Synthesis and Anti-Melanoma Activity of L-Cysteine-Coated Iron Oxide Nanoparticles Loaded with Doxorubicin.

In this study, we report on the synthesis of L-Cysteine (L-Cys)-coated magnetic iron oxide nanoparticles (NPs) loaded with doxorubicin (Dox). The Fe3O4-L-Cys-Dox NPs were extensively characterized for their compositional and morpho-structural features using EDS, SAED, XRD, FTIR and TEM. XPS, MÓ§ssbauer spectroscopy and SQUID measurements were also performed to determine the electronic and magnetic properties of the Fe3O4-L-Cys-Dox nanoparticles. Moreover, by means of a FO-SPR sensor, we evidenced and confirmed the binding of Dox to L-Cys. Biological tests on mouse (B16F10) and human (A375) metastatic melanoma cells evidenced the internalization of magnetic nanoparticles delivering Dox. Half maximum inhibitory concentration IC50 values of Fe3O4-L-Cys-Dox were determined for both cell lines: 4.26 µg/mL for A375 and 2.74 µg/mL for B16F10, as compared to 60.74 and 98.75 µg/mL, respectively, for unloaded controls. Incubation of cells with Fe3O4-L-Cys-Dox modulated MAPK signaling pathway activity 3 h post-treatment and produced cell cycle arrest and increased apoptosis by 48 h. We show that within the first 2 h of incubation in physiological (pH = 7.4) media, ~10-15 µM Dox/h was released from a 200 µg/mL Fe3O4-L-Cys-Dox solution, as compared to double upon incubation in citrate solution (pH = 3), which resembles acidic environment conditions. Our results highlight the potential of Fe3O4-L-Cys-Dox NPs as efficient drug delivery vehicles in melanoma therapy.

Shaping in the Third Direction: Self-Assembly of Convex Colloidal Photonic Crystals on an Optical Fiber Tip by Hanging Drop Method.

High-quality convex colloidal photonic crystals can be grown on the tip of an optical fiber by self-assembly using the hanging drop method. They are convex-shaped, produce the diffraction of reflecting light with high efficiency (blazing colors), and have a high curvature. The convex colloidal crystals are easily detachable and, as free-standing objects, they are mechanically robust, allowing their manipulation and use as convex reflective diffraction devices in imaging spectrometers. Currently, the same characteristics are obtained by using gratings-based structures. The optical fiber/colloidal crystal interface is disordered; thus, no light diffraction can be registered. The ordering at this interface was highly increased by forming a polystyrene spacer on the optical fiber tip, which served as a self-assembly substrate for silica colloid, as a mechanical bond between the fiber and the crystal, and as a filler reservoir for an inverse-opal synthesis. The silica opal-like grown on the optical fiber tip can be transformed into a high-quality polystyrene (blazing colors) inverse-opal by using the polystyrene spacer as a filler. We found that the colloidal crystal axisymmetric self-assembles onto the optical fiber tip only if a maximum volume of the colloid drop is settled on a flat end of the polystyrene spacer.

Cadmium Ions' Trace-Level Detection Using a Portable Fiber Optic-Surface Plasmon Resonance Sensor.

Environmental pollution with cadmium (Cd) is a major concern worldwide, with prolonged exposure to this toxic heavy metal causing serious health problems, such as kidney damage, cancer, or cardiovascular diseases, only to mention a few. Herein, a gold-coated reflection-type fiber optic--surface plasmon resonance (Au-coated FO-SPR) sensor is manufactured and functionalized with (i) bovine serum albumin (BSA), (ii) chitosan, and (iii) polyaniline (PANI), respectively, for the sensitive detection of cadmium ions (Cd2+) in water. Then, the three sensor functionalization strategies are evaluated and compared one at a time. Out of these strategies, the BSA-functionalized FO-SPR sensor is found to be highly sensitive, exhibiting a limit of detection (LOD) for Cd2+ detection at nM level. Moreover, the presence of Cd2+ on the FO-SPR sensor surface was confirmed by the X-ray photoelectron spectroscopy (XPS) technique and also quantified consecutively for all the above-mentioned functionalization strategies. Hence, the BSA-functionalized FO-SPR sensor is sensitive, provides a rapid detection time, and is cheap and portable, with potential applicability for monitoring trace-level amounts of Cd within environmental or potable water.

Shaping in the Third Direction; Fabrication of Hemispherical Micro-Concavity Array by Using Large Size Polystyrene Spheres as Template for Direct Self-Assembly of Small Size Silica Spheres.

Silica and polystyrene spheres with a small size ratio (r = 0.005) form by sequential hanging drop self-assembly, a binary colloidal crystal through which calcination transforms in a silica-ordered concavity array. These arrays are capable of light Bragg diffraction and shape dependent optical phenomena, and they can be transformed into inverse-opal structures. Hierarchical 2D and 3D super-structures with ordered concavities as structural units were fabricated in this study.

Shaping in the Third Direction; Synthesis of Patterned Colloidal Crystals by Polyester Fabric-Guided Self-Assembly.

A polyester fabric with rectangular openings was used as a sacrificial template for the guiding of a sub-micron sphere (polystyrene (PS) and silica) aqueous colloid self-assembly process during evaporation as a patterned colloidal crystal (PCC). This simple process is also a robust one, being less sensitive to external parameters (ambient pressure, temperature, humidity, vibrations). The most interesting feature of the concave-shape-pattern unit cell (350 µm × 400 µm × 3 µm) of this crystal is the presence of triangular prisms at its border, each prism having a one-dimensional sphere array at its top edge. The high-quality ordered single layer found inside of each unit cell presents the super-prism effect and left-handed behavior. Wider yet elongated deposits with ordered walls and disordered top surfaces were formed under the fabric knots. Rectangular patterning was obtained even for 20 µm PS spheres. Polyester fabrics with other opening geometries and sizes (~300-1000 µm) or with higher fiber elasticity also allowed the formation of similar PCCs, some having curved prismatic walls. A higher colloid concentration (10-20%) induces the formation of thicker walls with fiber-negative replica morphology. Additionally, thick-wall PCCs (~100 µm) with semi-cylindrical morphology were obtained using SiO2 sub-microspheres and a wavy fabric. The colloidal pattern was used as a lithographic mask for natural lithography and as a template for the synthesis of triangular-prism-shaped inverted opals.

Sensitive pH Monitoring Using a Polyaniline-Functionalized Fiber Optic-Surface Plasmon Resonance Detector.

In this work, we report results on the fabrication and characterization of a surface plasmon resonance (SPR) pH sensor using platinum (Pt) and polyaniline (PANI) layers successively coated over an unclad core of an optical fiber (FO). The plasmonic thin Pt layer was deposited using a magnetron sputtering technique, while the pH-sensitive PANI layer was synthesized using an electroless polymerization method. Moreover, the formation of PANI film was confirmed by X-ray photoelectron spectroscopy (XPS) technique and its surface morphology was investigated using scanning electron microscopy (SEM). It was found that the PANI/Pt-coated FO-SPR pH sensor exhibits a fast and linear response in either acid or alkali solutions (pH operational range: 1 to 14). The proposed FO-SPR sensor could be used for biomedical applications, environmental monitoring or any remote, real-time on-site measurements.

A polyaniline/platinum coated fiber optic surface plasmon resonance sensor for picomolar detection of 4-nitrophenol.

The paper reports for the first time an innovative polyaniline (PANI)/platinum (Pt)-coated fiber optic-surface plasmon resonance (FO-SPR) sensor used for highly-sensitive 4-nitrophenol (4-NP) pollutant detection. The Pt thin film was coated over an unclad core of an optical fiber (FO) using a DC magnetron sputtering technique, while the 4-NP responsive PANI layer was synthetized using a cost-effective electroless polymerization method. The presence of the electrolessly-grown PANI on the Pt-coated FO was observed by field-emission scanning electron microscopy and subsequently evidenced by energy dispersive X-ray analysis. These FO-SPR sensors with a demonstrated bulk sensitivity of 1515 nm/RIU were then employed for 4-NP sensing, exhibiting an excellent limit-of-detection (LOD) in the low picomolar range (0.34 pM). The proposed sensor's configuration has many other advantages, such as low-cost production, small size, immunity to electromagnetic interferences, remote sensing capability, and moreover, can be operated as a "stand-alone device", making it thus well-suited for applications such as "on-site" screening of extremely low-level trace pollutants.

Nanoscale patterning of gold-coated optical fibers for improved plasmonic sensing.

Merging surface plasmon resonance (SPR) to fiber optic (FO) technology has brought remarkable achievements in the field by offering attractive advantages over the conventional prism-based SPR platforms, such as simplicity, cost-effectiveness and miniaturization. However, the performance of the existing FO-SPR instruments mainly depends on the device surface condition and in particular on the structural aspect of the thin gold (Au) plasmonic film deposited on the FO substrate. In this work, a simple cost-effective colloidal lithography technique (CLT) was adapted and applied for the first time to the micrometer-sized FO substrate, to design end reflection-type FO-SPR sensors with periodic arrays of Au triangularly-shaped nanostructures on the Au mirror FO tip distal end. The nanopatterned FO-SPR sensor tips were afterwards subjected to refractometric measurements in a sucrose dilution series and subsequently compared with their non-patterned counterparts. It was observed that the spectral dips of the nanopatterned FO-SPR sensor tips were shifted towards longer wavelengths after CLT patterning. Moreover, the sensor sensitivity was improved with up to 25% compared to the conventional non-patterned FO-SPR devices. The obtained results represent important steps in the development of a new generation of FO-SPR sensors with improved performance, which can ultimately be used in various applications, ranging from food analysis and environmental monitoring, to health control and medical diagnosis.