Heavy Metal Detection and Removal by Composite Carbon Quantum Dots/Ionomer Membranes.

The combination of ion exchange membranes with carbon quantum dots (CQDs) is a promising field that could lead to significant advances in water treatment. Composite membranes formed by sulfonated poly(ether ether ketone) (SPEEK) with embedded CQDs were used for the detection and removal of heavy metal ions, such as lead and cadmium, from water. SPEEK is responsible for the capture of heavy metals based on the cation exchange mechanism, while CQDs detect their contamination by exhibiting changes in fluorescence. Water-insoluble "red" carbon quantum dots (rCQDs) were synthesized from p-phenylenediamine so that their photoluminescence was shifted from that of the polymer matrix. CQDs and the composites were characterized by several techniques: FTIR, Raman, UV/VIS, photoluminescence, XPS spectroscopies, and AFM microscopy. The heavy metal ion concentration was analyzed by inductively coupled plasma-optical emission spectroscopy (ICP-OES). The concentration ranges were 10.8-0.1 mM for Pb2+ and 10.0-0.27 mM for Cd2+. SPEEK/rCQDs showed a more pronounced turn-off effect for lead. The composite achieved 100% removal efficiency for lead and cadmium when the concentration was below a half of the ion exchange capacity of SPEEK. The regeneration of membranes in 1 M NaCl was also studied. A second order law was effective to describe the kinetics of the process.

Three-Dimensional Printed Filters Based on Poly(ethylene glycol) Diacrylate Hydrogels Doped with Silver Nanoparticles for Removing Hg(II) Ions from Water.

Nowadays, due to water pollution, more and more living beings are exposed to dangerous compounds, which can lead to them contracting diseases. The removal of contaminants (including heavy metals) from water is, therefore, a necessary aspect to guarantee the well-being of living beings. Among the most used techniques, the employment of adsorbent materials is certainly advantageous, as they are easy to synthesize and are cheap. In this work, poly(ethylene glycol) diacrylate (PEGDA) hydrogels doped with silver nanoparticles (AgNPs) for removing Hg(II) ions from water are presented. AgNPs were embedded in PEGDA-based matrices by using a photo-polymerizable solution. By exploiting a custom-made 3D printer, the filters were synthesized. The kinetics of interaction was studied, revealing that the adsorption equilibrium is achieved in 8 h. Subsequently, the adsorption isotherms of PEGDA doped with AgNPs towards Hg(II) ions were studied at different temperatures (4 °C, 25 °C, and 50 °C). In all cases, the best isotherm model was the Langmuir one (revealing that the chemisorption is the driving process and the most favorable one), with maximum adsorption capacities equal to 0.55, 0.57, and 0.61 mg/g, respectively. Finally, the removal efficiency was evaluated for the three temperatures, obtaining for 4 °C, 25 °C, and 50 °C the values 94%, 94%, and 86%, respectively.

Photocatalytic Degradation of Organic Pollutants-Nile Blue, Methylene Blue, and Bentazon Herbicide-Using NiO-ZnO Nanocomposite.

Water pollution poses a significant threat to both human health and ecosystem integrity. Chemical pollutants such as dyes and pesticides affect the water quality and endanger aquatic life. Among the methods for water purification from organic pollutants, photodegradation is certainly a valid technique to decrease such contaminants. In this work, pristine NiO, ZnO, and NiO-ZnO photocatalysts were synthesized by the homogeneous co-precipitation method. X-ray diffraction confirms the formation of a photocatalyst consisting of ZnO (Hexagonal) and NiO (Cubic) structures. The crystalline size was calculated by the Scherrer formula, which is 19 nm for the NiO-ZnO photocatalyst. The band gap measurements of the prepared samples were obtained using the Tauc Plot, equation which is 2.93 eV, 3.35 eV and 2.63 eV for NiO, ZnO, and NiO-ZnO photocatalysts, respectively. The photocatalytic performance of NiO-ZnO nanocomposite was evaluated through the degradation of Methylene Blue and Nile Blue dyes under sunlight, and Bentazon herbicide under a UV light. Photocatalyst degradation efficiency was 95% and 97% for Methylene Blue and Nile Blue in 220 min under sunlight while a degradation of 70% for Bentazon after 100 min under UV light source was found.

Functionalized Gels for Environmental Applications.

A gel is a type of material that exhibits a semi-solid, jelly-like state, characterized by a three-dimensional network of interconnected particles or molecules dispersed within a liquid or solid medium [...].

Poly(ethylene glycol) Diacrylate Hydrogel with Silver Nanoclusters for Water Pb(II) Ions Filtering.

Poly(ethylene glycol) diacrylate (PEGDA) hydrogels modified with luminescent silver nanoclusters (AgNCs) are synthesized by a photo-crosslinking process. The hybrid material thus obtained is employed to filter Pb(II) polluted water. Under the best conditions, the nanocomposite is able to remove up to 80-90% of lead contaminant, depending on the filter composition. The experimental results indicate that the adsorption process of Pb(II) onto the modified filter can be well modeled using the Freundlich isotherm, thus revealing that the chemisorption is the driving process of Pb(II) adsorption. In addition, the parameter n in the Freundlich model suggests that the adsorption process of Pb(II) ions in the modified hydrogel is favored. Based on the obtained remarkable contaminant uptake capacity and the overall low cost, this hybrid system appears to be a promising sorbent material for the removal of Pb(II) ions from aqueous media.

Colorimetric Detection of Chromium(VI) Ions in Water Using Unfolded-Fullerene Carbon Nanoparticles.

Water pollution caused by hexavalent chromium (Cr(VI)) ions represents a serious hazard for human health due to the high systemic toxicity and carcinogenic nature of this metal species. The optical sensing of Cr(VI) through specifically engineered nanomaterials has recently emerged as a versatile strategy for the application to easy-to-use and cheap monitoring devices. In this study, a one-pot oxidative method was developed for the cage opening of C60 fullerene and the synthesis of stable suspensions of N-doped carbon dots in water-THF solutions (N-CDs-W-THF). The N-CDs-W-THF selectively showed variations of optical absorbance in the presence of Cr(VI) ions in water through the arising of a distinct absorption band peaking at 550 nm, i.e., in the transparency region of pristine material. Absorbance increased linearly, with the ion concentration in the range 1-100 µM, thus enabling visual and ratiometric determination with a limit of detection (LOD) of 300 nM. Selectivity and possible interference effects were tested over the 11 other most common heavy metal ions. The sensing process occurred without the need for any other reactant or treatment at neutral pH and within 1 min after the addition of chromium ions, both in deionized and in real water samples.

Biocompatible Silver Nanoparticles: Study of the Chemical and Molecular Structure, and the Ability to Interact with Cadmium and Arsenic in Water and Biological Properties.

In the field of research for designing and preparing innovative nanostructured systems, these systems are able to reveal the presence of heavy metals in water samples, and can efficiently and selectively interact with them, allowing for future applications in the field of water remediation. We investigated the electronic and molecular structure, as well as the morphology, of silver nanoparticles stabilized by mixed biocompatible ligands (the amino acid L-cysteine and the organic molecule citrate) in the presence of cadmium and arsenic ions. The molecular, electronic, and local structure at the ligands/silver nanoparticles interface was probed by the complementary synchrotron radiation-induced techniques (SR-XPS, NEXAFS and XAS). The optical absorption (in the UV-Vis range) of the nanosystem was investigated in the presence of Cd(II) and As(III) and the observed behavior suggested a selective interaction with cadmium. In addition, the toxicological profile of the innovative nanosystem was assessed in vitro using a human epithelial cell line HEK293T. We analyzed the viability of the cells treated with silver nanoparticles, as well as the activation of antioxidant response.

Detection of Heavy Metals in Water Using Graphene Oxide Quantum Dots: An Experimental and Theoretical Study.

In this work, we investigate by ab initio calculations and optical experiments the sensitivity of graphene quantum dots in their use as devices to measure the presence, and concentration, of heavy metals in water. We demonstrate that the quenching or enhancement in the optical response (absorption, emission) depends on the metallic ion considered. In particular, two cases of opposite behaviour are considered in detail: Cd2+, where we observe an increase in the emission optical response for increasing concentration, and Pb2+ whose emission spectra, vice versa, are quenched along the concentration rise. The experimental trends reported comply nicely with the different hydration patterns suggested by the models that are also capable of reproducing the minor quenching/enhancing effects observed in other ions. We envisage that quantum dots of graphene may be routinely used as cheap detectors to measure the degree of poisoning ions in water.

Top-Down N-Doped Carbon Quantum Dots for Multiple Purposes: Heavy Metal Detection and Intracellular Fluorescence.

In the present study, we successfully synthesized N-doped carbon quantum dots (N-CQDs) using a top-down approach, i.e., hydroxyl radical opening of fullerene with hydrogen peroxide, in basic ambient using ammonia for two different reaction times. The ensuing characterization via dynamic light scattering, SEM, and IR spectroscopy revealed a size control that was dependent on the reaction time, as well as a more pronounced -NH2 functionalization. The N-CQDs were probed for metal ion detection in aqueous solutions and during bioimaging and displayed a Cr3+ and Cu2+ selectivity shift at a higher degree of -NH2 functionalization, as well as HEK-293 cell nuclei marking.

Intrinsically Conductive Polymers for Striated Cardiac Muscle Repair.

One of the most important features of striated cardiac muscle is the excitability that turns on the excitation-contraction coupling cycle, resulting in the heart blood pumping function. The function of the heart pump may be impaired by events such as myocardial infarction, the consequence of coronary artery thrombosis due to blood clots or plaques. This results in the death of billions of cardiomyocytes, the formation of scar tissue, and consequently impaired contractility. A whole heart transplant remains the gold standard so far and the current pharmacological approaches tend to stop further myocardium deterioration, but this is not a long-term solution. Electrically conductive, scaffold-based cardiac tissue engineering provides a promising solution to repair the injured myocardium. The non-conductive component of the scaffold provides a biocompatible microenvironment to the cultured cells while the conductive component improves intercellular coupling as well as electrical signal propagation through the scar tissue when implanted at the infarcted site. The in vivo electrical coupling of the cells leads to a better regeneration of the infarcted myocardium, reducing arrhythmias, QRS/QT intervals, and scar size and promoting cardiac cell maturation. This review presents the emerging applications of intrinsically conductive polymers in cardiac tissue engineering to repair post-ischemic myocardial insult.

Extrinsically Conductive Nanomaterials for Cardiac Tissue Engineering Applications.

Myocardial infarction (MI) is the consequence of coronary artery thrombosis resulting in ischemia and necrosis of the myocardium. As a result, billions of contractile cardiomyocytes are lost with poor innate regeneration capability. This degenerated tissue is replaced by collagen-rich fibrotic scar tissue as the usual body response to quickly repair the injury. The non-conductive nature of this tissue results in arrhythmias and asynchronous beating leading to total heart failure in the long run due to ventricular remodelling. Traditional pharmacological and assistive device approaches have failed to meet the utmost need for tissue regeneration to repair MI injuries. Engineered heart tissues (EHTs) seem promising alternatives, but their non-conductive nature could not resolve problems such as arrhythmias and asynchronous beating for long term in-vivo applications. The ability of nanotechnology to mimic the nano-bioarchitecture of the extracellular matrix and the potential of cardiac tissue engineering to engineer heart-like tissues makes it a unique combination to develop conductive constructs. Biomaterials blended with conductive nanomaterials could yield conductive constructs (referred to as extrinsically conductive). These cell-laden conductive constructs can alleviate cardiac functions when implanted in-vivo. A succinct review of the most promising applications of nanomaterials in cardiac tissue engineering to repair MI injuries is presented with a focus on extrinsically conductive nanomaterials.

Metal Nanostructures for Environmental Pollutant Detection Based on Fluorescence.

Heavy metal ions and pesticides are extremely dangerous for human health and environment and an accurate detection is an essential step to monitor their levels in water. The standard and most used methods for detecting these pollutants are sophisticated and expensive analytical techniques. However, recent technological advancements have allowed the development of alternative techniques based on optical properties of noble metal nanomaterials, which provide many advantages such as ultrasensitive detection, fast turnover, simple protocols, in situ sampling, on-site capability and reduced cost. This paper provides a review of the most common photo-physical effects impact on the fluorescence of metal nanomaterials and how these processes can be exploited for the detection of pollutant species. The final aim is to provide readers with an updated guide on fluorescent metallic nano-systems used as optical sensors of heavy metal ions and pesticides in water.

Bifunctionalized Silver Nanoparticles as Hg2+ Plasmonic Sensor in Water: Synthesis, Characterizations, and Ecosafety.

In this work, hydrophilic silver nanoparticles (AgNPs), bifunctionalized with citrate (Cit) and L-cysteine (L-cys), were synthesized. The typical local surface plasmon resonance (LSPR) at λ max = 400 nm together with Dynamic Light Scattering (DLS) measurements (<2RH> = 8 ± 1 nm) and TEM studies (Ø = 5 ± 2 nm) confirmed the system nanodimension and the stability in water. Molecular and electronic structures of AgNPs were investigated by FTIR, SR-XPS, and NEXAFS techniques. We tested the system as plasmonic sensor in water with 16 different metal ions, finding sensitivity to Hg2+ in the range 1-10 ppm. After this first screening, the molecular and electronic structure of the AgNPs-Hg2+ conjugated system was deeply investigated by SR-XPS. Moreover, in view of AgNPs application as sensors in real water systems, environmental safety assessment (ecosafety) was performed by using standardized ecotoxicity bioassay as algal growth inhibition tests (OECD 201, ISO 10253:2006), coupled with determination of Ag+ release from the nanoparticles in fresh and marine aqueous exposure media, by means of ICP-MS. These latest studies confirmed low toxicity and low Ag+ release. Therefore, these ecosafe AgNPs demonstrate a great potential in selective detection of environmental Hg2+, which may attract a great interest for several biological research fields.

Polystyrene Opals Responsive to Methanol Vapors.

Photonic crystals (PCs) show reflectance spectra depending on the geometrical structure of the crystal, the refractive index (neff), and the light incident angle, according to the Bragg-Snell law. Three-dimensional photonic crystals (3D-PCs) composed of polymeric sub-micrometer spheres, are arranged in an ordered face cubic centered (fcc) lattice and are good candidates for vapor sensing by exploiting changes of the reflectance spectra. We synthesized high quality polystyrene (PS) 3D-PCs, commonly called opals, with a filling factor f near to the ideal value of 0.74 and tested their optical response in the presence of different concentrations of methanol (MeOH) vapor. When methanol was present in the voids of the photonic crystals, the reflectance spectra experienced energy shifts. The concentration of methyl alcohol vapor can be inferred, due to a linear dependence of the reflectance band maximum wavelength as a function of the vapor concentration. We tested the reversibility of the process and the time stability of the system. A limit of detection (LOD) equal to 5% (v/v0), where v was the volume of methanol and v0 was the total volume of the solution (methanol and water), was estimated. A model related to capillary condensation for intermediate and high methanol concentrations was discussed. Moreover, a swelling process of the PS spheres was invoked to fully understand the unexpected energy shift found for very high methanol content.

Plasmonic Sensor Based on Interaction between Silver Nanoparticles and Ni2+ or Co2+ in Water.

Silver nanoparticles capped with 3-mercapto-1propanesulfonic acid sodium salt (AgNPs-3MPS), able to interact with Ni2+ or Co2+, have been prepared to detect these heavy metal ions in water. This system works as an optical sensor and it is based on the change of the intensity and shape of optical absorption peak due to the surface plasmon resonance (SPR) when the AgNPs-3MPS are in presence of metals ions in a water solution. We obtain a specific sensitivity to Ni2+ and Co2+ up to 500 ppb (part per billion). For a concentration of 1 ppm (part per million), the change in the optical absorption is strong enough to produce a colorimetric effect on the solution, easily visible with the naked eye. In addition to the UV-VIS characterizations, morphological and dimensional studies were carried out by transmission electron microscopy (TEM). Moreover, the systems were investigated by means of dynamic light scattering (DLS), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), and high-resolution X-ray photoelectron spectroscopy (HR-XPS). On the basis of the results, the mechanism responsible for the AgNPs-3MPS interaction with Ni2+ and Co2+ (in the range of 0.5⁻2.0 ppm) looks like based on the coordination compounds formation.

Discriminating between Different Heavy Metal Ions with Fullerene-Derived Nanoparticles.

A novel type of graphene-like nanoparticle, synthesized by oxidation and unfolding of C60 buckminsterfullerene fullerene, showed multiple and reproducible sensitivity to Cu2+, Pb2+, Cd2+, and As(III) through different degrees of fluorescence quenching or, in the case of Cd2+, through a remarkable fluorescence enhancement. Most importantly, only for Cu2+ and Pb2+, the fluorescence intensity variations came with distinct modifications of the optical absorption spectrum. Time-resolved fluorescence study confirmed that the common origin of these diverse behaviors lies in complexation of the metal ions by fullerene-derived carbon layers, even though further studies are required for a complete explanation of the involved processes. Nonetheless, the different response of fluorescence and optical absorbance towards distinct cationic species makes it possible to discriminate between the presence of Cu2+, Pb2+, Cd2+, and As(III), through two simple optical measurements. To this end, the use of a three-dimensional calibration plot is discussed. This property makes fullerene-derived nanoparticles a promising material in view of the implementation of a selective, colorimetric/fluorescent detection system.

Sensitivity to Heavy-Metal Ions of Unfolded Fullerene Quantum Dots.

A novel type of graphene-like quantum dots, synthesized by oxidation and cage-opening of C60 buckminsterfullerene, has been studied as a fluorescent and absorptive probe for heavy-metal ions. The lattice structure of such unfolded fullerene quantum dots (UFQDs) is distinct from that of graphene since it includes both carbon hexagons and pentagons. The basic optical properties, however, are similar to those of regular graphene oxide quantum dots. On the other hand, UFQDs behave quite differently in the presence of heavy-metal ions, in that multiple sensitivity to Cu2+, Pb2+ and As(III) was observed through comparable quenching of the fluorescent emission and different variations of the transmittance spectrum. By dynamic light scattering measurements and transmission electron microscope (TEM) images we confirmed, for the first time in metal sensing, that this response is due to multiple complexation and subsequent aggregation of UFQDs. Nonetheless, the explanation of the distinct behaviour of transmittance in the presence of As(III) and the formation of precipitate with Pb2+ require further studies. These differences, however, also make it possible to discriminate between the three metal ions in view of the implementation of a selective multiple sensor.

Scaffold-in-Scaffold Potential to Induce Growth and Differentiation of Cardiac Progenitor Cells.

The design of reliable biocompatible and biodegradable scaffolds remains one of the most important challenges for tissue engineering. In fact, properly designed scaffolds must display an adequate and interconnected porosity to facilitate cell spreading and colonization of the inner layers, and must release physical signals concurring to modulate cell function to ultimately drive cell fate. In this study, a combination of optimal mechanical and biochemical properties has been considered to design a one-component three-dimensional (3D) multitextured hydrogel scaffold to favor cell-scaffold interactions. A polyethylene glycol diacrylate woodpile (PEGDa-Wp) structure of the order of 100 µm has been manufactured using a microstereolithography process. Subsequently, the PEGDa-Wp has been embedded in a PEGDa hydrogel to obtain a 3D scaffold-in-scaffold (3D-SS) system. Finally, the 3D-SS capability to address cell fate has been assessed using human Lin- Sca-1+ cardiac progenitor cells (hCPCs). Results have shown that a multitextured 3D scaffold represents a favorable microenvironment to promote hCPC differentiation and orientation. In fact, while cultured on 3D-SS, hCPCs adopt an ordered 3D spatial orientation and activate the expression of structural proteins, such as the α-sarcomeric actinin, a specific marker of the cardiomyocyte phenotype, and connexin 43, the principal gap junction protein of the heart. Although preliminary, this study demonstrates that complex multitextured scaffolds closely mimicking the extracellular matrix structure and function are efficient in driving progenitor cell fate. A leap forward will be determined by the use of advanced 3D printing technologies that will improve multitextured scaffold manufacturing and their biological efficiency.

The Diatom Staurosirella pinnata for Photoactive Material Production.

A native isolate of the colonial benthic diatom Staurosirella pinnata was cultivated for biosilica production. The silicified cell walls (frustules) were used as a source of homogeneous and structurally predictable porous biosilica for dye trapping and random laser applications. This was coupled with the extraction of lipids from biomass showing potential to fabricate photoactive composite materials sustainably. The strain was selected for its ease of growth in culture and harvesting. Biosilica and lipids were obtained at the end of growth in indoor photobioreactors. Frustules were structurally characterized microscopically and their chemistry analyzed with Fourier Transform Infrared Spectroscopy. Frustule capacity of binding laser dyes was evaluated on a set of frustules/Rhodamine B (Rho B) solutions and with respect to silicon dioxide and diatomite by Fluorescence Spectroscopy demonstrating a high affinity for the organic dye. The effect of dye trapping property in conveying Rho B emission to frustules, with enhancement of scattering events, was analyzed on Rho B doped polyacrylamide gels filled or not with frustules. Amplified spontaneous emission was recorded at increasing pump power indicating the onset of a random laser effect in frustule filled gels at lower power threshold compared to unfilled matrices.

Hydrophilic silver nanoparticles with tunable optical properties: application for the detection of heavy metals in water.

Due their excellent chemo-physical properties and ability to exhibit surface plasmon resonance, silver nanoparticles (AgNPs) have become a material of choice in various applications, such as nanosensors, electronic devices, nanobiotechnology and nanomedicine. In particular, from the environmental monitoring perspective, sensors based on silver nanoparticles are in great demand because of their antibacterial and inexpensive synthetic method. In the present study, we synthesized AgNPs in water phase using silver nitrate as precursor molecules, hydrophilic thiol (3-mercapto-1-propanesulfonic acid sodium salt, 3MPS) and sodium borohydride as capping and reducing agents, respectively. The AgNPs were characterized using techniques such as surface plasmon resonance (SPR) spectroscopy, dynamic light scattering (DLS), zeta potential (ζ-potential) measurements and scanning tunneling microscopy (STM). Further, to demonstrate the environmental application of our AgNPs, we also applied them for heavy metal sensing by detecting visible color modification due to SPR spectral changes. We found that these negatively charged AgNPs show good response to nickel (II) and presented good sensibility properties for the detection of low amount of ions in water in the working range of 1.0-0.1 ppm.