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.

     

Effect of Berezinskii-Kosterlitz-Thouless vortex fluctuations on the nuclear spin relaxation rate

In this work we examine the influence of the diffusive motion of vortices in highly anisotropic high-T_c superconductors near the Berezinskii-Kosterlitz-Thouless (BKT) transition temperature T _bkt on the spin-lattice relaxation rate T ₁ ^–1 .We find a jump in T ₁ ^–1 at the temperature T _bkt .     

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.     

A quantitative approach to ranking corporate law precedents in the Brazilian Superior Court of Justice

This paper aims to contribute to the goal of finding influential legal precedents by quantitative methods. A lot of work has been made in this direction worldwide, especially in the context of common law jurisdictions. However, this type of work is extremely scarce in the Brazilian literature. In addition, our work also contributes to the research of network analysis and the law by applying these methods to unprecedented amount of data and narrowing our inquiry to a single law area, corporate law. Furthermore, whereas most of the literature applying network analysis to judicial decisions had access to readily available data on the citations to precedent within each ruling, our raw data was nothing but the full text of decisions. We focus on data produced by the Superior Court of Justice (STJ), the highest court in Brazil for matters of federal law, including statutory interpretation of civil, criminal and corporate law. The Court issued an astonishing 282040 opinions tagged as related to corporate law between 2008 and 2018. This amount of cases is unparalleled internationally for superior courts and for studies in network analysis and law. In our results, we rank precedents quantitatively based on the citations they receive and make. We also qualitatively analyze some of the results, especially related to groups identified in the network with the Modularity algorithm. Our findings also reveal that corporate law jurisprudence in the STJ is quantitatively dominated by a few legal issues around one single theme that is only tangentially related to corporate law. That is, a type of contract used for the expansion of telephone landlines, which also allowed the consumer to become a shareholder of the telecommunication company. This comparison is especially pertinent because the utter lack of data on the quantitative weight of STJ precedents means the national literature has been operating in a void of objective measurements, one which has been filled with cherry-picked rulings and subjective ranking criteria.

     

Nanoporous Superalloy Membranes: A Review

The ability to produce metallic membrane materials with porosity on the nanoscale from Ni‐based superalloys, hitherto used exclusively for high temperature applications, has been discovered 15 years ago. The basic principle is to first convert the initial γ/γ′ microstructure, containing isolated γ′‐precipitates, into a bi‐continuous network where both phases are in themselves continuous and interpenetrate each other. Then, one of the two phases is selectively removed, so that a rigid structure consisting of the remaining phase with pores on the location of the removed phase results. This article reviews the progress made so far. In that time period, a number of ways to fabricate these unique materials have emerged, utilizing 1) single crystals and polycrystals as precursor materials as well as 2) coarsening of coherent and incoherent γ′‐precipitates to realize bi‐continuity of the microstructure. Consequently, a family of superalloy membranes has emerged with specific microstructures, properties, advantages, and limitations. It is the intention of this article to give an overview on these various manufacturing routes, as well as on resulting microstructures and properties. Finally, possible fields of applications are outlined. It is demonstrated that the particular manufacturing process from a solid to the porous material leads to certain advantages, such as the ability to structure the material in porous and solid areas as required by the application.

     

Effect of brain edema on the recurrence pattern of malignant gliomas

PURPOSE: To assess the influence of initial preoperative brain edema in malignant gliomas on regrowth patterns. SUBJECTS AND METHODS: 79 patients with histologically verified supratentorial malignant glioma were prospectively studied by magnetic resonance imaging (MRI) before and every 2-3 months after surgery. The median follow-up time was 11 months. We correlated the configuration of the initial vasogenic edema on T2-weighted images with tumor regrowth patterns on contrast-enhanced T1-weighted images. RESULTS: 35/47 tumor regrowths (75%) imitated the initial edema configuration, while 11/47 occurred within the initial tumor bed; in one case tumor recurrence was multilocal. CONCLUSION: In glioblastoma, tumor regrowth patterns correlate positively with the configuration of the initial vasogenic brain edema. The initial, "presurgical" peritumoral edema should thus be considered when planning further treatment.     

The shadow approach: An orphan detection protocol for mobile agents

Orphan detection in distributed systems is a well-researched field for which many solutions exist. These solutions exploit well defined parent-child relationships given in distributed systems. But they are not applicable in mobile agent systems, since no similar natural relationship between agents exist. Thus new protocols have to be developed. In this paper one such protocol for controlling mobile mobile agents and for orphan detection is presented. The shadow approach presented in this paper uses the idea of a placeholder (shadow) which is assigned by the agent system to each new agent. This defines an artificial relationship between agents and shadow. The shadow records the location of all dependent agents. Removing the root shadow implies that all dependent agents are declared orphan and are eventually be terminated. We introduce agent proxies that create a path from shadow to every agent. In an extension of the basic protocol we additionally allow the shadow to be mobile.The shadow approach can be used for termination of groups of agents even if the exact location of each single agent is not known.     

Monitored high-dose azathioprine treatment reduces acute rejection episodes after renal transplantation

A novel complex mutation consisting of a small deletion/insertion (3958del5ins4) was found in the breast cancer-1 gene (BRCA-1) in three unrelated French breast and/or ovarian cancer families. These mutations occurred at the same nucleotide position of the 3' end of exon 11. The wild-type sequence, CTCAG, was deleted and replaced by AGGC in the three families. The consequence is the generation of a stop codon, TAG, resulting in a truncated protein. We propose two different mechanisms to explain the generation of this complex mutation: (i) the simultaneous occurrence of a deletion and an insertion in a stem-loop structure and (ii) the abortive integration of a human transposable element (Tigger 1) that deleted 5 nucleotides and inserted a 4-nucleotide "scar", corresponding to the 5' extremity of the transposon.