Superhydrophobic coatings reduce human bacterial foodborne pathogen attachment to woods used in fresh produce harvest and postharvest packing.

Wood is reportedly more difficult to maintain in hygienic condition versus other food contact materials, yet its use in produce packing and retail warrants efforts to reduce the risk of microbial pathogen contamination and attachment. This study characterized antifouling capabilities of fluorinated silanes applied to wood used in fresh edible produce handling to render the wood superhydrophobic and less supportive of bacterial pathogen attachment. Pine and oak cubic coupon surfaces were treated with 1% (w/w) silane or left untreated. Treated and untreated coupons were inoculated with Salmonella enterica or Listeria monocytogenes and held to facilitate pathogen attachment for 1, 4, or 8 h. Silane treatment of wood produced significant reductions in the proportions of strongly attaching cells for both pathogens versus loosely attaching cells (P < 0.01). Salmonella attachment demonstrated a dependency on wood treatment; silane-treated wood supported a lower fraction of strongly adhering cells (1.87 ± 1.24 log CFU/cm2) versus untreated wood (3.72 ± 0.67 log CFU/cm2). L. monocytogenes demonstrated significant declines in strongly attaching cells during extended exposure to silane-treated wood, from 7.59 ± 0.14 to 5.27 ± 0.68 log CFU/cm2 over 8 h post-inoculation. Microscopic analysis demonstrated silane treatment increased the surface roughness of both woods, leading to superhydrophobic conditions on wood surfaces, consequently decreasing strong attachment of pathogenic bacteria.

Anti-Cracking TEOS-Based Hybrid Materials as Reinforcement Agents for Paper Relics.

Tetraethoxysilane (TEOS) is the most commonly used silicon-based reinforcement agent for conserving art relics due to its cost-effectiveness and commercial maturity. However, the resulting silica gel phase is prone to developing cracks as the gel shrinks during the sol-gel process, potentially causing severe damage to the objects being treated. In this study, dodecyltrimethoxysilane (DTMS) was introduced into TEOS to minimize this shrinkage by adding elastic long chains to weaken the capillary forces. The gel formed from the DTMS/TEOS hybrid material was transparent and crack-free, featuring a dense microstructure without mesopores or micropores. It exhibited excellent thermal stability, with a glass transition temperature of up to 109.64 °C. Evaluation experiments were conducted on artificially aged, handmade bamboo paper. The TEOS-based hybrid material effectively combined with the paper fibers through the sol-gel process, polymerizing into a network structure that enveloped the paper surface or penetrated between the fibers. The surface of the treated paper displayed excellent hydrophobic properties, with no significant changes in appearance, color, or air permeability. The mechanical properties of the treated bamboo paper improved significantly, with longitudinal and transverse tensile strengths increasing by up to 36.63% and 44.25%, respectively. These research findings demonstrate the promising potential for the application of DTMS/TEOS hybrid materials in reinforcing paper relics.

Drug Delivery through Epidermal Tissue Cells by Functionalized Biosilica from Diatom Microalgae.

Diatom microalgae are a natural source of fossil biosilica shells, namely the diatomaceous earth (DE), abundantly available at low cost. High surface area, mesoporosity and biocompatibility, as well as the availability of a variety of approaches for surface chemical modification, make DE highly profitable as a nanostructured material for drug delivery applications. Despite this, the studies reported so far in the literature are generally limited to the development of biohybrid systems for drug delivery by oral or parenteral administration. Here we demonstrate the suitability of diatomaceous earth properly functionalized on the surface with n-octyl chains as an efficient system for local drug delivery to skin tissues. Naproxen was selected as a non-steroidal anti-inflammatory model drug for experiments performed both in vitro by immersion of the drug-loaded DE in an artificial sweat solution and, for the first time, by trans-epidermal drug permeation through a 3D-organotypic tissue that better mimics the in vivo permeation mechanism of drugs in human skin tissues. Octyl chains were demonstrated to both favour the DE adhesion onto porcine skin tissues and to control the gradual release and the trans-epidermal permeation of Naproxen within 24 h of the beginning of experiments. The evidence of the viability of human epithelial cells after permeation of the drug released from diatomaceous earth, also confirmed the biocompatibility with human skin of both Naproxen and mesoporous biosilica from diatom microalgae, disclosing promising applications of these drug-delivery systems for therapies of skin diseases.

The Effect of Mesoporous Structure of the Support on the Oxidation of Dibenzothiophene.

A source of Brønsted acid centers, generated on the surface of two mesoporous silica supports of different structures (SBA-15 and MCF), was 3-(trihydroxysilyl)-1-propanesufonic acid (TPS). The materials obtained were characterized and applied as catalysts for the oxidative desulfurization of dibenzothiophene (DBT) with hydrogen peroxide as a model ODS (oxidative desulfurization) process. The properties of the materials were examined via nitrogen physisorption, XRD (X-ray Diffraction) and elemental analysis showing the preservation of the support structure after modification with organosilane species. Due to the aggregation of catalyst particles in the reaction mixture, the SBA-15 based catalyst was not very effective in DBT oxidation. Contrary, TPS/MCF catalyst exhibited a very good activity (almost total conversion of DBT after 1 h in optimized reaction conditions) and stability in dibenzothiophene oxidation in mild reaction conditions.

Functionalized Magnetite Nanoparticles: Characterization, Bioeffects, and Role of Reactive Oxygen Species in Unicellular and Enzymatic Systems.

The current study evaluates the role of reactive oxygen species (ROS) in bioeffects of magnetite nanoparticles (MNPs), such as bare (Fe3O4), humic acids (Fe3O4-HA), and 3-aminopropyltriethoxysilane (Fe3O4-APTES) modified MNPs. Mössbauer spectroscopy was used to identify the local surrounding for Fe atom/ions and the depth of modification for MNPs. It was found that the Fe3O4-HA MNPs contain the smallest, whereas the Fe3O4-APTES MNPs contain the largest amount of Fe2+ ions. Bioluminescent cellular and enzymatic assays were applied to monitor the toxicity and anti-(pro-)oxidant activity of MNPs. The contents of ROS were determined by a chemiluminescence luminol assay evaluating the correlations with toxicity/anti-(pro-)oxidant coefficients. Toxic effects of modified MNPs were found at higher concentrations (>10−2 g/L); they were related to ROS storage in bacterial suspensions. MNPs stimulated ROS production by the bacteria in a wide concentration range (10−15−1 g/L). Under the conditions of model oxidative stress and higher concentrations of MNPs (>10−4 g/L), the bacterial bioassay revealed prooxidant activity of all three MNP types, with corresponding decay of ROS content. Bioluminescence enzymatic assay did not show any sensitivity to MNPs, with negligible change in ROS content. The results clearly indicate that cell-membrane processes are responsible for the bioeffects and bacterial ROS generation, confirming the ferroptosis phenomenon based on iron-initiated cell-membrane lipid peroxidation.

A new organosilane passivation agent prepared at ambient temperatures to inhibit pyrite oxidation for acid mine drainage control.

Acid mine drainage (AMD) is a significant environmental problem caused by the oxidation of pyrite and other metal sulfide ores. Organosilane passivation is an effective strategy to inhibit pyrite oxidation. However, synthetic organic silane passivation agents generally require temperatures of 50-80 °C, resulting in high energy consumption and high synthesis cost. In this study, a 3-aminopropyltrimethoxysilane -methyltrimethoxysilane (APS-MTMS) coatings was successfully prepared at ambient temperatures of 15-40 °C as a passivation agent to inhibit pyrite oxidation. Chemical leaching tests were used to study the inhibition performance of APS-MTMS for pyrite oxidation. The experimental results showed that the release of the total Fe from APS-MTMS-coated pyrite was 11.31 mg/L after chemical oxidation for 7 hours, and the passivation rate can reach 77.78%. The contact angle of the APS-MTMS-coated pyrite was significantly larger (140.4°) than that of the bare pyrite (58.8°), indicating that APS-MTMS prompted the formation of a superhydrophobic surface of pyrite, improving the oxidation resistance. Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied to probe the interaction mechanism of APS-MTMS with pyrite. The results indicated that APS accelerated the Si-O-Si formation by amino protonation and enriched a crosslinked network of Si-O-Si and Fe-O-Si on the pyrite surface to prevent pyrite oxidation. This study provides a novel method for preparing organosilane passivation materials at ambient temperatures for AMD control.

Micro-mesoporous submicron silica particles with pore size tunable in a wide range: synthesis, properties and prospects for LED manufacturing.

An approach has been developed that allows the synthesis of submicron spherical silica particles with a controlled micro-mesoporous structure possessing a large specific surface area (up to 1300 m2g-1). Particle synthesis is carried out by the hydrolysis of a mixture of various organosilanes mostly associated either with CTAB or with each other. A change in the concentration of CTAB in the reaction mixture apparently leads to a change in the formation mechanism of nuclei for the silica particle growth, which allows for varying the diameter of the synthesized particles in the range from 40-450 nm. The effect of the composition of the silica precursor ([3-(methacryloyloxy)propyl]trimethoxysilane, (3-aminopropyl)triethoxysilane and tetraethoxysilane) on the formation process and porosity of the resulting particles is studied. It was shown that by simply varying the ratio of organosilanes in the composition of the precursor, one can control the pore diameter of the particles in a wide range from 0.6-15 nm. The large-pore (up to 15 nm) silica particles are used as a matrix for the spatial distribution of luminescent carbon dots. The incorporation of carbon dots into SiO2particles prevents their aggregation leading to emission quenching after drying, thus allowing us to obtain highly luminescent composite particles. LEDs based on the obtained composite material show bright visible luminescence with spectral characteristics similar to that of a commercial cold white LED.

Antimicrobial coating is associated with significantly lower aerobic colony counts in high-touch areas in an orthopedic ward environment.

BACKGROUND: Hospital acquired infections (HAI) are the most common complication found in the hospital environment. The aim of the study was to examine whether the use of an antimicrobial coating in high-touch areas in an orthopedic ward could reduce bacterial growth and HAI. METHODS: From December 2017 to February 2018, HAI were registered on two orthopedic wards. A second registration was performed from December 2018 to February 2019. On the second occasion, an antimicrobial organosilane coating was applied just before the study period and thereafter weekly on one ward, while the other ward served as a control. Twenty defined high-touch areas on each ward were cultured before treatment and after 1, 2, 4, 8, 12, 14 and 16 weeks. Samples were cultured for aerobic colony counts, Staphylococcus aureus and E. coli. RESULTS: The total aerobic colony counts were 47% lower on the treated ward compared with the non-treated ward over the study period (p = 0.02). The colony counts for Staphylococcus aureus and E. coli were low on both wards. During the first registration period, the incidence of HAI was 22.7% and 20.0% on the non-treated and subsequently treated ward respectively. On the second occasion, after treatment, the incidence was 25.0% and 12.5% (treated ward) respectively (p = 0.0001). CONCLUSIONS: The use of a long-lasting antimicrobial organosilane coating appears to reduce the bioburden and reduce HAI. Since the incidence of HAI varies substantially over time, longer observation times are needed.

The Effect of Silica Fume and Organosilane Addition on the Porosity of Cement Paste.

The present work systematically investigates the influence of silica fume and organosilane addition on the hydration dynamics and the capillary pore formation of a cement paste. The cement samples were prepared with two water-to-cement ratios with increasing amounts of silica fume and of (3-Aminopropyl)triethoxysilane (APTES) organosilane. Low-field 1H nuclear magnetic resonance (NMR) relaxation measurements were performed during the hydration of the samples and after hydration, in order to reveal the dynamics of water molecules and the pore distribution. Increasing concentrations of silica fume impact the perceived hydration dynamics through the addition of magnetic impurities to the pore solution. However, there is a systematic change in the capillary pore size distribution with an increase in silica fume concentration. The results also show that the addition of APTES majorly affects the hydration dynamics, by prolonging the dormancy and hardening stages. While it does not influence the pore size distribution of capillary pores, it prevents cyclohexane from saturating the capillary pores.

A Direct Silanization Protocol for Dialdehyde Cellulose.

Cellulose derivatives have many potential applications in the field of biomaterials and composites, in addition to several ways of modification leading to them. Silanization in aqueous media is one of the most promising routes to create multipurpose and organic-inorganic hybrid materials. Silanization has been widely used for cellulosic and nano-structured celluloses, but was a problem so far if to be applied to the common cellulose derivative "dialdehyde cellulose" (DAC), i.e., highly periodate-oxidized celluloses. In this work, a straightforward silanization protocol for dialdehyde cellulose is proposed, which can be readily modified with (3-aminopropyl)triethoxysilane. After thermal treatment and freeze-drying, the resulting product showed condensation and cross-linking, which was studied with infrared spectroscopy and 13C and 29Si solid-state nuclear magnetic resonance (NMR) spectroscopy. The cross-linking involves both links of the hydroxyl group of the oxidized cellulose with the silanol groups (Si-O-C) and imine-type bonds between the amino group and keto functions of the DAC (-HC=N-). The modification was achieved in aqueous medium under mild reaction conditions. Different treatments cause different levels of hydrolysis of the organosilane compound, which resulted in diverse condensed silica networks in the modified dialdehyde cellulose structure.

Lights and Shadows of Gold Introduction into Beta Zeolite.

Four different methods for gold deposition on Beta zeolite, namely impregnation, ion-exchange, deposition-reduction, and grafting on (3-aminopropyl)trimethoxysilane functionalized support, were applied to investigate their influence on textural/structural changes in the zeolite support and its surface acidity. The as-prepared materials were fully characterized by XRD, N2 physisorption, ICP-OES, XPS, TEM, and pyridine adsorption. The obtained results indicated that bifunctional redox-acidic materials prepared within this work were characterized not only by different gold loading and gold particle size, but also different textural parameters and acidity. All these features were strongly affected by the procedure applied for gold deposition. The introduction of Au into Beta zeolite by ion exchange caused a significant decrease in the Si/Al ratio in the zeolite framework. The size of Au particles determined the textural parameters of the zeolite and the number of Lewis acid sites (LAS). The Brønsted acid sites (BAS) number was decreased if (3-aminopropyl)trimethoxysilane or NaBH4 were used in the procedure of gold deposition. The highest BAS/LAS ratio was achieved for the sample prepared by ion exchange in the ammonium form of Beta zeolite. The presented results permit making a proper choice of the gold modification procedure for the preparation of bifunctional (redox-acidic) materials, addressed to a desired application.

Synthesis of six-membered silacycles by borane-catalyzed double sila-Friedel-Crafts reaction.

We have developed a catalytic synthetic method to prepare phenoxasilins. A borane-catalyzed double sila-Friedel-Crafts reaction between amino group-containing diaryl ethers and dihydrosilanes can be used to prepare a variety of phenoxasilin derivatives in good to excellent yields. The optimized reaction conditions were also applicable for diaryl thioethers to afford their corresponding six-membered silacyclic products. The gram-scale synthesis of a representative bis(dimethylamino)phenoxasilin and the transformation of its amino groups have also been demonstrated.

Monitoring Silane Sol-Gel Kinetics with In-Situ Optical Turbidity Scanning and Dynamic Light Scattering.

Organosilanes (e.g., R'-SiOR3) provide hydrophobic functionality in thin-film coatings, porous gels, and particles. Compared with tetraalkoxysilanes (SiOR4), organosilanes exhibit distinct reaction kinetics and assembly mechanisms arising from steric and electronic properties of the R' group on the silicon atom. Here, the hydrolysis and condensation pathways of n-propyltrimethoxy silane (nPM) and a tri-fluorinated analog of nPM, 3,3,3-trifluoropropyl trimethoxy silane (3F), were investigated under aqueous conditions at pH 1.7, 2.0, 3.0, and 4.0. Prior to hydrolysis, 3F and nPM are insoluble in water and form a lens at the bottom (3F) or top (nPM) of the solutions. This phase separation was employed to follow reaction kinetics using a Turbiscan instrument to monitor hydrolysis through solubilization of the neat silane lens while simultaneously tracking condensation-induced turbidity throughout the bulk solution. Dynamic light scattering confirmed the silane condensation and particle aggregation processes reported by the turbidity scanning. Employing macroscopic phase separation of the starting reactants from the solvent further allows for control over the reaction kinetics, as the interfacial area can be readily controlled by reaction vessel geometry, namely by controlling the surface area to volume. In-situ turbidity scanning and dynamic light scattering revealed distinct reaction kinetics for nPM and 3F, attributable to the electron withdrawing and donating nature of the fluoro- and organo-side chains of 3F and nPM, respectively.

Modulating receptor-ligand binding in biorecognition by setting surface wettability.

Modulation of support wettability used for microarray format biosensing has led to an improvement of results. Hydrophobicity of glass chips was set by derivatizing with single vinyl organosilanes of different chain length and silane mixtures. Thiol-ene photochemical linking has been used as effective chemistry for covalent anchoring of thiolated probes. Lowest unspecific binding and highest signal intensity and SNR were obtained with large hydrocarbon chain (C22) silanes or a shorter one (C10) containing fluorine atoms. SNR resulting values are improved, reaching levels higher than 1500 in some cases, when using vinyl silanes modified with 1% C10 alkyl fluorinated one, because mild hydrophobicity was achieved (water contact angle ca. 110°) for all silanes, including the short C2 and C3, thus giving rise to smaller and better defined array spots. In addition, unspecific binding of reagents and targets was totally withdrawn. Hence, good-performing surfaces for biosensing applications can be built using appropriate organosilane reagent selection, including fluorinated ones. Graphical abstract ᅟ.

Formation of organosilica nanoparticles with dual functional groups and simultaneous payload entrapment.

A mixed organosilane system for simultaneous formation of organosilica nanoparticles has been systematically studied for loading of various compounds with a wide range of log P values. The molecule-entrapping system was understood by investigating the effects of adjusting various experimental parameters on particle formation and molecule entrapment. Particularly, rhodamine 6 G (R6G) loaded colloidal particles were prepared and characterised in detail. The results show that whereas most molecules had entrapment efficiency (EE%) in the range of 20-80%, R6G exhibited near 100% efficiency. Moreover, the colloidal system can be tuned to incorporate R6G with the extent of entrapment spanning at least 2 orders of magnitude (i.e. from 0.04 to 4 mg) and a maximum EE% of 98%. In conclusion, the study demonstrates the promise of the proposed mixed organosilane system in forming colloidal particles containing multiple functional groups with selective loading of highly hydrophobic molecules.

Highly Efficient Recyclable Sol Gel Polymer Catalyzed One Pot Difunctionalization of Alkynes.

Amino-bridged gel polymer P1 was discovered to catalyze alkyne halo-functionalization in excellent yields, regioselectivity, functional group compatibility, and recyclability. We have observed that both aromatic and aliphatic alkynes can be converted to α,α-dihalogenated ketones in the presence of polymer P1 under metal-free conditions at room temperature within a short reaction time.

Surface immobilization of thermo-responsive poly(N-isopropylacrylamide) by simple entrapment in a 3-aminopropyltriethoxysilane network.

In a previous study, we demonstrated the feasibility of retaining poly(N-isopropylacrylamide) (pNIPAAm) on hydroxylated surfaces by spin-coating a blend of pNIPAAm with a small amount of 3-aminopropyltriethoxysilane (APTES), an organosilane, followed by thermal annealing. In this study, we detail the conditions for retaining pNIPAAm films by APTES. Our results show that the difference in surface energy between pNIPAAm and APTES in the blended film resulted in the segregation of APTES molecules to the film/substrate interface, as verified by XPS, during annealing, and the segregated APTES molecules cross-linked to form the APTES network, thus entrapping pNIPAAm. The retained pNIPAAm films (25-35 nm) exhibited thermo-responsive behavior, determined by water contact angles and film thickness in water at temperatures above and below the lower critical solution temperature of pNIPAAm, as well as good cell attachment and rapid detachment (<10 minutes). The gained insights would allow a better design of these thermo-responsive surfaces for cell sheet engineering and other relevant applications.

Titania-Silica Materials for Enhanced Photocatalysis.

Mesoporous titania-organosilica nanoparticles comprised of anatase nanocrystals crosslinked with organosilica moieties have been prepared by direct co-condensation of a titania precursor, tetrabuthylortotitanate (TBOT), with two organosilica precursors, 1,4-bis(triethoxysilyl) benzene (BTEB) and 1,2-bis(triethoxysilyl) ethane (BTEE), in mild conditions and in the absence of surfactant. These hybrid materials show both high surface areas (200-360 m(2) g(-1) ) and pore volumes (0.3 cm(3) g(-1) ) even after calcination, and excellent photoactivity in the degradation of rhodamine 6G and in the partial oxidation of propene under UV irradiation, especially after the calcination of the samples. During calcination, there is a change in the Ti(IV) coordination and an increase in the content of SiOTi moieties in comparison with the uncalcined materials, which seems to be responsible for the enhanced photocatalytic activity of hybrid titania-silica materials as compared to both uncalcined samples and the control TiO2 .

Ordered hybrids from template-free organosilane self-assembly.

Despite considerable achievements over the last two decades, nonporous organic-inorganic hybrid materials are mostly amorphous, especially in the absence of solvothermal processes. The organosilane self-assembly approach is one of the few opportunities for creating a regular assembly of organic and inorganic moieties. Additionally, well-established organosilicon chemistry enables the introduction of numerous organic functionalities. The synthesis of periodically ordered hybrids relies on mono-, bis-, or multisilylated organosilane building blocks self-assembling into hybrid mesostructures or superstructures, subsequently cross-linked by siloxane Si-O-Si condensation. The general synthesis procedure is template-free and one-step. However, three concurrent processes underlie the generation of self-organized hybrid networks: thermodynamics of amphiphilic aggregation, dynamic self-assembly, and kinetically controlled sol-gel chemistry. Hence, the set of experimental conditions and the precursor structure are of paramount importance in achieving long-range order. Since the first developments in the mid-1990s, the subject has seen considerable progress leading to many innovative advanced nanomaterials providing promising applications in membranes, pollutant remediation, catalysis, conductive coatings, and optoelectronics. This work reviews, comprehensively, the primary evolution of this expanding field of research.

Hybrid silica nanoparticles functionalized with pyrazolone-tethered organosilane: Synthesis and application for Sn (II) ion sensing in tap water.

Pyrazolone tethered triazole functionalized organosilane and their hybrid silica nanoparticles (HSNPs) have been synthesised for the selective detection of Sn(II) using spectrophotometric techniques. The prepared compounds are characterized by FT-IR, NMR (1H and 13C), XRD, mass spectrometry and FE-SEM spectral analyses. The synthesized hybrid silica nanoparticles gave improved detection limit of 4.3 × 10-8 M and stoichiometry of complex between analyte and probe was found to be 1:1. The association constant calculated for organosilane and their HSNPs came out to be 9.54 × 104 M-1 and 7.47 × 104 M-1 while the presence of other ions showed no interference in the sensing behaviour. The results of the use of this sensing system in tap water facilitate its applicability in real samples with the recovery % more than 98.