BackgroundAmorphous silica nanoparticles (SiO2 NPs) have been regarded as relatively benign nanomaterials, however, this widely held opinion has been questioned in recent years by several reports on in vitro and in vivo toxicity. Surface chemistry, more specifically the surface silanol content, has been identified as an important toxicity modulator for SiO2 NPs. Here, quantitative relationships between the silanol content on SiO2 NPs, free radical generation and toxicity have been identified, with the purpose of synthesizing safer-by-design fumed silica nanoparticles.ResultsConsistent and statistically significant trends were seen between the total silanol content, cell membrane damage, and cell viability, but not with intracellular reactive oxygen species (ROS), in the macrophages RAW264.7. SiO2 NPs with lower total silanol content exhibited larger adverse cellular effects. The SAEC epithelial cell line did not show any sign of toxicity by any of the nanoparticles. Free radical generation and surface reactivity of these nanoparticles were also influenced by the temperature of combustion and total silanol content.ConclusionSurface silanol content plays an important role in cellular toxicity and surface reactivity, although it might not be the sole factor influencing fumed silica NP toxicity. It was demonstrated that synthesis conditions for SiO2 NPs influence the type and quantity of free radicals, oxidative stress, nanoparticle interaction with the biological milieu they come in contact with, and determine the specific mechanisms of toxicity. We demonstrate here that it is possible to produce much less toxic fumed silicas by modulating the synthesis conditions.

Due to the unique physicochemical properties exhibited by materials with nanoscale dimensions, there is currently a continuous increase in the number of engineered nanomaterials (ENMs) used in consumer goods. However, several reports associate ENM exposure to negative health outcomes such as cardiovascular diseases. Therefore, understanding the pathological consequences of ENM exposure represents an important challenge, requiring model systems that can provide mechanistic insights across different levels of ENM-based toxicity. To achieve this, we developed a mussel-inspired 3D microphysiological system (MPS) to measure cardiac contractility in the presence of ENMs. While multiple cardiac MPS have been reported as alternatives to in vivo testing, most systems only partially recapitulate the native extracellular matrix (ECM) structure. Here, we show how adhesive and aligned polydopamine (PDA)/polycaprolactone (PCL) nanofiber can be used to emulate the 3D native ECM environment of the myocardium. Such nanofiber scaffolds can support the formation of anisotropic and contractile muscular tissues. By integrating these fibers in a cardiac MPS, we assessed the effects of TiO and Ag nanoparticles on the contractile function of cardiac tissues. We found that these ENMs decrease the contractile function of cardiac tissues through structural damage to tissue architecture. Furthermore, the MPS with embedded sensors herein presents a way to non-invasively monitor the effects of ENM on cardiac tissue contractility at different time points. These results demonstrate the utility of our MPS as an analytical platform for understanding the functional impacts of ENMs while providing a biomimetic microenvironment to in vitro cardiac tissue samples. Graphical Abstract Heart-on-a-chip integrated with mussel-inspired fiber scaffolds for a high-throughput toxicological assessment of engineered nanomaterials.

We report for the first time the fabrication of single-crystal metastable manganese sulfide nanowires (γ-MnS NWs) conformally coated with graphitic carbon via chemical vapor deposition technique using a single-step route. Advanced spectroscopy and electron microscopy techniques were applied to elucidate the composition and structure of these NWs at the nanoscale, including Raman, XRD, SEM, HRTEM, EELS, EDS, and SAED. No evidence of α-MnS and β-MnS allotropes was found. The γ-MnS/C NWs have hexagonal cross-section and high aspect ratio (∼1000) on a large scale. The mechanical properties of individual γ-MnS/C NWs were examined via in situ uniaxial compression tests in a TEM-AFM. The results show that γ-MnS/C NWs are brittle with a Young's modulus of 65 GPa. The growth mechanism proposed suggests that the bottom-up fabrication of γ-MnS/C NWs is governed by vapor-liquid-solid mechanism catalyzed by bimetallic Au-Ni nanoparticles. The electrochemical performance of γ-MnS/C NWs as an anode material in lithium-ion batteries indicates that they outperform the cycling stability of stable micro-sized α-MnS, with an initial capacity of 1036 mAh g(-1) and a reversible capacity exceeding 503 mAh g(-1) after 25 cycles. This research advances the integration of carbon materials and metal sulfide nanostructures, bringing forth new avenues for potential miniaturization strategies to fabricate 1D core/shell heterostructures with intriguing bifunctional properties that can be used as building blocks in nanodevices.

Dopamine (DA) is one of the most important catecholamine neurotransmitters of the human central nervous system, and is involved in many behavioral responses and brain functions. Below normal DA levels in biological fluids can lead to different neurodegenerative conditions. For excess DA levels, a failure in energy metabolism is indicated. In this study, a facile room-temperature phosphorescence sensor is developed to detect DA based on l-cysteine capped Mn doped ZnS quantum dots (l-cys ZnS:Mn QDs). The QDs display a prominent orange emission band peaking at ~598nm, which is strongly quenched upon addition of DA in alkaline medium. The sensor exhibits a linear working range of ~0.15-3.00μM, and a limit of detection of ~7.80nM. These results are explained in terms of a pH-dependent electron transfer process, in which the oxidized dopamine quinone functions as an efficient electron acceptor. The QDs-based sensor shows a high selectivity to DA over common interfering biomolecules (including some amino acids, ascorbic acid, chloride and glucose). The sensor has been successfully applied for the detection of DA in urine samples, yielding recoveries as high as 93%. Our findings indicate that our developed sensor exhibits high sensitivity and reproducibility to determine DA even in biological fluids where DA is at low levels, e.g., in the central nervous system, which is the usual clinical profile of a neurodegenerative disorder associated to the Parkinson's disease.