Publication database
Capturing an initial intermediate during the P450nor enzymatic reaction using time-resolved XFEL crystallography and caged-substrate
Time-resolved serial femtosecond crystallography using an X-ray free electron laser (XFEL) in conjunction with a photosensitive caged-compound offers a crystallographic method to track enzymatic reactions. Here we demonstrate the application of this method using fungal NO reductase, a heme-containing enzyme, at room temperature. Twenty milliseconds after caged-NO photolysis, we identify a NO-bound form of the enzyme, which is an initial intermediate with a slightly bent Fe-N-O coordination geometry at a resolution of 2.1 Å. The NO geometry is compatible with those analyzed by XFEL-based cryo-crystallography and QM/MM calculations, indicating that we obtain an intact Fe3+-NO coordination structure that is free of X-ray radiation damage. The slightly bent NO geometry is appropriate to prevent immediate NO dissociation and thus accept H− from NADH. The combination of using XFEL and a caged-compound is a powerful tool for determining functional enzyme structures during catalytic reactions at the atomic level.
CIGS thin-film solar module processing: case of high-speed laser scribing
In this paper, we investigate the laser processing of the CIGS thin-film solar cells in the case of the high-speed regime. The modern ultra-short pulsed laser was used exhibiting the pulse repetition rate of 1 MHz. Two main P3 scribing approaches were investigated – ablation of the full layer stack to expose the molybdenum back-contact, and removal of the front-contact only. The scribe quality was evaluated by SEM together with EDS spectrometer followed by electrical measurements. We also modelled the electrical behavior of a device at the mini-module scale taking into account the laser-induced damage. We demonstrated, that high-speed process at high laser pulse repetition rate induced thermal damage to the cell. However, the top-contact layer lift-off processing enabled us to reach 1.7 m/s scribing speed with a minimal device degradation. Also, we demonstrated the P3 processing in the ultra-high speed regime, where the scribing speed of 50 m/s was obtained. Finally, selected laser processes were tested in the case of mini-module scribing. Overall, we conclude, that the top-contact layer lift-off processing is the only reliable solution for high-speed P3 laser scribing, which can be implemented in the future terawatt-scale photovoltaic production facilities.
Corrosion Resistive Laser Marking of Stainless Steel by Atlantic Series Picosecond Laser
Medical tools and other devices made of stainless steel (SS) require laser markings for unique device identification (UDI). These markings need to be corrosion resistant in order to withstand numerous autoclave cycles. EKSPLA with FTMC has developed a picosecond laser marking system – for reliable UDI marks on surgical and spring grade of stainless steel for corrosion resistive applications.
Detecting Rat’s Kidney Inflammation Using Real Time Photoacoustic Tomography
Photoacoustic Tomography (PAT) is a promising medical imaging modality that combines optical imaging contrast with the spatial resolution of ultrasound imaging. It can also distinguish the changes in biological features. But, real-time PAT system should be confirmed due to photoacoustic effect for tissue. Thus, we have developed a real-time PAT system using a custom-developed data acquisition board and ultrasound linear probe. To evaluate performance of our system, phantom test was performed. As a result of those experiments, the system showed satisfactory performance and its usefulness has been confirmed. We monitored the degradation of inflammation which induced on the rat’s kidney using real-time PAT.
Development and characterization of a laser-plasma soft X-ray source for contact microscopy
In this work, we present a compact laser-produced plasma source of X-rays, developed and characterized for application in soft X-ray contact microscopy (SXCM). The source is based on a double stream gas puff target, irradiated with a commercially available Nd:YAG laser, delivering pulses with energy up to 740 mJ and 4 ns pulse duration at 10 Hz repetition rate. The target is formed by pulsed injection of a stream of high-Z gas (argon) into a cloud of low Z-gas (helium) by using an electromagnetic valve with a double nozzle setup. The source is designed to irradiate specimens, both in vacuum and in helium atmosphere with nanosecond pulses of soft X-rays in the ‘‘water-window” spectral range. The source is capable of delivering a photon fluence of about 1.09 x 103 photon/µm2/pulse at a sample placed in vacuum at a distance of about 20 mm downstream the source. It can also deliver a photon fluence of about 9.31 x 102 - photons/µm2/pulse at a sample placed in a helium atmosphere at the same position. The source design and results of the characterization measurements as well as the optimization of the source are presented and discussed. The source was successfully applied in the preliminary experiments on soft X-ray contact microscopy and images of microstructures and biological specimens with ~80 nm half-pitch spatial resolution, obtained in helium atmosphere, are presented.
Discovery of cellulose surface layer conformation by nonlinear vibrational spectroscopy
Significant questions remain in respect to cellulose’s structure and polymorphs, particularly the cellulose surface layers and the bulk crystalline core as well as the conformational differences. Total Internal Reflection Sum Frequency Generation Vibrational Spectroscopy (TIR-SFG-VS) combined with conventional SFG-VS (non-TIR) enables selectively characterizing the molecular structures of surface layers and the crystalline core of cellulose, revealing their differences for the first time. From the SFG spectra in the C-H and O-H regions, we found that the surface layers of Avicel are essentially amorphous while the surface layers of Iβ cellulose are crystalline but with different structural and spectroscopic signatures compared with its crystalline core. The differences between hydrogen bonding networks of cellulose surface and crystalline core were also shown by the SFG signal. The discovery here represents yet another instance of the importance of spectroscopic observations in transformative advances to understand the structure of the cellulosic biomass.
Dye-sensitized solar cells for efficient power generation under ambient lighting
Solar cells that operate efficiently under indoor lighting are of great practical interest as they can serve as electric power sources for portable electronics and devices for wireless sensor networks or the Internet of Things. Here, we demonstrate a dye-sensitized solar cell (DSC) that achieves very high power-conversion efficiencies (PCEs) under ambient light conditions. Our photosystem combines two judiciously designed sensitizers, coded D35 and XY1, with the copper complex Cu(II/I)(tmby) as a redox shuttle (tmby, 4,4′,6,6′-tetramethyl-2,2′-bipyridine), and features a high open-circuit photovoltage of 1.1 V. The DSC achieves an external quantum efficiency for photocurrent generation that exceeds 90% across the whole visible domain from 400 to 650 nm, and achieves power outputs of 15.6 and 88.5 μW cm–2 at 200 and 1,000 lux, respectively, under illumination from a model Osram 930 warm-white fluorescent light tube. This translates into a PCE of 28.9%.
Excited State Dynamics of 6-Thioguanine
Here we present the excited state dynamics of jet-cooled 6-thioguanine (6-TG), using resonance-enhanced multiphoton ionization (REMPI), IR–UV double resonance spectroscopy, and pump–probe spectroscopy in the nanosecond and picosecond time domains. We report data on two thiol tautomers, which appear to have different excited state dynamics. These decay to a dark state, possibly a triplet state, with rates depending on tautomer form and on excitation wavelength, with the fastest rate on the order of 1010 s–1. We also compare 6-TG with 9-enolguanine, for which we observed decay to a dark state with a 2 orders of magnitude smaller rate. At increased excitation energy (∼+500 cm–1) an additional pathway appears for the predominant thiol tautomer. Moreover, the excited state dynamics for 6-TG thiols is different from that recently predicted for thiones.
Excited-State Dynamics of Isocytosine: A Hybrid Case of Canonical Nucleobase Photodynamics
We present resonant two-photon ionization (R2PI) spectra of isocytosine (isoC) and pump–probe results on two of its tautomers. IsoC is one of a handful of alternative bases that have been proposed in scenarios of prebiotic chemistry. It is structurally similar to both cytosine (C) and guanine (G). We compare the excited-state dynamics with the Watson–Crick (WC) C and G tautomeric forms. These results suggest that the excited-state dynamics of WC form of G may primarily depend on the heterocyclic substructure of the pyrimidine moiety, which is chemically identical to isoC. For WC isoC we find a single excited-state decay with a rate of ∼1010 s–1, while the enol form has multiple decay rates, the fastest of which is 7 times slower than for WC isoC. The excited-state dynamics of isoC exhibits striking similarities with that of G, more so than with the photodynamics of C.
Fluorecence Microscopy Study of CdS quantum dots Obtained by Laser Irradiation from a Single Source Precursor in Polymeric Film
Recently the quantum dots (QDs) synthesis from single source precursors (SSPs) showed a potential interest for patterning formation of nano-composites. In this approach the SSPs have to be mixed with a matrix that afterwards is treated selectively to obtain the desired nanocomposite. The study of the generation of the QDs from the SSPs is, therefore, crucial for the definition of its behaviour within the polymeric matrix. The formation of the CdS QDs via thermolysis of the cadmium diethyldithiocarbamate (CdDDTC) was performed and studied in the presence of a non coordinating solvent such as octadecene (ODE) in presence of myristic acid (MA) as ligand. The precursor is then studied in combination with the poly(methyl methacrylate) (PMMA) polymer for the generation of the CdS QDs under the laser irradiation within a film. The effect of the laser has been studied both on neat PMMA and on the polymer/precursor blend film with the aid of the fluorescence microscope. The results are used to identify the optimal laser parameters to obtain the decomposition of the precursor and to evaluate the effect of the laser irradiation on the polymer.