Determining Magnitudes of Forces at Known Locations through a Strain Gauge Force Transducer.

A novel strain gauge force transducer was developed to minimize the number of strain gauges needed to determine the magnitudes of loads when the locations are known. This innovative methodology requires only one strain gauge for each force magnitude desired, reducing the complexity and cost associated with traditional approaches. The theory was verified with laboratory experiments. Seven uniaxial strain gauges were attached to the underside of a simply supported, slender, aluminum beam. One or more loads were applied either directly atop strain gauges or in known positions between strain gauges. Experiments were conducted on several different single and double-load configurations to evaluate the extent of the new methodology which yielded average errors under 5% for the cases where loads were direct atop strain gauges and 6.6% for the cases where the loads were between strain gauges. These findings indicate the potential of this novel strain gauge force transducer to revolutionize load measurement in scenarios where load locations are predetermined.

Open-source feature detection for non-target LC-MS analytics.

RATIONALE: Non-target screening techniques using high-resolution mass spectrometers become more and more important for environmental sciences. Highly reliable and sophisticated software solutions are required to deal with the large amount of data obtained from such analyses. METHODS: Processing of high-resolution LC-HRMS data was performed upon conversion into an open, XML-based data format followed by an automated assignment of chromatographic peaks using the open-source programming language R. Raw data from three different LC-HRMS systems were processed as a proof of principle. RESULTS: We present a simple and straightforward algorithm to extract chromatographic peaks from previously m/z-centroided data based on the open-source programming language R and C++. The working principle and processing parameters are explained in detail. A ready-to-use script is provided in the supporting information. CONCLUSIONS: The developed algorithm enables a comprehensible automated peak picking of non-target LC-MS data. Application to three completely different HRMS raw data files showed reasonable False Positives and False Negatives detection and moderate calculation times.

Higher-order dispersion and the spectral behavior in a doubly resonant optical parametric oscillator.

In doubly resonant optical parametric oscillators (DROPOs), it is possible to generate, enhance, and phase lock two frequencies at once. Following intracavity phase conditions, a complex tuning behavior of the signal and idler spectra takes place in DROPOs, cumulating into degeneracy with phase self-locking and coherent wavelength doubling. In this work, we identify group delay matching as the important parameter determining the global tuning behavior and demonstrate the key role of higher-order dispersion in the spectral dependencies. Applicationwise, we suggest a simple way to control the phase self-locking region by varying the intracavity third-order dispersion.

Comparing mass, retention time and tandem mass spectra as criteria for the automated screening of small molecules in aqueous environmental samples analyzed by liquid chromatography/quadrupole time-of-flight tandem mass spectrometry.

RATIONALE: The adoption of database screening using high-resolution liquid chromatography/mass spectrometry data is promising as a river water monitoring and surveillance tool but depends on the ability to perform reliable data processing on a large number of samples in a unified workflow. Strategies to minimize errors have been proposed but automated procedures are rare. METHODS: High-resolution LC/ESI-QTOFMS/MS in data-dependent MS2 acquisition mode was performed for the analysis of surface water samples by direct injection. Data processing was achieved with software tools written in R. A database containing MS2 spectra of 693 compounds formed the basis of the workflow. Standard mixes and a time series of 361 samples of river water were analyzed and processed with the optimized workflow. RESULTS: Using the database and a mix of 70 standards for testing, it was found that an identification strategy including (i) mass, (ii) retention time, and (iii) MS2 spectral matching achieved a two- to three-fold improvement in the fraction of false positives compared with using only two criteria, while the number of false negatives remained low. The optimized workflow was applied to the sample series of river water. In total, 135 compounds were identified by a library match. CONCLUSIONS: The developed automated database screening approach minimizes the proportion of false positives, while still allowing for the screening of hundreds of water samples for hundreds of compounds in a single run.

Li+ Ion Conductors with Adamantane-Type Nitridophosphate Anions ß-Li10 P4 N10 and Li13 P4 N10 X3 with X=Cl, Br.

ß-Li10 P4 N10 and Li13 P4 N10 X3 with X=Cl, Br have been synthesized from mixtures of P3 N5 , Li3 N, LiX, LiPN2 , and Li7 PN4 at temperatures below 850 °C. ß-Li10 P4 N10 is the low-temperature polymorph of α-Li10 P4 N10 and crystallizes in the trigonal space group R3. It is made up of non-condensed [P4 N10 ]10- T2 supertetrahedra, which are arranged in sphalerite-analogous packing. Li13 P4 N10 X3 (X=Cl, Br) crystallizes in the cubic space group Fm3‾m . Both isomorphic compounds comprise adamantane-type [P4 N10 ]10- , Li+ ions, and halides, which form octahedra. These octahedra build up a face-centered cubic packing, whose tetrahedral voids are occupied by the [P4 N10 ]10- ions. The crystal structures have been elucidated from X-ray powder diffraction data and corroborated by EDX measurements, solid-state NMR, and FTIR spectroscopy. Furthermore, we have examined the phase transition between α- and ß-Li10 P4 N10 . To confirm the ionic character, the migration pathways of the Li+ ions have been evaluated and the ion conductivity and its temperature dependence have been determined by impedance spectroscopy. XPS measurements have been carried out to analyze the stability with respect to Li metal.

Spectroscopic characterization of lithium thiophosphates by XPS and XAS - a model to help monitor interfacial reactions in all-solid-state batteries.

Inspired by reports of redox active interphases in all-solid-state batteries employing fast conducting lithium thiophosphate solid-state electrolytes, we investigated the compositional depolymerization of interconnected PS4 tetrahedra in (Li2S)x(P2S5)100-x glasses (50 < x < 80) by X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). Based on the observed energy shifts with composition, we present a structural model of the three different bonding types describing the structures of either crystalline or amorphous thiophosphates. This model and reference data characterizes amorphous thiophosphates based on their inter-tetrahedral connectivity and helps to distinguish malign decomposition reactions from reversible redox reactions at the cathode active material/solid-state electrolyte interface. This work highlights the importance of a combined analytical approach and appropriate reference compounds to elucidate the interface reactions in all-solid-state battery systems.

Influence of Lattice Polarizability on the Ionic Conductivity in the Lithium Superionic Argyrodites Li6PS5X (X = Cl, Br, I).

In the search for novel solid electrolytes for solid-state batteries, thiophosphate ionic conductors have been in recent focus owing to their high ionic conductivities, which are believed to stem from a softer, more polarizable anion framework. Inspired by the oft-cited connection between a soft anion lattice and ionic transport, this work aims to provide evidence on how changing the polarizability of the anion sublattice in one structure affects ionic transport. Here, we systematically alter the anion framework polarizability of the superionic argyrodites Li6PS5X by controlling the fractional occupancy of the halide anions (X = Cl, Br, I). Ultrasonic speed of sound measurements are used to quantify the variation in the lattice stiffness and Debye frequencies. In combination with electrochemical impedance spectroscopy and neutron diffraction, these results show that the lattice softness has a striking influence on the ionic transport: the softer bonds lower the activation barrier and simultaneously decrease the prefactor of the moving ion. Due to the contradicting influence of these parameters on ionic conductivity, we find that it is necessary to tailor the lattice stiffness of materials in order to obtain an optimum ionic conductivity.

Li18 P6 N16 -A Lithium Nitridophosphate with Unprecedented Tricyclic [P6 N16 ]18- Ions.

Li18 P6 N16 was synthesized by reaction of LiPN2 and Li7 PN4 at 5.5 GPa and 1273 K employing the multi-anvil technique. It is the first lithium nitridophosphate obtained by high-pressure synthesis. Moreover, it is the first example received by reaction of two ternary lithium nitrides. The combination of high-pressure conditions with a Li3 N flux enabled a complete structure determination using single-crystal X-ray diffraction. The hitherto unknown tricyclic [P6 N16 ]18- anion is composed of six vertex-sharing PN4 tetrahedra forming one vierer- and two additional dreier-rings. To confirm the structure, Rietveld refinement, 7 Li and 31 P solid-state NMR spectroscopy, FTIR spectroscopy and EDX measurements were carried out. To validate the ionic properties, the migration pathways of the Li+ ions were evaluated, and the conductivity and its temperature dependence were determined by impedance spectroscopy measurements. In order to obtain a clearer picture of the formation mechanism of this compound class, different synthetic approaches were compared, enabling targeted syntheses of unprecedented P/N-anion topologies with intriguing properties.

Synthesis, Structural Characterization, and Lithium Ion Conductivity of the Lithium Thiophosphate Li2P2S6.

Inspired by the ongoing search for new superionic lithium thiophosphates for use in solid-state batteries, we present the synthesis and structural characterization of Li2P2S6, a novel crystalline lithium thiophosphate. Whereas M2P2S6 with the different alkaline elements (M = Na, K, Rb, Cs) is known, the lithium counterpart has not been reported yet. Herein, we present a combination of synchrotron pair distribution function analysis and neutron powder diffraction to elucidate the crystal structure and possible Li+ diffusion pathways of Li2P2S6. Additionally, impedance spectroscopy is used to evaluate its ionic conductivity. We show that Li2P2S6 possesses P2S62- polyhedral units with edge-sharing PS4 tetrahedra and only one-dimensional diffusion pathways with localized Li-Li pairs, leading to a low ionic conductivity for lithium.

Nontarget Analysis via LC-QTOF-MS to Assess the Release of Organic Substances from Polyurethane Coating.

A novel approach was investigated for the assessment of leaching from a one-component polyurethane (1C-PU) coating used for hydraulic structures using nontarget analysis via LC-QTOF-MS. Leaching behavior of the 1C-PU coating was studied using experiments in which the coating was exposed to water for defined periods (6 h, 24 h, 3 d, 14 d). Three hardening durations for the 1C-PU coating were tested (0 h, 24 h, 14 d) as well as two water matrices (ultrapure water and river water), including a successive water renewal. Dissolved organic carbon, total nitrogen bound and nontarget measurements via LC-QTOF-MS showed that under all tested conditions organic substances were leached out of the 1C-PU coating. The shorter the hardening duration and the longer the leaching duration, the higher were the number and quantities of the eluted substances, while the influence of the water matrix was minor with respect to substance elution. Based on the MS2 spectra from the LC-QTOF-MS measurements, 30 substances released from the 1C-PU coating were tentatively identified. These substances belong to five chemical groups: derivatives of (i) N-(tosyl)carbamate, (ii) p-toluenesulfonamide (PTSA), (iii) 4,4'-methylenediphenyl diisocyanate (4,4'-MDI), (iv) toluenediisocyanate (TDI), and (v) oligo(ethylene) ([C2H4O]n) as well as p-toluenesulfonic acid. The identity of seven substances was confirmed by authentic reference standards, all of which exhibited an elevated bacterial toxicity to Aliivibrio fischeri. p-Toluenesulfonic acid was present in a German canal (Teltowkanal) with concentrations of up to 11 µg L-1.

Li47 B3 P14 N42 -A Lithium Nitridoborophosphate with [P3 N9 ]12- , [P4 N10 ]10- , and the Unprecedented [B3 P3 N13 ]15- Ion.

Li47 B3 P14 N42 , the first lithium nitridoborophosphate, is synthesized by two different routes using a Li3 N flux enabling a complete structure determination by single-crystal X-ray diffraction data. Li47 B3 P14 N42 comprises three different complex anions: a cyclic [P3 N9 ]12- , an adamantane-like [P4 N10 ]10- , and the novel anion [P3 B3 N13 ]15- . [P3 B3 N13 ]15- is the first species with condensed B/N and P/N substructures. Rietveld refinement, 6 Li, 7 Li, 11 B, and 31 P solid-state NMR spectroscopy, FTIR spectroscopy, EDX measurements, and elemental analyses correspond well with the structure model from single-crystal XRD. To confirm the mobility of Li+ ions, their possible migration pathways were evaluated and the temperature-dependent conductivity was determined by impedance spectroscopy. With the Li3 N flux route we gained access to a new class of lithium nitridoborophosphates, which could have a great potential for unprecedented anion topologies with interesting properties.

Availability of pesticide-treated seeds on the soil surface in different crops and countries: A comprehensive data set reflecting modern agronomic practice.

For plant protection products applied as seed treatments, the risk to birds and mammals possibly feeding on such treated seeds needs to be addressed in the EU, in order to register these products for commercial use. For this purpose, the European Food Safety Food Authority (EFSA) has provided guidance on how to execute such a risk assessment. The risk assessment follows a tiered approach. In the Tier 1 risk assessment of the EFSA guidance (2023), it is assumed that birds or mammals have ad libitum access to treated seeds and exclusively feed on treated seeds. Due to this conservative assumption, the Tier I risk assessment typically indicates an unacceptable risk to birds and mammals and higher-tier refinements are required. One option for refinement is to use data on the availability of treated seeds on the soil surface directly after drilling. Published data on seed counts are, however, limited to a few countries and crops, and often these data are not contemporary, that is, do not reflect advances in sowing technology and current agronomic practice. To address this data gap, we provide recently generated data from industry field trials (the studies were conducted from 2000 to 2022, >70% between 2019 and 2022), covering 270 fields from seven countries (Austria, France, Germany, Hungary, Poland, Spain, UK) for spring and winter cereals, winter oilseed rape, and sunflower. This comprehensive data set realistically reflects modern agronomic practice and is thus suitable for consideration in a regulatory context for refining the risk assessment for birds and mammals. Integr Environ Assess Manag 2024;20:1706-1714. © 2024 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Ozonation products of zidovudine and thymidine in oxidative water treatment.

Ozonation is an advanced treatment technology that is increasingly used for the removal of organic micropollutants from wastewater and drinking water. However, reaction of organic compounds with ozone can also result in the formation of toxic transformation products. In the present study, the degradation of the antiviral drug zidovudine during ozonation was investigated. To obtain further insights into the reaction mechanisms and pathways, results of zidovudine were compared with the transformation of the naturally occurring derivative thymidine. Kinetic experiments were accompanied by elucidation of formed transformation products using lab-scale batch experiments and subsequent liquid chromatography - high resolution mass spectrometry (LC-HRMS) analysis. Degradation rate constants for zidovudine with ozone in the presence of t-BuOH as radical scavenger varied between 2.8 ∙ 104 M-1 s-1 (pH 7) and 3.2 ∙ 104 M-1 s-1 (pH 3). The structural difference of zidovudine to thymidine is the exchange of the OH-moiety by the azide function at position 3'. In contrast to inorganic azide, no reaction with ozone was observed for the organic bound azide. In total, nine transformation products (TPs) were identified for both zidovudine and thymidine. Their formation can be attributed to the attack of ozone at the C-C-double bond of the pyrimidine-base. As a result of rearrangements, the primary ozonide decomposed in three pathways forming two different TPs, including hydroperoxide TPs. Rearrangement reactions followed by hydrolysis and subsequent release of H2O2 further revealed a cascade of TPs containing amide moieties. In addition, a formyl amide riboside and a urea riboside were identified as TPs indicating that oxidations of amide groups occur during ozonation processes.

Reduction of variability for the assessment of side effects of toxicants on honeybees and understanding drivers for colony development.

The statistical power of studies for the assessment of side effects of toxicants on honeybees conducted according to current guidelines is often limited. A new test design and modified field methods have therefore been developed to decrease uncertainty and variability and to be able to detect small effects. The new test design comprises a monitoring phase (before the tunnel phase) for the selection of honeybee colonies and modified methods, which include assessments of colony strength, an evaluation of the cell content of all cells of hives using photos and digital analysis, and the use of video recordings for the assessment of foraging activity and forager mortality. With the proposed new study design and the modified field methods variability between hives was considerably reduced, which resulted in a marked reduction of the minimum detectable difference (MDD). This makes it possible to address the Specific Protection Goals defined by the European Food Safety Authority and to gain unprecedented insight into the development of hives and driving factors.

New methodical approaches for the investigation of weathered epoxy resins used for corrosion protection of steel constructions.

Epoxy resin coatings applied to steel constructions for corrosion protection purposes are often exposed to UV-irradiation and weathering during the construction process. Chemical alteration of the hardened coating might lead to i) the release of potentially harmful substances into the environment and ii) delamination of the polyurethane top layer. However, chemical processes and mechanisms occurring on the surfaces of exposed epoxy resin coatings are not fully understood yet. Herein, we present an innovative approach combining time-of-flight secondary ion mass spectrometry (ToF-SIMS) with inductively coupled plasma mass spectrometry (ICP-MS) and liquid chromatography mass spectrometry (LC-MS) enabling the elucidation of underlying chemical processes and the identification of released organic and inorganic photolytic products. IR-spectroscopy and experiments targeting the acidity/pH-value changes on top of weathered surfaces complement our investigations. It was confirmed that UV-A irradiation leads to photooxidative degradation of the epoxy resin and that inorganic photolytic products are exposed on the weathered surfaces. Polar moieties (hydroxyls, carbonyls, carboxyls, amines) and released metalloids form a hydrophilic surface layer, which hinders adhesion and eventually prevents profound chemical linkage of the polyurethane top layer. Thus, an early delamination of the top layer might occur very likely.

Application of a non-target workflow for the identification of specific contaminants using the example of the Nidda river basin.

Non-target screening of water samples from the Nidda river basin in central Germany was conducted with the goal to identify previously unknown chemical contaminants and their emission sources. The focus was on organic, water-borne contaminants which were not typical to municipal wastewater. Grab samples of river water from 13 locations on the Nidda and 15 of its tributaries, in sum 112 samples, were analysed with high resolution LC-QToF-MS/MS. To facilitate the identification of substances, features originating from the same compound such as adducts and isotopologues as well as in-source fragments and species with multiple charge states were registered and grouped by a componentization step utilizing both retention times and peak shapes of the features to combine them in a single component. This led to a reduction of the number of features by an average of 1235 per sample (46%). These grouped features were prioritized if these were detected only in specific tributaries or specific river sections, reducing the number of components by an average of 913 per sample (78%). In addition, grouped features were labelled as typically found in municipal wastewater by combining data from 16 wastewater treatment plants located across Germany and Switzerland and comparing this to components detected in the Nidda basin. These were removed, leading to a further reduction of components by an average of 72 per sample (30%) for an average total reduction of 2536 per sample (93%). Finally, nine compounds, with emission sources in three specific tributaries, were identified, including the textile additive Nylostab S-EED®, which was previously not known to be an environmental contaminant, as well as naturally occurring compounds such as highly toxic microcystins.

The optical cell rotator.

The optical cell rotator (OCR) is a modified dual-beam laser trap for the holding and controlled rotation of suspended dielectric microparticles, such as cells. In contrast to optical tweezers, OCR uses two counter-propagating divergent laser beams, which are shaped and delivered by optical fibers. The rotation of a trapped specimen is carried out by the rotation of a dual-mode fiber, emitting an asymmetric laser beam. Experiments were performed on human erythrocytes, promyelocytic leukemia cells (HL60), and cell clusters (MCF-7). Since OCR permits the rotation of cells around an axis perpendicular to the optical axis of any microscope and is fully decoupled from imaging optics, it could be a suitable and expedient tool for tomographic microscopy.

Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery.

All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degradation mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy density, the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO2 cathode and the Li10GeP2S12 solid electrolyte interface. Indium and Li4Ti5O12 are used as anode materials to avoid the instability problems associated with Li-metal anodes. Capacity fading and increased impedances are observed during long-term cycling. Postmortem analysis with scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy show that electrochemically driven mechanical failure and degradation at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochemically more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.

A validation study of reconstructed rapid prototyping models produced by two technologies.

OBJECTIVE: To determine the accuracy (trueness and precision) of two different rapid prototyping (RP) techniques for the physical reproduction of three-dimensional (3D) digital orthodontic study casts, a comparative assessment using two 3D STL files of two different maxillary dentitions (two cases) as a reference was accomplished. MATERIALS AND METHODS: Five RP replicas per case were fabricated using both stereolithography (SLA) and the PolyJet system. The 20 reproduced casts were digitized with a highly accurate reference scanner, and surface superimpositions were performed. Precision was measured by superimposing the digitized replicas within each case with themselves. Superimposing the digitized replicas with the corresponding STL reference files assessed trueness. Statistical significance between the two tested RP procedures was evaluated with independent-sample t-tests (P < .05). RESULTS: The SLA and PolyJet replicas showed statistically significant differences for trueness and precision. The precision of both tested RP systems was high, with mean deviations in stereolithographic models of 23 (±6) µm and in PolyJet replicas of 46 (±13) µm. The mean deviation for trueness in stereolithographic replicas was 109 (±4) µm, while in PolyJet replicas, it was 66 (±14) µm. CONCLUSIONS: Comparing the STL reference files, the PolyJet replicas showed higher trueness than the SLA models. But the precision measurements favored the SLA technique. The dimensional errors observed in this study were a maximum of 127 µm. In the present study, both types of reproduced digital orthodontic models are suitable for diagnostics and treatment planning.