Polymer nanoparticle identification and concentration measurement using fiber-enhanced raman spectroscopy

We present a measurement technique for chemical identification and concentration measurement of polymer nanoparticles in aqueous solution, which is achieved using Raman spectroscopy. This work delivers an improvement in measurement sensitivity of 40 times over conventional Raman measurements in cuvettes by loading polymer nanoparticles into the hollow core of a microstructured optical fiber. We apply this "fiber-enhanced" system to measure the concentration of two separate samples of polystyrene particles (diameters of 60 nm and 120 nm respectively) with concentrations in the range from 0.07 to 0.5 mg/mL. The nanoliter volume formed by the fiber presents unique experimental conditions where nanoparticles are confined within the fiber core and prevented from diffusing outside the incident electromagnetic field, thereby enhancing their interaction. Our results suggest an upper limit on the size of particle that can be measured using the hollow-core photonic crystal fiber, as the increasing angular distribution of scattered light with particle size exceeds the acceptance angle of the liquid-filled fiber. We investigate parameters such as the fiber filling rate and optical properties of the filled fiber, with the aim to deliver repeatable and quantifiable measurements. This study thereby aids the on-going process to create compact systems that can be integrated into nanoparticle production settings for in-line measurements

Patterning of polymer brushes made easy using titanium dioxide: direct and remote photocatalytic lithography

Photocatalytic lithography is proved for the realization of micropatterned polymer brushes. Initiator-functionalized titanium dioxide or silicon surfaces are respectively exposed directly to near-UV light through a photomask (direct approach) or through a transparent photoactive TiO2 film (remote approach). Initiator patterns are then amplified as polymer brushes with SI-ATRP. Features down to 10 \u3bcm could be obtained using simple equipment. The process is intrinsically parallel, has high throughput and scalable to wafer size, making it powerful for microfabrication purposes

Preparation and Properties of PTFE-PMMA Core-Shell Nanoparticles and Nanocomposites

he preparation of polytetrafluoroethylene-poly(methyl methacrylate) (PTFE-PMMA) core-shell particles was described, featuring controlled size and narrow size distribution over a wide compositional range, through a seeded emulsion polymerization starting from a PTFE seed of 26 nanometers. Over the entire MMA/PTFE range, the particle size increases as the MMA/PTFE ratio increases. A very precise control over the particle size can be exerted by properly adjusting the ratio between the monomer and the PTFE seed. Particles in the 80240 nm range can be prepared with uniformity indexes suited to build 2D and 3D colloidal crystals. These core-shell particles were employed to prepare nanocomposites with different compositions, through an annealing procedure at a temperature higher than the glass transition temperature of the shell forming polymer. A perfect dispersion of the PTFE particles within the PMMA matrix was obtained and optically transparent nanocomposites were prepared containing a very high PTFE amount

Fabrication of flexible silicon nanowires by self-assembled metal assisted chemical etching for surface enhanced Raman spectroscopy

A homogenous array of flexible gold coated silicon nanowires was fabricated by the combination of nano spheres lithography and metal assisted chemical etching to obtain highly effective Surface Enhanced Raman Spectroscopy (SERS) substrates. 3D nanostructures with different aspect ratios and well-defined geometries were produced by adjusting the fabrication parameters in order to select the best configuration for SERS analysis. The optimum flexible nanowires with an aspect ratio of 1 : 10 can self-close driven by the microcapillary force under exposure to liquid and trap the molecules at their metallic coated ``fingertips'', thus generating hot spots with ultrahigh field enhancement. The performance of these SERS substrates was evaluated using melamine as the analyte probe with various concentrations from the millimolar to the picomolar range. Flexible gold coated SiNWs demonstrated high uniformity of the Raman signal over large area with a variability of only 10% and high sensitivity with a limit of detection of 3.20 x 10(-7) mg L-1 (picomolar) which promotes its application in several fields such food safety, diagnostic and pharmaceutical. Such an approach represents a low-cost alternative to the traditional nanofabrication processes to obtain well ordered silicon nanostructures, offering multiple degrees of freedom in the design of different geometries such as inter-wire distance, density of the wires on the surface as well as their length, thus showing a great potential for the fabrication of SERS substrates

Self-cleaning properties in engineered sensors for dopamine electroanalytical detection

Fouling and passivation are the major drawbacks for a wide applicability of electroanalytical sensors based on nanomaterials, especially in biomedical and environmental fields. The production of highly engineered devices, designed ad hoc for specific applications, is the key factor in the direction of overcoming the problem and accessing effective sensors. Here, the fine-tuning of the system, composed of a highly ordered distribution of silver nanoparticles between a bottom silica and a top titania layer, confers multifunctional properties to the device for a biomedical complex challenge: dopamine detection. The crucial importance of each component towards a robust and efficient electroanalytical system is studied. The total recovery of the electrode performance after a simple UV-A cleaning step (self-cleaning), due to the photoactive interface and the aging resistance, is deeply investigated

Persistent Dystrophin Protein Restoration 90 Days after a Course of Intraperitoneally Administered Naked 2′OMePS AON and ZM2 NP-AON Complexes in mdx Mice

In Duchenne muscular dystrophy, the exon-skipping approach has obtained proof of concept in animal models, myogenic cell cultures, and following local and systemic administration in Duchenne patients. Indeed, we have previously demonstrated that low doses (7.5 mg/Kg/week) of 2  -O-methyl-phosphorothioate antisense oligoribonucleotides (AONs) adsorbed onto ZM2 nanoparticles provoke widespread dystrophin restoration 7 days after intraperitoneal treatment in mdx mice. In this study, we went on to test whether this dystrophin restoration was still measurable 90 days from the end of the same treatment. Interestingly, we found that both western blot and immunohistochemical analysis (up to 7% positive fibres) were still able to detect dystrophin protein in the skeletal muscles of ZM2-AON-treated mice at this time, and the level of exon-23 skipping could still be assessed by RT real-time PCR (up to 10% of skipping percentage). In contrast, the protein was undetectable by western blot analysis in the skeletal muscles of mdx mice treated with an identical dose of naked AON, and the percentage of dystrophin-positive fibres and exon-23 skipping were reminiscent of those of untreated mdx mice. Our data therefore demonstrate the long-term residual efficacy of this systemic low-dose treatment and confirm the protective effect nanoparticles exert on AON molecules

Persistent Dystrophin Protein Restoration 90 Days after a Course of Intraperitoneally Administered Naked 2′OMePS AON and ZM2 NP-AON Complexes in mdx Mice

In Duchenne muscular dystrophy, the exon-skipping approach has obtained proof of concept in animal models, myogenic cell cultures, and following local and systemic administration in Duchenne patients. Indeed, we have previously demonstrated that low doses (7.5 mg/Kg/week) of 2 -O-methyl-phosphorothioate antisense oligoribonucleotides (AONs) adsorbed onto ZM2 nanoparticles provoke widespread dystrophin restoration 7 days after intraperitoneal treatment in mdx mice. In this study, we went on to test whether this dystrophin restoration was still measurable 90 days from the end of the same treatment. Interestingly, we found that both western blot and immunohistochemical analysis (up to 7% positive fibres) were still able to detect dystrophin protein in the skeletal muscles of ZM2-AON-treated mice at this time, and the level of exon-23 skipping could still be assessed by RT real-time PCR (up to 10% of skipping percentage). In contrast, the protein was undetectable by western blot analysis in the skeletal muscles of mdx mice treated with an identical dose of naked AON, and the percentage of dystrophin-positive fibres and exon-23 skipping were reminiscent of those of untreated mdx mice. Our data therefore demonstrate the long-term residual efficacy of this systemic low-dose treatment and confirm the protective effect nanoparticles exert on AON molecules

Glowing teacup demonstration: Trautz-schorigin reaction of natural polyphenols

A safe, versatile demonstration of singlet oxygen chemiluminescence by means of Trautz-Schorigin reaction is described. Instead of toxic pyrogallol, green tea is used as a source of polyphenols. The effect of an antioxidant (ascorbic acid) and of boric acid on chemiluminescence is studied. This demonstration is suitable either for organic chemistry and general chemistry courses and can also be performed as an experiment by students