Determination of Irgarol 1051 in Western Mediterranean sediments. Development and application of supercritical fluid extraction-immunoaffinity chromatography procedure

A supercritical fluid extraction (SFE) procedure for Irgarol 1051 (i.e. 2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-1,3,5-triazine) determination in marine sediments, which minimises the solvent usage, is developed and compared to a conventional extraction technique (i.e. sonication). First, the use of methanol (MeOH) in the presence of trifluoroacetic acid (TFA) as secondary modifier of supercritical carbon dioxide was evaluated. Extraction efficiency was strongly dependent on the modifier content but lesser on pressure (100-410 bar) and temperature (60-200 degrees C). In the selected extraction conditions (20% MeOH/TFA 0.65M, 370 bar, 150 degrees C) recoveries higher than 87% were obtained and the limit of detection was 3 ngg(-1) and the relative standard deviation of 10% (N=3) by GC coupled to mass spectrometry (GC-MS) in the electron impact mode. The developed SFE procedure is more convenient to extract Irgarol 1051 than the agitation plus sonication methods concerning on solvent usage (1.5 vs. 20 mL) being compatible with immunochemical procedures avoiding any solvent transfer step. The developed SFE combined with immunoaffinity chromatography (IAC) is highly selective allowing the determination of Irgarol by gas chromatography with nitrogen-phosphorus detection or in sediments at low ngg(-1) level (11-35 ngg(-1)) from Mediterranean marina and harbour sediments.     

11,12 Epoxyeicosatrienoic Acid Rescues Deteriorated Wound Healing in Diabetes

Epoxyeicosatrienoic acids (EET) facilitate regeneration in different tissues, and their benefit in dermal wound healing has been proven under normal conditions. In this study, we investigated the effect of 11,12 EET on dermal wound healing in diabetes. We induced diabetes by i.p. injection of streptozotocin 2 weeks prior to wound creation on the dorsal side of the mouse ear. 11,12 EET was applied every second day on the wound, whereas the control groups received only solvent. Epithelialization was monitored every second day intravitally up to wound closure. Wounds were stained for VEGF, CD31, TGF-β, TNF-α, SDF-1α, NF-κB, and Ki-67, and fibroblasts were counted after hematoxylin-eosin stain on days 3, 6, 9, and 16 after wounding. After induction of diabetes, wounds closed on day 13.00 ± 2.20 standard deviation (SD). Local 11,12 ETT application improved wound closure significantly to day 8.40 ± 1.39 SD. EET treatment enhanced VEGF and CD31 expression in wounds on day 3. It also seemed to raise TNF-α level on all days investigated as well as TGF-β level on days 3 and 6. A decrease in NF-κB could be observed on days 9 and 16 after EET application. The latter findings were not significant. SDF-1α expression was not influenced by EET application, and Ki-67 was significantly less in the EET group on day 9 after EET application. The number of fibroblasts was significantly increased on day 9 after the 11,12 EET application. 11,12 EET improve deteriorated wound healing in diabetes by enhancing neoangiogenesis, especially in the early phase of wound healing. Furthermore, they contribute to the dissolution of the initial inflammatory reaction, allowing the crucial transition from the inflammatory to proliferative phase in wound healing.     

Routing of barge container ships by mixed-integer programming heuristics

We investigate the optimization of transport routes of barge container ships with the objective to maximize the profit of a shipping company. This problem consists of determining the upstream and downstream calling sequence and the number of loaded and empty containers transported between any two ports. We present a mixed integer linear programming (MILP) formulation for this problem. The problem is tackled by the commercial CPLEX MIP solver and improved variants of the existing MIP heuristics: Local Branching, Variable Neighborhood Branching and Variable Neighborhood Decomposition Search. It appears that our implementation of Variable Neighborhood Branching outperforms CPLEX MIP solver both regarding the solution quality and the computational time. All other studied heuristics provide results competitive with CPLEX MIP solver within a significantly shorter amount of time. Moreover, we present a detailed case study transportation analysis which illustrates how the proposed approach can be used by managers of barge shipping companies to make appropriate decisions and solve real life problems.     

Life Cycle Energy Assessment of biohydrogen production via biogas steam reforming: Case study of biogas plant on a farm in Serbia

The aim of this paper is to demonstrate and to quantify energy flows in a life cycle of biogas to biohydrogen production, starting from feedstock materials via anaerobic digestion, biogas upgrading, biohydrogen production, to the end of biogas system (application of digestate as fertilizer in agriculture). The performance of the biogas plant of Mirotin dairy farm in Serbia has been assessed. According to Life Cycle Energy Assessment approach, results obtained in this study have shown that biohydrogen production via biogas steam reforming has negative energy balance (with ?16,837 GJ). It has also been demonstrated that this process is energy unsustainable in an environmental context. In future analysis it would be necessary to consider the other aspects of sustainability, e.g. the economical and social factors in order to estimate the overall sustainability of the biogas utilization pathways, especially having in mind that the technology of converting biogas to hydrogen is still in the development phase.     

Orthogonally Stimulated Assembly/Disassembly of Depsipeptides by Rational Chemical Design

Controlling the assembly and disassembly of cross-β-sheet-forming peptides is one of the predominant challenges for this class of supramolecular material. As they constitute a continuously propagating material, every atomic change can be exploited to bring about distinct responses at the architectural level. We report herein that, by using rational chemical design, serine and methionine can both be used as orthogonal chemical triggers to signal assembly/disassembly through their corresponding stimuli. Serine is used to construct an ester-bond oligopeptide that can undergo O,N-acyl rearrangement, whereas methionine is sensitive to oxidation by H₂O₂. Using the example peptide sequence, KIKISQINM, we demonstrate that assembly and disassembly can be independently controlled on demand.     

Chemical composition and antimicrobial activity of Vitex agnus-castus L. fruits and leaves essential oils

The following study deals with the chemical composition, antimicrobial activity of essential oils of Vitex agnus-castus L. and their main constituents in vitro and in vivo. The main compounds in the oil of unripe fruits were sabinene (17.8%) and 1,8-cineole (17.5%), while in the oil of the ripe fruits dominant compounds were 1,8-cineole (16.3%) and sabinene (13.4%). The leaves oil contained an abundance of 1,8-cineole (22.0%), as well. All of the oils tested were rich sources of α-pinene (12.2%, 9.4% and 9.4%, respectively). Antimicrobial activity was tested using bacterial and fungal strains by the microdilution method. Using the same technique 1,8-cineole and α-pinene showed very high antimicrobial potency as well. As 1,8-cineole was the predominant constituent of the oils, we have chosen to test it further in an in vivo experiment. Randomly chosen apples were treated with 1,8-cineol solution and infected with Aspergillus niger in order to provoke Aspergillus rot in apples. Disease incidence was recorded.     

Modeling of petroleum products sampling processes

Abstract

This paper describes a holistic approach to operation processes in the domain of petroleum products sampling which is important in validating the performance of custody transfer measurements. The acquisition and process visualization is followed by a detailed analysis of all relevant processes and discussion. In that way, the most important aspects related to sampling, which comply with the most rigorous requirements for custody transfer, will be shown. In order to represent petroleum products sampling, a model has been defined and connected to the defined processes in a BPMN 2.0 notation. Thereafter, the notation was enriched with new elements, representing other complex segments, such as defining selection criteria, sampling handling and operational considerations. In that regard, different situations and factors were integrated and enriched with new details, enabling guidance for the correct selection and smooth running of a sampling system.