Novel Probe for Thermally Controlled Raman Spectroscopy Using Online IR Sensing and Emissivity Measurements.

Temperature rise during Raman spectroscopy can induce chemical alterations of the material under analysis and seriously affect its characterization. Thus, such photothermal side effects can represent a serious problem to be carefully controlled in order to safeguard the integrity of the material and its spectral features. In this work, an innovative probe for thermally controlled portable Raman spectroscopy (exc. 785 nm) equipped with infrared sensing lines was developed. It included an infrared source and two thermopile sensors, which allowed to perform real-time measurements of the local emissivity of the material surface under laser excitation. The emissivity, which is needed in order to monitor the temperature of the irradiated surface through infrared radiation measurements, represents the complementary component of the reflectance in the radiative energy balance. Thus, total reflectance, temperature measurements and Raman spectroscopy were integrated in the present probe. After independently assessing the reliability of the former in order to derive the emissivity of variety of materials, the probe was successfully applied on pigments, paint layers, and a painting on canvas. The results achieved evidence the significant exploitation potential of the novel tool.

Nanoscopic insights into the surface conformation of neurotoxic amyloid ß oligomers.

Raman spectroscopy assisted by localized plasmon resonances generating effective hot spots at the gaps between intertwined silver nanowires is herein adopted to unravel characteristic molecular motifs on the surface of Aß42 misfolded oligomers that are critical in driving intermolecular interactions in neurodegeneration.

Terahertz Time-Domain Reconstruction of Coating Microstratigraphy on Gilded Surfaces.

Here, a systematic study in order to assess the potential of THz time domain reflectometry for measuring the thicknesses of overpaint layers applied on original gilded surfaces was carried out. The work is part of a thorough characterization campaign, which is going on at the Rijksmuseum for addressing the conservation problems of a set of 19th century gilded picture frames on which heavy coatings were applied in previous undocumented restoration interventions. To perform such non-invasive thickness measurements, an analytical protocol based on Gaussian fits of the THz pulse-echo temporal profiles was optimized through the preparation of suitable technical samples and the comparison with direct thickness measurements. Finally, the methodology was validated by characterizing the microstratigraphy of an original sculptural element from a gilded picture frame in the Rijksmuseum collection. The results achieved show the effectiveness of the present approach in revealing multi-layered dielectric microstructures with a spatial resolution of about 30 µm when using a spectral range up to 1.5 THz.

1064-nm-resonant gold nanorods for photoacoustic theranostics within permissible exposure limits.

Therapeutic and diagnostic methods based on photomechanical effects are attracting much current attention in contexts as oncology, cardiology and vascular surgery, for such applications as photoacoustic imaging or microsurgery. Their underlying mechanism is the generation of ultrasound or cavitation from the interaction of short optical pulses with endogenous dyes or targeted contrast agents. Among the latter, gold nanorods are outstanding candidates, but their use has mainly been reported for photoacoustic imaging and photothermal treatments. Conversely, much less is still known about their value as a precision tool for photomechanical manipulations, such as to impart local damage with high spatial resolution through the expansion and collapse of microbubbles. Here, we address the feasibility of gold nanorods exhibiting a distribution of surface plasmon resonances between about 900 to above 1100 nm as a contrast agent for photoacoustic theranostics. After testing their cytotoxicity and cellular uptake, we discuss their photostability and use to mediate cavitation and the photomechanical destruction of targeted cells. We find that the choice of a plasmonic band peaking around 1064 nm is key to enhance the translational potential of this approach. With respect to the standard alternative of 800 nm, at 1064 nm, relevant regulations on optical exposure are less restrictive and the photonic technology is more mature.

Raman spectrometer for the automated scan of large painted surfaces.

In this work, a novel Raman scanner capable of performing point-to-point mapping of relatively large surface of paintings is presented. This device employs an excitation wavelength of 1064 nm, and it is equipped with a high efficiency probe in order to collect the back-scattered light from each point of analysis. The use of long depth-of-field optics as well as an autofocus system allowed maintaining the best conditions for the Raman signal acquisition during the scanning, regardless of the surface irregularities. The small dimension of the optical components and the reasonable size of mechanical parts made this instrumentation particularly suitable for on-site measurements. Finally, the Raman scanner was also equipped with an online temperature control using a thermal sensor, which allows modulating automatically the output power of the laser source in order to prevent overheating and alteration effects during the scanning process. The capabilities of the Raman scanner were evaluated scanning two valuable paintings one attributed to Ambrogio Lorenzetti and the other to Duccio da Buoninsegna of the fourteenth century.