Grzegorz Celichowski

Detection limits of DLS and UV-Vis spectroscopy in characterization of polydisperse nanoparticles colloids

Dynamic light scattering is a method that depends on the interaction of light with particles. This method can be used for measurements of narrow particle size distributions especially in the range of 2-500 nm. Sample polydispersity can distort the results, and we could not see the real populations of particles because big particles presented in the sample can screen smaller ones. Although the theory and mathematical basics of DLS technique are already well known, little has been done to determine its limits experimentally. The size and size distribution of artificially prepared polydisperse silver nanoparticles (NPs) colloids were studied using dynamic light scattering (DLS) and ultraviolet-visible (UV-Vis) spectroscopy. Polydisperse colloids were prepared based on the mixture of chemically synthesized monodisperse colloids well characterized by atomic force microscopy (AFM), transmission electron microscopy (TEM), DLS, and UV-Vis spectroscopy. Analysis of the DLS results obtained for polydisperse colloids reveals that several percent of the volume content of bigger NPs could screen completely the presence of smaller ones. The presented results could be extremely important from nanoparticles metrology point of view and should help to understand experimental data especially for the one who works with DLS and/or UV-Vis only.

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.

Assessment of in vitro cellular responses of monocytes and keratinocytes to tannic acid modified silver nanoparticles

Hydrolyzable tannins are known to exhibit diverse biological effects, which can be used in combination with silver nanoparticles (AgNPs). In this study, we tested toxic and inflammatory properties of tannic-acid modified 13, 33, 46 nm and unmodified 10-65 nm AgNPs using murine 291.03C keratinocyte and RAW 264.7 monocyte cell lines. Both cell lines exposed for 24h to 1-10 μg/ml of 13 nm, 33 nm, 46 nm and unmodified AgNPs showed dose-dependent toxicity and decreased cell proliferation. Only small-sized AgNPs induced production of ROS by monocytes, but not keratinocytes. Monocytes internalized large aggregates of 33, 46 nm and 10-65 nm AgNPs in cytoplasmic vacuoles, whereas keratinocytes accumulated less particles. AgNPs of 13 nm were localized ubiquitously within both cell types. The tested AgNPs strongly down-regulated production of tumor necrosis factor-α (TNF-α) by monocytes, whereas keratinocytes exposed to AgNPs showed an opposite effect. Unmodified but not tannic acid-modified AgNPs increased production of the pro-inflammatory MCP-1 by monocytes and keratinocytes. In summary, low inflammatory potential and lack of ROS production by tannic-acid modified AgNPs sized above 30 nm suggests that tannic acid modification of large silver nanoparticles may help to increase AgNPs biosafety.

Superhydrophobic surface by replication of laser micromachined pattern in epoxy/alumina nanoparticle composite

Superhydrophobic surfaces were obtained by superposition of microstructure—defined by replication of laser micromachined masters, with nanostructure—created by durable epoxy/γ-Al2O3 nanoparticle composite, used for replication. Hierarchical surface topography thus obtained consisted of hexagonally spaced microcavities and nanoparticle agglomerates, exposed on the replica surface by radio frequency (RF) air plasma etching. Surface topography was further enhanced by rims around the microcavity edges, resulting from nanosecond laser micromachining defects in aluminum masters. Subsequent wet chemical hydrophobization with 1H,1H,2H,2H-perfluorotetradecyltriethoxysilane (PFTDTES) provided superhydrophobic behavior in replicas with a microcavity spacing of 30 μm, as indicated by a water contact angle of 160° and a sliding angle of 8°. The preparation method is relatively simple, inexpensive, and potentially scalable.

Effect of the alkyl chain length of secondary amines on the phase transfer of gold nanoparticles from water to toluene.

In the present paper we describe a phase transfer of aqueous synthesized gold nanoparticles (AuNPs) from water to toluene using secondary amines: dioctylamine, didodecylamine, and dioctadecylamine. The effect of the hydrocarbon chain length and amount of amines on the transfer efficiency were investigated in the case of nanoparticles (NPs) with three different sizes: 5, 9, and 13 nm. Aqueous colloids were precisely characterized before the transfer process using UV-vis spectroscopy, dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). Nanoparticles were next transferred to toluene and characterized using UV-vis and DLS techniques. It was found that dioctadecylamine provides the most effective transfer of nanoparticles. No time-dependent changes in the NP size were observed after 12 days, showing that the dioctadecylamine-stabilized nanoparticles dispersed in toluene were stable. This indicates that long hydrocarbon chains of dioctadecylamine exhibit sufficiently hydrophobic properties of nanoparticles and consequently their good dispersibility in nonpolar solvent.

Hydrophobization of epoxy nanocomposite surface with 1H,1H,2H,2H-perfluorooctyltrichlorosilane for superhydrophobic properties

Nature inspires the design of synthetic materials with superhydrophobic properties, which can be used for applications ranging from self-cleaning surfaces to microfluidic devices. Their water repellent properties are due to hierarchical (micrometer- and nanometre-scale) surface morphological structures, either made of hydrophobic substances or hydrophobized by appropriate surface treatment. In this work, the efficiency of two surface treatment procedures, with a hydrophobic fluoropolymer, synthesized and deposited from 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTS) is investigated. The procedures involved reactions from the gas and liquid phases of the PFOTS/hexane solutions. The hierarchical structure is created in an epoxy nanocomposite surface, by filling the resin with alumina nanoparticles and micron-sized glass beads and subsequent sandblasting with corundum microparticles. The chemical structure of the deposited fluoropolymer was examined using XPS spectroscopy. The topography of the modified surfaces was characterized using scanning electron microscopy (SEM), and atomic force microscopy (AFM). The hydrophobic properties of the modified surfaces were investigated by water contact and sliding angles measurements. The surfaces exhibited water contact angles of above 150° for both modification procedures, however only the gas phase modification provided the non-sticking behaviour of water droplets (sliding angle of 3°). The discrepancy is attributed to extra surface roughness provided by the latter procedure.

The role of tannic acid and sodium citrate in the synthesis of silver nanoparticles

AbstractWe describe herein the significance of a sodium citrate and tannic acid mixture in the synthesis of spherical silver nanoparticles (AgNPs). Monodisperse AgNPs were synthesized via reduction of silver nitrate using a mixture of two chemical agents: sodium citrate and tannic acid. The shape, size and size distribution of silver particles were determined by UV–Vis spectroscopy, dynamic light scattering (DLS) and scanning transmission electron microscopy (STEM). Special attention is given to understanding and experimentally confirming the exact role of the reagents (sodium citrate and tannic acid present in the reaction mixture) in AgNP synthesis. The oxidation and reduction potentials of silver, tannic acid and sodium citrate in their mixtures were determined using cyclic voltammetry. Possible structures of tannic acid and its adducts with citric acid were investigated in aqueous solution by performing computer simulations in conjunction with the semi-empirical PM7 method. The lowest energy structures found from the preliminary conformational search are shown, and the strength of the interaction between the two molecules was calculated. The compounds present on the surface of the AgNPs were identified using FT-IR spectroscopy, and the results are compared with the IR spectrum of tannic acid theoretically calculated using PM6 and PM7 methods. The obtained results clearly indicate that the combined use of sodium citrate and tannic acid produces monodisperse spherical AgNPs, as it allows control of the nucleation, growth and stabilization of the synthesis process. Graphical abstractᅟ

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.

Hydrophobic and superhydrophobic surfaces fabricated by plasma polymerization of perfluorohexane, perfluoro(2-methylpent-2-ene), and perfluoro(4-methylpent-2-ene)

Fluoropolymer films were deposited on silicon (1 0 0) wafers, glass, epoxy, and hierarchical dual-sized filler epoxy composite surfaces by plasma polymerization of perfluorohexane, perfluoro(2-methylpent-2-ene), and perfluoro(4-methylpent-2-ene). The procedure involved continuous wave plasma-enhanced deposition, followed by a discharge-off period, with the monomer gas feed maintained. Silanization of silicon wafers and glass surfaces with triethoxyvinylsilane was employed to improve plasma fluoropolymer bonding to these substrates. The presence of double bonds in perfluoro(2-methylpent-2-ene) and perfluoro(4-methylpent-2-ene) was found to influence fluoropolymer coating topography, thereby increasing surface roughness in modified glass and epoxy substrates. All fluorocarbons provided a similar level of hydrophobization of flat substrates, exhibited by water contact angles (WCA) of about 110°. Hydrophobization of nanocomposite hierarchical surfaces by plasma polymerization provided superhydrophobic surfaces, with WCA of 160° and contact angle hysteresis below 8°.

Dynamic contact of droplet with superhydrophobic surface in conditions favour icing

Flight like droplet impact with superhydrophobic substrate in conditions favour icing is discussed in this work. Test stand with fast camera and equipment eligible to obtain temperatures and humidity at different ranges, lead to results which can prove, that superhydrophobic surface might be good ice repellent substrate. The influence of air humidity on droplet freezing was confirmed.