Removal of Hexamethyldisiloxane via a Novel Hydrophobic (3-Aminopropyl)Trimethoxysilane-Modified Activated Porous Carbon.

Volatile methyl siloxanes (VMS) must be removed because the formation of silica in the combustion process seriously affects the resource utilization of biogas. Herein, a series of APTMS ((3-aminopropyl)trimethoxysilane)-modified activated porous carbon (APC) adsorbents (named APTMS@APC) were prepared for VMS efficient removal. The as-prepared adsorbents were characterized using SEM, FTIR, Raman, X-ray diffraction analyses, and N2 adsorption/desorption. The results showed that the surface modification with APTMS enhanced the hydrophobicity of APC with the water contact angle increasing from 74.3° (hydrophilic) to 127.1° (hydrophobic), and meanwhile improved its texture properties with the SBET increasing from 981 to 1274 m2 g-1. The maximum breakthrough adsorption capacity of APTMS@APC for hexamethyldisiloxane (L2, model pollutant) was 360.1 mg g-1. Effects of an inlet L2 concentration (31.04-83.82 mg L-1) and a bed temperature (0-50 °C) on the removal of L2 were investigated. Meanwhile, after five adsorption-desorption cycles, the APTMS@APC demonstrated a superior cycling performance. This indicated that the hydrophobic APTMS@APC has a great significance to remove VMS.

MAPLE Processed Nanostructures for Antimicrobial Coatings.

Despite their great benefits for debilitated patients, indwelling devices are prone to become easily colonized by resident and opportunistic microorganisms, which have the ability to attach to their surfaces and form highly specialized communities called biofilms. These are extremely resistant to host defense mechanisms and antibiotics, leading to treatment failure and device replacement, but also to life-threatening complications. In this study, we aimed to optimize a silica (SiO2)-coated magnetite (Fe3O4)-based nanosystem containing the natural antimicrobial agent, eugenol (E), suitable for MAPLE (matrix-assisted pulsed laser evaporation) deposition as a bioactive coating for biomedical applications. X-ray diffraction, thermogravimetric analysis, Fourier-transform infrared spectroscopy, and transmission electron microscopy investigations were employed to characterize the obtained nanosystems. The in vitro tests evidenced the superior biocompatibility of such nanostructured coatings, as revealed by their non-cytotoxic activity and ability to promote cellular proliferation and sustain normal cellular development of dermal fibroblasts. Moreover, the obtained nanocoatings did not induce proinflammatory events in human blood samples. Our studies demonstrated that Fe3O4 NPs can improve the antimicrobial activity of E, while the use of a SiO2 matrix may increase its efficiency over prolonged periods of time. The Fe3O4@SiO2 nanosystems showed excellent biocompatibility, sustaining human dermal fibroblasts' viability, proliferation, and typical architecture. More, the novel coatings lack proinflammatory potential as revealed by the absence of proinflammatory cytokine expression in response to human blood sample interactions.

Acetone-induced polymerisation of 3-aminopropyltrimethoxysilane (APTMS) as revealed by NMR spectroscopy.

We followed the reactivity of acetone with 3-aminopropyltrimethoxysilane, a potential organosilane coupling agent, by (1)H, (13)C and (29)Si NMR spectroscopy. Selective 1D and 2D-edited NMR experiments significantly contributed to simplify the spectral complexity of reaction solution and elucidated molecular structures within progressive reaction phases. The course of the 3-aminopropyltrimethoxysilane reaction with acetone was shown by a progressive decrease of both reactants, and a concomitant appearance of water and methanol, due to formation of imine and hydrolysis of alkoxysilane groups, respectively. The occurrence of multiple siloxane linkages in a progressively larger cross-linked macromolecular structure was revealed by DOSY-NMR experiments and new signals in (29)Si-NMR spectra at different reaction times. The NMR approach described here may be applied to investigate the reactivity of other γ-aminopropylalkoxysilanes and contribute to define procedures for the preparation of silica-based materials.

Syntheses of APTMS-Coated ZnO: An Investigation towards Penconazole Detection.

Extrinsic chemiluminescence can be an efficient tool for determining pesticides and fungicides, which do not possess any intrinsic fluorescent signal. On this basis, (3-aminopropyl) trimethoxysilane (APTMS)-coated ZnO (APTMS@ZnO) was synthesized and tested as an extrinsic probe for the fungicide penconazole. Several synthetic routes were probed using either a one-pot or two-steps method, in order to ensure both a green synthetic pathway and a good signal variation for the penconazole concentration. The synthesized samples were characterized using X-ray diffraction (XRD), infrared (IR), Raman and ultraviolet-visible (UV-Vis) spectroscopy, scanning electron microscopy (SEM) imaging and associated energy-dispersive X-ray (EDX) analysis. The average size of the synthesized ZnO nanoparticles (NPs) is 54 ± 10 nm, in line with previous preparations. Of all the samples, those synthesized in two steps, at temperatures ranging from room temperature (RT) to a maximum of 40 °C, using water solvent (G-APTMG@ZnO), appeared to be composed of nanoparticles, homogeneously coated with APTMS. Chemiluminescence tests of G-APTMG@ZnO, in the penconazole concentration range 0.7-1.7 ppm resulted in a quenching of the native signal between 6% and 19% with a good linear response, thus indicating a green pathway for detecting the contaminant. The estimated detection limit (LOD) is 0.1 ± 0.01 ppm.

Property Characterization and Mechanism Analysis of Polyoxometalates-Functionalized PVDF Membranes by Electrochemical Impedance Spectroscopy.

Polyoxometalates (POMs) has proved its advantage in constructing high-performance nanocomposite membranes such as catalytic membranes, adsorptive membranes, and forward osmosis membranes. However, it is challenging or tedious to characterize its distribution and effect on the membrane structures due to the equipment resolution limitation, discrete nano-scaled structures of POMs, and limited doping amount compared to the polymeric membrane matrix. In this paper, POMs-functionalized polyvinylidene fluoride (PVDF) membranes were fabricated by phase inversion combined with the sol-gel method, and electrochemical impedance spectroscopy (EIS) was utilized to analyze the nanocomposite membrane intrinsic properties. Through adjusting the additives in the sol-forming process, a set of membranes with varied intrinsic properties were developed accordingly. The wetting degree of the membranes related to the hydrophilic nature of the membrane surfaces had a crucial influence on the impedance measurements at the early stage. Through EIS analysis, it was demonstrated that the amination of the membrane matrix through (3-aminopropyl)trimethoxysilane (APTMS) treatment and the immobilization of POMs through electrostatic attraction would not generate new pore structures into the membrane and only alter the membrane surface roughness and composition. To my knowledge, it is the first time that EIS was utilized to characterize the hydrophilicity of the membranes and pore structures of the POMs-modified membranes. Our findings indicate that EIS can provide valuable information for probing the structures of other nano-materials-incorporated membranes.

Fe3O4 Nanoparticles for Complex Targeted Delivery and Boron Neutron Capture Therapy.

Magnetic Fe3O4 nanoparticles (NPs) and their surface modification with therapeutic substances are of great interest, especially drug delivery for cancer therapy, including boron-neutron capture therapy (BNCT). In this paper, we present the results of boron-rich compound (carborane borate) attachment to previously aminated by (3-aminopropyl)-trimethoxysilane (APTMS) iron oxide NPs. Fourier transform infrared spectroscopy with Attenuated total reflectance accessory (ATR-FTIR) and energy-dispersive X-ray analysis confirmed the change of the element content of NPs after modification and formation of new bonds between Fe3O4 NPs and the attached molecules. Transmission (TEM) and scanning electron microscopy (SEM) showed Fe3O4 NPs' average size of 18.9 nm. Phase parameters were studied by powder X-ray diffraction (XRD), and the magnetic behavior of Fe3O4 NPs was elucidated by Mössbauer spectroscopy. The colloidal and chemical stability of NPs was studied using simulated body fluid (phosphate buffer-PBS). Modified NPs have shown excellent stability in PBS (pH = 7.4), characterized by XRD, Mössbauer spectroscopy, and dynamic light scattering (DLS). Biocompatibility was evaluated in-vitro using cultured mouse embryonic fibroblasts (MEFs). The results show us an increasing of IC50 from 0.110 mg/mL for Fe3O4 NPs to 0.405 mg/mL for Fe3O4-Carborane NPs. The obtained data confirm the biocompatibility and stability of synthesized NPs and the potential to use them in BNCT.

Indocyanine green loaded APTMS coated SPIONs for dual phototherapy of cancer.

Superparamagnetic iron oxide nanoparticles (SPIONs) have been recently recognized as highly efficient photothermal therapy (PTT) agents. Here, we demonstrate, for the first time to our knowledge, dose and laser intensity dependent PTT potential of small, spherical, 3-aminopropyltrimethoxysilane coated cationic superparamagnetic iron oxide nanoparticles (APTMS@SPIONs) in aqueous solutions upon irradiation at 795 nm. Indocyanine green (ICG) which has been recently used for photodynamic therapy (PDT), was loaded to APTMS@SPIONs to improve the stability of ICG and to achieve an effective mild PTT and PDT (dual therapy) combination for synergistic therapeutic effect on cancer cells via a single laser treatment in the near infrared (NIR). Neither APTMS@SPIONs nor ICG-APTMS@SPIONs showed dark toxicity on MCF7 breast and HT29 colon cancer cell lines. A safe laser procedure was determined as 10 min irradiation at 795 nm with 1.8 W/cm2 of laser intensity, at which APTMS@SPION did not cause a significant cell death. However, free ICG reduced cell viability at and above 10 µg/ml under these conditions along with generation of reactive oxygen species (ROS), more effectively in MCF7. ICG-APTMS@SPION treated cells showed 2-fold increase in ROS generation and near complete cell death at and below 5 µg/ml ICG dose, even in less sensitive HT29 cells after a single laser treatment at NIR, which would be safe for the healthy tissue and provide a longer penetration depth. Besides, both components can be utilized for diagnosis and the overall composition may be used for optical-image guided phototherapy in the NIR region.

Exploring the Control in Antibacterial Activity of Silver Triangular Nanoplates by Surface Coating Modulation.

In the present work, the synthesis and characterization of silver triangular nanoplates (AgNTs) and their silica coating composites are reported. Engineering control on the surface coating has demonstrated the possibility to modulate the antibacterial effect. Several AgNT-coated nanomaterials, such as PVP (Polyvinylpyrrolidone) and MHA (16-mercaptohexadecanoic acid) as a stable organic coating system as well as uniform silica coating (≈5 nm) of AgNTs, have been prepared and fully characterized. The antibacterial properties of the systems reported, organic (MHA) and inorganic (amine and carboxylic terminated SiO2) coating nanocomposites, have been tested on Gram-positive and Gram-negative bacteria strains. We observed that the AgNTs' organic coating improved antimicrobial properties when compared to other spherical silver colloids found in the literature. We have also found that thick inorganic silica coating decreases the antimicrobial effect, but does not cancel it. In addition, the effect of surface charge in AgNTs@Si seems to play a crucial role toward S. aureus ATCC 25923 bacteria, obtaining MIC/MBC values compared to the AgNTs with an organic coating.

A prominent anchoring effect on the kinetic control of drug release from mesoporous silica nanoparticles (MSNs).

This work demonstrated kinetically controlled release of model drugs (ibuprofen, FITC) from well-tailored mesoporous silica nanoparticles (MSNs) depending on the surface charges and molecular sizes of the drugs. The molecular interactions between entrapped drugs and the pore walls of MSNs controlled the release of the drugs through the pore channels of MSNs. Also, polydopamine (PDA) layer-coated MSNs (MSNs@PDA) was quite effective to retard the release of large FITC, in contrast to a slight retardation effect on relatively small Ibuprofen. Of all things, FITC (Fluorescein isothiocyanate)-labeled APTMS (3-aminopropyltrimethoxysilane) (APTMS-FITC conjugates) grafted onto the MSNs generate a pinch-effect on the pore channel (so-called a prominent anchoring effect), which was highly effective in trapping (or blocking) drug molecules at the pore mouth of the MSNs. The anchored APTMS-FITC conjugates provided not only tortuous pathways to the diffusing molecules, but also sustained release of the ibuprofen over a long period of time (∼7days). The fast release kinetics was predicted by an exponential equation based on Fick's law, while the slow release kinetics was predicted by Higuchi model.

Mesoporous silica nanoparticles for drug and gene delivery.

Mesoporous silica nanoparticles (MSNs) are attracting increasing interest for potential biomedical applications. With tailored mesoporous structure, huge surface area and pore volume, selective surface functionality, as well as morphology control, MSNs exhibit high loading capacity for therapeutic agents and controlled release properties if modified with stimuli-responsive groups, polymers or proteins. In this review article, the applications of MSNs in pharmaceutics to improve drug bioavailability, reduce drug toxicity, and deliver with cellular targetability are summarized. Particularly, the exciting progress in the development of MSNs-based effective delivery systems for poorly soluble drugs, anticancer agents, and therapeutic genes are highlighted.

Metallic Nanoshells with Sub-10 nm Thickness and Their Performance as Surface-Enhanced Spectroscopy Substrate.

As a crucial structural parameter, shell thickness greatly influences the optical properties of metallic nanoshells. However, there still lacks a reliable approach to prepare ultrathin core-shell nanoparticles. To solve this problem, a two-step gold seeding process was pointed out to increase the packing density of gold seeds on the silica core. With use of this method, the packing density of gold seeds reaches ∼60%, enabling us to successfully reduce the shell thickness to the sub-10 nm range. Afterward, we investigated optical properties of the as-prepared ultrathin nanoshells. It is found that thinner nanoshells exhibit a wider optical tunability and a greater electromagnetic field enhancement than their thicker counterparts, which makes ultrathin nanoshells an ideal substrate for surface-enhanced spectroscopes.

A direct method of quantification of maximal chemisorption of 3-aminopropylsilyl groups on silica gel using DRIFT spectroscopy.

3-Aminopropylsilyl (APS) modified silica gel plays an important role as a precursor for further modifications, where APS acts as a spacer or bridging molecule. A monolayer of APS which is most suitable for this purpose was obtained in anhydrous conditions. The properties of the APS-modified silica gel depend on the amount of molecules chemisorbed on the surface. A direct quantitative method using Diffuse Reflectance Infrared Fourier Transform (DRIFT) spectroscopy was proposed. The obtained results were further supported by elemental analysis. The conclusion was that the proposed methodology can be used for the quantification of APS groups chemisorbed on silica gel when the grafting chemical reaction was mainly irreversible.

Protein attachment to silane-functionalized porous silicon: A comparison of electrostatic and covalent attachment.

Porous silicon (pSi) is a prosperous biomaterial, biocompatible, and biodegradable. Obtaining regularly functionalized pSi surfaces is required in many biotechnology applications. Silane-PEG-NHS (triethoxysilane-polyethylene-glycol-N-hydroxysuccinimide) is useful for single-molecule studies due to its ability to attach to only one biomolecule. We investigate the functionalization of pSi with silane-PEG-NHS and compare it with two common grafting agents: APTMS (3-aminopropylotrimethoxysilane) as electrostatic linker, and APTMS modified with glutaraldehyde as covalent spacer. We show the arrangement of two proteins (collagen and bovine serum albumin) as a function of the functionalization and of the pore size. FTIR is used to demonstrate correct functionalization while fluorescence confocal microscopy reveals that silane-PEG-NHS results in a more uniform protein distribution. Reflection interference spectroscopy (RIfS) is used to estimate the attachment of linker and proteins. The results open a way to obtain homogenous chemical modified silicon supports with a great value in biosensing, drug delivery and cell biology.