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In optical materials energy is usually extracted only from the lowest excited state, resulting in fundamental energy-efficiency limits such as the Shockley–Queisser limit for single-junction solar cells. Photon-cutting materials provide a way around such limits by absorbing high-energy photons and ‘cutting’ them into multiple low-energy excitations that can subsequently be extracted. The occurrence of photon cutting or quantum cutting has been demonstrated in a variety of materials, including semiconductor quantum dots, lanthanides and organic dyes. Here we show that photon cutting results in bunched photon emission on the timescale of the excited-state lifetime, even when observing a macroscopic number of optical centres. Our theoretical derivation matches well with experimental data on NaLaF₄:Pr³⁺, a material that can cut deep-ultraviolet photons into two visible photons. This signature of photon cutting can be used to identify and characterize new photon-cutting materials unambiguously.

Rose bengal (RB) is a halogenated xanthene dye that has been used to mediate antimicrobial photodynamic inactivation for several years. While RB is highly active against Gram-positive bacteria, it is largely inactive in killing Gram-negative bacteria. We have discovered that addition of the nontoxic salt potassium iodide (100 mM) potentiates green light (540-nm)-mediated killing by up to 6 extra logs with the Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa, the Gram-positive bacterium methicillin-resistant Staphylococcus aureus, and the fungal yeast Candida albicans. The mechanism is proposed to be singlet oxygen addition to iodide anion to form peroxyiodide, which decomposes into radicals and, finally, forms hydrogen peroxide and molecular iodine. The effects of these different bactericidal species can be teased apart by comparing the levels of killing achieved in three different scenarios: (i) cells, RB, and KI are mixed together and then illuminated with green light; (ii) cells and RB are centrifuged, and then KI is added and the mixture is illuminated with green light; and (iii) RB and KI are illuminated with green light, and then cells are added after illumination with the light. We also showed that KI could potentiate RB photodynamic therapy in a mouse model of skin abrasions infected with bioluminescent P. aeruginosa.

Quantitative concentrations measurements using time-resolved laser-induced fluorescence have been demonstrated for nitric oxide (NO) in flame. Fluorescence lifetimes measured using a picosecond Nd:YAG laser and optical parametric amplifier system have been used to directly compensate the measured signal for collisional quenching and evaluate NO concentration. The full evaluation also includes the spectral overlap between the ∼15 cm⁻¹ broad laser pulse and multiple NO absorption lines as well as the populations of the probed energy levels. Effective fluorescence lifetimes of 1.2 and 1.5 ns were measured in prepared NO/N₂/O₂ mixtures at ambient pressure and temperature and in a premixed NH₃-seeded CH₄/N₂/O₂ flame, respectively. Concentrations evaluated from measurements in NO/N₂/O₂ mixtures with NO concentrations of 100–600 ppm were in agreement with set values within 3% at higher concentrations. An accuracy of 13% was estimated by analysis of experimental uncertainties. An NO profile measured in the flame showed concentrations of ∼1000 ppm in the post-flame region and is in good agreement with NO concentrations predicted by a chemical mechanism for NH₃ combustion. An accuracy of 16% was estimated for the flame measurements. The direct concentration evaluation from time-resolved fluorescence allows for quantitative measurements in flames where the composition of major species and their collisional quenching on the probed species is unknown. In particular, this is valid for non-stationary turbulent combustion and implementation of the presented approach for measurements under such conditions is discussed.

While the emission spectrum of fluorescein monoanions isolated in vacuo displays a broad and featureless band, that of resorufin, also belonging to the xanthene family, has a sharp band maximum, clear vibronic structure, and experiences a small Stokes shift. Excited-state proton transfer in fluorescein can account for the differences.

The lipopeptide surfactin produced by certain strains of Bacillus subtilis is a powerful biosurfactant possessing potentially useful antimicrobial properties. In order to better understand its surface behavior, we have used surface sensitive sum frequency generation (SFG) vibrational spectroscopy in the C—H and C═O stretching regions to determine its structure at the air/water interface. Using surfactin with the leucine groups of the peptide ring perdeuterated, we have shown that a majority of the SFG signals arise from the 4 leucine residues. We find that surfactin forms a robust film, and that its structure is not affected by the number density at the interface or by pH variation of the subphase. The spectra show that the ring of the molecule lies in the plane of the surface rather than perpendicular to it, with the tail lying above this, also in the plane of the interface.

Sum frequency generation vibrational spectroscopy (SFG-VS) has become one of the most appealing technologies to characterize molecular structures at interfaces. In this focal point review, we focus on SFG-VS studies at buried polymer interfaces and review many of the recent publications in the field. We also cover the essential theoretical background of SFG-VS and discuss the experimental implementation of SFG-VS.

In this chapter, we present a number of sensitive measurement modalities for the study and analysis of human cancer-affected colon and gastric tissue using terahertz (THz) spectroscopy. Considerable advancements have been reached in characterization of bio-tissue with some accuracy, although too dawn, and still long and exhaustive work have to be done towards well-established and reliable applications. The advent of the THz-time-domain spectroscopy (THz-TDS) test modality at a sub-picosecond time resolution has arguably fostered an intensive work in this field’s research line. The chapter addresses some basic theoretical aspects of this measurement modality with the presentation of general experimental laboratory setup diagrams for THz generation and detection, sample preparation aspects, samples optical parameters calculation procedures and data analysis.

In recent years, efforts have been made in catalysis related surface science studies to explore the possibilities to perform experiments at conditions closer to those of a technical catalyst, in particular at increased pressures. Techniques such as high pressure scanning tunneling/atomic force microscopy (HPSTM/AFM), near ambient pressure x-ray photoemission spectroscopy (NAPXPS), surface x-ray diffraction (SXRD) and polarization-modulation infrared reflection absorption spectroscopy (PM-IRAS) at semi-realistic conditions have been used to study the surface structure of model catalysts under reaction conditions, combined with simultaneous mass spectrometry (MS). These studies have provided an increased understanding of the surface dynamics and the structure of the active phase of surfaces and nano particles as a reaction occurs, providing novel information on the structure/activity relationship. However, the surface structure detected during the reaction is sensitive to the composition of the gas phase close to the catalyst surface. Therefore, the catalytic activity of the sample itself will act as a gas-source or gas-sink, and will affect the surface structure, which in turn may complicate the assignment of the active phase. For this reason, we have applied planar laser induced fluorescence (PLIF) to the gas phase in the vicinity of an active model catalysts. Our measurements demonstrate that the gas composition differs significantly close to the catalyst and at the position of the MS, which indeed should have a profound effect on the surface structure. However, PLIF applied to catalytic reactions presents several beneficial properties in addition to investigate the effect of the catalyst on the effective gas composition close to the model catalyst. The high spatial and temporal resolution of PLIF provides a unique tool to visualize the on-set of catalytic reactions and to compare different model catalysts in the same reactive environment. The technique can be applied to a large number of molecules thanks to the technical development of lasers and detectors over the last decades, and is a complementary and visual alternative to traditional MS to be used in environments difficult to asses with MS. In this article we will review general considerations when performing PLIF experiments, our experimental set-up for PLIF and discuss relevant examples of PLIF applied to catalysis.

A relatively simple setup for collection and detection of light emitted from isolated photo-excited molecular ions has been constructed. It benefits from a high collection efficiency of photons, which is accomplished by using a cylindrical ion trap where one end-cap electrode is a mesh grid combined with an aspheric condenser lens. The geometry permits nearly 10% of the emitted light to be collected and, after transmission losses, approximately 5% to be delivered to the entrance of a grating spectrometer equipped with a detector array. The high collection efficiency enables the use of pulsed tunable lasers with low repetition rates (e.g., 20 Hz) instead of continuous wave (cw) lasers or very high repetition rate (e.g., MHz) lasers that are typically used as light sources for gas-phase fluorescence experiments on molecular ions. A hole has been drilled in the cylinder electrode so that a light pulse can interact with the ion cloud in the center of the trap. Simulations indicate that these modifications to the trap do not significantly affect the storage capability and the overall shape of the ion cloud. The overlap between the ion cloud and the laser light is basically 100%, and experimentally >50% of negatively charged chromophore ions are routinely photodepleted. The performance of the setup is illustrated based on fluorescence spectra of several laser dyes, and the quality of these spectra is comparable to those reported by other groups. Finally, by replacing the optical system with a channeltron detector, we demonstrate that the setup can also be used for gas-phase action spectroscopy where either depletion or fragmentation is monitored to provide an indirect measurement on the absorption spectrum of the ion.

In this work, we examined photoreactivity of synthetic eumelanins, formed by autooxidation of DOPA, or enzymatic oxidation of 5,6-dihydroxyindole-2-carboxylic acid and synthetic pheomelanins obtained by enzymatic oxidation of 5-S-cysteinyldopa or 1:1 mixture of DOPA and cysteine. Electron paramagnetic resonance oximetry and spin trapping were used to measure oxygen consumption and formation of superoxide anion induced by irradiation of melanin with blue light, and time-resolved near-infrared luminescence was employed to determine the photoformation of singlet oxygen between 300 and 600 nm. Both superoxide anion and singlet oxygen were photogenerated by the synthetic melanins albeit with different efficiency. At 450-nm, quantum yield of singlet oxygen was very low (~10⁻⁴) but it strongly increased in the UV region. The melanins quenched singlet oxygen efficiently, indicating that photogeneration and quenching of singlet oxygen may play an important role in aerobic photochemistry of melanin pigments and could contribute to their photodegradation and photoaging.