Mapping the broadband circular dichroism of copolymer films with supramolecular chirality in time and space

Measurements of the electronic circular dichroism (CD) are highly sensitive to the absolute configuration and conformation of chiral molecules and supramolecular assemblies and have therefore found widespread application in the chemical and biological sciences. Here, we demonstrate an approach to simultaneously follow changes in the CD and absorption response of photoexcited systems over the ultraviolet−visible spectral range with 100 fs time resolution. We apply the concept to chiral polyfluorene copolymer thin films and track their electronic relaxation in detail. The transient CD signal stems from the supramolecular response of the system and provides information regarding the recovery of the electronic ground state. This allows for a quantification of singlet−singlet annihilation and charge-pair formation processes. Spatial mapping of chiral domains on femtosecond time scales with a resolution of 50 μm and diffraction-limited steady-state imaging of the circular dichroism and the circularly polarised luminescence (CPL) of the films is demonstrated.

Efficient near-infrared quantum cutting by cooperative energy transfer in Bi3TeBO9:Nd3+ phosphors

An efficient near-infrared quantum cutting process by cooperative down-conversion of active Bi3+ and Nd3+ ions was demonstrated in Bi3TeBO9:Nd3+ phosphors. In particular, the near-infrared emission of Nd3+ ions enhanced by Bi3+ ions of a series of novel Bi3TeBO9:Nd3+ microcrystalline powders doped with Nd3+ ions in various concentrations was investigated. In order to investigate the luminescent properties of BTBO:Nd3+ powders, the excitation and emission spectra and the fluorescence decay time were measured and analyzed. In particular, the emission of Bi3TeBO9:Nd3+ at 890 and 1064 nm was excited at 327 nm (via energy transfer from Bi3+ ions) and at 586.4 nm (directly by Nd3+ ions). The highest intensity emission bands in near-infrared were detected in the spectra of Bi3TeBO9:Nd3+ doped with 5.0 and 0.5 at.% of Nd3+ ions upon excitation in ultraviolet and visible spectral range, respectively. The fluorescence decay lifetime monitored at 1064 nm for Bi3TeBO9:Nd3+ powders shows the single- or double-exponential character depending on the concentrations of Nd3+ ions. The possible mechanisms of energy relaxation after excitation Bi3TeBO9:Nd3+ powders in ultraviolet or visible spectral range were discussed. The investigated Bi3TeBO9:Nd3+ phosphors efficiently concentrate the ultraviolet/visible radiation in the near-infrared spectral range and can be potentially used as effective spectral converters. Graphical abstract

Quasi-CW Pumping of a Single-Frequency Fiber Amplifier for Efficient SHG in PPLN Crystals with Reduced Thermal Load

Single-frequency lasers are essential for high-resolution spectroscopy and sensing applications as they combine high-frequency stability with low noise and high output power stability. For many of these applications, there is increasing interest in power-scaling single-frequency sources, both in the near-infrared and visible spectral range. We report the second-harmonic generation of 670 µJ at 532 nm of a single-frequency fiber amplifier signal operating in the quasi-continuous-wave mode in a 10-mm periodically poled Mg-doped lithium niobate (MgO:PPLN) crystal, while increasing compactness. To the best of our knowledge, this is the highest pulse energy generated in this crystal, which may find applications in the visible and UV such as remote Raman spectroscopy.

Effect of Different Catalysts and Growth Temperature on the Photoluminescence Properties of Zinc Silicate Nanostructures Grown via VLS Method

Herein, we explore the photoluminescence properties of zinc silicate (Zn2SiO4) nanostructures synthesized by vapor-liquid-solid (VLS) mode of growth using three different catalysts (Sn, Ag and Mn). Different catalysts significantly influence the growth rate which in turn has an impact on the structure and hence the photoluminescence of the prepared zinc silicate nanostructures. Zn2SiO4 has a wide bandgap of about 5.5 eV and in its pure form, it does not emit in visible region due to its inner shell electronic transitions between the 3d5 energy levels. However, the incorporation of different catalysts (Sn, Ag and Mn) at different growth temperatures into the Zn2SiO4 crystal growth kinetics provides wide visible spectral range of photoluminescence (PL) emissions. PL analysis shows broad multi-band spectrum in the visible region and distinct colours (red, yellow, green, blue, cyan and violet) are obtained depending on the crystalline structure of the prepared nanostructures. The allowed transitions due to the effect of different catalysts on zinc silicate lattice offer a huge cross-section of absorption that generates strong photoluminescence. The correlation between the structural and optical properties of the synthesized nanostructures is discussed in detail. The synthesized photoluminescent nanostructures have potential applications in solid-state lighting and display devices.

Using high refractive index nanoparticles to inhibition of spontaneous emission

The article discusses the issues of inhibition of spontaneous emission of molecules by using silicon spherical nanoparticles and dimers made from them. It is shown that at different wavelengths of the visible spectral range, the value of the total spontaneous transitions rate in a molecule located at an optimal distance with respect to the structure with silicon nanospheres and at an optimal size of the structure can be up to 5–10 times lower than the transition rate in the case when the nanoparticles are absent.

Ablation-Free Laser Printing of Structural Colors in Reflection at 25,000 DPI

Using direct femtosecond laser patterning of metal-insulator-metal (MIM) sandwich designed to support Fabry-Perot mode in the visible spectral range we demonstrate new practically relevant strategy for high-resolution color printing. Irradiation of the MIM sandwich by tightly focused laser pulses allows to produce unique 3D surface nanostructures – hollow nanobumps and nanojets - locally modulating surface reflectivity. Laser processing parameters control the 3D shape of such nanostructures allowing to gradually tune the reflected color from reddish brown to pure green. Up-scalable ablation-free laser fabrication method paves the way towards various applications ranging from large-scale structural color printing to optical sensors and security labeling at a lateral resolution of 25,000 dots per inch.

Three-dimensional mapping of the optical centers in the bulk of natural diamond by photoluminescent spectroscopy

Optically active defects in natural diamonds form specific spectral bands in the optical absorption and luminescence spectra and are called optical centers. Optical centers in the visible spectral range and their corresponding defects are called color centers. Spectral absorption and luminescence bands usually occupy several tens of nanometers in the spectral range and often have a complex structure. This spectral structure is unique to each optical center. The stationary broadband UV-MIR characterization of the set of optically active defects in the bulk of natural diamond with a widely varying concentration of impurities was carried out in this work. Comparison of the initial and modified impurity-defect structures of near-surface diamond layers was carried out by the method of cathodoluminescence and cathodoluminescence topography.

Antioxidant Power on Dermal Cells by Textiles Dyed with an Onion (Allium cepa L.) Skin Extract

In this study, the phenol loading and antioxidant activity of wool yarn prepared with the aqueous extract of onion (Allium cepa L.) skin was enhanced by implementing the dyeing process with the use of alum as a mordant. Spectrophotometric and chromatographic methods were applied for the characterization of polyphenolic substances loaded on the wool yarn. The antioxidant/anti-inflammatory properties were evaluated by determining the level of intra- and extra-cellular reactive oxygen species (ROS) production in keratinocytes and dermal fibroblasts pre-treated with lipopolysaccharide put in contact with artificial sweat. An elevated dye uptake on wool was observed for the pre-mordanted sample, as demonstrated by high absorbance values in the UV-Visible spectral range. Chromatographic results showed that protocatechuic acid and its glucoside were the main phenolic acid released in artificial sweat by the wool yarns, while quercetin-4′-glucoside and its aglycone quercetin were more retained. The extract released from the textile immersed in artificial sweat showed a significant reducing effect on the intra-and extracellular ROS levels in the two cell lines considered. Cytofluorimetric analyses demonstrated that the selected mordant was safe at the concentration used in the dyeing procedure. Therefore, alum pre-mordanted textiles dyed with onion-skin extracts may represent an interesting tool against skin diseases.

The NO₂ camera based on Gas Correlation Spectroscopy

Monitoring of NO2 is in the interest of public health, because NO2 contributes to the decline of air quality in many urban regions. Its abundance can be a direct cause of asthmatic and cardiovascular diseases and plays a significant part in forming other pollutants such as ozone or particulate matter. Spectroscopic methods have proven to be reliable and of high selectivity by utilizing the characteristic spectral absorption signature of trace gasses such as NO2. However, they typically lack the spatio-temporal resolution required for real-time imaging measurements of NO2 emissions. We propose imaging measurements of NO2 in the visible spectral range using a novel instrument, an NO2 camera based on the principle of Gas Correlation Spectroscopy (GCS). For this purpose two gas cells (cuvettes) are placed in front of two camera modules. One gas cell is empty, while the other is filled with a high concentration of the target gas. The filled gas cell operates as a non-dispersive spectral filter to the incoming light, maintaining the two-dimensional imaging capability of the sensor arrays. NO2 images are generated on the basis of the signal ratio between the two images in the spectral window between 430 and 445 nm, where the NO2 absorption cross section is strongly structured. The capabilities and limits of the instrument are investigated in a numerical forward model. The predictions of this model are verified in a proof-of-concept measurement, in which the column densities in specially prepared reference cells were measured with the NO2 camera and a conventional DOAS instrument. Finally, results from measurements at a large power plant, the Großkraftwerk Mannheim (GKM), are presented. NO2 column densities of the plume emitted from a GKM chimney are quantified at a spatio-temporal resolution of 1/6 frames per second (FPS) and 0.92 m × 0.92 m. A detection limit of 1.89 · 1016 molec cm−2 was reached. An NO2 mass flux of Fm = (7.41 ± 4.23) kg h−1 was estimated on the basis of momentary wind speeds obtained from consecutive images. The camera results are verified by comparison to NO2 slant column densities obtained from elevation scans with a MAX-DOAS instrument. The instrument prototype is highly portable and cost-efficient at building costs of below 2,000 Euro.