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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.

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.

Organic nanomaterials are attracting a great deal of interest for use in flexible electronic applications such as logic circuits, displays and solar cells. These technologies have already demonstrated good performances, but flexible organic memories are yet to deliver on all their promise in terms of volatility, operational voltage, write/erase speed, as well as the number of distinct attainable levels. Here, we report a multilevel non-volatile flexible optical memory thin-film transistor based on a blend of a reference polymer semiconductor, namely poly(3-hexylthiophene), and a photochromic diarylethene, switched with ultraviolet and green light irradiation. A three-terminal device featuring over 256 (8 bit storage) distinct current levels was fabricated, the memory states of which could be switched with 3 ns laser pulses. We also report robustness over 70 write–erase cycles and non-volatility exceeding 500 days. The device was implemented on a flexible polyethylene terephthalate substrate, validating the concept for integration into wearable electronics and smart nanodevices.

In CH₃NH₃PbI₃-based high efficiency perovskite solar cells (PSCs), tiny amount of PbI₂ impurity was often found with the perovskite crystal. However, for two-step solution process-based perovskite films, most of findings have been based on the films having different morphologies between with and without PbI₂. This was mainly due to the inferior morphology of pure perovskite film without PbI₂, inevitably produced when the remaining PbI₂ forced to be converted to perovskite, so advantages of pure perovskite photoactive layer without PbI₂ impurity have been overlooked. In this work, we designed a printing-based two-step process, which could not only generate pure perovskite crystal without PbI₂, but also provide uniform and full surface coverage perovskite film, of which nanoscale morphology was comparable to that prepared by conventional two-step solution process having residual PbI₂. Our results showed that, in two-step solution process-based PSC, pure perovskite had better photon absorption and longer carrier lifetime, leading to superior photocurrent generation with higher power conversion efficiency. Furthermore, this process was further applicable to prepare mixed phase pure perovskite crystal without PbI₂ impurity, and we showed that the additional merits such as extended absorption to longer wavelength, increased carrier lifetime and reduced carrier recombination could be secured.

A magnetically controlled elastically driven electroporation phenomenon, or magneto-elasto-electroporation (MEEP), is discovered while studying the interactions between core-shell magnetoelectric nanoparticles (CSMEN) and biological cells in the presence of an a.c. magnetic field. In this paper we report the effect of MEEP observed via a series of in-vitro experiments using core (CoFe₂O₄)-shell (BaTiO₃) structured magnetoelectric nanoparticles and human epithelial cells (HEP2). The cell electroporation phenomenon and its correlation with the magnetic field modulated CSMEN are described in detail. The potential application of CSMEN in electroporation is confirmed by analyzing crystallographic phases, multiferroic properties of the fabricated CSMEN, influences of d.c. and a.c. magnetic fields on the CSMEN and cytotoxicity tests. The mathematical formalism to quantitatively describe the phenomena is also reported. The reported findings provide insights into the underlying MEEP mechanism and demonstrate the utility of CSMEN as an electric pulse-generating nano-probe in electroporation experiments with a potential application toward accurate and efficient targeted cell permeation.

Broadband, mid-infrared supercontinuum generation in a step-index fluoroindate fibre is reported. By using ~70-picosecond laser pulses at 2.02 μm, provided by an optical parametric generator, a wide spectrum with a cut-off wavelength at 5.25 μm and a 5-dB bandwidth covering the entire 2–5 μm spectral interval has been demonstrated for the first time. The behaviour of the supercontinuum was investigated by changing the peak power and the wavelength of the pump pulses. This allowed the optimal pumping conditions to be determined for the nonlinear medium that was used. The optical damage threshold for the fluoroindate fibre was experimentally found to be ~200 GW/cm².

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.