Analysis of dithiocarbamate fungicides. Second-derivative UV-spectroscopic determination of CS2, COS, and thiram (TMTD)

The application of second-derivative UV-spectroscopy offers a highly sensitive and selective method for the determination of CS₂ and COS, as acid hydrolysis products of dithiocarbamate und thiuram disulphide fungicides, using a methanolic amine absorption reagent (ethylenediamine, piperidine). With standard concentrations of 0.08–1.1 g CS₂/ml and 0.3 to 2.0 g COS/ml, respectively, calibration curves with good correlation coefficients (r>0.999) were obtained. In comparison to the official method of the Deutsche Forschungsgemeinschaft (DFG method S15) the proposed alternative is at least 100 times more sensitive to CS₂. Using the second derivative method it is possible not only to clearly differentiate between CS₂ and COS but also to quantify both gases without resorting to tedious background corrections as compared to the direct photometric methods. Additionally, second derivative spectroscopy allows the direct determination of thiram in the concentration range 1–10 g/ml after its extraction with chloroform. For example, thiram in water (10 g/l) and in thiram/talc standards (10 mg/g) were determined with good precision (±2.0%).

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Analytik der Dithiocarbamat-Fungicide. Bestimmung von CS₂, COS sowie Thiram (TMTD) mittels Derivativ-UV-Spektroskopie

Zusammenfassung Die Anwendung der Derivativ-UV-Spektroskopie (2. Ableitung) erlaubt eine sehr empfindliche Bestimmung von CS₂ und COS als Hydrolyseprodukte der Dithiocarbamat- und Thiuramdisulfid-Fungicide nach Absorption in einem methanolischem Amin-Reagens (Ethylendiamin, Piperidin). Mit Standard-Konzentrationen von 0,08–1,1 g CS₂/ml bzw. 0,3–2,0 g COS/ml zeigten die Eichgeraden gute Korrelationskoeffizienten (r<0,999). Im Vergleich zur DFG-Methode S15 zeichnet sich die vorgeschlagene Alternative durch eine um zwei Zehnerpotenzen höhere Empfindlichkeit bei der CS₂-Bestimmung aus. In der 2. Ableitung wird nicht nur die Unterscheidung von COS und CS₂ eindeutig, sondern auch deren Quantifizierung ohne rechnerische Untergrundkorrekturen ermöglicht. Mit Hilfe der Derivativspektroskopie konnte außerdem Thiram (TMTD) in Konzentrationen von 1–10 g/ml direkt erfaßt werden. So ließen sich nach Extraktion mit Chloroform 10 g/L Thiram in Wasser mit einer Präzision von ±2,0% direkt bestimmen oder Thiram/Talkum-Standards (10 mg/g) überprüfen.

     

Fungicides and photochemistry: Photodegradation of the azole fungicide penconazole

In order to examine the photostability of the fungicide penconazole (1-(2,4-dichloro--propylphenethyl)-1H-1,2,4-triazole,1) in the field, model experiments with organic solvents were performed. Photodegradation (>280 nm) of penconazole was found to be more efficient in isopropanol and cyclohexane solution than in the presence of cyclohexene. Photolysis in isopropanol and cyclohexane resulted in considerable formation of 1-(4-chloro--propylphenethyl)-1H-1,2,4-triazole (2) and 5H,6H-(1,2,4-triazolo)-[5,1-a]-9-chloro-6-propyl-isoquinoline (3). Furthermore, photodehalogenation of3 yielded traces of 5H,6H-(1,2,4-triazolo)-[5,1-a]-6-propyl-isoquinoline (4) and, in the presence of isopropanol 5H,6H-(1,2,4-triazolo)-[5,1-a]-9-(2-hydroxy-2-methylethyl)-6-propyl-isoquioline (5). Additionally, a lot of polar products were found in high yields which could not be isolated and characterized individually. In the presence of cyclohexene, on the other hand, photodecomposition and photodehalogenation to photoproduct2 were found to be the main degradation pathways and photoproduct3 was only detected as a trace component.

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Fungicide und Photochemie: Photoabbau des Azol-Fungicides Penconazol

Zusammenfassung Zur Voruntersuchung der Photostabilität des Fungicides Penconazol (1-(2,4-Dichlor--propylphenethyl)-1H-1, 2,4-triazol,1) wurden Modellexperimente in organischen Lösungsmitteln durchgeführt. Der Photoabbau (>280 nm) nimmt von Cyclohexen zu Cyclohexan und Isopropanol hin deutlich zu. Bei Bestrahlung in Isopropanol oder Cyclohexan entstehen als Hauptprodukte (1-(4-Chlor--propylphenethyl)-1H-1, 2,4-triazol (2) und 5H,6H-(1,2,4-Triazolo)-[5,1,-a]-9-chlor-6-propyl-isochinolin (3). Photodehalogenierung von 3 führt in geringem Umfang zu 5H,6H-(1,2,4-Triazo-lo)-[5, 1-a]-6-propyl-isochinolin(4) und in Gegenwart von Isopropanol zu 5H,6H-(1,2,4-Triazolo)-[5,1-a]-9-(2-hydroxy-2-methylethyl)-6-propyl-isochinolin (5) als Photoadditionsprodukt. Daneben entsteht in hohem Ausmaß eine komplexe Fraktion polarer Komponenten, die einer Einzelisolierung und -charakterisierung nicht mehr zugänglich waren. In Cyclohexen hingegen erfolgte neben Photodehalogenierung zu2 hauptsächlich Photolyse zu polaren Komponenten, während Photoprodukt3 nur in Spuren entstand.

     

Covalent Adaptable Microstructures via Combining Two-Photon Laser Printing and Alkoxyamine Chemistry: Toward Living 3D Microstructures

Manufacturing programmable materials, whose mechanical properties can be adapted on demand, is highly desired for their application in areas ranging from robotics, to biomedicine, or microfluidics. Herein, the inclusion of dynamic and living bonds, such as alkoxyamines, in a printable formulation suitable for two-photon 3D laser printing is exploited. On one hand, taking advantage of the dynamic covalent character of alkoxyamines, the nitroxide exchange reaction is investigated. As a consequence, a reduction of the Young´s Modulus by 50%, is measured by nanoindentation. On the other hand, due to its “living” characteristic, the chain extension becomes possible via nitroxide mediated polymerization. In particular, living nitroxide mediated polymerization of styrene results not only in a dramatic increase of the volume (≈8 times) of the 3D printed microstructure but also an increase of the Young's Modulus by two orders of magnitude (from 14 MPa to 2.7 GPa), while maintaining the shape including fine structural details. Thus, the approach introduces a new dimension by enabling to create microstructures with dynamically tunable size and mechanical properties.     

Glyphosate Adsorption from Water Using Hierarchically Porous Metal–Organic Frameworks

The selective removal of one ligand in mixed-ligand MOFs upon thermolysis provides a powerful strategy to introduce additional mesopores without affecting the overall MOF structure. By varying the initial ligand ratio, MOFs of the MIL-125-Ti family with two distinct hierarchical pore architectures are synthesized, resembling either large cavities or branching fractures. The performance of the resulting hierarchically porous MOFs is evaluated toward the adsorptive removal of glyphosate (N-(phosphonomethyl)glycine) from water, and the adsorption kinetics and mechanism are examined. Due to their strong affinity for phosphoric groups, the numerous Ti–OH groups resulting from the selective ligand removal act as natural anchor points for effective glyphosate uptake. The relationships between contact duration, glyphosate concentration, and adsorbent dosage are investigated, and the impact of these parameters on the effectiveness of glyphosate removal from contaminated water samples is examined. The introduction of additional mesopores has increased the adsorption capacities by nearly 3 times with record values exceeding 440.9 mg g⁻¹, which ranks these MOFs among the best-reported adsorbents.     

Efficient numerical methods for the large‐scale,parallel solution of elastoplastic contact problems

Quasi‐static elastoplastic contact problems are ubiquitous in many industrial processes and other contexts, and their numerical simulation is consequently of great interest in accurately describing and optimizing production processes. The key component in these simulations is the solution of a single load step of a time iteration. From a mathematical perspective, the problems to be solved in each time step are characterized by the difficulties of variational inequalities for both the plastic behavior and the contact problem. Computationally, they also often lead to very large problems. In this paper, we present and evaluate a complete set of methods that are (1) designed to work well together and (2) allow for the efficient solution of such problems. In particular, we use adaptive finite element meshes with linear and quadratic elements, a Newton linearization of the plasticity, active set methods for the contact problem, and multigrid‐preconditioned linear solvers. Through a sequence of numerical experiments, we show the performance of these methods. This includes highly accurate solutions of a three‐dimensional benchmark problem and scaling our methods in parallel to 1024 cores and more than a billion unknowns. Copyright © 2015 John Wiley & Sons, Ltd.     

Cytosolic Calcium Concentration Changes in Neuronal Cells Under Clinorotation and in Parabolic Flight Missions

All life on earth has been established under conditions of stable gravity of 1g. Nevertheless, in numerous experiments the direct gravity dependence of biological processes has been shown on all levels of organization, from single molecules to humans. To study the effects especially of microgravity on biological systems, a variety of platforms are available, from drop towers to the ISS. Due to the costs of these platforms and their limited availability, as an alternative, numerous simulators have been developed for so called “simulated” microgravity. A classical systems is a clinostat, basically rotating a sample around one axis, and by integration of the gravity vector for 360° arguing that thus the effects of gravity are depleted. Indeed, a variety of studies has shown that taking out the direction of gravity from a biological system often results in consequences similar to the exposure of the system to real microgravity. Nevertheless, the opposite has been shown, too, and as a consequence the relevance of clinostats in microgravity research is still under discussion. To get some more insight into this problem we have constructed a small fluorescence clinostat and have studied the effects of clinorotation on the cytosolic calcium concentration of neuroglioma cells. The results have been compared to experiments with identical cells in real microgravity, utilizing parabolic flight missions. Our results show that in case of a cell suspension used in a small florescence clinostat within a tube diameter of 2mm, the effects of clinorotation are comparable to those under real microgravity, both showing a significant increase in intracellular calcium concentration.     

Kältemittel‐Schnüffler

Testing refrigerant sniffers The technical generation of coldness is typically done by machines based on a closed thermodynamic process using a refrigerant. As refrigerants usually halogenated hydrocarbons are used since these have good thermodynamic properties. Unfortunately, the halogens are harmful to the environment: They destroy the ozone layer. Therefore, the machines must be tight and must not loose the refrigerant. To check a machine for leakage, mobile leak sniffers are available which can be reliably and quantitatively controlled by test leaks.     

A Perspective on Emerging and Future Sintering Technologies of Ceramic Materials

Novel sintering methods have emerged in the recent past years, which have raised great interest in the scientific community. Relying on electric field effects, high heating rates, the use of mechanical pressure, or hydrothermal conditions, they offer fundamental advantages compared to conventional sintering routes like minimizing the energy consumption and enhancing the process efficiency. This perspective aims at explaining these effects in a general way and presenting the status quo of using them for the processing of high-performing ceramic materials. In detail, this work focuses on flash sintering, ultrafast high-temperature sintering, spark plasma sintering, cold sintering, and photonic sintering methods based on different light sources. The specificities, potentials, and limitations of each method are compared, especially in the light of a possible industrialization.     

Surface-Inspection-Pad (SIP)

Surface Inspection Pad (SIP) – A novel approach to resource-efficient sampling for contamination control of component surfaces The Surface Inspection Pad, or SIP for short, offers a cost-effective and resource-saving alternative to sampling for vacuum-assisted contamination control of component surfaces. The analysis of the surface chemistry of the component is then carried out by analyzing the SIP surface. In addition to other methods, surface-sensitive time-of-flight secondary ion mass spectrometry (ToF-SIMS) can be used for the analysis. The components to be examined therefore no longer must be removed from the process and destroyed for the analysis. The user can save enormous costs in this way. Furthermore, SIPs can be used for contamination control in lubricant circuits and liquids. To date, silicone oil (PDMS) has been detected in liquids with a detection limit of less than 10^–6 (ppm).     

Infrastructure Federation Through Virtualized Delegation of Resources and Services

Infrastructure federation is becoming an increasingly important issue for modern Distributed Computing Infrastructures (DCIs): Dynamic elasticity of quasi-static Grid environments, incorporation of special-purpose resources into commoditized Cloud infrastructures, cross-community collaboration for increasingly diverging areas of modern e-Science, and Cloud Bursting pose major challenges on the technical level for many resource and middleware providers. Especially with respect to increasing costs of operating data centers, the intelligent yet automated and secure sharing of resources is a key factor for success. With the D-Grid Scheduler Interoperability (DGSI) project within the German D-Grid Initiative, we provide a strategic technology for the automatically negotiated, SLA-secured, dynamically provisioned federation of resources and services for Grid-and Cloud-type infrastructures. This goal is achieved by complementing current DCI schedulers with the ability to federate infrastructure for the temporary leasing of resources and rechanneling of workloads. In this work, we describe the overall architecture and SLA-secured negotiation protocols within DGSI and depict an advanced mechanism for resource delegation through means of dynamically provisioned, virtualized middleware. Through this methodology, we provide the technological foundation for intelligent capacity planning and workload management in a cross-infrastructure fashion.