Two-Photon Absorption and Multiphoton Excited Fluorescence of Acetamide-Chalcone Derivatives: The Role of Dimethylamine Group on the Nonlinear Optical and Photophysical Properties.

This work studied the effect of different electron-withdrawing and electron-donating groups on the linear and nonlinear optical properties of acetamide-chalcone derivatives. The results showed that the addition of the dimethylamine group led to a large fluorescence emission (71% of fluorescence quantum yield in DMSO solution) that can be triggered by two and three-photon excitations, which is essential for biological applications. Furthermore, dimethylamine also red-shifts the lower energy state by approximately 90 nm, increasing the two-photon absorption cross-section of the lower energy band by more than 100% compared with the other studied compounds. All compounds presented two-electronic states observed through one and two-photon absorption spectroscopy and confirmed by Quantum Chemistry Calculations (QCCs). QCC results were also used to model the experimental two-photon absorption cross-sectional spectrum by the Sum-Over-States (SOS) approach, revealing a dependence between the coupling of the ground state with the first excited state and the transition dipole moment between these states.

Measurement of the refractive index profile of waveguides using defocusing microscopy.

Defocusing microscopy (DM) is a bright-field optical microscopy technique often used to obtain structural parameters of objects with low difference in refractive index in relation to the surrounding medium (phase objects). We show a use of this technique to measure the refractive index (n) profile of waveguides produced by femtosecond laser micromachining inside the bulk of a sodalime glass. The results are used to analyze the influence of production parameters on n. The methodology requires only a bright-field optical microscope and has proved to be easily applied. Results provide important insights on the waveguide microfabrication process, since translation speed, rather than intensity, has shown to be more important for achieving greater variations in refractive indices. Index of refraction differences between the waveguide and the substrate of the order of 10-4 were measured for a series of straight waveguides fabricated with different parameters. Low sample scan speeds and pulse energies near 1.20 µJ used for fabrication showed the highest values of refractive index change for waveguides in sodalime glasses.

Femtosecond Laser Patterning of the Biopolymer Chitosan for Biofilm Formation.

Controlling microbial growth is crucial for many biomedical, pharmaceutical and food industry applications. In this paper, we used a femtosecond laser to microstructure the surface of chitosan, a biocompatible polymer that has been explored for applications ranging from antimicrobial action to drug delivery. The influence of energy density on the features produced on chitosan was investigated by optical and atomic force microscopies. An increase in the hydrophilic character of the chitosan surface was attained upon laser micromachining. Patterned chitosan films were used to observe Staphylococcus aureus (ATCC 25923) biofilm formation, revealing an increase in the biofilm formation in the structured regions. Our results indicate that fs-laser micromachining is an attractive option to pattern biocompatible surfaces, and to investigate basic aspects of the relationship between surface topography and bacterial adhesion.

Mechanism of the Zn(II)Phthalocyanines' Photochemical Reactions Depending on the Number of Substituents and Geometry.

In this work, the synthesis and the nonlinear absorption and population dynamics investigation of a series of zinc phthalocyanines (ZnPcs) dissolved in chloroform are reported. In order to determine the relevant spectroscopic parameters, such as absorption cross-sections of singlet and triplet excited states, fluorescence relaxation times, intersystem crossing, radiative decay and internal conversion, different optical and spectroscopic techniques were used. By single pulse and pulse train Z-scan techniques, respectively, singlet and triplet excited states' absorption cross-section were determined at 532 nm. Furthermore, the intersystem crossing time was obtained by using both techniques combined with the fluorescence lifetime determined by time-resolved fluorescence. The radiative and internal conversion rates were determined from the fluorescence quantum yield of the samples. Such spectroscopy parameters are fundamental for selecting photosensitizers used in photodynamic therapy, as well as for many other applications.

Comparison of hydrophilic and hydrophobic nano topographic surfaces of titanium alloys on pre-osteoblastic cell interaction.

This work aimed to assess the influence of different structured substrates with hydrophilic and hydrophobic properties on micro and nano topographies developed on titanium alloys over pre-osteoblastic cell behavior. Nano topography influences small dimension levels of cell morphology by inducing filopodia formation in cell membranes, irrespectively to the wettability behavior of the surface. Therefore, micro and nanostructured surfaces of titanium-based samples using different techniques of surface modification processing, such as chemical treatments, micro-arc anodic oxidation (MAO), and MAO combined to laser irradiation were developed. Isotropic and anisotropic texture morphologies, wettability, topological parameters and compositional alterations were measured after the surface treatments. Finally, cell viability, adhesion and morphological responses were assessed to investigate the influence of distinct topologies on osteoblastic cells aiming to encounter the conditions to better promote mineralization events. Our study demonstrated that the hydrophilic behavior improves cell adhesion, amplified when effective surface area increases. Surfaces presenting nano topography have a direct influence on cell morphology and play a key role for filopodia formation.

Indirect doping of microstructures fabricated by two-photon polymerization with gold nanoparticles.

Nanoplasmonics and metamaterials sciences are rapidly growing due to their contributions to photonic devices fabrication with applications ranging from biomedicine to photovoltaic cells. Noble metal nanoparticles incorporated into polymer matrix have great potential for such applications due to their distinctive optical properties. However, methods to indirectly incorporate metal nanoparticles into polymeric microstructures are still on demand. Here we report on the fabrication of two-photon polymerized microstructures doped with gold nanoparticles through an indirect doping process, so they do not interfere in the two-photon polymerization (2PP) process. Such microstructures present a strong emission, arising from gold nanoparticles fluorescence. The microstructures produced are potential candidates for nanoplasmonics and metamaterials devices applications and the nanoparticles production method can be applied in many samples, heated simultaneously, opening the possibility for large scale processes.

Enhancement of optical properties of new purine nucleobases containing electron-donating and -withdrawing peripheral groups.

Nowadays, a great deal of attention has been focused on synthesizing highly fluorescent unnatural base analogs. This has been motivated by the need to overcome the lack of fluorescence of nucleic acids' natural bases. Fluorescent unnatural base analogs, such as purines, may be used in several applications, such as DNA or RNA optical spectroscopy studies. Moreover, for purines base analogs, the optical properties, for example, emission, can be tunable through molecular engineering, improving their applications as fluorescent probes. Looking in this direction, the synthesis and optical spectroscopic studies of a new set of purines base analogs are of foremost relevance. Here, an increase in the fluorescence quantum yield was observed in molecules with NH-π-CN arrangement. The two-photon absorption (2PA) cross-sections also increased for the lower energy 2PA state. The enhancement of both properties results in a two-photon brightness of 5 and 10 times higher than in compounds lacking the NH-π-CN arrangement. For the higher energy 2PA state, an excited state absorption contribution to the 2PA cross-section values was observed, that was verified through ultrafast transient absorption measurements. The higher 2PA brightness makes the purines base analogs promising candidates as fluorescent probes in RNA and DNA spectroscopic studies.

Investigation of the triplet excited state and application of cationic meso-tetra(cisplatin)porphyrins in antimicrobial photodynamic therapy.

In this manuscript, we report, the photophysical study of triplet excited states and antimicrobial photoinactivation of positively charged tetra-cisplatin porphyrin derivatives against Gram + and Gram ‒ bacterial strains. Isomeric cisplatin-porphyrins were used and applied in aPDT assays in the bacilli Escherichia coli, Klebsiella pneumoniae and Pseudomonas aeruginosa (Gram negative) and a cocci Staphylococcus aureus (Gram positive) strains. The results show that compound substituted at meta position (3-cis-PtTPyP) is the more efficient photosensitizer against bacteria culture. In this way, tetra-cationic porphyrins containing cisplatin derivatives might be promising aPDT agents with potential applications in clinical infections.

Unconventional Magnetization Generated from Electron Beam and Femtosecond Irradiation on α-Ag2WO4: A Quantum Chemical Investigation.

Novel magnetic metals and metal oxides that use both the spin and charge of an electron offer exciting technological applications. Their discovery could boost research on functional nanoscale materials. Here, for the first time, we report the magnetization of α-Ag2WO4 under electron beam and femtosecond laser irradiation. The formation and growth of silver oxides (AgO, Ag2O, and Ag3O4) and Ag nanofilaments can be observed on the surface of α-Ag2WO4 crystals. These features were also present in the composition of an extruded material and could open new avenues for surface magnetism studies. In order to understand these results, we used first-principles density functional theory calculations. This allowed us to investigate several potential scenarios for controlling magnetic properties. The effect of electron addition on the crystalline structures of α-Ag2WO4, Ag3O4, Ag2O, and AgO has been analyzed in detail. The creation of Ag and O vacancies on these compounds was also analyzed. Based on structural and electronic changes at the local coordination site of Ag, a mechanism was proposed. The mechanism illustrates the processes responsible for the formation and growth of metallic Ag and the magnetic response to electron beam irradiation.

Optical properties and antiangiogenic activity of a chalcone derivate.

Chalcones and their derivatives exhibit numerous pharmacological activities such as antibacterial, antifungal, cytotoxic, antinociceptive and anti-inflammatory. Recently, they have been assessed aiming for novel application in nonlinear optics and in the treatment of immune diseases and cancers. In this study, we investigate the optical properties of synthetic chalcona 1E,4E-1-(4-chlorophenyl)-5-(2,6,6-trimethylcyclohexen-1-yl)penta-1,4-dien-3-one (CAB7ß) and its antiangiogenic potential using the chorioallantoic membrane (CAM) with the S180 sarcoma cell line. Experimental and theoretical results show intense absorption in the UVA-UVC region, which is associated with a π → π* transition with intramolecular charge transfer from the trimethyl-cyclohexen-1-yl ring to the chlorophenyl ring. Quantum chemical calculations of the first hyperpolarizability, accounting for both solvent and frequency dispersion effects, are in very good concordance with hyper-Rayleigh scattering measurements. In addition, two-photon absorption allowed band centered at 650 nm was observed. Concerning antiangiogenic activity, CAB7ß causes a significant reduction in the total number, junctions, length and caliber of blood vessels stimulated by S180 cells reducing the presence of blood vessels, inflammatory cells and others elements related to angiogenic process. It is found that CAB7ß is a versatile compound and a promising candidate for linear and nonlinear optical applications, in therapy against sarcoma and phototherapy.

Observation of Distinct Two-Photon Transition Channels in CdTe Quantum Dots in a Regime of Very Strong Confinement.

We report here on the direct observation of distinct two-photon transition channels in glutathione-capped (GSH) CdTe quantum dots (QDs) in a very strong confinement regime. CdTe-GSH QDs with different average diameters (2.5, 3.0, and 3.3 nm) were synthesized through the one-pot method and their two-photon absorption (2PA) spectrum determined by a femtosecond wavelength-tunable Z-scan. Our results show that the two lower-energy one-photon-allowed excitonic transitions, 1S3/2(h) → 1S(e) and 2S3/2(h) → 1S(e), are also accessed via 2PA. These results were ascribed to the relaxation of the parity selection rules due to the noncentrosymmetric structure of the CdTe QDs (zinc-blended structure), whose magnitude are determined by surface defects and structural irregularities present in CdTe-GSH QDs, in the strong confinement regime.

Single-Walled Carbon Nanotubes Functionalized with Carboxylic Acid for Fabricating Polymeric Composite Microstructures.

Carbon nanotube composites are promising materials for mechanical and electrical applications. However, methodologies to incorporate carbon nanotubes in polymeric matrices are on high demand, especially for fabricating devices in the micro-nanoscale. In this paper we show the fabrication of 3D polymeric microstructures with functionalized single-walled carbon nanotubes (SWCNT), by means of two-photon polymerization (2PP). We used a range of SWCNT concentrations (0.01-1 wt%) in the resin to fabricate the composite material. Scanning electron microscopy images show the fabricated microstructures surface quality. Raman spectroscopy was used to confirm the presence and evaluate the distribution of SWCNT in the microstructures. Atomic force microscopy was used to evaluate the mechanical properties of the fabricated microstructures.

Temperature variation at soft periodontal and rat bone tissues during a medium-power diode laser exposure.

OBJECTIVE: The aim of this study was to evaluate temperature variation induced by a diode laser in periodontal repair. BACKGROUND DATA: A diode laser operating with medium power can constitute an alternative device for bacterial reduction at periodontal pockets. This procedure will probably avoid any kind of undesirable thermal damage to the irradiated tissues. METHODS: The temperature variation induced by a 810-nm diode laser was investigated in an in vitro study, varying the soft tissue thickness, and in an in vivo study for soft periodontal and bone tissues. The laser powers used were 600 mW, 800 mW, 1.0 W, and 1.2 W, and the light was delivered by a 300-microm fiber. RESULTS: The laser parameters and irradiation time used did not induce a temperature variation high enough to cause thermal irreversible damage to the periodontal tissues investigated. CONCLUSIONS: This study contributes to the establishment of thermally safe working parameters of a diode medium power laser.

Microbial reduction in periodontal pockets under exposition of a medium power diode laser: an experimental study in rats.

BACKGROUND AND OBJECTIVE: This work evaluates the application of a 810 nm diode laser operating in the range of 400-1,200 mW for bacterial reduction at periodontal treatment. The aim of this study is to examine the immediate effect of the diode medium power laser in reducing the bacterial concentration at periodontal pockets induced in Wistar rats. STUDY DESIGN/MATERIALS AND METHODS: Two bacterial collections were performed on each animal. Microbiological samples were collected before and immediately after laser irradiation. In each group of laser power, eight animals were used, totaling 40 animals. RESULTS: The initial and the final bacterial count revealed that laser irradiation induces considerable bacterial elimination, especially for Prevotella sp, Streptococcus beta-hemolitico, Fusobacterium sp, Pseudomonas sp. CONCLUSIONS: Our results indicate that this laser can constitute an alternative device to traditional infrared systems for bacterial reduction, with some advantage when economical and practical standpoints are considered.