Photosensitive nanocarriers for specific delivery of cargo into cells.

Nanoencapsulation is a rapidly expanding technology to enclose cargo into inert material at the nanoscale size, which protects cargo from degradation, improves bioavailability and allows for controlled release. Encapsulation of drugs into functional nanocarriers enhances their specificity, targeting ability, efficiency, and effectiveness. Functionality may come from cell targeting biomolecules that direct nanocarriers to a specific cell or tissue. Delivery is usually mediated by diffusion and erosion mechanisms, but in some cases, this is not sufficient to reach the expected therapeutic effects. This work reports on the development of a new photoresponsive polymeric nanocarrier (PNc)-based nanobioconjugate (NBc) for specific photo-delivery of cargo into target cells. We readily synthesized the PNcs by modification of chitosan with ultraviolet (UV)-photosensitive azobenzene molecules, with Nile red and dofetilide as cargo models to prove the encapsulation/release concept. The PNcs were further functionalized with the cardiac targeting transmembrane peptide and efficiently internalized into cardiomyocytes, as a cell line model. Intracellular cargo-release was dramatically accelerated upon a very short UV-light irradiation time. Delivering cargo in a time-space controlled fashion by means of NBcs is a promising strategy to increase the intracellular cargo concentration, to decrease dose and cargo side effects, thereby improving the effectiveness of a therapeutic regime.

Albumin Nanocarriers, γ- Irradiated Crosslinked, Combined with Therapeutic Drugs for Cancer Therapy>.

Albumin polymeric Nanoparticles (NPs) have opened a great expectancy as for controlled drug delivery due to their therapeutic potency. Concomitantly biodegradable NPs technologies with target linked structures to pave the way of personalised medicine are becoming increasingly important in sight of a therapeutically effective research technology. This is particularly attractive for nanoparticle-based cancer delivery systems, based on the known limitations and efforts to overcome. This new group of gamma irradiated-NPs inherited both the protein delivery properties and robustness of polymer forming structures, and gamma irradiation techniques that leave clean, innocuous and biodegradable NPs. These protein NPs made of serum albumin are referred to SA NPs that possesses several characteristics making them especially attractive to be considered as a drug delivery system. This review focused on methodologies actually being used in the synthesis and characterisation of albumin NPs and different author's opinions on strategic ways to treat cancerous cell-lines with NPs. Utterly, challenges being overthrown by researchers are brought up to anneal an effective, all in one targeted albumin NPs to passed through in vitro and preclinical trials.

Use of Spectroscopic Techniques for Evaluating the Coupling of Porphyrins on Biocompatible Nanoparticles. A Potential System for Photodynamics, Theranostics, and Nanodrug Delivery Applications.

Modern medicine has been searching for new and more efficient strategies for diagnostics and therapeutics applications. Considering this, porphyrin molecules have received great interest for applications in photodiagnostics and phototherapies, even as magnetic nanoparticles for drug-delivery systems and magnetic-hyperthermia therapy. Aiming to obtain a multifunctional system, which combines diagnostics with therapeutic functions on the same platform, the present study employed UV/vis absorption and fluorescence spectroscopies to evaluate the interaction between meso-tetrakis(p-sulfonatofenyl)porphyrin (TPPS) and maghemite nanoparticles (γ-Fe2O3). These spectroscopic techniques allowed us to describe the dynamics of coupling porphyrins on nanoparticles and estimate the number of 21 porphyrins per nanoparticle. Also, the binding parameters, such as the association constants (Ka = 8.89 × 105 M-1) and bimolecular quenching rate constant (kq = 2.54 × 1014 M-1 s-1) were obtained. These results suggest a static quenching process where the electrostatic attraction plays an essential role. The work shows that spectroscopic techniques are powerful tools to evaluate the coupling of organic molecules and nanoparticles. Besides, the system studied provides a relevant background for potential applications in bionanotechnology and nanomedicine, such as (1) nanodrug delivery system, (2) photodiagnostics/theranostics, and/or (3) a combined action of photodynamic and hyperthermia therapies, working in a synergetic way.

Simultaneous encapsulation of magnetic nanoparticles and zinc phthalocyanine in poly(methyl methacrylate) nanoparticles by miniemulsion polymerization and in vitro studies.

The aim of this work was the simultaneous encapsulation of magnetic nanoparticles (MNPs) and zinc(II) phthalocyanine (ZnPc) in poly(methyl methacrylate) (PMMA) (MNPsZnPc-PMMA) nanoparticles (NPs) by miniemulsion polymerization and to evaluate the photobiological activity and/or hyperthermia (HPT) against human glioblastoma cells (U87MG). MNPsZnPc-PMMA NPs presented an average diameter of 104 ± 2.5 nm with a polydispersity index (PdI) of 0.14 ± 0.03 and negative surface charge - 47 ± 2.2 mV (pH 7.4 ± 0.1). The encapsulation efficiency (EE%) of ZnPc was 85.7% ± 1.30. The release of ZnPc from PMMA NPs was slow and sustained without the presence of burst effect, indicating a homogeneous distribution of the drug in the polymeric matrix. In the biological assay, MNPsZnPc-PMMA NPs showed considerable cytotoxic effect on U87MG cells only after activation with visible light at 675 nm (photodynamic therapy, PDT) or after application of an alternating magnetic field. The simultaneous encapsulation of MNPs and ZnPc in a drug delivery system with sustained release can be a new alternative for cancer treatment leading to significant tumor regression after minimum doses of heat dissipation and light.

Model of waterlike fluid under confinement for hydrophobic and hydrophilic particle-plate interaction potentials.

Molecular dynamic simulations were employed to study a waterlike model confined between hydrophobic and hydrophilic plates. The phase behavior of this system is obtained for different distances between the plates and particle-plate potentials. For both hydrophobic and hydrophilic walls, there are the formation of layers. Crystallization occurs at lower temperature at the contact layer than at the middle layer. In addition, the melting temperature decreases as the plates become more hydrophobic. Similarly, the temperatures of maximum density and extremum diffusivity decrease with hydrophobicity.

High temperature stability of anatase in titania-alumina semiconductors with enhanced photodegradation of 2, 4-dichlorophenoxyacetic acid.

The incorporation of aluminum acetylacetonate as alumina source during the gelation of titanium alkoxide reduces the nucleation sites for the formation of large rutile crystals on temperatures ranging from 400 to 800°C. As a result, the aggregation of anatase crystals is prevented at high temperature. A relationship among the specific surface area, pore size, energy band gap, crystalline structure and crystallite size as the most relevant parameters are evaluated and discussed. According to the results for the photocatalytic degradation of 2,4-dichlorophenoxyacetic acid, the specific surface area, pore size, Eg band gap are not determinant in the photocatalytic properties. It was found that the anatase crystallite size is the mores important parameter affecting the degradation efficiency.

Direct in situ observation of the electron-driven synthesis of Ag filaments on α-Ag2WO4 crystals.

In this letter, we report, for the first time, the real-time in situ nucleation and growth of Ag filaments on α-Ag2WO4 crystals driven by an accelerated electron beam from an electronic microscope under high vacuum. We employed several techniques to characterise the material in depth. By using these techniques combined with first-principles modelling based on density functional theory, a mechanism for the Ag filament formation followed by a subsequent growth process from the nano- to micro-scale was proposed. In general, we have shown that an accelerated electron beam from an electronic microscope under high vacuum enables in situ visualisation of Ag filaments with subnanometer resolution and offers great potential for addressing many fundamental issues in materials science, chemistry, physics and other fields of science.

Elastic mediated force between nanoparticles adsorbed on smectic films under an external field.

Within the harmonic approximation, we analytically determine the elastic-mediated interaction between colloidal nanoparticles adsorbed on the surface of smectic films under the influence of an external field. Both cases of free-standing films and films deposited over a solid substrate are considered. We show that the asymptotic decay (1/R in free-standing and exponential in deposited films) is not altered by the external field. However, the external field plays distinct roles according to the film configuration, the interparticle distance, the film thickness, and the surface tension at the film-gas interface. We provide a detailed discussion under the light of the distinct mechanisms controlling the undulations of the surface layer.

Synthesis and characterization of gold/alanine nanocomposites with potential properties for medical application as radiation sensors.

Radiation dose assessment is essential for several medical treatments and diagnostic procedures. In this context, nanotechnology has been used in the development of improved radiation sensors, with higher sensitivity as well as smaller sizes and energy dependence. This paper deals with the synthesis and characterization of gold/alanine nanocomposites with varying mass percentage of gold, for application as radiation sensors. Alanine is an excellent stabilizing agent for gold nanoparticles because the size of the nanoparticles does not augment with increasing mass percentage of gold, as evidenced by UV-vis spectroscopy, dynamic light scattering, and transmission electron microscopy. X-ray diffraction patterns suggest that the alanine crystalline orientation undergoes alterations upon the addition of gold nanoparticles. Fourier transform infrared spectroscopy indicates that there is interaction between the gold nanoparticles and the amine group of the alanine molecules, which may be the reason for the enhanced stability of the nanocomposite. The application of the nanocomposites as radiation detectors was evaluated by the electron spin resonance technique. The sensitivity is improved almost 3 times in the case of the nanocomposite containing 3% (w/w) gold, so it can be easily tuned by changing the amount of gold nanoparticles in the nanocomposites, without the size of the nanoparticles influencing the radiation absorption. In conclusion, the featured properties, such as homogeneity, nanoparticle size stability, and enhanced sensitivity, make these nanocomposites potential candidates for the construction of small-sized radiation sensors with tunable sensitivity for application in several medical procedures.

Femtosecond third-order nonlinear spectra of lead-germanium oxide glasses containing silver nanoparticles.

This work reports on the spectral dependence of both nonlinear refraction and absorption in lead-germanium oxide glasses (PbO-GeO2) containing silver nanoparticles. We have found that this material is suitable for all-optical switching at telecom wavelengths but at the visible range it behaves either as a saturable absorber or as an optical limiter.

Photostability and skin penetration of different E-resveratrol-loaded supramolecular structures.

It is desirable and challenging to prevent E-resveratrol (E-RSV) from photoisomerizing to its Z-configuration to preserve its biological and pharmacological activities. The aim of this research was to evaluate the photostability of E-RSV-loaded supramolecular structures and the skin penetration profile of chemically and physically stable nanoestructured formulations. Different supramolecular structures were developed to act as carriers for E-RSV, that is, liposomes, polymeric lipid-core nanocapsules and nanospheres and solid lipid nanoparticles. The degrees of photostability of these formulations were compared with that of an ethanolic solution of E-RSV. The skin penetration profiles of the stable formulations were obtained using vertical diffusion cells (protected from light and under UVA radiation) with porcine skin as the membrane, followed by tape stripping and separation of the viable epidermis and dermis in a heated water bath. Photoisomerization was significantly delayed by the association of resveratrol with the nanocarriers independently of the supramolecular structure. Liposomes were the particles capable of maintaining E-RSV concentration for the longest time. On the other hand, E-RSV-loaded liposomes reduced in size showing low physical stability under UVA radiation. In the dark, the skin penetration profiles were very similar, but under UVA radiation the E-RSV-loaded nanocarriers showed increasing amounts in the total epidermis.

Effect of the addition of silanated silica on the mechanical properties of microwave heat-cured acrylic resin.

OBJECTIVES: The purpose of this study was to evaluate the flexural strength and Vickers hardness of a microwave energy heat-cured acrylic resin by adding different concentrations of silane surface-treated nanoparticle silica. METHODS: Acrylic resin specimens with dimensions of 65 × 10 × 2.5 mm were formed and divided into five experimental groups (n = 10) according to the silica concentration added to the acrylic resin mass (weight %) prior to polymerisation : G1, without silica; G2, 0.1% silica; G3, 0.5% silica; G4, 1.0% silica; and G5, 5.0% silica. The specimens were submitted to a three-point flexural strength test and to the Vickers hardness test (HVN). The data obtained were statistically analysed by anova and the Tukey test (α = 0.05). RESULTS: Regarding flexural strength, G5 differed from the other experimental groups (G1, G2, G3 and G4) presenting the lowest mean, while G4 presented a significantly higher mean, with the exception of group G3. Regarding Vickers hardness, a decrease in values was observed, in which G1 presented the highest hardness compared with the other experimental groups. CONCLUSION: Incorporating surface-treated silica resulted in direct benefits in the flexural strength of the acrylic resin activated by microwave energy; however, similar results were not achieved for hardness.

Femtosecond laser induced synthesis of Au nanoparticles mediated by chitosan.

This paper reports the synthesis of Au nanoparticles by 30-fs pulses irradiation of a sample containing HAuCl4 and chitosan, a biopolymer used as reducing agent and stabilizer. We observed that it is a multi-photon induced process, with a threshold irradiance of 3.8 × 10(11) W/cm2 at 790 nm. By transmission electron microscopy we observed nanoparticles from 8 to 50 nm with distinct shapes. Infrared spectroscopy indicated that the reduction of gold and consequent production of nanoparticles is related to the fs-pulse induced oxidation of hydroxyl to carbonyl groups in chitosan.

Inversion of gradient forces for high refractive index particles in optical trapping.

The unexpected fact that a spherical dielectric particle with refractive index higher than the surrounding medium will not always be attracted towards high intensity regions of the trapping beam is fully demonstrated here using a simple ray optics approach. This unusual situation may happen due to the inversion of gradient forces, as shown here. Therefore, conventional schemes, such the one based on the use of two counter-propagating beams to cancel the scattering forces, will fail to trap the particle. However, effective trapping still can be obtained by adopting suitable incident laser beams.

Polymerization shrinkage stress of composites photoactivated by different light sources.

The purpose of this study was to compare the polymerization shrinkage stress of composite resins (microfilled, microhybrid and hybrid) photoactivated by quartz-tungsten halogen light (QTH) and light-emitting diode (LED). Glass rods (5.0 mm x 5.0 cm) were fabricated and had one of the surfaces air-abraded with aluminum oxide and coated with a layer of an adhesive system, which was photoactivated with the QTH unit. The glass rods were vertically assembled, in pairs, to a universal testing machine and the composites were applied to the lower rod. The upper rod was placed closer, at 2 mm, and an extensometer was attached to the rods. The 20 composites were polymerized by either QTH (n=10) or LED (n=10) curing units. Polymerization was carried out using 2 devices positioned in opposite sides, which were simultaneously activated for 40 s. Shrinkage stress was analyzed twice: shortly after polymerization (t40s) and 10 min later (t10min). Data were analyzed statistically by 2-way ANOVA and Tukey's test (alpha=5%). The shrinkage stress for all composites was higher at t10min than at t40s, regardless of the activation source. Microfilled composite resins showed lower shrinkage stress values compared to the other composite resins. For the hybrid and microhybrid composite resins, the light source had no influence on the shrinkage stress, except for microfilled composite at t10min. It may be concluded that the composition of composite resins is the factor with the strongest influence on shrinkage stress.

Polymerization shrinkage stress of composites photoactivated by different light sources

The purpose of this study was to compare the polymerization shrinkage stress of composite resins (microfilled, microhybrid and hybrid) photoactivated by quartz-tungsten halogen light (QTH) and light-emitting diode (LED). Glass rods (5.0 mm x 5.0 cm) were fabricated and had one of the surfaces air-abraded with aluminum oxide and coated with a layer of an adhesive system, which was photoactivated with the QTH unit. The glass rods were vertically assembled, in pairs, to a universal testing machine and the composites were applied to the lower rod. The upper rod was placed closer, at 2 mm, and an extensometer was attached to the rods. The 20 composites were polymerized by either QTH (n=10) or LED (n=10) curing units. Polymerization was carried out using 2 devices positioned in opposite sides, which were simultaneously activated for 40 s. Shrinkage stress was analyzed twice: shortly after polymerization (t40s) and 10 min later (t10min). Data were analyzed statistically by 2-way ANOVA and Tukey's test (a=5 percent). The shrinkage stress for all composites was higher at t10min than at t40s, regardless of the activation source. Microfilled composite resins showed lower shrinkage stress values compared to the other composite resins. For the hybrid and microhybrid composite resins, the light source had no influence on the shrinkage stress, except for microfilled composite at t10min. It may be concluded that the composition of composite resins is the factor with the strongest influence on shrinkage stress.

Este estudo comparou a contração de polimerização de resinas compostas fotoativadas por luz halógena (QTH) e diodo emissor de luz (LED). Foram confeccionados bastões de vidro (5,0 mm x 5,0 cm), e uma de suas extremidades sofreu jateamento com óxido de alumínio, sobre a qual foi aplicado um adesivo e fotoativado com luz halógena. Os bastões de vidro foram acoplados verticalmente, em pares, em uma máquina universal de ensaios (EMIC DL-2000) e as resinas compostas aplicadas no bastão inferior. A distância entre os bastões foi padronizada em 2 mm e um extensômetro foi acoplado a eles. As resinas foram fotoativadas (n=20), sendo 10 por QTH e 10 por LED utilizando dois aparelhos posicionados em lados opostos, acionados simultaneamente por 40 s. A tensão de contração foi analisada em dois momentos: logo após a polimerização (t40s) e 10 min após (t10min). A tensão de contração apresentada por todas as resinas foi maior em t10min do que em t40s, independente da fonte ativadora. A resina de micropartículas apresentou menores valores de tensão de contração com valores estatisticamente significantes em relação às demais resinas. Para as resinas híbrida e microhíbrida não houve influência da unidade ativadora sobre a tensão de contração, com exceção para a resina de micropartículas em t10min. Concluiu-se que a composição da resina composta foi o fator que mais interferiu na tensão de contração da resina composta.

Influence of light-polymerization modes on the degree of conversion and mechanical properties of resin composites: a comparative analysis between a hybrid and a nanofilled composite.

This study analyzed the influence of the light polymerization mode on the degree of conversion (DC) and mechanical properties of two resin composites: a hybrid (Filtek P60) and a nanofilled composite (Filtek Supreme). The composites were light activated by three light polymerization modes (Standard-S: 650 mW/cm2 for 30 seconds; High intensity-H: 1000 mW/cm2 for 20 seconds and Gradual-G: 100 up to 1000 mW/cm2 for 10 seconds + 1000 mW/cm2 for 10 seconds). The DC (%) was measured by FT-Raman spectroscopy. Flexural strength and flexural modulus were obtained from bar-shaped specimens (1 x 2 x 10 mm) submitted to the three-point bending test. Microhardness was evaluated by Knoop indentation (KHN). Data were analyzed by ANOVA and Student-Newman-Keuls multiple range test and linear regression analysis. The results showed the following DC: H > S > G (p < 0.0001) and hybrid > nanofilled (p < 0.005). Correlation was found between DC and the radiant exposure (R2 = 0.92). With respect to mechanical properties, only KHN was significantly influenced by the light polymerization mode, as follow: H > S = G (p < 0.0001). The hybrid composite presented higher flexural strength and flexural modulus than the nanofilled composite (p < 0.0001). No significant difference was found in KHN between thetwo composites (p = 0.1605). The results suggest that nanofilled composites may present a lower degree of conversion and reduced mechanical properties compared to hybrid composites.

Light transmission on dental resin composites.

OBJECTIVES: The purposes of this study was: (1) to examine the light transmittance characteristics of two light-cured resin composites, for different thickness, (2) to correlate the light transmittance through the resin composites and the filler contents, and (3) to determine the penetration depth of the light as a function of the wavelength. METHODS: Two resin composites (Filtek Z250, shade A2 and Filtek Supreme XT, shade A2E) were used. Specimens of six different thicknesses (0.15, 0.25, 0.30, 0.36, 0.47 and 0.75 mm) were prepared (n=3). The transmittance at wavelengths from 400 to 800 nm was measured using a UV-visible spectrophotometer, before and after light polymerization. RESULTS AND SIGNIFICANCE: Significant differences were found in the wavelength dependence of transmittance between the two materials, and between the unpolymerized and polymerized stages of each resin composite. At lower wavelengths, the light transmittance of the Filtek Supreme XT resin composite was lower than the Filtek Z250. At the higher wavelengths, however, Filtek Supreme XT presented higher light transmittance. For both resin composites, the penetration depth was higher after polymerization. However, Filtek Supreme XT showed a higher gain in transmittance at the 0.15 mm thickness. The difference in light transmittance characteristics of the resin composites may affect their depth of polymerization.

Growth aspects of photochemically synthesized silver triangular nanoplates.

Aspects of the growth mechanism of silver triangular nanoplates by photochemical synthesis were addressed by detailed characterization using ultraviolet-visible spectroscopy, electron microscopies, and atomic force microscopy. The quantitative characterization of their size and thickness during the reaction showed that both increase with time as well as the aspect ratio. Samples irradiated by different wavelengths showed that the size of the nanoplates can be controlled by the incident wavelength and it is responsible for the increase of the aspect ratio, but the thickness seems to be determined by the conditions of the initial seeds. It was also found that irradiation with wavelength out of resonance with the surface plasmon of the initial seeds leads to a slower kinetics. The results suggested that rational exploration of the synthesis parameter such as the type of the initial seeds in combination with the wavelength irradiation may lead to a broader type of particles already obtained by this method.

Dynamic scaling of polymer gels comprising nanoparticles.

We present dynamic light scattering (DLS) measurements of soft poly(methyl-methacrylate) (PMMA) and polyacrylamide (PA) polymer gels prepared with trapped bodies (latex spheres or magnetic nanoparticles). We show that the anomalous diffusivity of the trapped particles can be analyzed in terms of a fractal Gaussian network gel model for the entire time range probed by DLS technique. This model is a generalization of the Rouse model for linear chains extended for structures with power law network connectivity scaling, which includes both percolating and uniform bulk gel limits. For a dilute dispersion of strongly scattering particles trapped in a gel, the scattered electric field correlation function at small wavevector ideally probes self-diffusion of gel portions imprisoning the particles. Our results show that the time-dependent diffusion coefficients calculated from the correlation functions change from a free diffusion regime at short times to an anomalous subdiffusive regime at long times (increasingly arrested displacement). The characteristic time of transition between these regimes depends on scattering vector as approximately q(-2), while the time decay power exponent tends to the value expected for a bulk network at small q. The diffusion curves for all scattering vectors and all samples were scaled to a single master curve.