression in HSV-2-infected DCs was reversed when HSV-2 was treated with TA-NPs sized >30 nm. On the other hand, small-sized TA-AgNPs helped to better internalize HSV-2 antigens. HSV-2 treated with both types of NPs stimulated activation of JAWS II and memory CD8+ T cells, while TA-AgNPs treatment induced IFN-γ producing CD4+ and CD8+ T cells. Our study shows that TA-AgNPs or TA-AuNPs are good activators of DCs, albeit their final effect upon maturation and activation may be metal and size dependent. We conclude that TA-Ag/AuNPs consist of a novel class of nano-adjuvants, which can help to overcome virus-induced suppression of DCs activation.

Nanoforest: Polyaniline Nanotubes Modified with Carbon Nano-Onions as a Nanocomposite Material for Easy-to-Miniaturize High-Performance Solid-State Supercapacitors.

This article describes a facile low-cost synthesis of polyaniline nanotube (PANINT)⁻carbon nano-onion (CNO) composites for solid-state supercapacitors. Scanning electron microscopic (SEM) analyses indicate a uniform and ordered composition for the conducting polymer nanotubes immobilized on a thin gold film. The obtained nanocomposites exhibit a brush-like architecture with a specific capacitance of 946 F g-1 at a scan rate of 1 mV s-1. In addition, the nanocomposites offer high conductivity and a porous and well-developed surface area. The PANINT⁻CNO nanocomposites were tested as electrodes with high potential and long-term stability for use in easy-to-miniaturize high-performance supercapacitor devices.

Toxicity of tannic acid-modified silver nanoparticles in keratinocytes: potential for immunomodulatory applications.

Hydrolyzable tannins are known to exhibit anti-inflammatory activity, which can be used in combination with silver nanoparticles (AgNPs) for dermal uses. In this study, we investigated the effects of tannic acid-modified 13, 33, 46nm and unmodified 10-65nm AgNPs using the human-derived keratinocyte HaCaT and VK2-E6/E7 cell lines in the form of stationary and spheroids cultures. After exposition to tannic acid-modified AgNPs, VK2-E6/E7 cells showed higher toxicity, increased production of reactive oxygen species (ROS) and activity of JNK stress kinase, while HaCaT cell line demonstrated less ROS production and activation of ERK kinase. AgNPs internalization was detected both in the superficial and internal layers of spheroids prepared from both cell lines. Tannic acid modified AgNPs sized above 30nm did not induce DNA breaks in comet assay performed in both cell lines. Tannic acid-modified but not unmodified AgNPs down-regulated TNF-α and LPS-triggered production of IL-8 in VK2-E6/E7 but not in HaCaT cells. In summary, tannic acid-modified AgNPs sized above 30nm show good toxicological profile both in vitro and possess immunomodulatory properties useful for potential dermal applications in humans.

Optimizing calcium selective fluorimetric nanospheres.

Recently it was shown that optical nanosensors based on alternating polymers e.g. poly(maleic anhydride-alt-1-octadecene) were characterized by a linear dependence of emission intensity on logarithm of concentration over a few of orders of magnitude range. In this work we focus on the material used to prepare calcium selective nanosensors. It is shown that alternating polymer nanosensors offer competitive performance in the absence of calcium ionophore, due to interaction of the nanospheres building blocks with analyte ions. The emission increase corresponds to increase of calcium ions contents in the sample within the range from 10(-4) to 10(-1) M. Further improvement in sensitivity (from 10(-6) to 10(-1) M) and selectivity can be achieved by incorporating calcium ionophore in the nanospheres. The optimal results were obtained for core-shell nanospheres, where the core was prepared from poly(styrene-co-maleic anhydride) and the outer layer from poly(maleic anhydride-alt-1-octadecene). Thus obtained chemosensors were showing linear dependence of emission on logarithm of calcium ions concentration within the range from 10(-7) to 10(-1) M.

Tannic acid modified silver nanoparticles show antiviral activity in herpes simplex virus type 2 infection.

The interaction between silver nanoparticles and herpesviruses is attracting great interest due to their antiviral activity and possibility to use as microbicides for oral and anogenital herpes. In this work, we demonstrate that tannic acid modified silver nanoparticles sized 13 nm, 33 nm and 46 nm are capable of reducing HSV-2 infectivity both in vitro and in vivo. The antiviral activity of tannic acid modified silver nanoparticles was size-related, required direct interaction and blocked virus attachment, penetration and further spread. All tested tannic acid modified silver nanoparticles reduced both infection and inflammatory reaction in the mouse model of HSV-2 infection when used at infection or for a post-infection treatment. Smaller-sized nanoparticles induced production of cytokines and chemokines important for anti-viral response. The corresponding control buffers with tannic acid showed inferior antiviral effects in vitro and were ineffective in blocking in vivo infection. Our results show that tannic acid modified silver nanoparticles are good candidates for microbicides used in treatment of herpesvirus infections.

Alternating polymer micelle nanospheres for optical sensing.

A novel concept of nanosized fluorimetric sensors is proposed, using alternating polymers as self assembling micelles that can be crosslinked resulting in stable polymeric nanoparticles. The thus obtained nanospheres have sizes close to 250 nm or 130 nm, depending on the preparation procedure and the negative surface charge, due to the presence of carboxyl groups on the surface. By a simple procedure, the nanospheres can be effectively loaded with compounds of choice, e.g. ionophores and ion-exchangers previously used to induce ionic sensitivity in polyacrylate or poly(vinyl chloride) micro- and nanospheres (miniature optrodes), thus allowing for optical or fluorimetric quantification of analytes. As a proof of concept, H(+) sensitive colorimetric and fluorimetric sensors and K(+) fluorimetric sensors using classical optrode approach were prepared and tested. The obtained sensors were characterized by high sensitivity, fast and reversible responses. Both K(+) and H(+) sensors were characterized by a broad response range resulting from the significant effect of processes occurring on the surface of the nanospheres. Due to this effect, the fluorimetric responses of the obtained spheres are significantly different from those typically observed for miniature optrode systems, and were linear within a range of at least 5 logarithmic units of analyte concentration. As shown, the surface groups of the herein proposed nanospheres can be used for the covalent linking of fluorophores that can be used as markers (if applied alone) or as reference dyes for fluorescent ion-sensitive nanospheres.

Modification of electrode surfaces: deposition of thin layers of polypyrrole--Au nanoparticle materials using a combination of interphase synthesis and dip-in method.

Formation of thin layers of the composite material by a method based on interphase polymerization induced by a transport-controlled redox reaction is described. The obtained films were of 0.2-1 microm thickness, consisted of polypyrrole and gold nanoparticles (up to 13.5 at. %), strongly adhered to the substrate surface, and were uniform. Different carbon materials and glass wool were employed as the substrates. The first step in the synthesis was deposition of an organic layer on the substrate. This was followed by dipping the substrate in an aqueous solution containing an oxidizer and appropriate washing and drying the composite film.