Plasmonic and Photothermal Effects of CuS Nanoparticles Biosynthesized from Acid Mine Drainage with Potential Drug Delivery Applications.

In this work, the plasmonic and photothermal effects of CuS nanoparticles biosynthesized from acid mine drainage (AMD) were studied. CuS were formed by delivering the H2S generated by a sulfidogenic bioreactor to an off-line system containing the AMD. The precipitates collected after contact for an hour were washed and physico-chemically characterized, showing a nanoparticle with a mean diameter of 33 nm, crystalline nature and semiconductor behavior with a direct band gap of 2.2 eV. Moreover, the CuS nanoparticles exhibited localized surface plasmonic resonance in the near infrared range, with a high absorption band centered at 973 nm of wavelength, which allowed an increase in the temperature of the surrounding media under irradiation. Finally, the cytotoxicity of the CuS nanoparticles as well as their potential use as part of drug delivery platforms were investigated.

Bio-recovery of CuS nanoparticles from the treatment of acid mine drainage with potential photocatalytic and antibacterial applications.

In the present work, CuS nanoparticles were biorecovered from a real acid mine drainage (AMD) and its photocatalytic and antibacterial activities were studied. CuS were formed by delivering biogenic H2S produced by a continuous sulfidogenic bioreactor to an off-line vessel containing the AMD. The main physico-chemical properties of CuS nanoparticles were analyzed by UV-vis spectroscopy, TEM, FE-SEM, XRD and XPS. Moreover, its photocatalytic activity on the photodegradation of organic dyes in water and its antibacterial activity against several bacterial strains were studied and compared with CuS nanoparticles synthetized from a CuSO4 aqueous solution based on the same synthesis method. CuS nanoparticles from the real AMD showed similar physico-chemical properties and photocatalytic and antibacterial activities in comparison to CuS nanoparticles formed with the copper solutions. These results open the way to recover valorous CuS nanoparticles from AMD with potential industrial applications using a metal bioremediation process based on sulfidogenic bioreactors.

Antibacterial Films of Silver Nanoparticles Embedded into Carboxymethylcellulose/Chitosan Multilayers on Nanoporous Silicon: A Layer-by-Layer Assembly Approach Comparing Dip and Spin Coating.

The design and engineering of antibacterial materials are key for preventing bacterial adherence and proliferation in biomedical and household instruments. Silver nanoparticles (AgNPs) and chitosan (CHI) are broad-spectrum antibacterial materials with different properties whose combined application is currently under optimization. This study proposes the formation of antibacterial films with AgNPs embedded in carboxymethylcellulose/chitosan multilayers by the layer-by-layer (LbL) method. The films were deposited onto nanoporous silicon (nPSi), an ideal platform for bioengineering applications due to its biocompatibility, biodegradability, and bioresorbability. We focused on two alternative multilayer deposition processes: cyclic dip coating (CDC) and cyclic spin coating (CSC). The physicochemical properties of the films were the subject of microscopic, microstructural, and surface-interface analyses. The antibacterial activity of each film was investigated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) bacteria strains as model microorganisms. According to the findings, the CDC technique produced multilayer films with higher antibacterial activity for both bacteria compared to the CSC method. Bacteria adhesion inhibition was observed from only three cycles. The developed AgNPs-multilayer composite film offers advantageous antibacterial properties for biomedical applications.

Sulfidogenic Bioreactor-Mediated Formation of ZnS Nanoparticles with Antimicrobial and Photocatalytic Activity.

The use of sulfidogenic bioreactors is a biotechnology trend to recover valuable metals such as copper and zinc as sulfide biominerals from mine-impacted waters. In the present work, ZnS nanoparticles were produced using "green" H2S gas generated by a sulfidogenic bioreactor. ZnS nanoparticles were physico-chemically characterized by UV-vis and fluorescence spectroscopy, TEM, XRD and XPS. The experimental results showed spherical-like shape nanoparticles with principal zinc-blende crystalline structure, a semiconductor character with an optical band gap around 3.73 eV, and fluorescence emission in the UV-visible range. In addition, the photocatalytic activity on the degradation of organic dyes in water, as well as bactericidal properties against several bacterial strains, were studied. ZnS nanoparticles were able to degrade methylene blue and rhodamine in water under UV radiation, and also showed high antibacterial activity against different bacterial strains including Escherichia coli and Staphylococcus aureus. The results open the way to obtain valorous ZnS nanoparticles from the use of dissimilatory reduction of sulfate using a sulfidogenic bioreactor.

Phonon Structure, Infra-Red and Raman Spectra of Li2MnO3 by First-Principles Calculations.

The layer-structured monoclinic Li2MnO3 is a key material, mainly due to its role in Li-ion batteries and as a precursor for adsorbent used in lithium recovery from aqueous solutions. In the present work, we used first-principles calculations based on density functional theory (DFT) to study the crystal structure, optical phonon frequencies, infra-red (IR), and Raman active modes and compared the results with experimental data. First, Li2MnO3 powder was synthesized by the hydrothermal method and successively characterized by XRD, TEM, FTIR, and Raman spectroscopy. Secondly, by using Local Density Approximation (LDA), we carried out a DFT study of the crystal structure and electronic properties of Li2MnO3. Finally, we calculated the vibrational properties using Density Functional Perturbation Theory (DFPT). Our results show that simulated IR and Raman spectra agree well with the observed phonon structure. Additionally, the IR and Raman theoretical spectra show similar features compared to the experimental ones. This research is useful in investigations involving the physicochemical characterization of Li2MnO3 material.

Hybrid porous silicon/green synthetized Ag microparticles as potential carries for Ag nanoparticles and drug delivery.

In the present work, the fabrication of hybrid porous silicon/green synthetized Ag microparticles was shown and the potential use as carriers for Ag nanoparticles and drug delivery was explored. Hybrid microparticles were fabricated by incorporating green synthetized Ag nanoparticles into porous silicon matrix. The main physicochemical characteristics of the hybrid systems were studied by several techniques including UV-vis spectroscopy, TEM, SEM, XRD and XPS. The toxicology of these hybrid systems was investigated by cell viability, MTT, and comet assays. In addition, the possibility to aggregate different drug to use as drug delivery system was demonstrated by using florfenicol as drug model, due to its importance in salmon industry. The experimental results showed the potential to use these hybrid systems as carries for drug delivery in salmon industry.

Use of nPSi-ßCD Composite Microparticles for the Controlled Release of Caffeic Acid and Pinocembrin, Two Main Polyphenolic Compounds Found in a Chilean Propolis.

Propolis is widely recognized for its various therapeutic properties. These are attributed to its rich composition in polyphenols, which exhibit multiple biological properties (e.g., antioxidant, anti-inflammatory, anti-angiogenic). Despite its multiple benefits, oral administration of polyphenols results in low bioavailability at the action site. An alternative to face this problem is the use of biomaterials at nano-micro scale due to its high versatility as carriers and delivery systems of various drugs and biomolecules. The aim of this work is to determine if nPSi-ßCD microparticles are a suitable material for the load and controlled release of caffeic acid (CA) and pinocembrin (Pin), two of the main components of a Chilean propolis with anti-atherogenic and anti-angiogenic activity. Polyphenols and nPSi-ßCD microparticles cytocompatibility studies were carried out with human umbilical vein endothelial cells (HUVECs). Results from physicochemical characterization demonstrated nPSi-ßCD microparticles successfully retained and controlled release CA and Pin. Furthermore, nPSi-ßCD microparticles presented cytocompatibility with HUVECs culture at concentrations of 0.25 mg/mL. These results suggest that nPSi-ßCD microparticles could safely be used as an alternate oral delivery system to improve controlled release and bioavailability of CA or Pin-and eventually other polyphenols-thus enhancing its therapeutic effect for the treatment of different diseases.

Assessing the effectiveness of green synthetized silver nanoparticles with Cryptocarya alba extracts for remotion of the organic pollutant methylene blue dye.

In the present work, silver nanoparticles (AgNPs) synthetized with Cryptocarya alba (Peumo) leaf extract were studied. The fabrication method was fast, low cost, and eco-friendly, and the final properties of AgNPs were determined by experimental parameters, such as AgNO3 and Peumo extract concentrations used. Setting suitable experimental conditions, crystalline AgNPs with apparent spherical forms and average diameter around 3.5 nm were obtained. In addition, the capability of synthesized Peumo-AgNPs to remove methylene blue dye (MB) in aqueous solution as well as their catalytic effectiveness was also investigated. The results showed that green synthesized AgNPs can remove fast and effectively the MB dye from aqueous medium by itself, but better results were found acting like catalyst by using sodium borohydride (NaBH4) in the reaction. In addition, this green nanomaterial can be recycling several times maintaining initial properties for removal of MB. Thus, AgNPs synthetized with Peumo leaf extracts could be an excellent catalyst candidate for degradation of blue methylene dye in chemical industries.

Formation of antireflection Zn/ZnO core-shell nano-pyramidal arrays by O2+ ion bombardment of Zn surfaces.

ZnO is probably one of the most studied oxides since ZnO nanostructures are a very rich family of nanomaterials with a broad variety of technological applications. Although several chemical techniques offer the possibility to obtain such ZnO nanostructures, here we show that the controlled modification of the zinc surface by low-energy O2+ bombardment leads to the formation of core-shell Zn/ZnO nano-pyramidal arrays that suppress the reflection of light decreasing the reflectivity below 6% in the wavelength range of 300-900 nm. This controlled and scalable protocol opens the door to a broad range of possibilities for the use of ion bombardment to produce surface modifications for technological applications in the field of photoelectric devices and solar cells.

Nanostructured copper/porous silicon hybrid systems as efficient sound-emitting devices.

In the present work, the photo-acoustic emission from nanostructured copper/porous silicon hybrid systems was studied. Copper nanoparticles were grown by photo-assisted electroless deposition on crystalline silicon and nanostructured porous silicon (nanoPS). Both the optical and photo-acoustic responses from these systems were determined. The experimental results show a remarkable increase in the photo-acoustic intensity when copper nanoparticles are incorporated to the porous structure. The results thus suggest that the Cu/nanoPS hybrid systems are suitable candidates for several applications in the field of thermoplasmonics, including the development of sound-emitting devices of great efficiency.

Laser fabrication of porous silicon-based platforms for cell culturing.

In this study, we explore the selective culturing of human mesenchymal stem cells (hMSCs) on Si-based diffractive platforms. We demonstrate a single-step and flexible method for producing platforms on nanostructured porous silicon (nanoPS) based on the use of single pulses of an excimer laser to expose phase masks. The resulting patterns are typically 1D patterns formed by fringes or 2D patterns formed by circles. They are formed by alternate regions of almost unmodified nanoPS and regions where the nanoPS surface has melted and transformed into Si nanoparticles. The patterns are produced in relatively large areas (a few square millimeters) and can have a wide range of periodicities and aspect ratios. Direct binding, that is, with no previous functionalization of the pattern, alignment, and active polarization of hMSCs are explored. The results show the preferential direct binding of the hMSCs along the transformed regions whenever their width compares with the dimensions of the cells and they escape from patterns for smaller widths suggesting that the selectivity can be tailored through the pattern period. © 2013 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2013.

Laser fabrication of porous silicon-based platforms for cell culturing.

In this study, we explore the selective culturing of human mesenchymal stem cells (hMSCs) on Si-based diffractive platforms. We demonstrate a single-step and flexible method for producing platforms on nanostructured porous silicon (nanoPS) based on the use of single pulses of an excimer laser to expose phase masks. The resulting patterns are typically 1D patterns formed by fringes or 2D patterns formed by circles. They are formed by alternate regions of almost unmodified nanoPS and regions where the nanoPS surface has melted and transformed into Si nanoparticles. The patterns are produced in relatively large areas (a few square millimeters) and can have a wide range of periodicities and aspect ratios. Direct binding, that is, with no previous functionalization of the pattern, alignment, and active polarization of hMSCs are explored. The results show the preferential direct binding of the hMSCs along the transformed regions whenever their width compares with the dimensions of the cells and they escape from patterns for smaller widths suggesting that the selectivity can be tailored through the pattern period.

Highly flexible method for the fabrication of photonic crystal slabs based on the selective formation of porous silicon.

A novel fabrication method of Si photonic slabs based on the selective formation of porous silicon is reported. Free-standing square lattices of cylindrical air holes embedded in a Si matrix can be achieved by proton beam irradiation followed by electrochemical etching of Si wafers. The photonic band structures of these slabs show several gaps for the two symmetry directions for reflection through the z-plane. The flexibility of the fabrication method for tuning the frequency range of the gaps over the near- and mid-infrared ranges is demonstrated. This tunability can be achieved by simply adjusting the main parameters in the fabrication process such as the proton beam line spacing, proton fluence, or anodization current density. Thus, the reported method opens a promising route towards the fabrication of Si-based photonic slabs, with high flexibility and compatible with the current microelectronics industry.

Silicon-based photonic crystals fabricated using proton beam writing combined with electrochemical etching method.

A method for fabrication of three-dimensional (3D) silicon nanostructures based on selective formation of porous silicon using ion beam irradiation of bulk p-type silicon followed by electrochemical etching is shown. It opens a route towards the fabrication of two-dimensional (2D) and 3D silicon-based photonic crystals with high flexibility and industrial compatibility. In this work, we present the fabrication of 2D photonic lattice and photonic slab structures and propose a process for the fabrication of 3D woodpile photonic crystals based on this approach. Simulated results of photonic band structures for the fabricated 2D photonic crystals show the presence of TE or TM gap in mid-infrared range.