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Polarimetry is generally used to determine the polarization state of light beams in various research fields, such as biomedicine, astronomy, and materials science. In particular, the rotating quarter-wave plate polarimeter is an inexpensive and versatile option used in several single-wavelength applications to determine the four Stokes parameters. Extending this technique to broadband spectroscopic measurements is of great scientific interest since the information on light polarization is highly sensitive to anisotropic phenomena. However, the need for achromatic polarizing elements, especially quarter-wave plates, requires special attention in their modeling. In this study, we implemented a rotating retarder spectropolarimeter for broadband measurements using a commercially available quasi-achromatic biplate retarder over the visible range. Here, we present a comprehensive approach for troubleshooting this type of spectropolarimeter through the observation of artifacts stemming from the standard single-plate retarder model. Then, we derive a more suitable model for a quasi-achromatic retarder consisting of a biplate junction. This new biplate model requires knowledge of the intrinsic dispersive properties of the biplate, namely the equivalent retardance, fast axis tilt, and rotatory angle. Hence, in this study, we also show a self-consistent methodology to determine these biplate properties using the same polarimeter apparatus so that accurate Stokes parameters can be determined independently. Finally, the comparison of data generated with the standard single-plate and new biplate models shows a significant improvement in the measurement precision of the investigated polarization states, which confirms that remodeling the retarder for reliable spectropolarimetry is necessary.

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The present work reports the effects of meso-tetrakis (4-sulfonatophenyl) porphyrin (TPPS4) aggregation on its excited states absorption spectra, triplet states quenching by molecular oxygen and singlet oxygen production. Experimental techniques such as optical absorption, Z-scan with a white light continuum source and the Laser Flash Photolysis were used to fulfil the study. J-aggregates possess reverse saturable absorption in the 505-660 nm spectral range with a peak centered close to 540 nm. These facts together with their fast relaxation time suggest that they can be employed as material for ultrafast optical limiting and switching. Even though aggregation reduces the porphyrin excited-state lifetimes and quantum yields, it does not reduce the probability of the contact between the quencher and the excited aggregate. Aggregation does not change the contribution of energy transfer mechanisms to triplet state quenching by molecular oxygen. The production of singlet oxygen, the intense absorption in the phototherapeutic window and the high efficiency of conversion of light energy into heat, allow consider J-aggregates as a theranostic agent for photomedicine. It is proposed to use J-aggregates for diagnostics by photoacoustic images and in combination with a near-infrared photodynamic/photothermal dual mode therapy, thus improving synergistically the therapeutic response.

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Linear carbon chains (LCCs) are one-dimensional materials with unique properties, including high Debye temperatures and restricted selection rules for phonon interactions. Consequently, their Raman C-band frequency's temperature dependence is a probe to their thermal properties, which are well described within the Debye formalism even at room temperatures. Therefore, with the basis on a semiempirical approach we show how to use the C band to evaluate the LCCs' internal energy, heat capacity, coefficient of thermal expansion, thermal strain, and Grüneisen parameter, providing universal relations for these quantities in terms of the number of carbons atoms and the temperature.

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Complexes derived from meso-tetra(thienyl)porphyrins (TThP) and meso-tetra(pyridyl)porphyrin (TPyP) containing peripheral ruthenium complexes with general formulas {TPyP[RuCl(dppb)(5,5'-Mebipy)]4}(PF6)4, {TThP[RuCl(dppb)(5,5'-Mebipy)]4}(PF6)4, and {TThP-me-[RuCl(dppb)(5,5'-Mebipy)]4}(PF6)4 [5,5'-Mebipy = 5,5'-dimethyl-2,2'-bipyridine and dppb = 1,4-bis(diphenylphosphino)butane] were synthesized and characterized by spectroscopy techniques (1H- and 31P{1H}-NMR, IR, UV/vis, fluorescence, and electron paramagnetic resonance (EPR)), cyclic voltammetry, coulometry, molar conductivity, and elemental analysis. Voltammetry and UV/vis studies demonstrated differentiated electronic properties for ruthenium appended with TThP and TThP-me when compared to ruthenium appended with TPyP. The UV/vis analysis for the ruthenium complex derived from TThP and TThP-me, as well as the Soret and Q bands, characteristics of porphyrins, showed a band at 700 nm referring to the Ru → S electronic transition, and porphyrin TThP-me showed another band at 475 nm from the Ru-N transition. The attribution of these bands was confirmed by spectroelectrochemical analysis. Cyclic voltammetry analysis for the ruthenium complex derived from TPyP exhibited only an electrochemical process with E1/2 = 0.47 V assigned to the Ru(II)/Ru(III) redox pair (Fc/Fc+). On the other hand, two processes were observed for the ruthenium complexes derived from TThP and TThP-me, with E1/2 around 0.17 and 0.47 V, which were attributed to the formation of a mixed valence tetranuclear species containing Ru(II) and Ru(III) ions, showing that the peripheral groups are not oxidized at the same potential. Fluorescence spectroscopic experiments show the existence of a mixed state of emission in the supramolecular porphyrin moieties. The results suggest the formation of Ru(II)-Ru(III) mixed valence complexes when oxidation potential was applied around 0.17 V in the {TThP[RuCl(dppb)(5,5'-Mebipy)]4}(PF6)4 and {TThP-me-[RuCl(dppb)(5,5'-Mebipy)]4}(PF6)4 species.

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This work addresses the problem of how a nano-object adheres to a supporting media. The case of study are the serpentine-like structures of single-wall carbon nanotubes (SWNTs) grown on vicinal crystalline quartz. We develop in situ nanomanipulation and confocal Raman spectroscopy in such systems, and to explain the results, we propose a dynamical equation in which static friction is treated phenomenologically and implemented as cutoff for velocities, via Heaviside step function and an adhesion force tensor. We demonstrate that the strain profiles observed along the SWNTs are due to anisotropic adhesion, adhesion discontinuities, strain avalanches, and memory effects. The equation is general enough to make predictions for various one- and two-dimensional nanosystems adhered to a supporting media.

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An imidazolium tetrasubstituted cationic porphyrin derivative (the free base and its Zn(II) complex) with five-membered heterocyclic groups in the meso-positions were synthesized using microwave irradiation, and the compounds obtained characterized by (1)H-NMR and mass spectrometry. We observed that under microwave irradiation the yield is similar to when the synthesis is performed under conventional heating, however, the time required to prepare the porphyrins decreases enormously. In order to investigate the electronic state of these compounds, we employed UV-Vis and fluorescence spectroscopy combined with quantum chemical calculations. The results reveal the presence, in both compounds, of a large number of electronic states involving the association between the Soret and a blue-shifted band. The Soret band in both compounds also shows a considerable solvent dependence. As for emission, these compounds present low quantum yield at room temperature and no solvent influence on the fluorescence spectra was observed.

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Cd(1-x)Mn(x)S nanocrystals (NCs) were successfully grown in a glass matrix and investigated by photoluminescence (PL), electron paramagnetic resonance (EPR) and magnetic force microscopy (MFM). We verified that the luminescent properties of these NCs can be controlled both by changing the x concentration and by thermal annealing of the samples. The EPR and PL data showed that the characteristic emission of Mn(2+) ions ((4)T(1)-(6)A(1)) is only observed when this magnetic impurity is substitutionally incorporated in the Cd(1-x)Mn(x)S NC core (site S(I)). Besides, it was observed that the emission ((4)T(1)-(6)A(1)) suppression, caused by the Mn(2+) ion presence near the surface (site S(II)) of the Cd(1-x)Mn(x)S NCs, is independent of the host material. The MFM images also confirmed the high quality of the Cd(1 - x)Mn(x)S NC samples, showing a uniform distribution of total magnetic moments in the nanoparticles.

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We study single wall carbon nanotubes (SWNTs) deposited on quartz. Their Raman spectrum depends on the tube-substrate morphology, and in some cases, it shows that the same SWNT-on-quartz system exhibits a mixture of semiconductor and metal behavior, depending on the orientation between the tube and the substrate. We also address the problem using electric force microscopy and ab initio calculations, both showing that the electronic properties along a single SWNT are being modulated via tube-substrate interaction.

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The control of emission properties in luminescent polymers such as poly(p-phenylene vinylene) (PPV) is important for various applications, and may be achieved with suitable molecular architectures in nanostructured films. This paper reports on optical properties of PPV films, using ellipsometry measurements for emitted light in the scope of the Stokes' theory. Organized PPV films obtained with the Langmuir-Blodgett (LB) method exhibited high degree of polarization for the emitted light, while cast films emitted mainly non-polarized light. From ellipsometry data, a secondary structure was inferred for poly(xylylidene tetrahydrothiophenium) chloride (PTHT), a PPV precursor, in solution, which is retained only to a small extent in the PPV cast film as thermal conversion was performed close to the glass transition temperature of PPV. On the other hand, a higher intensity of emitted light with circular polarization was observed for the LB film, which is attributed to PPV molecular secondary structure that was enhanced during the LB film deposition. Circular dichroism experiments were performed to corroborate this hypothesis. It is suggested that such a secondary structure has not been predicted in theoretical models for PPV because possible conformational changes induced in the processing steps are not taken into account.

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The nanoscale interactions between adjacent layers of layer-by-layer (LBL) films from poly(allylamine hydrochloride) (PAH) and azodye Brilliant Yellow (BY) have been investigated, with the films employed for optical storage and the formation of surface-relief gratings. Using Fourier transform infrared spectroscopy, we identified interactions involving SO3- groups from BY and NH+ groups from PAH. These electrostatic interactions were responsible for the slow kinetics of writing in the optical storage experiments, due to a tendency to hinder photoisomerization and the subsequent reorientation of the azochromophores. The photoinduced birefringence did not saturate after one hour of exposure to the writing laser, whereas in azopolymer films, saturation is normally reached within a few minutes. On the other hand, the presence of such interactions prevented thermal relaxation of the chromophores after the writing laser was switched off, leading to a very stable written pattern. Moreover, the nanoscale interactions promoted mass transport for photoinscription of surface-relief gratings on PAH/BY LBL films, with the azochromophores being able to drag the inert PAH chains when undergoing the trans-cis-trans photoisomerization cycles. A low level of chromophore degradation was involved in the SRG photoinscription, which was confirmed with micro-Raman and fluorescence spectroscopies.

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