Polylactic Acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier-Transform Infrared (FTIR) spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron Spectroscopy (XPS) in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning Electron Microscopy (SEM) and Differential Scanning Calorimetry (DSC) were used to characterize morphology, crystallinity, and the glass transition temperature following printing. Analysis revealed calcium carbonate-based additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro and sub-micron scale roughness that will also impact potential applications.

Polyhydroxyalcanoates (PHAs) are biodegradable polymers synthesized in cytoplasmic granules in bacteria, such as Cupriavidus necator (Ralstonia eutropha), Alcaligenes latus, Pseudomonas spp., Comamonas spp. and other species. PHAs accumulation occurs in response to stress conditions, i.e. under high carbon and low nitrogen (24:1 ratio). PHA can be synthesized using recombinant microorganisms (provided with the operon phbA/phbB/phbC), escaping the constrains of nutrient request, except addition of high amount of sugar (glucose, lactose, fructose). In this study; E. coli was genetically modified for PHB production in biofermentors. The production of PHA at industrial scale requires a continuous supplementation of fermentable sugars to support the availability of nutrients and to assess the level of the exponential growth phase; since sugars are required either for bacterial growth either for PHA synthesis and energy storage. The biofermentors need to be run in automated system. Sensors are used at many points in fermentators; in the evaluation of parameters: consumption of sugars; cell density; quantification of PHB synthesis. The need of operational control during the fermentation has prompted us to application of three measurements; one unit linked to a Nanodrop to evaluate OD; one linked to a reaction chamber to measure sugars consumed by enzyme based fluorescence detection; and one for bacteria Nile Blue staining and fluorescence intensity reads. The growth of bacteria on three different plant by-products was monitored and PHB production in four days using a banana by-product feed was optimised. These detectors will make possible to exploit the full potential of bioreactors optimizing the time of use and maximizing the number of bacteria synthesizing PHA.

A portable laser photoacoustic sensor based on a Field-Programmable Gate Array (FPGA) is reported for methane detection. A tunable DFB diode laser in the 1654 nm wavelength range is used as an excitation source. The photoacoustic signal processing was implemented by a FPGA device. A small resonant photoacoustic cell is designed. The minimum detection limit (1σ) of 10 ppm for methane (CH₄) is demonstrated.

Functional Near Infrared Spectroscopy (fNIRS) systems for e-health applications usually suffer of poor signal detection mainly due to a low end-to-end signal to noise ratio of the electronics chain. Lock-In Amplifiers (LIA) historically represent a powerful technique helping to improve performances in such circumstances. In this work it has been designed and implemented a digital LIA system, based on a Zynq® Field Programmable Gate Array (FPGA), trying to explore if this technique might improve fNIRS system performances. More broadly, FPGA based solution flexibility has been investigated, with particular emphasis applied to digital filter parameters, needed in the digital LIA, and it has been evaluated its impact on the final signal detection and noise rejection capability. The realized architecture was a mixed solution between VHDL hardware modules and software ones, running within a softcore microprocessor. Experimental results have shown the goodness of the proposed solutions and comparative details among different implementation will be detailed. Finally a key aspect taken into account throughout the design was its modularity, allowing an ease increase of the input channels while avoiding the growth of the design cost of the electronics system.

Diabetic patients need long-term and frequent glucose monitoring to assist in insulin intake. The current finger-prick devices are painful and costly which make noninvasive glucose sensors highly demanded. In this review paper, we discuss several advanced electromagnetic (EM) wave based technologies for noninvasive glucose measurement, including infrared (IR) spectroscopy, photoacoustic (PA) spectroscopy, Raman spectroscopy, fluorescence, optical coherent tomography (OCT) and microwave sensing. Development and progress of each method are discussed regarding fundamental principle, system setup and experimental results. Despite the promising achievements reported previously, there is no established product to obtain FDA approval or survive marketing test. Limitations and prospects of these techniques are discussed at the end of this review.

Our understanding of the fate and distribution of micro- and nano- plastics in the marine environment and their impact on the biota compartment is limited by the intrinsic difficulties of conventional analytical techniques (light scattering, FT-IR, Raman, optical and electron microscopies) in the detection, quantification and chemical identification of small particles in liquid samples. Here we propose the use of optical tweezers, a technique awarded in 2018 with the Nobel prize, as an analytical tool for the study of micro- and nano- plastics in sea water. In particular, we exploit the combination of optical tweezers with Raman spectroscopy (Raman Tweezers, RTs) to optically trap plastic particles with sizes from tens of µm down to 90 nm and unambiguously reveal their chemical composition. RTs applications are shown on particles made of the most common plastic pollutants, including polyethylene, polypropylene, nylon and polystyrene, that are artificially fragmented and aged directly in seawater. RTs allow us to assess the size and shapes of microparticles (beads, fragments, fibers) and can be applied to investigate particles covered with organic layers. Furthermore, operating at the single particle level, RTs enable unambiguous distinction of plastic particles from marine microorganisms and seawater minerals, overcoming the capacities of standard Raman spectroscopy in liquid, limited to average measurements. Coupled to suitable extraction and concentration protocols, RTs could have a strong impact in the study of the fate of micro and nanoplastics in marine environment, as well as in the understanding of the fragmentation processes on a multi-scale level.

Cocrystallizaiton could improve most physicochemical properties of specific active pharmaceutical ingredients, which has great potential in pharmaceutical development. In this study, the cocrystal of nitrofurantoin and 4-aminobenzoic acid was prepared with solid-state (solvent-free or green-chemistry) grinding approach, and the above cocrystal has been characterized by Raman and terahertz vibrational spectroscopic techniques. Spectral results show that the vibrational modes of the cocrystal within the whole spectral region are different from those of the corresponding parent materials. The dynamic process of such pharmaceutical cocrystal formation has also been monitored directly with Raman spectra. These results offer us unique means for characterizing the cocrystal conformation from molecule-level and also provide us rich information about the reaction dynamic of cocrystal formation within pharmaceutical fields.

Propolis is a bee product widely used as a dietary supplement and included in sweets or baby foods due to its well-known antioxidant and nutritional properties that are directly correlated with its phenolic composition. For this reason, this study analysed the total contents of flavones and flavonols, flavanones and dihydroflavonols, and the antioxidant capacity by using the methods of ABTS and linoleic acid/β-carotene in 99 samples of propolis from Spain and Chile. A rapid method was developed for quantifying these parameters in raw propolis using near infrared (NIR) spectroscopy with an optical fibre probe of remote reflectance applied directly to the ground up sample. The models developed allow the determination of the total of flavones and flavonols (0-183 mg rutin/ g propolis), of the total of flavanones and dihydroflavonols (9-109 mg pinocembrin/ g propolis extract), and the antioxidant capacity by the ABTS method (0-3212 nmolesTrolox/ mg of propolis) and of linoleic acid/β-carotene (22-86% inhibition). The NIR spectroscopy models were applied in external validation to different samples of the calibration group, which led to the conclusion that the methods developed provide significantly identical data to the initial chemical data of reference.

Urea cycle disorders (UCDs) are common inborn errors of metabolism, with an incidence of one in 30,000 births. They are caused by deficiencies in any of six enzymes and two carrier proteins, the most common being Ornithine Transcarbamylase Deficiency (OTCD). OTCD results in impairment to excrete nitrogen, causing toxic buildup of ammonia with resultant encephalopathy. Hyperammonemia (HA) induces the conversion of glutamate to glutamine in the brain. Excess glutamine in the brain causes osmotic changes cerebral edema, changes in astrocyte morphology, and cell death. Acute symptoms of HA include vomiting, hyperventilation, seizures, and irritability. Long-term neurological changes include deficits in working memory and executive function. To date, there are no predictors of prognosis of infants with neonatal onset OTCD outside of plasma ammonia level at presentation and duration of hyperammonemic coma. We provide a comprehensive analysis of a 16-year-old male with neonatal onset of OTCD as an example of how brain biomarkers may be useful to monitor disease course and outcome. This male presented at 8 days post natal with plasma ammonia and glutamine of 677 and 4024 micromol/L and had a missense mutation in Exon 4 (p.R129H). Treatment included protein restriction, sodium benzoate, and citrulline, arginine, and iron. He suffered recurrent acute hyperammonemic episodes despite compliance, triggered by infections or catabolic stressors. We discuss the long-term effects of the hyperammonemic episodes by following MRI based disease biomarkers.

In the field of construction, materials referred to as sustainable are currently undergoing a process of technological development. This study aims to contribute to the understanding of the behavior of the fundamental properties of concretes prepared with recycled coarse aggregates that incorporate in their matrix a polyethylene terephthalate-based additive in an attempt to reduce their high porosity. Techniques to measure the gas adsorption, water porosity and x-ray diffraction (XRD) were used to evaluate the effect of the additive on the physical, mechanical and microstructural properties of these concretes. Porosity reductions of up to 30.60% are achieved with the addition of 1, 3, 4, 5, 7 and 9% of the additive, defining a new state in the behavioral model of the additive (the overdosage point) in the concrete matrix; in addition, the porous network of these concretes and their correlation whit other physical and mechanical properties are also explained.

Nickel nitrate diammine, Ni(NH₃)₂(NO₃)₂, can be synthesised from the thermal decomposition of the nickel nitrate hexammine, Ni[(NH₃)₆](NO₃)₂. The hexammine decomposes in 2 distinct steps; the first releases 4 equivalents of ammonia while the second involves the release of NO_x, N₂ and H₂O to yield NiO. The intermediate diammine compound can be isolated following the first deammoniation step or synthesised as a single phase from the hexammine under vacuum. Powder X-ray diffraction (PXD) experiments have allowed the structure of Ni(NH₃)₂(NO₃)₂ to be solved for the first time. The compound crystallises in orthorhombic space group Pca2₁ (a = 11.0628 (5) Å, b = 6.0454 (3) Å, c = 9.3526 (4) Å; Z = 4) and contains 11 non-hydrogen atoms in the asymmetric unit. Fourier Transform Infrared (FTIR) spectroscopy demonstrates that the bonding in the ammine is consistent with the structure determined by PXD.

Infrared spectroscopy is an effective method for the determination of compositions and concentrations of liquids, with advantages of fast response, no-sampling, flexible in use and is able for on-line monitoring. However, for trace substances in drinking water, such as nitrates and heavy metals, infrared spectroscopy is not sensitive enough for the quantitative and qualitative measurement. In this study, we improved the sensitivity of infrared spectroscopy for nitrite determination by developing an ion-exchange-enhanced diffuse reflectance spectroscopy, which consist of an accessory based on ion-exchange resin for enrichment and a FTIR spectrometer for measurement. Using this method, the limit of detection for nitrate is 1.7 mg/L, which is enough for drinking water sensing. We also verified the quantitative measurement ability of the method. Furthermore, the limit of detection and quantitative measuring range could be adjusted by changing the mass of resin and adsorption time. This study demonstrated the method can be used to detect trace nitrites in drinking water, can be applied in the field, and is sensitive, rapid, and inexpensive with a wide dynamic range.

Titanium dioxide (TiO2) and aluminum oxide (Al2O3) coatings have been investigated in a wide range of bio-applications due to their biodegradation and biocompatibility properties, that are key parameters for their use in the food packaging and biomedical devices fields. The present study evaluates and compares the electrochemical behavior of the non-coated, commercial resin-coated, TiO2-coated and Al2O3-coated aluminum in commercial beer electrolyte. For this, TiO2 and Al2O3 thin films were deposited on aluminum (Al) substrates using atomic layer deposition (ALD). The evaluation of the corrosion barrier layer properties was performed by linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). In addition, profilometry, grazing incidence X-ray diffractometry (GIXRD), scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FT-IR) analyses were performed to investigate the physical and chemical properties of the pristine and / or corroded samples. TiO2 and Al2O3 films presented an amorphous structure, a morphology that follows Al substrate surface, and a thickness of around 100 nm. Analysis of LSV data showed that ALD coatings promoted a considerable increase in corrosion barrier efficiency being 86.3% for TiO2-coated Al and 80% for Al2O3-coated Al in comparison with 7.1% of commercial resin-coated Al. This is mainly due to the lower electrochemical porosity, 11.4% for TiO2-coated Al and 20.4% for Al2O3-coated Al in comparison with 96% of the resin-coated Al, i.e. an increase of up to twofold in the protection of Al when coated with TiO2 compared to Al2O3 coated. The EIS results allow us to complement the discussions about the reduced corrosion barrier efficiency of the Al2O3 film for beer electrolyte once SEM and FT-IR analyzes did not show drastic changes in both investigated ALD films after the corrosion assays. The above results indicate that ALD TiO2 and Al2O3 films may be a viable alternative to replace the synthetic resin coatings frequently used in aluminum cans of use in the food industry.

This work communicates results from optical emission spectroscopy following laser-induced optical breakdown at or near nanomaterial. Selected atomic lines of silver are evaluated for consistent determination of electron density. Comparisons are presented with Balmer series hydrogen results. Of particular interest are measurements free of self-absorption effects. For several silver lines, asymmetries are observed in the recorded line profiles. Electron densities of interest range from 0.5 to 3 × 10¹⁷ cm^-3, for 5 nanosecond Q-switched Nd:YAG radiation at wavelengths of 1064, 532, and 355 nm, and for selected silver emission lines including 328.0, 338.2, 768.7, and 827.3 nm, and the hydrogen alpha Balmer series line at 656.3 nm. Line asymmetries are presented for the 328.0 nm Ag I line that is measured following generation of the plasma due to multiple photon absorption. This work explores electron density variations for different irradiance levels, and reports spectral line asymmetry of resonance lines for different laser fluence levels.

We attempted to apply the optoelectronic sensor entitled 'OPT101' in intensive care unit clinics, based on its optoelectronic response characteristics in near-infrared wavelength range and near-infrared spectroscopy principle. The successful novel applications in our lab include early-diagnosis and therapeutic effect tracking of thrombus, noninvasive monitoring of patients' shock severity, and fatigue evaluation. This study also expects further improvements of the detector in noninvasive clinical applications.

The present study evaluates the bioremediation potential of indigenous bacterial species isolated from dye-contaminated soil samples from small dyeing outlet located in Ilorin. The water pollution index was estimated based on the physicochemical characteristics and heavy metal concentrations of the raw (Day 0) and treated textile wastewater such as pH, biochemical oxygen demand-5, chemical oxygen demand, total suspended solids and total dissolved solid with mean values of 8.85±0.45 mg/L, 1200±21.3 mg/L, 2440±31.3 mg/L, 1660±17.2 mg/L and 2650±28.1 mg/L respectively, similarly, Lead was the most abundant heavy metal detected in the sample while Cadmium concentration was the lowest with the mean values of 3.52±0.00 mg/L and 2.18±0.00 mg/L respectively. The bacterial strain with highest dye decolorization capacity was screened and identified as Bacillus licheniformis ZUL012.The isolate was consequently used for the bioremediation of the wastewater over a period of 10 days. The results showed an incredible reduction in the physiochemical characteristics and heavy metal concentrations of the textile wastewater in the following ranges (8.85-6.55), (1200-300) mg/L, (2440-518) mg/L, (1660-666) mg/L and (2650-920) mg/L with the highest removal efficiency of 75 %, 78 %, 60%, 65%, recorded for biochemical oxygen demand, chemical oxygen demand, total suspended solid, total dissolved solid, respectively while that of heavy metals such as lead, cadmium, chromium and nickel were 80 %, 60 %, 67 %, 72 % reduction, respectively. Laccase and Azoreductase activities tend to decrease as the pH gradually moved towards acidic condition during the bioremediation process. Toxicity of the treated effluent was assessed using Maize and Bean seed germination test. Conclusively, these research findings can serve as a framework for the outlet design of wastewater treatment plant for local textile outlets.

Near-infrared spectroscopy (NIRS) was implemented to monitor the moisture content of broadleaf litters. Partial least-squares regression (PLSR) models, incorporating optimal wavelength selection techniques, have been proposed to better predict the litter moisture of forest floor. Three broadleaf litters were used to sample the reflection spectra corresponding the different degrees of litter moisture. Maximum normalization preprocessing technique was successfully applied to remove unwanted noise from the reflectance spectra of litters. Four variable selection methods were also employed to extract the optimal subset of measured spectra for establishing the best prediction model. The results showed that the PLSR model with the peak of beta coefficients method was the best predictor among all candidate models. The proposed NIRS procedure is thought to be a suitable technique for on-the-spot evaluation of litter moisture.

A gold(I) complex with a triphenylphosphine and a monodentate N,N-dimethyldithiocarbamate ligand was synthesized and characterized by Raman spectroscopy and single crystal X-ray diffraction. DFT calculations (Gaussian 09, PBE1PBE/Lanl2dz) were undertaken for a single complex in the gas-phase. The DFT-optimized structure is in good agreement with the crystal structure and the DFT-calculated Raman spectrum also is in excellent agreement with the experimental spectrum. Assignments of the Raman peaks are based on these DFT calculations. Frontier molecular orbitals were calculated and their nature is discussed.

The crack geometry and associated strain field around Berkovich and Vickers indents on silicon have been studied by X-ray diffraction imaging and micro-Raman spectroscopy scanning. The techniques are complementary, the Raman data coming from within a few micrometers of the indentation, whereas the X-ray image probes the strain field at a distance of typically tens of micrometers. For example, Raman data provides an explanation for the central contrast feature in the X-ray images of an indent. Strain relaxation from breakout and high temperature annealing are examined and it is demonstrated that millimeter length cracks, similar to those produced by mechanical damage from misaligned handling tools, can be generated in a controlled fashion by indentation within 75 micrometers of the bevel edge of 200mm diameter wafers.

The biophysical consequences of nanoscale curvature have been challenging to resolve due to size-dependent membrane behavior and the experimental resolution limits imposed by optical diffraction. Recent advances in nanoengineering and super-resolution techniques have enabled new capabilities for creating and observing curvature. In particular, draping supported lipid bilayers over lithographically patterned substrates provides a model system for endocytic pits. The experiments and simulations presented below describe the possible detection of membrane curvature through fluorescence recovery after photobleaching (FRAP), fluorescence correlation spectroscopy (FCS), single particle tracking (SPT), and polarized localization microscopy (PLM). FRAP and FCS depend on diffraction-limited illumination and detection. In particular, a simulation of FRAP shows no effects on lipids diffusion due to a 50 nm diameter membrane bud at any stage in the budding process. Simulated FCS demonstrated small effects due to a 50 nm radius membrane bud that was amplified with curvature-dependent lipid mobility changes. However, PLM and SPT achieve sub-diffraction-limited resolution of membrane budding and lipid mobility through the identification of the single-lipid positions with ≤15 nm spatial and ≤20 ms temporal resolution. By mapping the single-lipid step lengths to locations on the membrane, the effects of curvature on lipid behavior have been resolved.

Solvent-free, single-ion conducting electrolytes are sought after for use in electrochemical energy storage devices. Here, we investigate the ionic conductivity and how this property is influenced by segmental mobility and conducting ion number in crosslinked single-ion conducting polyether-based electrolytes with varying tethered anion and counter-cation types. Crosslinked electrolytes are prepared by the polymerization of poly(ethylene glycol) diacrylate (PEGDA), poly(ethylene glycol) methyl ether acrylate, and ionic monomers. The ionic conductivity of the electrolytes is measured and interpreted in the context of differential scanning calorimetry and Raman spectroscopy measurements. A lithiated crosslinked electrolyte prepared with PEG₃₁DA and STFSI monomers is found to have a lithium ion conductivity of 3.2 × 10^-6 and 1.8 × 10⁻⁵ S/cm at 55 and 100 °C, respectively. The percentage of unpaired anions for this electrolyte was estimated at about 23% via Raman spectroscopy. Despite the large variances in metal cation – STFSI binding energies as predicted via DFT and large variations in ionic conductivity, STFSI-based crosslinked electrolytes with the same charge density and varying cations (Li, Na, K, Mg, and Ca) were estimated to all have unpaired anion populations in the range of 19 to 29%.

Food pathogens contaminate food products that allow their growth on the shelf and also under refrigerated conditions. Therefore, it is of utmost importance to lower the limit of detection (LOD) of the method used and to obtain the results within hours to few days. Biosensor methods exploit the available technologies to individuate and provide an approximate quantification of the bacteria present in a sample. The main bottleneck of these methods depend on the aspecific binding to the surfaces and on a change in sensitivity when bacteria are in a complex food matrix in respect to bacteria in a liquid food sample. In this review we introduce Surface Plasmon Resonance (SPR), new advancements in SPR techniques, and Electrochemical Impedance Spectroscopy (EIS), as label-free biosensing technologies for the detection of L. monocytogenes in foods. The application of the two methods has made possible the detection of L. monocytogenes with LOD of 1 log CFU/mL. Further advancement are envisaged through the combination of biosensor methods with immunoseparation of bacteria from larger volumes.

This research focuses on the effect of trampling on vegetation in high-mountain ecosystems through the electromagnetic spectrum’s interaction with plant pigments, cell structure, water content and other substances that have a direct impact on leaf properties. The most heavily visited part of the High Tatras in Poland was divided into polygons and, after selecting the dominant species within alpine swards, a detailed analysis of trampled and reference patterns was performed. An ASD FieldSpec 3 was used to acquire high-resolution spectral properties of plants, their fluorescence and the leaf chlorophyll content with the ts-ta temperature index and fraction of accumulated radiation in the range of photosynthesis (fAPAR) used as reference data. The results show that, along tourist trails, vegetation adapts to trampling with the impact depending on the species. A lower chlorophyll value was confirmed by a decrease in fluorescence, and the state of cellular structures was degraded in trampled compared to reference species, with a lower leaf reflectance. Also, at the extreme, trampling can eliminate certain species such as Luzula alpino-pilosa.

Throughout the ages and times, the need to use everything that reflects women's beauty and helps them maintain their vision and health, and if the need to use the precious materials has been put in place, it is important that they produce the desired results without attention to the harmful chemicals and heavy metals that they contain. Over time, the toxicity of these heavy metals increases in our environment because of their long-term exposure to these pollutants, whether low or high-level in toxicity, animal-prednmost, environment, including air we breathe, water, food, etc. Cosmetics are one of these sources through which humans are exposed to heavy toxic metals. Heavy metals have been estimated in a number of previous studies, and in our study here, we aim to estimate the amount of cadmium metal and study it in various cosmetics such as Lipstick, Eye shadow, Face whitening cream. Two samples were taken from each of the locomoys and cadmium was estimated using the photometer of atomic absorption, one of the samples being expensive and the other low-cost, and purchased from the wholesale markets of Taiz City. Cadmium has been found prominently in these products and the highest rate found in the lowest cost-effective, Eye shadow, that the use of these cosmetic products exposes users to low- conc. heavy metals, which may pose a danger to their health. They are known to be clustered in their biological systems over time, resulting in an imbalance of body and environment. The results found that the low-priced color samples contained a higher concentration of cadmium than the high-price samples in low-priced samples, cadmium concentration was in order of eye shadow > lipstick = face whitening cream. The similar pattern are shown also for higher price product, which are lipstick > face whitening cream > eye shadow.

This paper presents the design and implementation of a multichannel bio-impedance spectroscopy system on field programmable gate arrays (FPGA). The proposed system is capable of acquiring multiple signals from multiple bio-impedance sensors, process the data on the FPGA and store the final data in the on-board Memory. The system employs the Digital Automatic Balance Bridge (DABB) method to acquire data from biosensors. The DABB measures initial data of a known impedance to extrapolate the value of the impedance for the device under test. This method offers a simpler design because the balancing of the circuit is done digitally in the FPGA rather than using an external circuit. Calculations of the impedance values for the device under test were done in the processor. The final data is sent to an onboard Flash Memory to be stored for later access. The control unit handles the interfacing and the scheduling between these different modules (Processor, Flash Memory) as well as interfacing to multiple Balance Bridge and multiple biosensors. The system has been simulated successfully and has comparable performance to other FPGA based solutions. The system has a robust design that is capable of handling and interfacing input from multiple biosensors. Data processing and storage is also performed with minimal resources on the FPGA.

In laser joining of copper (Cu) and aluminum (Al) sheets, the Al sheet is widely chosen as the top surface for laser irradiation because of increased absorption of laser beam and lower melting temperature of Al in contrast to Cu. This research focus on welding from Cu side to Al sheet. The main objective of irradiating the laser beam from the copper side (Cu on top) is to exploit higher solubility of Al in Cu. A significantly lower laser power can be used with 515 nm laser in comparison to 1030 nm. In addition to low laser power, a stable welding is obtained with 515 nm. Because of this advantage, 515 nm is selected for the current research. By fusion of Cu and Al the two sheet metals are welded, with presence of beneficial Cu solid solution phase and Al+Al2Cu in the joint with the brittle phases intermixed between the ductile phase. Therefore the mixed composition strengthens the joint. However excessive mixing leads to formation of more detrimental phases and less ductile phases. Therefore optimum mixing must be maintained. Energy dispersive X-ray spectroscopy (EDS) analysis indicate that large amount of beneficial Cu solid solution and Al rich phases is formed in the strong joint. From the tensile shear test for a strong joint, fracture is obtained on the heat-affected zone (HAZ) of Al. Therefore the key for welding from copper side is to have optimum melt with beneficial phases like Cu and Al+ Al2Cu and the detrimental phases intermixed between the ductile phases

A fatty hydroxamic acid (FHA) mixture synthesized from olive oil triacylglycerides by hydroxylaminolysis and composed predominantly of oleyl and linoleyl hydroxamic acid (OHA and LHA, respectively) was characterized by means of IR, Raman, MS and 1D and 2D ¹H- and ¹³C-NMR spectroscopy. The ratio of OHA and LHA (4:1) was confirmed by MALDI TOF/TOF mass spectrometry. The radical scavenging and the Fe²⁺-chelating activity, as well as antioxidant activity in β-carotene-linoleic acid and the Fe³⁺-reducing power assays of the FHAs yielded positive results. The results of FHA cell toxicity on normal fibroblast (BJ) and a tumour cell line (HeLa) revealed that the normal cell line was sensitive to FHAs within the entire range of applied concentrations (5 × 10⁻⁴ mg/mL to 5 × 10⁻¹ mg/mL), while the HeLa tumour cell line was sensitive only at the highest FHA concentration (5 × 10⁻¹ mg/mL). In silico target prediction indicated cannabinoid receptors 1 and 2, the fatty-acid amide hydrolase 1 and hystone deacetylases as the most probable targets of OHA and LHA. According to ADMET predictor analysis, the safety profiles of OHA and LHA are comparable to that of SAHA (vorinostat) the histone deacetylase inhibitor in use as an antineoplastic and immunomodulating agent.

One of the most common limits to gas sensor performance is the presence of unwanted interference fringes or etalons arising, for example, from multiple reflections between surfaces in the optical path. Additionally, since the amplitude and the frequency of these interference depend on the distance and alignment of the optical elements, they are affected by temperature changes and mechanical disturbances, giving rise to a drift of the signal. In this work, we present a novel semi-parametric algorithm which allows the extraction of a signal, like the spectroscopic absorption line of a gas molecule, from a background containing arbitrary disturbances, without having to make any assumption on the functional form of these disturbances. The algorithm is applied first to simulated data and then to oxygen absorption measurements in presence of strong fringes.To the best of the authors' knowledge, the algorithm enables an unprecedented accuracy particularly if the fringes have a free spectral range and amplitude comparable to those of the signal to be detected. The described method presents the advantage of being based purely on post processing, and to be of extremely straightforward implementation if the functional form of the Fourier transform of the signal is known. Therefore it has the potential to enable interference-immune absorption spectroscopy. Finally, its relevance goes beyond absorption spectroscopy for gas sensing since it can be applied to any kind of spectroscopic data.

This case report describes evidence of intratubular biomineralization in root canal filled with calcium enriched material after 8 years of clinical maintenance. The schematic findings of dentinal tubules were investigated with scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). The root canal obturation material was closely adapted to root dentin surface, suggesting the possibility of chemical bonding between the two interfaces. SEM and EDS observation of dentinal tubules showed intratubular biomineralized crystal structures with Ca/P ratio in a range of 1.30–2.12, suggesting bioactive capacity of calcium enriched cement.

A novel type of graphene-like quantum dots, synthesized by oxidation and cage-opening of C60 buckminsterfullerene, has been studied as a fluorescent and absorptive probe for heavy-metal ions. The lattice structure of such unfolded fullerene quantum dots (UFQDs) is distinct from that of graphene since it includes both carbon hexagons and pentagons. The basic optical properties, however, are similar to those of regular graphene oxide quantum dots. On the other hand, UFQDs behave quite differently in the presence of heavy-metal ions, in that multiple sensitivity to Cu2+, Pb2+ and As(III) was observed through comparable quenching of the fluorescent emission and different variations of the transmittance spectrum. By dynamic light scattering measurements we confirmed, for the first time in metal sensing, that this response is due to multiple complexation and subsequent aggregation of UFQDs. Nonetheless, the explanation of the distinct behaviour of transmittance in the presence of As(III) and the formation of precipitate with Pb2+ require further studies. These differences, however, also make it possible to discriminate between the three metal ions in view of the implementation of a selective multiple sensor.

Since coffee has been shown to influence positively the metabolism of subjects with metabolic syndrome (MetS), we aimed to evaluate the short- and long-term effects of a coffee-based supplement on different features of diet-induced MetS. 24 Sprague Dawley rats were divided into control or nutraceuticals groups to receive a high-fat/high fructose diet with or without a mixture of caffeic acid (30 mg/day), trigonelline (20 mg/day), and cafestol (1 mg/day) for 12 weeks. An additional 11 rats were assigned to an acute crossover study. In the chronic experiment, nutraceuticals did not alter body weight or glycemic control but improved fed hyperinsulinemia and HOMA-IR, and plasma adiponectin levels. The impact of nutraceuticals on post-prandial glycemia tended to be more pronounced after acute administration than at the end of the chronic study. Circulating and intrahepatocellular alanine transaminase activity, assessed by hyperpolarized-¹³C NMR spectroscopy, were reduced by coffee nutraceuticals at endpoint. There was also a tendency towards lower liver triglyceride content and histological steatosis score in the intervention group. In conclusion, a mixture of coffee nutraceuticals improved insulin sensitivity and exhibited hepatoprotective effects in a rat model of MetS. Higher dosages with or without caffeine deserve to be studied in the future.

In the last 20 years, a huge amount of experimental results about halogen bonding (XB) has been produced. Most of the systems have been characterized by solid state X-ray crystallography, whereas in solution the only routine technique is the titration (by using ¹H and ¹⁹F NMR, IR, UV-Vis or Raman spectroscopies, depending on the nature of the system), with the aim of characterizing the strength of the XB interaction. Unfortunately, the titration techniques have many intrinsic limitations and they should be coupled with other, more sophisticated techniques to have an accurate and detailed description of the geometry and stoichiometry of the XB adduct in solution. In this review, it will be shown how crucial information about XB adducts can be obtained by advanced NMR techniques, as Nuclear Overhauser Effect-based Spectroscopies (NOESY, ROESY, HOESY…) and diffusion NMR techniques (PGSE or DOSY).

Knowledge of a lasers beam’s profile throughout a laser system and experiment can help immensely in diagnosing laser problems and assisting in beam alignment and focusing at a sample. Obtaining such profiles is a trivial task in the ultraviolet-visible wavelength range but more challenging with near-infrared to infrared beams. Scientific grade bolometer arrays, suitable for such a task, do exist but are extremely costly, relatively large and have a large pixel size, of the order of 80 μm, which is adequate for profiling larger beams but poses an issue when trying to profile sub 100 μm beams for example at a focal point. This communication identifies a micro-bolometer array for near- to mid-infrared laser beam profiling, which is extremely low cost. In addition, the device is very compact, enabling use in confined spaces, and has a small, 12 μm, pixel size permitting the profiling of focused laser beams. The best scientific grade device identified has a pixel size of 17 μm. This device is a powerful tool for infrared laser spectroscopists, reducing the time required to measure the spot size of beams and to achieve spatial overlap of multiple infrared beams as used in two-dimensional infrared spectroscopy, saving many hours of setup time. The use of the bolometer array as a spectrographic detector and probe of long-term beam drifts is also demonstrated.

With an ever broadening use of composite materials manufacturers are in high demand of efficient curing cycles to reduce costs and speed up production cycles. One method to to archive this goal is active cure monitoring to determine the exact time of curing needed. This article provides a novel method to measure the cure inside of closed tools by using ultrasonic spectroscopy. For this a simple experiment is used to show the change of the ultrasonic spectrum during the cure of an epoxy. The results clearly show a direct correlation of amplitude and state of cure where the amplitude reaches a global minimum at the glass point.

A series of Si-bearing MgAl₂O₄-spinels were synthesized at 1500-1650 °C and 3–6 GPa. These spinels had SiO₂ contents up to ~1.03 wt%, and showed a substitution mechanism of Si⁴⁺ + Mg²⁺ = 2Al³⁺. Unpolarized Raman spectra were collected from polished single grains, and displayed a set of well-defined Raman peaks at ~610, 823, 856 and 968 cm^-1 which had not been observed before. Aided with the Raman features of natural Si-free MgAl₂O₄-spinel, synthetic Si-free MgAl₂O₄-spinel, natural low quartz, synthetic coesite, synthetic stishovite and synthetic forsterite, we infer that these Raman peaks should belong to the SiO₄ groups. The relations between the Raman intensities and SiO₂ contents of the Si-bearing MgAl₂O₄-spinels suggest that at some P-T conditions some Si must adopt the M-site. Unlike the SiO₄ groups with very intense Raman signals, the SiO₆ groups are largely Raman-inactive. We have further found that the Si cations primarily appear on the T-site at P-T conditions ≤ ~3–4 GPa and 1500 °C, but attain a random distribution between the T-site and M-site at P-T conditions ≥ ~5–6 GPa and 1630–1650 °C. This Si-disordering process observed for the Si-bearing MgAl₂O₄-spinels hints that similar Si-disordering might happen to the (Mg,Fe)₂SiO₄-spinels (ringwoodite), the major phase in the lower part of the mantle transition zone of the Earth and the index mineral for the very strong shock stage experienced by extraterrestrial materials. The likely consequences have been explored.

Background: Diabetes is among the most prevalent diseases worldwide, of all the affected individuals a significant proportion of the population remains undiagnosed because of a lack of specific symptoms early in this disorder and inadequate diagnostics. Diabetes and its associated sequela, i.e., comorbidity are associated with microvascular and macrovascular complications. As diabetes is characterized by an altered metabolism of key metabolites and regulatory pathways. Metabolic phenotyping can provide us with a better understanding of the unique set of regulatory perturbations that predispose to diabetes and its associated comorbidities. Methodology: The present study utilizes the analytical platform NMR spectroscopy coupled with Random Forest statistical analysis to identify the discriminatory metabolites of diabetes (DB) and diabetes-related comorbidity (DC) along with the healthy control (HC) subjects. A combined and pairwise analysis was performed, between the serum samples of HC (n=50), and DB (n=38), and DC (n=35) individuals to identify the discriminatory metabolites responsible for class separation. The perturbed metabolites were further rigorously validated using t-test, AUROC analysis to examine the statistical significance of the identified metabolites. Results: The DB and DC patients were well discriminated from HC. However, 15 metabolites were found to be significantly perturbed in DC patients compared to DB, the identified panel of metabolites are TCA cycle (succinate, citrate), methylamine metabolism (trimethylamine, methylamine, betaine), -intermediates; energy metabolites (glucose, lactate, pyruvate); and amino acids (valine, arginine, glutamate, methionine, proline and threonine). The metabolites were further used to identify the perturbed metabolic pathway and correlation of metabolites in DC patients. Conclusion: The 1H NMR metabolomics may prove a promising technique to differentiate and predict diabetes and its comorbidities on their onset or progression by determining the altered levels of the metabolites in serum.

Tourmalines are a group of minerals which may concentrate various accessory components, e.g. Cu, Ni, Zn, Bi, Ti, Sn. The paper presents fluor-elbaite and elbaite from a dyke of the Julianna pegmatitic system at Piława Górna, at the NE margin of the Bohemian Massif, SW Poland, containing up to 6.32 and 7.37 wt.% ZnO, respectively. Such high amounts of ZnO are almost two times higher than in the second most Zn-enriched tourmaline known to date. The compositions of the Zn-rich tourmalines from Piława Górna, studied by electron microprobe and Raman spectroscopy, correspond to the formulae: (Na0.73Ca0.01•0.25)Σ1(Al1.03Li0.79Zn0.76Fe2+0.33Mn0.09)Σ3Al6B3Si6O27(OH)3(F0.66OH0.34), and (Na0.78Ca0.01•0.21)Σ1(Al1.06Li0.87Zn0.88Fe2+0.10Mn0.09)Σ3Al6B3Si6O27(OH)3(OH0.84F0.16), respectively, with Zn as one of the main octahedral occupants. A comparison with other tourmalines and associated Zn-rich fluor-elbaite and elbaite from the pegmatite indicates that atypically high Zn-enrichment is not a result of Zn-Fe fractionation, but dissolution and reprecipitation induced by a late (Na,Li,B,F)-bearing fluid within the assemblage of gahnite spinel and primary schorl-type tourmaline. This strongly suggests Na-Li-B-F metasomatism of gahnite-bearing mineral assemblages as that is the only environment that can promote crystallization of a hypothetical Zn-dominant tourmaline. The compositions of the Zn-rich fluor-elbaite and elbaite suggest three possible end-members for such a hypothetical tourmaline species: NaZn3Al6B3Si6O27(OH)3(OH), •(Zn2Al)Al6B3Si6O27(OH)3(OH) and Na(Zn2Al)Al6B3Si6O27(OH)3O.

Background: Lithium di-silicate dental ceramics bonding, realized by using different resins, is strictly dependent on micro-mechanical retention and chemical adhesion. The aim of this in vitro study was to investigate the capability of a 1070 nm fiber laser for their surface treatment. Methods: Samples were irradiated by a pulsed fiber laser at 1070 nm with different parameters (Peak Power from 5 kW to 5 kW, RR 20 kHz, speed from 10 to 50 mm/s, total Energy Density from 1.3 to 27 kW/cm²) and the thermal elevation during the experiment was recorded by a Fiber Bragg Grating (FBG) temperature sensor. Subsequently, the surface modifications were analysed by optical microscope, Scanning Electron Microscope (SEM) and Energy Dispersive X-ray Spectroscopy (EDS). Results: With a Peak Power of 5 kW, RR of 20 kHz and speed of 50 mm/s, the microscopic observation of the irradiated surface showed increased roughness with small areas of melting and carbonization. EDS analysis revealed that, with these parameters, there are no evident differences between laser-processed samples and controls. Thermal elevation during laser irradiation ranged between 5 °C and 9 °C. Conclusions: 1070 nm fiber laser can be considered as a good device to increase the adhesion of Lithium di-silicate ceramics.

Vibrational spectroscopies (FTIR, Raman) are exceptionally valuable tools for the identification and crystal-chemical study of fibrous minerals, and asbestos amphiboles in particular. Raman spectroscopy has been widely applied in toxicological studies and thus a large corpus of reference data on regulated species is found in the literature. However, FTIR spectroscopy has been mostly used in crystal-chemical studies and very few data are found on asbestos amphiboles. This paper is intended to fill this gap; we report new FTIR data collected on a suite of well-characterized samples of the five regulated amphibole species: anthophyllite, amosite and crocidolite, provided by the Union for International Cancer Control (UICC) Organization, and tremolite and actinolite, from two well-known occurrences. The data from these reference samples have been augmented by results from additional specimens to clarify some aspects of their spectroscopic features. We show that the FTIR spectra in both the OH-stretching region and in the lattice modes region can be effective for rapid identification of the asbestos type.

Our study aims to implement a strategy to reduce the carbon steel corrosion rate in sulfuric acid solution, using an expired drug with adsorption affinity on the metal surface. To investigate the corrosion protection efficiency of an environmental friendly inhibitor, namely neomycin sulfate (NMS), the electrochemical measurements were applied on carbon steel immersed in 1.0 M H₂SO₄ solution with and without NMS. The protective layer formed on the steel surface was studied by atomic force microscopy (AFM). The potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) showed that the presence of the neomycin sulfate in acid solution leads to the decrease in corrosion current density (i_corr) and the increase of polarization resistance (R_p). The mixed mechanism between physical and chemical adsorption of NMS molecules on the steel surface was proposed according to the Langmuir adsorption isotherm. The Atomic Force Microscopy (AFM) indicated that the NMS molecules contributed to a protective layer formation by their adsorption on the steel surface. The AFM parameters such as: root-mean-square roughness (R_q); average roughness (R_a) and maximum peak to valley height (R_p-v) revealed that in the presence of NMS a smoother surface of carbon steel was obtained, compared to the steel surface corroded in sulfuric acid blank solution.

Nanostructured materials have already become an integral part of our daily life. In many applications ion mobility decisively affects the performance of, e.g., batteries and sensors. Nanocrystalline ceramics often exhibit enhanced transport properties due to their heterogeneous structure showing crystalline (defect-rich) grains and disordered interfacial regions. In particular, anion conductivity in nonstructural binary fluorides easily exceeds that of their coarse-grained counterparts. To further increase ion dynamics aliovalent substitution is a practical method to influence the number of (i) defect sites and (ii) the charge carrier density. Here, we used high energy-ball milling to incorporate Y³⁺ ions into the cubic structure of SrF₂. As compared to pure nanocrystalline SrF2 the ionic conductivity of Sr_1-xYxF_2+x with x = 0.3 increased by 4 orders of magnitude reaching 0.8 x 10 ^-5 S/cm^-1 at 450 K. We discuss the effect of YF₃ incorporation on conductivities isotherms determined by both activation energies and Arrhenius pre-factors. The enhancement seen is explained by size mismatch of the cations involved, which are forced to form a cubic crystal structure with extra F anions if x is kept smaller than 0.5

Functional osseoconductive coatings based on hydroxylapatite (HAp) and applied preferentially by atmospheric plasma spraying to medical implant surfaces are a mainstay of modern implantology. During contact with the hot plasma jet, HAp particles melt incongruently and undergo complex dehydration and decomposition reactions that alter their phase composition and crystallographic symmetry, and thus, the physical and biological properties of the coatings. Surface analytical methods such as laser-Raman and nuclear magnetic resonance (NMR) spectroscopies are useful tools to assess the structural changes of HAp imposed by heat treatment during their flight along the hot plasma jet. In this contribution, the controversial information on the existence or non-existence of oxyapatite, i.e. fully dehydrated HAp as a thermodynamically stable compound is highlighted.

Bottom-up systems biology entails the construction of kinetic models of cellular pathways by collecting kinetic information on the pathway components (e.g. enzymes) and collating this into a kinetic model, based for example on ordinary differential equations. This requires integration and data transfer between a variety of tools, ranging from data acquisition in kinetics experiments, to fitting and parameter estimation, to model construction, evaluation and validation. Here, we present a workflow that uses the Python programming language, specifically the modules from the SciPy stack, to facilitate this task. Starting from raw kinetics data, acquired either from spectrophotometric assays with microtitre plates or from NMR spectroscopy time courses, we demonstrate the fitting and construction of a kinetic model using scientific Python tools. The analysis takes place in a Jupyter notebook, which keeps all information related to a particular experiment together in one place and thus serves as an e-labbook, enhancing reproducibility and traceability. The Python programming language serves as an ideal foundation for this framework because it is powerful yet relatively easy to learn for the non-programmer, has a large library of scientific routines and active user community, is open-source and extensible, and many computational systems biology software tools are written in Python or have a Python API. Our workflow thus enables investigators to focus on the scientific problem at hand rather than worrying about data integration between disparate platforms.

JBIR-99 is a secondary metabolite of marine fungi that has been shown to possess strong antibiotic activity. An efficient approach using a combination of size exclusion chromatography with a Sephadex LH-20 and high-speed counter-current chromatography (HSCCC) has been successfully developed for the isolation and purification of a polyketide from the solid-state fermentation of Meyerozyma guilliermondii. The active compound was isolated with purity >95% by HSCCC using an optimized solvent system composed of petroleum ether–ethyl acetate– 95% ethanol–water (5:3:5:3, v/v/v/v) after size exclusion chromatography. This compound was successfully purified in the quantity of 68 mg from 120 mg of the crude extract. The structure of JBIR-99 was elucidated and assigned by 1D, 2D NMR spectroscopic, and positive HRESITOFMS. Moreover, the relative configuration of compound JBIR-99, displaying a quite complex multi-ring structure, is determined by X-ray crystallography for the first time. The purification method developed for JBIR-99 will facilitate the further investigation and development of this antibiotic agent as a lead compound. Furthermore, it is suggested that the combination of size exclusion chromatography and HSCCC could be more widely applied for the isolation and purification of polyketides from marine fungi.

The phonon modes in YBa₂Cu₃O_7-δ and YBa_2-xLa_xCu₃O_7-δ systems have been systematically studied by Raman spectroscopy. The new phonon modes of 104 cm^-1, 94 cm^-1, and 89 cm^-1 were found in all these samples. A crude estimate about the wavenumber of the collective vibration of the stable CuO2 plane was given in this paper. The standard deviations of the new phonons in YBa₂Cu₃O_7-δ and YBa_2-xLa_xCu₃O_7-δ systems were discussed. The results of the calculation indicated that the 104 cm^-1 mode probably stands the c-direction collective vibration of the stable CuO2 plane, the 94 cm^-1 mode stands the a-direction vibration, and the 89 cm^-1 mode stands b-direction vibration. The relevance between these phonons and the superconductivity was discussed. It is found that, as the T_c decreased, the 104 cm^-1 mode and the 94 cm^-1 mode softened, and the 89 cm^-1 mode hardened slightly.

Even 20 years after the first crystal structures of [FeFe]-hydrogenase have been published, several aspects of biological hydrogen turnover are heatedly discussed. In this perspective, we give an overview on how the diversity of naturally occurring and artificially prepared, semi-synthetic [FeFe]-hydrogenases deepens our understanding of hydrogenase chemistry. In parallel, we cover new results from biophysical techniques that go beyond the scope of conventional electrochemistry, X-ray diffraction, EPR, and FTIR spectroscopy. Taking into account both proton transfer and electron transfer as well as the notorious sensitivity of [FeFe]-hydrogenases towards carbon monoxide, the discussion further touches upon the molecular proceedings of biological hydrogen turnover.

This work aimed to characterize a DBD plasma equipment through optical and electrical measurements, seeking to obtain a greater knowledge of the plasma production process and how it behaves through the adopted parameters, such as frequency and voltage applied between electrodes, at a fixed distance of 1.7 mm. In order to measure them, three different characterization techniques were applied. The first method was the Lissajous figures, a technique quite effective for a complete electrical characterization of DBD equipment. The second technique used was the Optical Emission Spectroscopy, a tool used for the diagnosis of plasma, being it possible to identify the excited species produced in filamentary and diffuse discharge in the plasma. And finally, the triple Langmuir probe technique was used to obtain the electron temperature and electron density. Based on this study, it was possible to identify the equipment efficiency in different regimes. The electron temperature measurement for both systems analyzed were 27.96 eV and 20.69 eV to the filamentary and diffuse regimes, respectively. The density of electrons number to these regimes were 1.09 × 10²¹ m⁻³ and 1.56 × 10²¹ m⁻³.

Hydrogenases are iron-sulfur enzymes that catalyze proton reduction and H₂ oxidation with outstanding efficiency. They are considered blueprints for the design of transition metal complexes, e.g. as heterogenous catalysts in the context of H₂ production from water. Moreover, hydrogenases are biological model systems for metal hydride chemistry and proton-coupled electron transfer. Depending on the composition of the active site cofactor, [NiFe]-hydrogenases are distinguished from [FeFe]-hydrogenases. The former binds a hetero bimetallic nickel/iron site, embedded in the protein by four cysteine ligands. The later, by contrast, carries a homo bimetallic iron/iron site attached to the protein by only a single cysteine. Carbon monoxide and cyanide ligands (CO/CN) at the active site facilitated detailed investigations of hydrogenase catalysis by infrared spectroscopy, owing to strong signals and redox-dependent frequency shifts. However, the details of proton transfer have not been addressed experimentally.We found that specific redox state transitions in [NiFe]- and [FeFe]-hydrogenase can be triggered by visible light to record extremely sensitive ‘light-minus-dark’ infrared difference spectra monitoring key amino acid residues as shown in the ToC figure. As these transitions are coupled to protonation changes, our data allowed investigating dynamic hydrogen-bonding changes that go well beyond the resolution of protein crystallography. In [NiFe]-hydrogenase, photolysis of the bridging hydride ligand in the ‘Ni-C’ state was followed by rapid accumulation of the ‘Ni-SI_a’ state and/or ‘Ni-L’ state. Infrared difference spectra in various isotopic media clearly indicated the formation of a protonated cysteine residue as well as hydrogen-bonding changes involving the COOH group of a glutamic acid residue and a ‘dangling water’ molecule. These findings are in excellent agreement with crystallographic analyses of [NiFe]-hydrogenase in the Ni-R state and allowed devising a molecular precise model of catalytic proton transfer. In [FeFe]-hydrogenase, an external redox dye was used to accumulate the ‘Hred’ state over the oxidized resting state ‘Hox’. Infrared difference spectra of wild-type enzyme and numerous amino acid variants indicated hydrogen-bonding changes involving the COOH groups of two glutamic acid residues. Moreover, we noted the deprotonation of an arginine residue. Crystallographic analyses of [FeFe]-hydrogenase in the Hox state failed to explain the rapid proton transfer due to a ‘breach’ in the succession of residues. To this end, our findings facilitated a molecular precise model of ‘discontinued’ proton transfer.The comparison of catalytic proton transfer in bimetallic hydrogenases emphasizes the role of the outer coordination sphere. We suggest that the stable protonation of a nickel-ligating cysteine in [NiFe]-hydrogenase has a crucial influence on the preferred direction of proton flow and catalysis (i.e., H₂ oxidation). On the contrary, proton transfer in [FeFe]-hydrogenase involves an adjacent cysteine as a relay group that promotes both proton release and proton uptake. We presume that this causes the notable bidirectionality of [FeFe]-hydrogenase. These observations must guide the design of biomimetic compounds for the production or consumption of H₂.

In biology molecules and macromolecules like sugars, proteins, DNA, and RNA are of utter importance. Detecting their presence as well as their conformation is still a challenge in many cases. It is well known that the vibrational states of such molecules lie from the infrared to the TeraHertz range. Spectroscopy can be used to detect such compounds and probe their conformation. Still, terahertz spectroscopy on biosample is a challenge for two main reasons: water absorption; and the small size of the samples. The sample volume is smaller than the cube of the TeraHertz wavelength; the light matter interactions are thus extremely reduced. In this paper, we present the design, fabrication, characterization and the first typical uses of a biophotonic device aiming at increasing light matter interaction to enable terahertz spectroscopy of minute samples on a broad band (0.2–2 THz). We demonstrate time domain spectroscopy experiments on few µl samples showing the validity of our approach.

A theoretical analysis of haemoglobin (Hb) concentration detection is presented in this work with the objective of achieving more sensitive detection and monitoring low concentrations. Surface-enhanced SPR spectroscopy on silver nanoparticles was employed for recording Hb concentrations less than 10 g/L. In this paper, Fe₃O₄@Au core-shell, nanocomposite spherical nanoparticle consisting of a spherical Fe₃O₄ core covered by Au shell, was used as an active material for biomolecules detection in the Surface Plasmon Resonance (SPR)-based biosensor in the wavelength 632.8 nm. We present the simulation of detection amplification technique through Attenuated Total Reflection (ATR) spectrum in the Kretschmann configuration. The system consists of a four-layer material i.e prism/Ag/Fe₃O₄@Au+Hb/air. Dielectric function determination of the core-shell nanoparticle (Fe₃O₄@Au) and the composite (Fe₃O₄@Au+Hb) was done by applying the Effective Medium Theory approximation and the calculation of the reflectivity is carried out by varying the size of core-shell (r₀). In this simulation, the refractive index of the BK7 prism is 1.51; the refractive index of Ag thin film is 0.13455+3.98651i with the thickness of 40 nm, and the refractive index of the composite is varied depending on the size of nanoparticle core-shell. Our results show that by varying the radius of the core and the shell thickness, the dip of the reflectivity (ATR) spectrum is shifted to the larger angle of incident light and the addition of core-shell in the conventional SPR-based biosensor leads to enhancement of the SPR biosensor sensitivity, for the core-shell radius 10 nm, the sensitivity increased by 1.35% for F = 0.1, and by 4.89% for F =0.8 compared to the sensitivity of the conventional SPR-based biosensor without core-shell addition.

A fast and effective determination method of different species of vegetable seeds oil is vital in the plant oil industry. The near-infrared reflectance spectroscopy (NIRS) method was developed in this study to massively analyze the oil and moisture contents of Camellia gauchowensis Chang and C. semiserrata Chi seeds kernels. In the prediction models of NIRS, the levels of accuracy obtained were sufficient for C. gauchowensis Chang and C. semiserrata Chi, the correlation coefficient of which oil were 0.983 and 0.962, respectively, while which of moisture were 0.937 and 0.907, respectively. The near infrared spectrum of crush seeds kernels was more precise compared to intact kernels. Based on the calibration models of the two Camellia species, the NIRS predictive oil contents of C. gauchowensis Chang and C. semiserrata Chi seeds kernels were 48.71 ± 8.94% and 31.71 ± 7.39%, respectively, and the NIRS predictive moisture contents were 4.39 ± 1.08% and 3.49 ± 0.71%, respectively. Compared with the traditional chemical measurement, the rapid, precise measurement of oil and moisture of C. gauchowensis Chang and C. semiserrata Chi seeds kernels can be actualized by NIRS method.

Understanding the chalk-fluid interactions and the associated mineralogical and mechanical alteration at sub-micron scale are major goals in Enhanced Oil Recovery. Mechanical strength, porosity, and permeability of chalk are linked to mineral dissolution that occurs during brine injections, and affect the reservoir potential. This paper presents a novel "single grain" methodology to recognize the varieties of carbonates in rocks and loose sediments: Raman spectroscopy is a non-destructive, quick, and user-friendly technique representing a powerful tool to identify minerals down to 1 µm. An innovative working technique for oil exploration is proposed, as the mineralogy of micron-sized crystals grown in two flooded chalk samples (Liége, Belgium) was successfully investigated by Raman spectroscopy. The drilled chalk cores were flooded with MgCl₂ for c. 1.5 (Long Term Test) and 3 years (Ultra Long Term Test) under North Sea reservoir conditions (Long Term Test: 130°C, 1 PV/day, 9.3 MPa effective stress; Ultra Long Term Test: 130°C, varying between 1-3 PV/day, 10.4 MPa effective stress). Raman spectroscopy was able to identify the presence of recrystallized magnesite along the core of the Long Term Test up to 4 cm from the injection surface, down to the crystal size of 1-2 µm. In the Ultra Long Term Test core the growth of MgCO₃ affected nearly the entire core (7 cm). In both samples, no dolomite or high-magnesium calcite secondary growth could be detected when analysing 557 and 90 Raman spectra on the Long and Ultra Long Term Test, respectively. This study can offer Raman spectroscopy as a breakthrough tool in petroleum exploration of unconventional reservoirs, due to its quickness, spatial resolution, and non-destructive acquisition of data. These characteristics would encourage its use coupled with electron microscopes and energy dispersive systems or even electron microprobe studies.

This work examines atomic and molecular signatures in laser-induced plasma in standard ambient temperature and pressure environments, including background contributions to the spectra that depend on the laser pulse-width. Investigations include solids, gases, and nano-particles. Abel inversions of measured line-of-sight data reveal insight into the radial plasma distribution. For nominal 6 nanosecond laser pulses and for pulse-energies in the range of 100 to 800 milli-Joules, expansion dynamics and turbulence due to shock phenomena are elucidated to address local equilibrium details that are frequently assumed in spatially averaged emission spectroscopy. Chemical equilibrium computations reveal temperature dependence of selected plasma species. Specific interests include atomic hydrogen (H) and cyanide (CN). The atomic H spectra, collected following optical breakdown in ultra-high-pure hydrogen and 9:1 mixtures of ultra-pure hydrogen and nitrogen gases, indicate spherical shell structures and isentropic expansion of the plasma kernel over and above the usual shockwave. The recombination radiation of CN emanates within the first 100 nanoseconds for laser-induced breakdown in a 1:1 CO₂:N₂ gas mixture when using nanosecond laser pulses to create the micro-plasma. The micro-plasma is generated using 1064 nm, 150 mJ, 6 ns Q-switched Nd:YAG laser radiation. Measurements of the optical emission spectra utilize a 0.64 m Czerny-Turner type spectrometer and an intensified charge-coupled device.

In this work, the parameters of plasma (electron temperature (T_e), electron density n_e, plasma frequency (f_p) , Debye length (λ_D) and Debye number (N_D)) have been studied by using the spectrometer that collect the spectrum of Laser produce Cadmium telluride plasma at different energies. The results of electron temperature for CdTe range 0.93-1.18 eV also the electron density 5 × 10¹⁰ – 3.8 × 10¹¹ cm^-3 have been measured under vacuum reaching 2.5 × 10^-2 mbar .Optical properties of CdTe were determined through the optical transmission method using ultraviolet visible spectrophotometer within the range 190 – 1100 nm.

Many strategies have been developed for the synthesis of silicon carbide (SiC) thin films on silicon (Si) substrates by plasma-based deposition techniques, especially plasma enhanced chemical vapor deposition (PECVD) and magnetron sputtering, due to importance of these materials for microelectronics and related fields. A drawback is the large lattice mismatch between SiC and Si. The insertion of a thin aluminum nitride (AlN) buffer layer between them has been shown useful to overcome this problem. Herein, the high-power impulse magnetron sputtering (HiPIMS) technique was used to grow SiC thin films on AlN/Si substrates. Furthermore, the SiC films were also grown on Si substrates. Comparisons of the structural and chemical properties of SiC thin films grown on the two types of substrates allowed us to evaluate the influence of AlN buffer layer on such properties. The chemical composition and stoichiometry of the samples were investigated by Rutherford backscattering spectrometry (RBS) and Raman spectroscopy, while the crystallinity was characterized by grazing incidence X-ray diffraction (GIXRD). Our set of results evidenced the versatility of HiPIMS technique to produce polycrystalline SiC thin films at near room temperature only varying the discharge power. In addition, this study opens up a feasible route for the deposition of crystalline SiC films with a good structural quality using AlN buffer layer.

This work communicates a review on Balmer series hydrogen beta line measurements and applications for analysis of white dwarf stars. Laser-induced plasma investigations explore electron density and temperature ranges comparable to white dwarf star signatures such as Sirius B, the companion to the brightest star observable from the earth. Spectral line shape characteristics of the hydrogen beta line include width, peak separation, and central dip-shift, thereby providing three indicators for electron density measurements. The hydrogen alpha line shows two primary line-profile parameters for electron density determination, namely, width and shift. Both Boltzmann plot and line-to-continuum ratios yield temperature. The line-shifts recorded with temporally- and spatially- resolved optical emission spectroscopy of hydrogen plasma in laboratory settings can be larger than gravitational redshifts that occur in absorption spectra from radiating white dwarfs. Published astrophysical spectra display significantly diminished Stark or pressure broadening contributions to red-shifted atomic lines. Gravitational redshifts allow one to assess the ratio of mass and radius of these stars, and subsequently, the mass from cooling models.

Friction and wear take place on two solid surfaces in sliding contact as a result of the mechanical, thermal and chemical interactions with the participation of environmental species. Electron microscopy and the associated spectroscopic analyses are powerful in probing these mechanisms in spatial resolutions from micro to atomic scale. This article provides a review of the author’s work in the wear and friction mechanisms of PVD hard coatings in which various SEM- and TEM-based microscopic and spectroscopic techniques were employed. Understanding on the failure mechanisms and the origin of self-adaptive friction has been improved to nano-scale. Other related issues are also discussed, such as sample preparation techniques for cross-sectional electron microscopy, energy dispersive X-ray spectroscopy and electron energy loss spectroscopy.

Literature is inconsistent as to how coffee affects the features of the metabolic syndrome (MetS), and which bioactive compounds are responsible for its metabolic effects. We aimed to compare the in-vivo effects of unfiltered coffee with a selected mixture of its compounds on diet-induced MetS. 24 male Sprague-Dawley rats were fed a high-fat (35% W/W) food plus 20% W/W fructose in drinking water for 14 weeks, and were randomized into three groups: control, coffee, or nutraceuticals (5-O-caffeoylquinic acid, caffeic acid, and trigonelline). Coffee or nutraceuticals were provided in drinking water in a dosage equal to 4 cups/day in a human. Compared to the controls, only coffee supplementation decreased total food intake, weight gain, and estimated average plasma glucose. Surrogate measures of insulin resistance (fasting insulin, HOMA-IR, and oral glucose tolerance) were improved at endpoint in the coffee group. Circulating triglyceride levels were also reduced by coffee. Histopathological and quantitative measurements indicated lower grades of liver steatosis after long-term coffee consumption. In conclusion, a combination of phenolic acids and trigonelline was not as effective as coffee per se in improving the components of the MetS. This points to the role of other coffee chemicals and a potential synergism between compounds.

Recently, two chicken breast fillet abnormalities, termed Wooden Breast (WB) and Spaghetti Meat (SM), have become a challenge for the chicken meat industry. The two abnormalities share some overlapping morphological features, including myofiber necrosis, intramuscular fat deposition, and collagen fibrosis, but display very different textural properties. WB has a hard, rigid surface, while the SM has a soft and stringy surface. Connective tissue is affected in both WB and SM, and accordingly, this study's objective was to investigate the major component of connective tissue, collagen. The collagen structure was compared with normal (NO) fillets using histological methods and Fourier transform infrared (FTIR) microspectroscopy and imaging. The histology analysis demonstrated an increase in the amount of connective tissue in the chicken abnormalities, particularly in the perimysium. The WB displayed a mixture of thin and thick collagen fibers, whereas the collagen fibers in SM were thinner, fewer, and shorter. For both, the collagen fibers were oriented in multiple directions. The FTIR data showed that WB contained more β-sheets than the NO and the SM fillets, whereas SM fillets expressed the lowest mature collagen fibers. This insight into the molecular changes can help to explain the underlying causes of the abnormalities.

A laser-based hydrogen (H₂) sensor using wavelength modulation spectroscopy (WMS) was developed for contactless measurements of molecular hydrogen. The sensor uses a distributed feedback (DFB) laser to target the H₂ quadrupole absorption line at 2121.8 nm. The H₂ absorption line exhibits weak collisional broadening and strong collisional narrowing effects. Both effects were investigated by comparing measurements of the absorption linewidth with detailed models using different line profiles that include collisional narrowing effects. The collisional broadening and narrowing parameters were determined for pure hydrogen as well as for hydrogen in nitrogen and air. Performance of the sensor was evaluated and the sensor applicability for H₂ measurements in a range of 0- 10 %v of H₂ was demonstrated. A precision of 0.02 %v was achieved with 1 meter of absorption pathlength (0.02 %v∙m) and 1 s of integration time. For the optimum averaging time of 20 s a precision of 0.005 %v∙m was achieved. A good linear relationship between H₂ concentration and the sensor response was observed. A simple and robust transmitter-receiver configuration of the sensor allows in-situ installations in harsh industrial environments.

Although the need to assess hydration is well recognized, laboratory tests and clinical impressions are impractical and lack sensitivity to be clinically meaningful. Different approaches use bioelectrical impedance measurements to overcome some of these limitations and aid in classification of hydration status. One indirect approach utilizes single or multiple frequency bioimpedance in regression equations and theoretical models, respectively, with anthropometric measurements to predict fluid volumes (bioelectrical impedance spectroscopy; BIS) and estimate fluid overload based on deviation of calculated to reference extracellular fluid volume. Alternatively, bioimpedance vector analysis (BIVA) uses direct phase-sensitive measurements of resistance and reactance, measured at 50 kHz, normalized for height, then plotted on a bivariate graph, resulting in a vector with length related to fluid content normalized by standing height, and direction with phase angle that indexes hydration status. Comparison with healthy population norms enables BIVA to classify (normal, under- and over-) and rank (change relative to pre-treatment) hydration independent of body weight. Each approach has wide-ranging uses in evaluation and management of clinical groups with overhydration with an evolving emphasis on prognosis. This review discusses the advantages and limitations of BIS and BIVA for hydration assessment with comments on future applications.

In this manuscript we are investigating the contribution of dynamic membrane properties of phospholipid membranes to coherent scattering signals under grazing incidence. Spectroscopic measurements under grazing incidence can provide useful insight into the properties of biological membranes, however are often impeded by weak signals. By using grazing-incidence small-angle neutron scattering (GISANS) to identify a dynamic scattering contribution we are able to independently corroborate the existence of a previously found dynamic mode found by grazing-incidence neutron spin echo spectroscopy (GINSES). Additionally, by increasing the speed of measurement compared to GINSES from several days to hours we were able to explore the temperature behavior of this mode in phospholipid membranes. These dynamic modes of the membranes show a wavelength of around 700 Å in-plane of the membrane and are most pronounced around 37°C and strongly decrease at lower temperatures below 25°C before vanishing at 20°C. We therefore speculate that they may be linked to biologically relevant functions of the membranes themselves.

A study is reported on the electrochemical alloying-dealloying properties of Mg₂Sn intermetallic compounds. ¹¹⁹Sn Mössbauer spectra of β-Sn powder, thermally alloyed cubic-Mg₂Sn and an intermediate MgSn nominal composition are used as references. The discharge of a Mg/micro-Sn half-cell led to significant changes in spectra line shape that are explained by a multiphase mechanism involving the coexistence of c-Mg₂Sn, distorted Mg_2-δSn and Mg-doped β-Sn. Capacities and capacity retention were improved by using nanoparticulate tin electrodes. This material reduces significantly the diffusion lengths for magnesium and contains surface SnO and SnO₂, which are partially electroactive. The half-cell potentials were suitable to be combined versus MgMn₂O₄ cathodes. Energy density and cycling properties of the resulting full Mg-ion cells are also scrutinized.

Toxicologically relevant levels of the psychoactive ∆9-tetrahydocannabinol (∆9-THC) as well as high levels of non-psychoactive cannabinoids potentially occur in CBD (cannabidiol) oils. For consumer protection in the fast-growing CBD oil market, facile and rapid quantitative methods to determine the cannabinoid content are crucial. However, the current standard method, i.e., liquid chromatography combined with tandem mass spectrometry (HPLC-MS/MS), requires a time-consuming multistep sample preparation. In this study, a quantitative nuclear magnetic resonance spectroscopy (qNMR) method for screening cannabinoids in CBD oils was developed. Contrary to the HPLC-MS/MS method, this qNMR features a facile sample preparation, i.e., only diluting the CBD oil in deuterochloroform. Pulse length-based concentration determination (PULCON) enables a direct quantification using an external standard. The signal intensities of the cannabinoids were enhanced during the NMR spectra acquisition by means of multiple suppression of the triglycerides which are a major component of the CBD oil matrix. The validation confirmed linearity for CBD, cannabinol (CBN), ∆9-THC and ∆8-THC in hemp seed oil with sufficient recoveries and precision for screening. Comparing the qNMR results to HPLC-MS/MS data for 46 commercial CBD oils verified the qNMR accuracy for ∆9-THC and CBD but with higher limits of detection. The developed qNMR method paves the way for increasing the sample throughput as a complementary screening before HPLC-MS/MS.

Achieving global goals on sustainable nutrition, health, and wellbeing will depend on delivering enhanced diets to humankind. This will require, among others, instantaneous access to information on food quality at key points within agri-food systems. Although stationary methods are usually used to quantify grain quality (wet-lab chemistry, benchtop NIR spectrometer); these do not suit many required user-cases, such as stakeholders in decentralized agri-food-chains that are typical for emerging economies. Therefore, we explored new technologies and models that might aid these particular user-cases. For this purpose, we generated the NIR spectra of 328 grain samples from multiple cereals (finger millet, foxtail millet, maize, pearl millet, sorghum) with a standard benchtop NIR Spectrometer (DS2500, FOSS) and a novel mobile NIR-based sensor (HL-EVT5, Hone). We explored a range of classical deterministic and novel machine learning (ML)-driven models to build calibrations out of the NIR spectra. We were able to build relevant calibrations out of both types of spectra. At the same time, ML-based methods enhanced the prediction capacity of calibration models compared to classical deterministic methods. We also documented that the prediction of grain protein content based on NIR spectra generated by a mobile sensor (HL-EVT5, Hone) was highly relevant for quantitative protein predictions (R2 = 0.91, RMSE = 0.97, RPD = 3.48). Thus, the findings of this study lay the foundations on which to expand the utilization of NIR spectroscopy applications for agricultural research and development.

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize nanofiltration (NF) membranes. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies were applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer, and (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in situ Fourier transform infrared (FT-IR) spectroscopy was firstly used to monitor the IP reaction of PIP/TMC with hydrophilic interlayers or macromolecular additives in the aqueous solution of PIP. Moreover, the formed polyamide layer growth on the substrate was studied in a real-time manner. The in situ FTIR experimental results confirmed that the IP reaction rates were effectively suppressed and that the formed polyamide thickness was reduced from 138 ± 24 nm to 46 ± 2 nm according to TEM observation. Furthermore, an optimized NF membrane with excellent performance was consequently obtained, which included boosted water permeation of about 141–238 (L/m²·h·MPa) and superior salt rejection of Na₂SO₄ > 98.4%.

Ubiquitin binding domains (UBDs) are modular elements that bind non-covalently to ubiquitin and act as downstream effectors and amplifiers of the ubiquitination signal. With few exceptions, UBDs recognize the hydrophobic path centered on Ile44 (Leu-8, Ile-44, Val-70). Nevertheless, a variety of different orientations, which can be attributed to specific contacts between each UBD and surface residues surrounding the hydrophobic patch, specify how each class of UBD recognizes ubiquitin. Here, we describe the structure of a novel ubiquitin-binding domain that we identified in NEDD4 binding protein 1 (N4BP1). By performing protein sequence analysis, mutagenesis and NMR spectroscopy of the ¹⁵N isotopically labelled protein, we demonstrate that a Phe-Pro motif in N4BP1 recognizes the canonical hydrophobic patch of ubiquitin. This recognition mode resembles the molecular mechanism evolved in the CUE (Coupling of ubiquitin conjugation to ER degradation) domain family, where an invariant proline, usually following a phenylalanine, is required for binding to ubiquitin. Interestingly, the UBD of N4BP1 is evolutionary related to CUBAN (Cullin binding domain associating with NEDD8) (40% identity and 47% similarity), a protein module that also recognizes the ubiquitin-like NEDD8, which is the closest relative of ubiquitin (58% identity and 80% similarity). By performing circular dichroism and ¹⁵N NMR chemical shift perturbation of N4BP1 in complex with ubiquitin, we demonstrate that the UBD of N4BP1 lacks the NEDD8 binding properties observed in CUBAN and it recognizes the Ile44-centered patch of ubiquitin through a dedicated binding site, which share some of the features observed in the CUE domain family. Moreover, we show that, in addition to mediating the interaction with ubiquitin and ubiquitinated substrates, both the CUBAN and the UBD of N4BP1 are poly-ubiquitinated in cells. This modification is dependent on the presence of a functional domain. We believe that the structural and functional characterization of this novel UBD will allow a deeper understanding of the molecular mechanisms governing N4BP1 function, while at the same time providing a valuable tool for clarifying how the discrimination between ubiquitin and the highly related NEDD8 is achieved.

The resonance spectra of neutral silver indicate self-absorption for the studied Ag I lines at the wavelengths of 327.9 nm and 338.2 nm. The center dip is associated with self-reversal due to self-absorption in the plasma. The Q-switched radiation of 355 nm, 532 nm, or 1064 nm from a Nd:YAG laser device generates the plasma at the surface of silver nano-material targets, with experiments conducted in standard ambient temperature and pressure laboratory air. Procedures for recovery of the spectral line shapes confirm that over and above the effects of self-reversal, line shape distortion are important in the analysis. The work discusses parameters describing self-absorption when using fluence levels of 2 to 33 J/cm² to generate the plasma. Furthermore, subsidiary calibration efforts that utilize the hydrogen alpha line of the Balmer series show that the Ag I lines at 827.35 nm and 768.7 nm are optically thin.

Amorphous silicon (α-Si) film present an inexpensive and promising material for optoelectronic and nanophotonic applications. Its basic optical and optoelectronic properties are known to be improved via phase transition from amorphous to polycrystalline phase. Infrared femtosecond laser radiation can be considered as a promising nondestructive and facile way to drive uniform in-depth and lateral crystallization of α-Si films that are typically opaque in UV-visible spectral range. However, so far only a few studies reported on utilization of near-IR radiation for laser-induced crystallization of α-Si providing no information regarding optical properties of the resultant polycrystalline Si films. The present work demonstrates efficient and gentle single-pass crystallization of α-Si films induced by their direct irradiation with near-IR femtosecond laser pulses coming at sub-MHz repetition rate. Comprehensive analysis of morphology and composition of laser-annealed films by atomic-force microscopy, optical, micro-Raman and energy-dispersive X-ray spectroscopy, as well as numerical modeling of optical spectra, confirmed efficient crystallization of α-Si and high-quality of the obtained films. Moreover, we highlight localized laser-driven crystallization of α-Si as a promising way for optical information encryption, anti-counterfeiting and fabrication of micro-optical elements.

A graphene-containing LDH was prepared by re-hydration of the oxides produced by the calcination of an organic LDH. While the memory effect is a widely recognized effect on oxides produced by inorganic LDHs, it is unprecedented from the calcination/re-hydration of organic ones. Different temperatures (400, 600 and 1100 °C) were tested, on the basis of thermogravimetric data. Water instead of a carbonate solution was used for the re-hydration, with CO₂ available from water itself and/or air to induce a slower process with an easier and better intercalation of the carbonaceous species within the layers. The samples were characterized by X-ray Powder Diffraction (XRPD), IR and Raman spectroscopy and scanning electron microscopy (SEM). XRPD indicate the presence of carbonate LDH mixed with a layered phase with a larger d-spacing. IR confirmed that the prevailing anion is carbonate, coming from the water used for the re-hydration and/or air. Raman data indicated the presence of low-ordered graphenic species moieties and SEM the absence of separated graphene of graphitic sheets, suggesting an intimate mixing of the carbonaceous phase with reconstructed LDH. Organic LDHs gave better memory effect after calcination at 400 °C. Conversely, the graphenic species are observed after rehydration of the sample calcined at 600 °C with a reduced memory effect, demonstrating the interference of the carbonaceous phase with LDH reconstruction and the bonding with LDH layers to form a graphene-LDH nanocomposite.

A controlled ammonia (NH₃) release experiment was performed at a grassland site to quantify the effect of dry deposition, at the field scale between the source and the receptors (NH₃ measurement locations), on the estimates of emission rates by means of inverse dispersion modelling. NH₃ was released for 3 hours at a constant rate of Q = 6.29 mg s⁻¹ from a grid of 36 orifices spread over an area of 250 m². The increase in line-integrated NH₃ concentration was measured with open-path optical miniDOAS devices at different locations downwind of the artificial source. Using a backward Lagrangian stochastic (bLS) dispersion model (bLSmodelR), the fraction of the modelled release rate to the emitted NH₃ (Q_bLS/Q) was calculated from the measurements of the individual instruments. Q_bLS/Q was found to be systematically lower than 1, on average between 0.69 and 0.91, depending on the location of the receptor. We hypothesized that NH₃ dry deposition to grass and soil surfaces was the main factor responsible for the observed depletion of NH₃ between source and receptor. A dry deposition algorithm based on a deposition velocity approach was included in the bLS modelling. Model deposition velocities were evaluated from a ‘big‑leaf’ canopy resistance analogy. Canopy resistances (generally termed Rc) that provided Q_bLS/Q = 1 ranged from 75 to 290 s m⁻¹, showing that surface removal of NH₃ by dry deposition can plausibly explain the original underestimation of Q_bLS/Q. The inclusion of a dry deposition process in dispersion modelling is crucial for emission estimates, which are based on concentration measurements of depositing tracers downwind of homogeneous area sources or heterogeneously distributed hot spots, such as e.g. urine patches on pastures in the case of NH₃.

Background: Maladaptive neuroplasticity related learned response in substance use disorder (SUD) can be ameliorated using non-invasive brain stimulation (NIBS); however, inter-individual variability needs to be addressed for clinical translation. Objective: Our first objective was to develop a hypothesis for NIBS for learned response in SUD based on competing neurobehavioral decision systems model. Next objective was to conduct computational simulation of NIBS of cortico-cerebello-thalamo-cortical (CCTC) loop in cannabis use disorder (CUD) related dysfunctional “cue-reactivity” – a closely related construct of “craving” that is a core symptom. Our third objective was to test the feasibility of our neuroimaging guided rational NIBS approach in healthy humans. Methods: “Cue-reactivity” can be measured using behavioral paradigms and portable neuroimaging, including functional near-infrared spectroscopy (fNIRS) and electroencephalogram (EEG), metrics of sensorimotor gating. Therefore, we conducted computational simulation of NIBS, including transcranial direct current stimulation(tDCS) and transcranial alternating current stimulation(tACS) of the cerebellar cortex and deep cerebellar nuclei(DCN), of the CCTC loop for its postulated effects on fNIRS and EEG metrics. We also developed a rational neuroimaging guided NIBS approach for cerebellar lobule (VII) and prefrontal cortex based on healthy human study. Results: Simulation study of cerebellar tDCS induced gamma oscillations in the cerebral cortex while tTIS induced gamma-to-beta frequency shift. Experimental fNIRS study found that 2mA cerebellar tDCS evoked similar oxyhemoglobin(HbO) response in-the-range of 5x10-6M across cerebellum and PFC brain regions (=0.01); however, infra-slow (0.01–0.10 Hz) prefrontal cortex HbO driven(phase-amplitude-coupling, PAC) 4Hz, ±2mA (max.) cerebellar tACS evoked HbO in-the-range of 10-7M that was statistically different (=0.01) across those brain regions. Conclusion: Our healthy human study showed the feasibility of fNIRS of cerebellum and PFC as well as fNIRS-driven ctACS at 4Hz that may facilitate cerebellar cognitive function via the frontoparietal network. Future work needs to combine fNIRS with EEG for multi-modal imaging.

Immunosensors have been widely developed to use antibodies to detect a pathogen of interest; it is interesting to look at the effect of nonspecific antibody binding to E. coli using electrochemical methods. IgG antibody not specific to E. coli O157:H7 was crosslinked onto a screen-printed carbon electrode. The presence of E. coli at 4, 4 × 10², 4 × 10⁵, and 4 × 10⁸ CFU/mL on the electrode surface was detected via linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS). Current transfer at both electrodes was reduced as the concentration of bacteria increased; however, the calibration of number of cells to decreased current was nonlinear for IgG-modified electrodes. The nonlinearity is confirmed by EIS measurements which showed highest impedance at 4 CFU/mL E. coli when impedance should be the lowest. FESEM images showed higher binding of cells when IgG is present compared to electrodes with reduced graphene oxide (rGO) alone. Electrodes with rGO alone show less attachment of E. coli, with EIS showing a linear calibration profile, while LSV shows not much difference in current values for all concentrations aside from the highest concentration. These results suggest that nonspecific binding can provide false signals in electrochemical measurements, and it is crucial to provide proper controls.

A 9,10-phenanthrenequinone (PQ) was electrochemically polymerized on a graphite rod electrode using potential cycling. The electrode modified by poly-9,10-phenanthrenequinone (poly-PQ) was studied by means of cyclic voltammetry, electrochemical impedance spectroscopy, atomic force microscopy and scanning electron microscopy. The poly-PQ shows variations in growth pattern depending on the number of potential cycles for the initiation of polymerization. Formed poly-PQ layer demonstrates good electric conductivity, great electrochemical capacitance and unique oxidation/reduction properties, which are suitable for broad technological applications, including applicability in biosensors, supercapacitors, and in some other electrochemical systems.

In this paper, the classical least square (CLS) method with molecular absorption spectrophotometric measurement was used to determine simultaneously of paracetamol (PAR), ibuprofen (IBU), and caffeine (CAF) in tablets. The absorbance spectra of the standard solutions and samples were measured over a wavelength from 220 to 300 nm with a 0.5 nm step. The concentration of PAR, IBU and CAF in the sample solutions were calculated by using a program called CLS-Excel written in Microsoft Excel 2016 and Visual Basic for Applications (VBA). The method and CLS-Excel program were tested on mixed standard laboratory samples with different PAR, IBU, and CAF concentration ratios, and they showed small errors and satisfying repeatability. An analytical procedure for tablets containing PAR, IBU, and CAF was developed. The reliability of the procedure was proved via the recovery and repeatability of the analysis results with an actual tablet sample and comparing the mean contents of active substances in the tablets obtained from the analytical procedure with the from the HPLC method. The procedure is simple with a reduced cost compared with the HPLC standard method.

This work reports measurements of calcified gallstone elemental compositions using laser-induced optical emission spectroscopy. The experimental results support the importance of the magnesium concentration in gallstone growth. Granular stones reveal an increased magnesium concentration at the periphery of the granules, suggesting the inhibition of further growth. Non-granular gallstones reveal lower overall magnesium concentrations but with higher values near the center.

The food additive sorbic acid is considered as an effective preservative for certain cereal products, and propionic acid is commonly added in bakery wares, e.g. bread and fine bakery wares. The aim of this study is to develop and validate a new nuclear magnetic resonance spectroscopy (¹H NMR) method for routine screening and quantification of sorbic and propionic acids in bread and several bakery products for quality control purposes. Results showed that none of the screened samples contained higher concentrations than regulatory maximum limits. However, for some samples, labelling of preservatives was lacking or they were used in food categories, for which the use is not approved. It can be concluded that the developed NMR method can be used for routine screening of bakery products.

Mineral surfaces have been demonstrated to play a central role in prebiotic reaction, which are supposed to be at the basis of the origin of life. Among the various molecules proposed as precursors for these reactions, one of the most interesting is formamide. Formamide has been shown to be a pluripotent molecule, generating a wide distribution of relevant pre-biotic products. In particular, the outcomes of its reactivity are strongly related to the presence of mineral phases, acting as catalysts toward specific reaction pathways. Even if the mineral-products relationship has been deeply studied for a large pool of materials, the fundamental description of the formamide reactivity over the mineral surface at a microscopic level is missing in the literature. In particular, a key step of formamide chemistry at surfaces is its adsorption on the available interaction sites. This report aims to investigate the adsorption of formamide over a well-defined amorphous silica, chosen as model mineral surface. An experimental IR investigation of formamide adsorption has been carried out and its outcomes have been interpreted on the basis of first principles simulation of the process adopting a realistic model of the amorphous silica.

High-resolution laboratory-based thermal infrared spectroscopy is an up-and-coming tool in the field of geological remote sensing. Its spatial resolution allows for detailed analyses at centimeter to sub-millimeter scale. However, this increase in resolution creates challenges with sample characteristics such as grain size, surface roughness and porosity that can influence the spectral signature. This research explores the effect of rock sample surface preparation on the TIR spectral signatures. We applied three surface preparation methods (split, saw and polish) to determine how the resulting differences in surface roughness affects both the spectral shape as well as the spectral contrast. The selected samples are a pure quartz sandstone, a quartz sandstone containing a small percentage of kaolinite, and an intermediate-grained gabbro. To avoid instrument or measurement type biases we conducted measurements on three TIR instruments, resulting in directional hemispherical reflectance spectra, emissivity spectra and bi-directional reflectance images. Surface imaging and analyses were performed with scanning electron microscopy and profilometer measurements. We demonstrate that surface preparation affects the TIR spectral signatures influencing both the spectral contrast as well as the spectral shape. The results show that polished surfaces predominantly display a high spectral contrast while the sawed and split surfaces display up to 25% lower reflectance values. Furthermore, the sawed and split surfaces display spectral signature shape differences at specific wavelengths, which we link to mineral transmission features, surface orientation effects and multiple reflections in fine-grained minerals. Hence, the influence of rock surface preparation should be taken in consideration to avoid an inaccurate geological interpretation.

The electrical and optical properties of sol-gel derived aluminum-doped0 zinc oxide thin films containing 2 at.% Al were investigated considering the modifying effects of 1) increasing the sol H₂O content; and 2) thermal treatment procedure with high-temperature approach followed by an additional heat-treatment step under a reducing atmosphere. According to the results obtained via the TG-DTA analysis, FT-IR spectroscopy, X-ray diffraction technique and four-point probe resistivity measurement, it is argued that the sol hydrolysis, decomposition of the deposited gel and crystallization of grains result in grains of larger crystallite size and stronger c-axis preferred orientation with slightly less microstrain in the modified sample. The consequent morphology and grain-boundary characteristics turn out as improved conductivity, implying higher values of concentration and mobility of charge carriers. A detailed investigation on samples optical properties, in terms of analyzing their absorption and dispersion behaviors through the UV-Vis-NIR spectroscopy, support our reasoning for the increase of the mobility, and to a lesser extent, the concentration of charge carriers, while causing only a slight degradation of optical transmission. Hence, an enhanced performance as a transparent conducting film is claimed for the modified sample by comparing the figure-of-merit values.

The development of efficient luminescent systems, such as microcavities, solid state lasers, integrated optical amplifiers, optical sensors is the main topic in glass photonics. The building blocks of these systems are glass-ceramics activated by rare earth ions because they exhibit specific morphologic, structural and spectroscopic properties. Among various materials that could be used as nanocrystals to be imbedded in silica matrix, tin dioxide presents some interesting peculiarities, e.g. the presence of tin dioxide nanocrystals allows increase in both solubility and emission of rare earth ions. Here, we focus our attention on Er³⁺ - doped silica – tin dioxide photonic glass-ceramics fabricated by sol-gel route. Although the SiO₂-SnO₂:Er³⁺ could be fabricated in different geometrical systems: thin films, monoliths and planar waveguides we herein limit ourselves to the monoliths. The effective role of tin dioxide as luminescence sensitizer for Er³⁺ ions is confirmed by spectroscopic measurements and detailed fabrication protocols are discussed.

ZnO has many technological applications which largely depend on its properties that can be tuned by controlled synthesis. Ideally, the most convenient ZnO synthesis is carried out at room temperature in aqueous solvent. However, the correct temperature values are often loosely defined. In the current paper we performed synthesis of ZnO in aqueous solvent, by varying reaction and drying temperature by 10°C steps and monitored the synthesis products primarily by XRD. We found out that a simple direct synthesis of ZnO, without additional surfactant, pumping of freezing, required both a reaction (TP) and a drying (TD) temperature of 40°C. Higher temperatures also afford ZnO, but lowering any of the TP or TD below the threshold value results either in the achievement of Zn(OH)2 or in a mixture of Zn(OH)2/ZnO. A more detailed Rietveld analysis of the ZnO samples reveals a density variation with the synthesis temperature and an increase of the nanoparticles average size also verified by SEM images. The optical properties of ZnO obtained by UV-Vis reflectance spectroscopy indicate a red shift of the band gap by ~0.1 eV.

Pathogens and adulterants in human feeding consumables can be readily identified according to their electrical properties. Electrical bioimpedance analysis (BIA) has been widely used for body contents characterization, such as blood, urine, lactate and sweat. If the blood glucose concentration alters the electrical properties of the blood medium, then the impedance spectrum obtained by BIA can be used to measure glycemia. In some applications, artificial neural networks allows the correlation of these parameters (impedance and glucose concentration) by means of symbolic and statistical rules. According to our literature review, there is any physical model that allows the interpretation of the relationship between blood’s electrical properties, obtained by BIA, and the concentration of glucose in the blood plasma. This article proposes a simplified physical model for blood electrical conductivity as a function of glucose concentration, based on Bruggeman’s effective medium theory. The equations of this model were obtained considering an insulating phase distribution diffused in a conductive matrix, in which red blood cells are represented by macroscopic insulating nuclei and glucose molecules by microscopic insulating particles. The impedance spectrum for different glucose concentrations (4.0 to 6.8 mmol/L) in a blood sample, published by Kamat Bagul (2014), were compared with the proposed model. The results showed a significant correlation with the experimental data, showing a maximum error of 5.2%. The proposed model might be useful in the design of noninvasive blood glucose monitoring systems.

We describe electron temperature measurements in the SSX MHD wind tunnel using two different methods. First, we estimate T_e along a chord by measuring the ratio of the C__III 97.7 nm to C_IV 155 nm line intensities using a vacuum ultraviolet monochrometer. Second, we record a biasing scan to a double Langmuir probe to obtain a local measurement of T_e. The aim of these studies is to increase the Taylor state lifetime, primarily by increasing the electron temperature. Also, a model is proposed to predict magnetic lifetime of relaxed states and is found of predict the lifetime satisfactorily. Furthermore, we find that proton cooling can be explained by equilibration with the electrons.

For a given set of plasma parameters, along a single series (Lyman, Balmer etc) the lines with higher principal quantum number(n) lines get progressively wider, closer to each other, and start merging for a certain critical n. In the present work four different codes(with further options) are used to calculate the entire Balmer series for moderate and high electron densities. Particular attention is paid to the relevant physics, such as the cutoff criteria, strong and penetrating electron collisions.

Earth-abundant transition metals like iron, nickel, copper, molybdenum, and vanadium have been identified as essential constituents of the cellular gas metabolism in all kingdoms of life. Associated with biological macromolecules, gas-processing metalloenzymes (GPMs) are formed that catalyse a variety of redox reactions. This includes the reduction of O₂ to water by cytochrome c oxidase (‘complex IV’), the reduction of N₂ to NH₄ by nitrogenase, as well as the reduction of protons to H₂ (and oxidation of the later) by hydrogenase. GPMs perform at ambient temperature and pressure, in the presence of water, and often extremely low educt concentrations, thus serving as natural examples for efficient catalysis. Facilitating the design of biomimetic catalysts, biophysicist thrive to understand the reaction principles of GPMs making use of various techniques. In this perspective, I will introduce Fourier-transform infrared spectroscopy in attenuated total reflection configuration (ATR FTIR) for the analysis of GPMs like cytochrome c oxidase, nitrogenase, and hydrogenase. Infrared spectroscopy provides information about the geometry and redox state of the catalytic cofactors, the protonation state of amino acid residues, the hydrogen-bonding network, and protein structural changes. I developed an approach to probe and trigger the reaction of GPMs by gas exchange experiments, exploring the reactivity of these enzymes with their natural reactants. This allows recording sensitive ATR FTIR difference spectra with seconds time resolution. Finally yet importantly, infrared spectroscopy is an electronically non-invasive technique that allows investigating protein samples under biologically relevant conditions, i.e., at ambient temperature and pressure, and in the presence of water.

The productivity of forests is often considered to be limited by the availability of phosphorus (P). Knowledge of the role of organic and inorganic P in humid subtropical forest soils is lacking. In this study, we used chemical fractionation and 31P nuclear magnetic resonance (NMR) spectroscopy to characterize the form of P and its distribution in undisturbed perhumid Chamaecyparis forest soils. The toposequence of transects was investigated for the humic layer from summit to footslope and lakeshore. The clay layer combined with a placic-like horizon in the subsoil may affect the distribution of soil P because both total P and organic P (Po) contents in all studied soils decreased with soil depth. In addition, Po content was negatively correlated with soil crystalline Fe oxide content, whereas inorganic P (Pi) content was positively correlated with soil crystalline Fe oxide content and slightly increased with soil depth. Thus, Pi may be mostly adsorbed by soil crystalline Fe oxides in the soils. Among all extractable P fractions, the NaOH-Po fraction appeared to be the major component, followed by NaHCO3-Po; the resin-P and HCl-Pi fractions were lowest. In addition, we found no typical trend for Pi and Po contents in soils with topographical change among the three sites. From the 31P-NMR spectra, the dominant Po form in soils from all study sites was monoesters with similar spectra. The 31P-NMR findings were basically consistent with those from chemical extraction. Soil formation processes may be the critical factor affecting the distribution of soil P. High precipitation and year-round high humidity may be important in the differentiation of the P species in this landscape.

Highly nonlinear characteristics of lithium-ion batteries (LIBs) are significantly influenced by the external and internal temperature of the LIB cell. Moreover, cell temperature beyond the manufacturer’s specified safe operating limit could lead to thermal runaway and even fire hazards and safety concerns to operating personnel. Therefore, accurate information of cell internal and surface temperature of LIB is highly crucial for effective thermal management and proper operation of a battery management system (BMS). Accurate temperature information is also essential to BMS for the accurate estimation of various important states of LIB such as state of charge, state of health and so on. High capacity LIB pack, used in electric vehicles and grid-tied stationary energy storage system essentially consists of thousands of individual LIB cells. Therefore, installing a physical sensor at each cell especially at the cell core is not practically feasible from the solution cost, space and weight point of view. A solution is to develop a suitable estimation strategy which led scholars to propose different temperature estimation schemes aiming to establish a balance among accuracy, adaptability, modelling complexity and computational cost. This article presented an exhaustive review of these estimation strategies covering recent developments, current issues, major challenges, and future research recommendations. The prime intention is to provide a detailed guideline to the researchers and industries towards developing a highly accurate, intelligent, adaptive, easy to implement and compute efficient online temperature estimation strategy applicable to health-conscious fast charging and smart onboard BMS.

This work explores the use of Kuhn verdazyl radicals as building blocks in multifunctional molecular materials in an exemplary study, focusing on the magnetic and the electron transfer (ET) characteristics, but also addressing the question whether chemical modification by cross-coupling is possible. The ET in solution is studied spectroscopically whereas solid state measurements afford information about the magnetic susceptibility or the conductivity of the given samples. The observed results are rationalized based on the chemical structures of the molecules, which have been obtained by X-ray crystallography. The crystallographically observed molecular structures as well as the interpretation based on the spectroscopic and physical measurements are backed up by DFT calculations. The measurements indicate that only weak, antiferromagnetic coupling is observed in Kuhn verdazyls owed to the low tendency to form face-to-face stacks, but also that steric reasons alone are not sufficient to explain this behavior. Furthermore, it is also demonstrated that ET reactions proceed rapidly in verdazyls/verdazylium redox couples and that Kuhn verdazyls are suited as donor molecules in ET reactions.

The use of Hyperspectral (HS) and LiDAR acquisitions has a great potential to enhance mapping and monitoring practices of endangered grasslands habitats, beyond conventional botanical field surveys. In this study we assess the potentiality of Recursive Feature Elimination (RFE) in combination with Random Forest (RF) classification in extracting the main HS and LiDAR features needed to map selected Natura 2000 grasslands along Polish lowland river valleys, in particular alluvial meadows 6440, lowland hay meadows 6510 and xeric and calcareous grasslands 6120. We developed an automated RFE-RF system capable to combine the potentials of both techniques and applied it to multiple acquisitions. Several LiDAR-based products and different Spectral Indexes (SI) were computed and used as input in the system, with the aim of shedding light on the best-to-use features. Results showed a remarkable increase in classification accuracy when LiDAR and SI products are added to the HS dataset, strengthening in particular the importance of employing LiDAR in combination with HS. Using only the 24 optimal features selection generalized over the three study areas, strongly linked to the highly heterogeneous characteristics of the habitats and landscapes investigated, it was possible to achieve rather high classification results (K around 0.7-0.77 and habitats F1 accuracy around 0.8-0.85), indicating that the selected Natura 2000 meadows and dry grasslands habitats can be automatically mapped by airborne HS and LiDAR data. Similar approaches might be considered for future monitoring activities in the context of habitats protection and conservation

In fuel-cell technological development, one of the most important objectives is to minimize the amount of Pt, the most employed material as oxygen reduction and methanol oxidation electro-catalyst. In this paper we report the synthesis and characterization of Te nanotubes (TeNTs) decorated with Pt nanoparticles, readily prepared from stirred aqueous solutions of PtCl2 containing a suspension of TeNTs and ethanol acting as a reducing agent, avoiding the use of any hydrophobic surfactants as capping stabilizing substance. The as obtained TeNTs decorated with Pt nanoparticles (TeNTs/PtNPs) have been fully characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area diffraction patterns (SAD), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). We demonstrate that the new material can be successfully employed in fuel cell either as anodic (for methanol oxidation reaction) and cathodic (for oxygen reduction reaction) electrode with high efficiency in terms of related mass activities and on-set improvement. Remarkably, the cell operates in aqueous electrolyte buffered at pH 7.0, thus avoiding acidic or alkaline conditions that may lead e. g. to Pt dissolution (at low pH) and paving the way for the development of biocompatible devices and on chip fuel cells.

Taste signaling is a complex process that is linked to obesity and its associated metabolic syndromes. The sweet taste is mediated through a heterodimeric G protein coupled receptor (GPRC) in a species-specific manner and at multi-tissue specific levels. The sweet receptor recognizes a large number of ligands with structural and functional diversities to modulate different amplitudes of downstream signaling pathway(s). The human sweet-taste receptor has been extremely difficult to study by biophysical methods due to inadequate methods for producing large homogeneous quantities of the taste-receptor protein and a lack of reliable in vitro assays to precisely measure productive ligand binding modes leading to activity upon their interactions with the receptor protein. We report a multimodal high throughput assays to monitor ligand binding, receptor stability and conformational changes to model the molecular interactions between ligand-receptor. We applied saturation transfer difference nuclear magnetic resonance spectroscopy (STD-NMR) complemented by differential scanning calorimetry (DSC), circular dichroism (CD) spectroscopy, and intrinsic fluorescence spectroscopy (IF) to characterize binding interactions. Our method using complementary NMR and biophysical analysis is advantageous to study the mechanism of ligand binding and signaling processes in other GPCRs.

Different contact materials along with optimization of the deposition techniques expand the possibilities to obtain high performance room temperature CdTe-based X/γ-ray detectors. The heterostructures with ohmic (MoOx) and Schottky (MoOx, TiOx, TiN, and In) contacts, created by DC reactive magnetron sputtering and vacuum thermal evaporation, as well as In/CdTe/Au diodes with a p-n junction, formed by laser-induced doping, were developed and investigated. Depending on the pre-treatment of the surface of semi-insulating p-CdTe crystals, deposition of a MoOx film formed an ohmic or Schottky contact. Based on the calculations and IV characteristics of the fabricated Mo-MoOx/р-CdTe/MoOx-Mo, In/CdTe/MoOx-Mo, Ti-TiOx/р-CdTe/MoOx-Mo, and Ti-TiN/р-CdTe/MoOx-Mo Schottky-diode detectors, the current transport processes were described in the models of the carrier generation-recombination within the space-charge region (SCR) at low bias voltages, and space-charge limited current at higher voltages, respectively. The energies of generation–recombination centers, density of trapping centers, and carrier lifetimes were determined. A sharp increase in the reverse current in the Mo-MoOx/р-CdTe/MoOx-Mo, Ti-TiOx/р-CdTe/MoOx-Mo, and Ti-TiN/р-CdTe/MoOx-Mo heterostructures at high bias was discussed in frames of the Poole–Frenkel emission model. Nanosecond laser irradiation of the In electrode, pre-deposited on the p-CdTe crystals, resulted in an increase in the voltage range, corresponding to the carrier generation-recombination in the SCR, in the IV characteristics of the In/CdTe/Au diodes. Such In/CdTe/Au p-n junction diodes demonstrated high energy resolutions (7%@59.5 keV, 4%@122 keV, and 1.6%@662 keV).

A focal plane array (FPA) detector was used for hyperspectral imaging in the infrared (IR) spectral region using thermal and synchrotron light sources. FPA Fourier-transform IR (FTIR) imaging microspectroscopy will be able to monitor real time changes at specific absorption bands when combined with high brightness synchrotron source. In this study, several types of samples with unique structural motifs were selected and used for assessing the capability of the FPA-FTIR imaging technique. It was shown that the time required for polariscopy at IR wavelengths can be substantially reduced by the FPA-FTIR imaging approach. By using natural and laser fabricated polymers with sub-wavelength features, alignment of absorbing molecular dipoles was revealed as well as higher order patterns (laser fabricated structures). Micro-spectroscopy of absorber orientation reveals alignment patterns even when they are not spatially resolved.

New pharmaceutically acceptable salts of trazodone for the treatment of central nervous system disorders are synthesized and described. Each salt (trazodone hydrogen bromide and trazodone 1-hydroxy-2-naphthoate) was obtained by two or three different methods leading to the same crystalline form. Although trazodone salts are poorly crystalline, single-crystal X-ray diffraction data for trazodone 1-hydroxy-2-naphthoate were collected and analyzed as well as compared to the previously described crystal structure of commercially available trazodone hydrochloride. The powder samples of all new salts were characterized by Fourier transform infrared spectroscopy and 13C solid-state nuclear magnetic resonance spectroscopy. Spectroscopic studies were supported by gauge including projector augmented wave (GIPAW) calculations of carbon chemical shielding constants. The main goal of our research was to find salts with better physicochemical properties and to make an attempt to associate them with both the anion structure and the most prominent interactions exhibited by the protonated trazodone cation. The dissolution profiles of trazodone from tablets prepared from various salts with lactose monohydrate were investigated. The studies revealed that salts with simple anions show a fast release of the drug while the presence of more complex anion, more strongly interacting with the cation, effects a slow-release profile of the active substance and can be used for the preparation of the tables with a delay or prolonged mode of action.

Fibroblast growth factor 14 (FGF14) is a member of the intracellular FGFs, a group of proteins with roles in neuronal ion channel regulation and synaptic transmission. We have previously demonstrated that a male Fgf14-/- mouse model recapitulates salient endophenotypes of synaptic dysfunction and behaviors associated with schizophrenia (SZ). As the underlying etiology of SZ and its sex-specific onset remain elusive, the Fgf14-/- model provides a valuable tool to interrogate pathways that might be related to the disease mechanism. Here, we performed label free quantitative proteomics and bioinformatics to identify enriched pathways at the proteome level in the male and female hippocampi from Fgf14+/+ and Fgf14-/- mice. We discovered that many differentially expressed proteins in Fgf14-/- animals are associated with SZ. In addition, measured changes in the proteome and signaling pathways were predominantly sex-specific with the male Fgf14-/- being distinctly enriched for pathways associated with neuropsychiatric disorders and addiction and the female exhibiting modest changes. In the male Fgf14-/- mouse the major protein changes that could in part explain the previously described neurotransmission and behavioral phenotype of this model were loss of ALDH1A1 and PRKAR2B. ALDH1A1 has been shown to mediate an alternative pathway for GABA synthesis, while PRKAR2B is essential for dopamine 2 receptor signaling, which is the basis of current antipsychotics. Collectively, our results provide new insights in the role of FGF14 and support the use of the Fgf14-/- mouse as a useful preclinical model of SZ for generating hypothesis on the disease mechanism, sex-specific manifestation and therapy.

The search for molecular biosignatures at the surface of Mars is complicated by an intense irradiation in the mid- and near- ultraviolet (UV) spectral range for several reasons: (i) many astrobiologically relevant molecules are electronically excited by efficient absorption of UV radiation and rapidly undergo photochemical reactions; (ii) even though the penetration depth of UV radiation is limited, aeolian erosion continually exposes fresh material to radiation; and (iii) UV irradiation generates strong oxidants such as perchlorates that can penetrate deep into soils and cause subsurface oxidative degradation of organics.As a consequence, it is crucial to investigate the effects of UV radiation on organic molecules embedded in mineral matrices mimicking the martian soil, in order to validate hypotheses about the nature of the organic compounds detected so far at the surface of Mars by the Curiosity rover, as well as organics that will be possibly found by the next rover missions Mars 2020 and ExoMars 2020. In addition, studying the alteration of possible molecular biosignatures in the martian environment will help to redefine the molecular targets for life detection missions and devise suitable detection methods.Here we report the results of mid-UV irradiation experiments of Mars soil analog samples obtained adsorbing relevant organic molecules on a clay mineral that is quite common on Mars, i.e. montmorillonite, doped with 1 wt% of magnesium perchlorate. Specifically, we chose to investigate the photostability of a plausible precursor of the chlorohydrocarbons detected on Mars by the Curiosity rover, namely phthalic acid, along with the biomarkers of extant life L-phenylalanine and L-glutamic acid, which are proteomic amino acids, and adenosine 5’-monophosphate, which is a nucleic acid component.We monitored the degradation of these molecules adsorbed on montmorillonite through in situ spectroscopic analysis, investigating the reflectance properties of the samples in the Near InfraRed (NIR) spectral region. Such spectroscopic characterization of molecular alteration products provides support for two upcoming robotic missions to Mars that will employ NIR spectroscopy to look for molecular biosignatures, through the instruments SuperCam on board Mars 2020, ISEM, Ma_Miss and MicrOmega on board ExoMars 2020.

Saponite is a trioctahedral 2:1 smectite with the ideal composition MxMg3AlxSi4-xO10(OH,F)2.nH2O (M = interlayer cation). Both the success of the saponite synthesis and the determination of its applications depends on robust knowledge of the structure and composition of saponite. Among the routine characterization techniques spectroscopic methods are the most common. This review, thus, provides an overview of various spectroscopic methods to characterize natural and synthetic saponite with focus on the extensive work by one of the authors (JTK). The IR and Raman spectra of natural and synthetic saponites are discussed in detail including the assignment of the observed bands. The crystallization of saponite is discussed based on the changes in the IR and Raman spectra and a possible crystallization model is provided. Infrared emission spectroscopy has been used to study the thermal changes of saponite in-situ including the dehydration and (partial) dehydroxylation up to 750˚C. 27Al and 29Si Magic-Angle-Spinning Nuclear Magnetic Resonance Spectroscopy is discussed (as well as 11B and 71Ga for B- and Ga-Si substitution) with respect to, in particular, Al(IV)/Al(VI) and Si/Al(IV) ratios. X-ray Photoelectron Spectroscopy provides besides chemical information also some information related to the local environments of the different elements in the saponite structure as reflected by their binding energies.

The paper focuses of the interaction between tungsten (W) wire and microwave field in carbon dioxide (CO2) atmosphere. Our experimental set-up uses a microwave plasma generator in order to generate the plasma from the metallic wires. The microwave plasma generator contain a cylindrical cavity - TM_011 propagation modes, commercial source (magnetron) having the 2.45 GHz frequency at 800 W microwave and power supply. In the focal point of the cylindrical cavity we have a high energy of the electromagnetic radiation. The metallic wires from this area will be vaporized and ionized having as effect CO2 dissociation. The electron temperature regarding metallic plasma produced was estimated using the ratio of atomic emission lines acquired by a high definition of the optical multichannel spectrometer. Determination of the CO2 dissociation quantity was estimated measuring of the carbon monoxide (CO) resulting of the CO2 dissociation process. We obtained a high electron temperature of the plasma and a strong dissociation of the CO2.

Bioimpedance measurements are used increasingly in health applications because bioelectric parameters have been associated with anatomical and physiological properties, thus enabling to distinguish medical conditions. For bone fracture diagnostics, nevertheless, there is no established non-invasive method. Ex vivo studies and In vivo bioimpedance procedures, both invasive and non-invasive, on mammalians long bones are associated with promising results. In this work, out of a total of 568 papers, we reviewd 59 articles that mention long bone integrity by electric properties, be it Bioimpedance Analysis, Electrical Impedance Spectroscopy or Electrical Impedance Tomography. The papers are described in three sections, “Ex vivo measurements”, “In vivo invasive measurements” and “In vivo non-invasive measurements”. This review allows to establish the basics to planning the development of new technology to detect bone fracture via bioimpedance measurements.