Federica Valentini

Low Doses of Pristine and Oxidized Single-Wall Carbon Nanotubes Affect Mammalian Embryonic Development

Several in vitro and in vivo studies suggest local and systemic effects following exposure to carbon nanotubes. No data are available, however, on their possible embryotoxicity in mammals. In this study, we tested the effect of pristine and oxidized single-wall carbon nanotubes (SWCNTs) on the development of the mouse embryo. To this end, SWCNTs (from 10 ng to 30 μg/mouse) were administered to female mice soon after implantation (postcoital day 5.5); 10 days later, animals were sacrificed, and uteri, placentas, and fetuses examined. A high percentage of early miscarriages and fetal malformations was observed in females exposed to oxidized SWCNTs, while lower percentages were found in animals exposed to the pristine material. The lowest effective dose was 100 ng/mouse. Extensive vascular lesions and increased production of reactive oxygen species (ROS) were detected in placentas of malformed but not of normally developed fetuses. Increased ROS levels were likewise detected in malformed fetuses. No increased ROS production or evident morphological alterations were observed in maternal tissues. No fetal and placental abnormalities were ever observed in control animals. In parallel, SWCNT embryotoxicity was evaluated using the embryonic stem cell test (EST), a validated in vitro assay developed for predicting embryotoxicity of soluble chemical compounds, but never applied in full to nanoparticles. The EST predicted the in vivo data, identifying oxidized SWCNTs as the more toxic compound.

Mimicking natural bio-mineralization processes: A new tool for osteochondral scaffold development

In recent years, the concept of regenerative medicine has gained great importance, particularly in the field of orthopaedics, in which current solutions are based mainly on the replacement of damaged tissues with devices that function only as structural replacements with limited regenerative capacity. New regenerative solutions can be obtained by taking inspiration from nature, which surrounds us with a multitude of organisms endowed with extraordinary performance. In particular, bio-mineralization, which is the basis of the formation of load-bearing structures in vertebrate and invertebrate organisms, can be exploited to achieve innovative devices for the repair and reconstruction of bone and osteo-cartilaginous tissues.

Cardiac autonomic regulation after lung exposure to carbon nanotubes

The ultrafine (UF) component of airborne pollution may impair cardiovascular autonomic control, a high-risk condition for cardiovascular adverse events. Since engineered nanoparticles, such as single-walled carbon nanotubes (SWCNTs) share physicochemical properties with UF, they might have similar adverse effects. Aim of the study was to evaluate arterial baroreflex function (BRF) at baseline, 24 h after the first instillation, immediately before the second one, and 2 weeks later, in adult Wystar-Kyoto conscious rats undergoing two intratracheal instillations of SWCNT (eight rats) or phosphate buffer saline (PBS) (five rats) at 2-week interval. During each session, 30-min continuous recording of arterial pressure and pulse interval was performed by a telemetered catheter implanted in the abdominal aorta of the rats. BRF was studied by the sequence technique. SWCNTs dispersed in PBS (1 mg/ml) were administered immediately after sonication (1 μg/g body weight). A significant decrease in the number of baroreflex sequences (from 498 ± 27.1 at baseline to 287 ± 40.2 at the recording performed after 4 weeks; P < 0.05) was observed in SWCNT-instilled rats, whereas no significant change was detected in controls. These data suggest that SWCNTs may alter the BRF, thus affecting the autonomic cardiovascular control regulation.

Changes in cardiac autonomic regulation after acute lung exposure to carbon nanotubes: implications for occupational exposure

Carbon nanotubes (CNTs) are among the most relevant engineered nanomaterials (ENMs). Given the expected rise of exposure to ENMs, there is concern that they may adversely affect health of exposed people. Aim of the study was to test the hypothesis that single wall carbon nanotubes (SWCNTs) pulmonary exposure acutely affect the autonomic cardiovascular regulation in conscious rats. We studied Wistar-Kyoto rats in which a telemetry transmitter for continuous arterial pressure (AP) and heart rate (HR) recordings was surgically implanted. SWCNTs dispersed in phosphate buffer saline (PBS) or PBS alone were randomly administered intratracheally. Immediately before, and 24 hours after each instillation a 30 min AP recording was performed. The sequence analysis was performed to evaluate the baroreflex function. In the control group, PBS instillation did not induce any significant changes. At variance the SWCNT exposure induced a significant reduction of baroreflex system (BRS) (3.5 ± 0.6 versus 2.6 ± 0.40 msec/mmHg) without significant changes in the occurrence of baroreflex sequences (7.5 ± 0.47% versus 7.4 ± 0.38%). Our results show that SWCNT pulmonary exposure might affect the cardiovascular autonomic regulation thus contributing to cardiac and arrhythmic events.

Carbon nanostructured materials for applications in nano-medicine, cultural heritage, and electrochemical biosensors

This review covers applications of pristine and functionalized single-wall carbon nanotubes (SWCNTs) in nano-medicine, cultural heritage, and biosensors. The physicochemical properties of these engineered nanoparticles are similar to those of ultrafine components of airborne pollution (UF) and might have similar adverse effects. UF may impair cardiovascular autonomic control (inducing a high-risk condition for adverse cardiovascular effects), cause mammalian embryo toxicity, and increase geno-cytotoxic risk. SWCNTs coated with a biopolymer, for example polyethylenimine (PEI), become extremely biocompatible, hence are useful for in-vivo and in-vitro drug delivery and gene transfection. It is also possible to successfully immobilize a human enteric virus on PEI/SWCNT composites, suggesting application as a carrier in non-permissive media. The effectiveness of carbon nanostructured materials in the cleaning, restoration, and consolidation of deteriorated historical surfaces has been widely shown by the use of carbon nanomicelles to remove black dendritic crust from stone surfaces. The nanomicelles, here, have the twofold role of delivery and controlled release of the cleaning agents. The high biocompatibility of functionalized SWCNTs with enzymes and proteins is a fundamental feature used in the assembly of electrochemical biosensors. In particular, a third-generation protoporphyrin IX-based biosensor has been assembled for amperometric detection of nitrite, an environmental pollutant involved in the biodeterioration and black encrustation of historical surfaces.

Nanomaterials and Analytical Chemistry

Abstract Nanomaterials play an important role in the area of sensor technology. In fact the sensitivity and the signal‐to‐noise ratio of many chemical sensors are significantly improved using nanomaterials. They have allowed the introduction of many strategies in sensors and biosensor technology. Recently, catalytic nanomotors were used for drug delivery, showing an oriented motion into the cells when they are assembled using magnetic nanowires. In this review, detailed bibliographic references are presented concerning the assembling of nanomaterial‐based sensors, and a brief discussion about the potential health risk of nanoparticles will be also presented.

Highly selective detection of Epinephrine at oxidized Single-Wall Carbon Nanohorns modified Screen Printed Electrodes (SPEs).

Oxidized Single-Wall Carbon Nanohorns (o-SWCNHs) were used, for the first time, to assemble chemically modified Screen Printed Electrodes (SPEs) selective towards the electrochemical detection of Epinephrine (Ep), in the presence of Serotonine-5-HT (S-5HT), Dopamine (DA), Nor-Epineprhine (Nor-Ep), Ascorbic Acid (AA), Acetaminophen (Ac) and Uric Acid (UA). The Ep neurotransmitter was detected by using Differential Pulse Voltammetry (DPV), in a wide linear range of concentration (2-2500 μM) with high sensitivity (55.77 A M(-1) cm(-2)), very good reproducibility (RSD% ranging from 2 to 10 for different SPEs), short response time for each measurement (only 2s) and low detection of limit (LOD=0.1 μM). o-SWCNHs resulted in higher analytical performances when compared with other nanomaterials used in literature for electrochemical sensors assembly.

Biomimesis and biomorphic transformations: new concepts applied to bone regeneration.

In the last decades the activity of material scientists was more and more directed to the development of biomimetic scaffolds, able to drive and address cell activity towards proper differentiation and the repair of diseased human tissues. In case of bone, this requires the synthesis of three-dimensional constructs able to exchange chemical signals promoting osteogenesis and to progressively be resorbed during the formation and remodelling of new bone. Besides, particularly for the regeneration of extensive portions of bone, a morphological and mechanical biomimesis is also required, to allow cell colonization and formation of a proper vascularization tree. The healing of load-bearing bones also requires scaffolds with a hierarchically organized morphology, to provide improved biomechanical behaviour and allow a proper mechano-transduction of the mechanical stimuli down to the cell level. The present paper is an overview of the current technologies and devices developed in the last decade for the regeneration of bone tissue. In particular, novel biomimetic and biomorphic scaffolds, obtained by the controlled transformation of native ligneous structures, promise to adequately face the problem of obtaining complex hierarchical structures, not achievable otherwise by any currently existing manufacturing techniques.

Single Walled Carbon Nanotubes/polypyrrole–GOx composite films to modify gold microelectrodes for glucose biosensors: Study of the extended linearity

A glucose biosensor was assembled using gold microelectrodes (diameter of 250 μm) coated by Single-Walled Carbon Nanotubes (SWCNTs), via the Electrophoresis Deposition Process (EPD). This nanostructured platform was successfully used to deposit the poly(pyrrole)/glucose oxidase film (PPy/GOx). The most important result of this biosensors was the wide linear range of concentration, ranging from 4 to100 mM (covering the hypo- and hyper-glycemia range, useful in diabetes). This extended linearity offered the possibility to measure glucose from 0.560 to 12.0 mM, with a detection limit of 50 μM (useful for hypo-glycemia disease).

Effects of single-wall carbon nanotubes in human cells of the oral cavity: Geno-cytotoxic risk

Single-wall carbon nanotubes (SWCNTs) are one of the most extensively produced carbon materials and the environmental, public and professional exposure is therefore dramatically increasing. Consequently the studies on bio-effects and safety of SWCNTs are highly needed. The goal of this study was investigate the effects in vitro of SWCNTs in cells of the oral cavity, never employed in this research field. We exposed human gingival fibroblasts to 50, 75, 100, 125, 150 μg/ml SWCNTs for 24 h and we investigated genotoxicity (Comet assay and micronucleus test), cytotoxicity, oxidative stress, as reactive oxygen species (ROS) generation, and stress response, as Heat shock protein 70 (Hsp70) expression. SWCNTs produced genotoxic effects at all doses, even if detected with different sensitiveness by the two tests, and at the two highest doses induced a strong decrease of the cell proliferation and cell survival, causing apoptosis too. Furthermore, we proved the ability of these nanomaterials to induce oxidative stress and Hsp70 expression. Finally, by inhibition of Hsp70 expression, we demonstrated that this heat shock protein conferred protection against SWCNT geno-cytotoxicity.