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Number of trace compounds (called biomarkers), which occur in human breath, provide an information about individual feature of the body, as well as on the state of its health. In this paper we present the results of experiments about detection of certain biomarkers using laser absorption spectroscopy methods of high sensitivity. For NO, OCS, C₂H₆, NH₃, CH₄, CO and CO(CH₃)₂ an analysis of the absorption spectra was performed. The influence of interferents contained in exhaled air was considered. Optimal wavelengths of the detection were found and the solutions of the sensors, as well as the obtained results were presented. For majority of the compounds mentioned above the detection limits applicable for medicine were achieved. The experiments showed that the selected optoelectronic techniques can be applied for screening devices providing early diseases detection.

Failure of cancer surgery to intraoperatively detect and eliminate microscopic residual disease (MRD) causes lethal recurrence and metastases, and the removal of important normal tissues causes excessive morbidity. Here, we show that a plasmonic nanobubble (PNB), a non-stationary laser pulse-activated nanoevent, intraoperatively detects and eliminates MRD in the surgical bed. PNBs were generated in vivo in head and neck cancer cells by systemically targeting tumours with gold colloids and locally applying near-infrared, low-energy short laser pulses, and were simultaneously detected with an acoustic probe. In mouse models, between 3 and 30 residual cancer cells and MRD (undetectable with current methods) were non-invasively detected up to 4 mm deep in the surgical bed within 1 ms. In resectable MRD, PNB-guided surgery prevented local recurrence and delivered 100% tumour-free survival. In unresectable MRD, PNB nanosurgery improved survival twofold compared with standard surgery. Our results show that PNB-guided surgery and nanosurgery can rapidly and precisely detect and remove MRD in simple intraoperative procedures.

Intensity fluctuations in lasers are commonly studied above threshold in some special configurations (especially when emission is fed back into the cavity or when two lasers are coupled) and related with their chaotic behaviour. Similar fluctuating instabilities are usually observed in random lasers, which are open systems with plenty of quasi-modes whose non orthogonality enables them to exchange energy and provides the sort of loss mechanism whose interplay with pumping leads to replica symmetry breaking. The latter however, had never been observed in plain cavity lasers where disorder is absent or not intentionally added. Here we show a fluctuating lasing behaviour at the lasing threshold both in solid and liquid dye lasers. Above and below a narrow range around the threshold the spectral line-shape is well correlated with the pump energy. At the threshold such correlation disappears, and the system enters a regime where emitted laser fluctuates between narrow, intense and broad, weak peaks. The immense number of modes and the reduced resonator quality favour the coupling of modes and prepares the system so that replica symmetry breaking occurs without added disorder.

Nile blue is used extensively in biology as a histological stain and fluorescent probe. Its absorption and emission spectra are strongly solvent dependent, with variations larger than 100 nm. The molecule is charged due to an iminium group, and it is therefore an obvious target for gas-phase ion spectroscopy. Here we report the absorption and emission spectra of the mass-selected bare ions isolated in vacuo, and based on our results we revisit the interpretation of solution-phase spectra. An accelerator mass spectrometer was used for absorption spectroscopy where the absorption is represented by the yield of photofragment ions versus excitation wavelength (action spectroscopy). The luminescence experiments were done with a newly built ion trap setup equipped with an electrospray ion source, and some details on the mass selection technique will be given which have not been described before. In vacuo, the absorption and emission maxima are at 580 ± 10 nm and 628 ± 1 nm. These values are somewhat blue-shifted relative to those obtained in most solvents; however, they are much further to the red than those in some of the most non-polar solvents. Furthermore, the Stokes shift in the gas phase (1300 cm⁻¹) is much smaller than that in these non-polar solvents but similar to that in polar ones. An explanation based on charge localization by solvent dipoles, or by counterions in some non-polar solvents, can fully account for these findings. Hence in the case of ions, it is nontrivial to establish intrinsic electronic transition energies from solvatochromic shifts alone.

We enhance the efficiency of upconverting nanoparticles by investigating the plasmonic coupling of 25 nm diameter NaYF₄:Yb, Er nanoparticles with a gold-shell coating, and study the physical mechanism of enhancement by single-particle, time-resolved spectroscopy. A three-fold overall increase in emission intensity, and five-fold increase of green emission for these plasmonically enhanced particles have been achieved. Using a combination of structural and fluorescent imaging, we demonstrate that fluorescence enhancement is based on the photonic properties of single, isolated particles. Time-resolved spectroscopy shows that the increase in fluorescence is coincident with decreased rise time, which we attribute to an enhanced absorption of infrared light and energy transfer from Yb³⁺ to Er³⁺ atoms. Time-resolved spectroscopy also shows that fluorescence life-times are decreased to different extents for red and green emission. This indicates that the rate of photon emission is not suppressed, as would be expected for a metallic cavity, but rather enhanced because the metal shell acts as an optical antenna, with differing efficiency at different wavelengths.

Poly(methyl methacrylate) (PMMA) terminated with elemental blocks containing polyhedral oligomeric silsesquioxane (POSS), hereafter referred to as PPMP, was synthesized by living anionic polymerization. Combining modern interfacial-sensitive spectroscopy with traditional contact angle measurements, static and dynamic structures at the surface of PPMP films in water were examined. The surface of the well-annealed PPMP films, where the POSS end groups were preferentially segregated, was flat at the sub-nanometer level. Once the PPMP film was immersed in water, the surface was reorganized, and the rate was much slower for PPMP than for the conventional PMMA. This implies that the POSS units hindered the interfacial dynamics of the polymer segments. Then, platelet-adhesion tests were performed on the PPMP films. The number of platelets adhered to the PPMP film was dependent on the pre-immersion time in phosphate-buffered saline before the platelet seeding, whereas that of the reference PMMA film was unaffected by the pre-immersion time. These results could be explained in terms of the aggregation states of water at the interface.

Eumelanin photoprotects pigmented tissues from ultraviolet (UV) damage. However, UVA-induced tanning seems to result from the photooxidation of preexisting melanin and does not contribute to photoprotection. We investigated the mechanism of UVA-induced degradation of 5,6-dihydroxyindole-2-carboxylic acid (DHICA)-melanin taking advantage of its solubility in a neutral buffer and using a differential spectrophotometric method to detect subtle changes in its structure. Our methodology is suitable for examining the effects of various agents that interact with reactive oxygen species (ROS) to determine how ROS is involved in the UVA-induced oxidative modifications. The results show that UVA radiation induces the oxidation of DHICA to indole-5,6-quinone-2-carboxylic acid in eumelanin, which is then cleaved to form a photodegraded, pyrrolic moiety and finally to form free pyrrole-2,3,5-tricarboxylic acid. The possible involvement of superoxide radical and singlet oxygen in the oxidation was suggested. The generation and quenching of singlet oxygen by DHICA-melanin was confirmed by direct measurements of singlet oxygen phosphorescence.

Sum-frequency generation vibrational spectroscopy (SFG-VS) was first developed in the 1980s and it has been proven a uniquely sensitive and surface/interface selective spectroscopic probe for characterization of the structure, conformation and dynamics of molecular surfaces and interfaces. In recent years, there have been many progresses in the development of methodology and instrumentation in the SFG-VS toolbox that have significantly broadened the application to complex molecular surfaces and interfaces. In this review, after presenting a unified view on the theory and methodology focusing on the SFG-VS spectral lineshape, as well as the new opportunities in SFG-VS applications with such developments, some of the controversial issues that have been puzzling the community are discussed. The aim of this review is to present to the researchers and students interested in molecular surfaces and interfacial sciences up-to-date perspectives complementary to the existing textbooks and reviews on SFG-VS.

Understanding interactions of calcium with lipid membranes at the molecular level is of great importance in light of their involvement in calcium signaling, association of proteins with cellular membranes, and membrane fusion. We quantify these interactions in detail by employing a combination of spectroscopic methods with atomistic molecular dynamics simulations. Namely, time-resolved fluorescent spectroscopy of lipid vesicles and vibrational sum frequency spectroscopy of lipid monolayers are used to characterize local binding sites of calcium in zwitterionic and anionic model lipid assemblies, while dynamic light scattering and zeta potential measurements are employed for macroscopic characterization of lipid vesicles in calcium-containing environments. To gain additional atomic-level information, the experiments are complemented by molecular simulations that utilize an accurate force field for calcium ions with scaled charges effectively accounting for electronic polarization effects. We demonstrate that lipid membranes have substantial calcium-binding capacity, with several types of binding sites present. Significantly, the binding mode depends on calcium concentration with important implications for calcium buffering, synaptic plasticity, and protein-membrane association.

Conventional photoluminescence (PL) yields at most one emitted photon for each absorption event. Downconversion (or quantum cutting) materials can yield more than one photon by virtue of energy transfer processes between luminescent centers. In this work, we introduce Gd₂O₂S:Tm³⁺ as a multi-photon quantum cutter. It can convert near-infrared, visible, or ultraviolet photons into two, three, or four infrared photons of ∼1800 nm, respectively. The cross-relaxation steps between Tm³⁺ ions that lead to quantum cutting are identified from (time-resolved) PL as a function of the Tm³⁺ concentration in the crystal. A model is presented that reproduces the way in which the Tm³⁺ concentration affects both the relative intensities of the various emission lines and the excited state dynamics and providing insight in the quantum cutting efficiency. Finally, we discuss the potential application of Gd₂O₂S:Tm³⁺ for spectral conversion to improve the efficiency of next-generation photovoltaics.