Step In Route Research Articles

Synthesis and band gap determination for 4-phenyl-7-(5-(thiazol-2-yl) thien-2-yl)benzo[c][1,2,5]thiadiazole, a new polyheterocyclic molecule with potential applications as a semiconductor in organic photovoltaic solar cells

Organic photovoltaic (OPV) solar cells are a promising emerging technology for sustainable energy generation. In these cells, the absorbing layer consists of a repeated series of aromatic organic rings with a system of π delocalized electrons, a feature that allows these materials to absorb sunlight and facilitate electron transfer. In the present work, a new tetrameric molecule with high structural complexity, 4-phenyl-7-(5-(thiazol-2-yl) thien-2-yl)benzo[c][1,2,5]thiadiazole, was synthesized by a convergent pathway. The final step of the synthetic route was the Suzuki coupling of two new dimeric molecules, obtained from commercially available raw materials such as thiophene and o-phenylenediamine. The band gap of the final compound was found to be 2.5 eV using an optical methodology and 2.38 eV using an electrochemical methodology. The results suggest that this tetrameric molecule has potential for application in OPV cells.

High Entropy Alloys as High Performance Catalysts for Electrolytic Water Splitting

Renewable energy driven electrolytic water splitting is a required technology for low-carbon hydrogen production to achieve the goal of net-zero CO2 emission by 2050. This technology also serves as a necessary energy storage route to resolve the intolerable intermittency and unreliability issues of renewable energies. The prevailing of this hydrogen production technology however is restricted by the high cost of electricity. Consequently, developments of cost–effective highly efficient and stable electrocatalysts to drive the electrolytic water splitting reactions are the key. In terms of catalyst developments, mono-component systems are first explored, followed by multi–component systems, taking advantages of possible positive synergy between constituent components. Recently, a new class of multi-component catalyst systems, entropy-stabilized materials, including alloys, oxides, sulfides, phosphides, etc., emerges and is demonstrated promising performances toward electrocatalysis. In light of the variable and flexible element compositions, entropy-stabilized materials provide infinite and enormous potentials for the design of promising electrocatalysts. The key is to maximize the synergy between constituent components. High entropy alloys (HEA), defined as alloys composed of five or more major metallic elements, have been under intensive and extensive development in past fifteen years for their extraordinary mechanical, magnetic, corrosion, and catalytic properties. Herein, an equi–molar FeCoNiCuMo HEA on nickel foam was developed as a breakthrough catalyst for electrocatalytic water splitting, in terms of both activity and stability, in pH-universal media and in severe industrial operation conditions. Furthermore, a new catalytic phenomenon is discovered. Two different catalytic mechanisms function simultaneously on different constituents of the catalyst, and the synergistic interactions between the two categorical domains leads to catalytic kinetics faster than the theoretical limit set by a single rate-limiting step, Tafel step of the Volmer-Tafel route. A new kinetic model is developed to predict a new theoretical lower limit of Tafel slopes of 15 mV/dec based on a synergistic interaction between the two categorical domains of the high entropy alloy catalyst. This new development proves that the theoretical lower limit of Tafel slope of 30 mV/dec posed for the Volmer-Tafel mechanism functioning on a single component catalyst can be further reduced to 15 mV/dec through synergistic interactions between two categorical domains of a multi-component catalyst. It is demonstrated that high entropy materials, composed of five or more atomically/molecularly well-mixed major components, are intrinsically promising candidates for realization of quantum leaps in catalytic performances of catalysts.

Total Synthesis of the Sex Pheromone of Clania variegata Snellen and Its Stereoisomers.

The paulownia bagworm, Clania variegata Snell, is an economically important pest of agriculture and forests. The sex pheromone of this pest and its stereoisomers were synthesized, and two of the stereoisomers were prepared for the first time. Our strategy was efficient and mainly included the ring-opening reaction of (S)-2-methyloxirane, the coupling of chiral sulfonate, the oxidative cleavage of olefin, and Yamaguchi esterification. Moreover, the overall yields of our synthesis were 23-29%, with eight steps in the longest route.

Migration and transformation mechanisms of Pb/Cd with HCl in organic solid waste incineration flue gas on the composite-modified kaolinite surface

Cadmium/lead (Cd/Pb) pollutants from organic solid wastes (OSW) incineration are of global concern due to high volatility and biotoxicity. The strong interaction between modified kaolinite and Cd/Pb species inspires its utilization for the elimination of heavy metals. However, the specific mechanism of the migration and transformation of Cd/Pb species is yet unclear. Consequently, the migration and transformation mechanisms of Cd/Pb species on the modified kaolinite (001) surface are examined by density functional theory (DFT), considering the effect of HCl. The outcomes show that the HCl significantly alters the characteristics of the kaolinite, which enhances the surface activity of kaolinite and promotes the adsorption and transformation of Cd/Pb species. Furthermore, the chlorination routes of Cd0/Pb0 are fully elucidated in both 2-step and 1-step routes. The first step of the 2-step route obeys the Langmuir-Hinshelwood mechanism and the second step obeys the Eley-Rideal mechanism, while the 1-step chlorination route obeys the Eley-Rideal mechanism. In addition, the oxidation route of Cd0/Pb0 follows the Mars-van Krevelen mechanism. The comparison of the energy barriers shows that the 1-step Cd0/Pb0 chlorination route has the lowest energy barrier. The kaolinite surface is found to have elevated activity for the adsorptive trapping of Cd/Pb species in the presence of HCl, which offers a preliminary theoretical framework for pollutant control on the modified kaolinite surface.

Breaking Free - Unlocking the Potential of Dynamic Hydrogen Bubble Templating Materials

In recent years, porous electrodes for electrochemical conversion devices, such as low-temperature fuel cells or water electrolyzers, have been engineered to address issues related to mass transport to and within the catalyst. For example, the addition of a layer with reduced pore size facing the catalyst layer (i.e., microporous layer) results in an increased performance[1–3]. Furthermore, chemical[4], as well as mechanical[5,6]. methods of creating dedicated liquid and gas pathways in the porous electrodes, have been investigated with promising results, highlighting the need for further optimization of state-of-the-art materials with regards to multi-phase transport. The range of possible modifications is intrinsically limited by the microstructure of the material they are applied to and add cost and complexity to the already costly electrode production procedure, motivating the development of novel materials which contain these desired features, offer a large morphological design space, and are cost competitive.To tackle these stringent targets, we investigate the dynamic hydrogen bubble templating (DHBT) method to generate hierarchical structures containing both a pore size gradient as well as dedicated water and gas pathways in the form of bimodal pore size distributions. It leverages simultaneous deposition of a metal and gas evolution on the same surface to form complex structures from solution using electricity. It results in a hierarchical structure of primary pores (~5-40 µm) separated by porous walls containing secondary pores (10-1000 nm) . This type of material has been used successfully to improve boiling heat transfer[7], another process limited by the counterflow of liquid and gas. They have also been investigated as high surface area material for microbial anodes[8] and have been postulated to be appealing in other electrochemical devices such as batteries or fuel cells[9]. A significant hurdle to unlock the full potential of DHBT foams is the attachment of the foam to the solid electrode surface it is generated on. The presence of the electrode blocks the transport of media in the through-plane direction of the foam and thereby prevents its use in many electrochemical applications. Due to its fragile nature, separation of the foam from this surface easily damages the structure, which is why previous research was done exclusively in the presence of the electrode. Overcoming this limitation would enable new applications for DHBT foams and has the potential to address a wide range of problems in electrochemical systems related to porous media.In this talk, I will discuss our work towards creating free-standing, hierarchically structured metal electrodes through DHBT and the developments needed to adapt this material for the use in electrochemical systems. Owing to its well-studied synthetic parameters and facile electrodeposition, we chose copper foams to advance DHBT materials in terms of characterization and mechanical properties. As a key step of the synthesis route, we realized a method to manufacture free-standing sheets from this material from copper metal while preserving its delicate microstructure. This was supported by an optimization of synthesis parameters to improve and ensure adequate mechanical stability of the freestanding foams after isolation. This development enables the application of a wide range of characterization methods such as XTM, BET, SEM and interferometry and I will discuss how the synthesis parameters link to the resulting material microstructure. Building on this initial success, current work focuses on the transferring this knowledge to the synthesis of foams made from other metals which are more relevant to electrochemical applications such as nickel for the use in alkaline electrolyzers and paves the way to develop DHBT material into the next generation transport layer for electrochemical systems.

Additive Manufacturing of Fe-Mn-Si-Based Shape Memory Alloys: State of the Art, Challenges and Opportunities.

Additive manufacturing (AM) constitutes the new paradigm in materials processing and its use on metals and alloys opens new unforeseen possibilities, but is facing several challenges regarding the design of the microstructure, which is particularly awkward in the case of functional materials, like shape memory alloys (SMA), as they require a robust microstructure to withstand the constraints appearing during their shape change. In the present work, the attention is focused on the AM of the important Fe-Mn-Si-based SMA family, which is attracting a great technological interest in many industrial sectors. Initially, an overview on the design concepts of this SMA family is offered, with special emphasis to the problems arising during AM. Then, such concepts are considered in order to experimentally develop the AM production of the Fe-20Mn-6Si-9Cr-5Ni (wt%) SMA through laser powder bed fusion (LPBF). The complete methodology is approached, from the gas atomization of powders to the LPBF production and the final thermal treatments to functionalize the SMA. The microstructure is characterized by scanning and transmission electron microscopy after each step of the processing route. The reversibility of the ε martensitic transformation and its evolution on cycling are studied by internal friction and electron microscopy. An outstanding 14% of fully reversible thermal transformation of ε martensite is obtained. The present results show that, in spite of the still remaining challenges, AM by LPBF offers a good approach to produce this family of Fe-Mn-Si-based SMA, opening new opportunities for its applications.

Total Synthesis of the Pyrrole Alkaloids Strychnuxinal and Strychnuxin

AbstractThe first asymmetric total syntheses of the fused-pyrrole alkaloids strychnuxinal and strychnuxin have been achieved in 6 and 7 steps, respectively, starting from commercially available (±)-4-chlorostyrene oxide. Key steps in the synthetic route include a regioselective epoxide opening, a reductive etherification sequence to form the central 1,4-oxazine ring, and a late-stage phenol synthesis using a mild palladium-catalyzed coupling reaction. Notably, the optimized synthetic sequence presented avoids the use of traditional protecting groups. Total synthesis of these two structurally related natural products confirmed both their constitution (via NMR and X-ray crystallography) and their absolute configuration (via optical rotation).

Organic synthesis of 1,2-dipalmitoyl-rac-glycero-3-phosphatidylethanolamine and its effect on the induction of apoptosis in normal human lung fibroblasts

Background /objectiveThe phospholipid 1,2-dipalmitoyl-rac-glycero-3-phosphatidylethanolamine (PE) comprises two fatty acid chains: glycerol, phosphate, and ethanolamine. PE participates in critical cellular processes such as apoptosis and autophagy, which places it as a target for designing new therapeutic alternatives in diseases such as pulmonary fibrosis. Therefore, this study aimed obtain PE through a six-step organic synthesis pathway and determine its biological effect on apoptosis induction in normal human lung fibroblasts (NHLF). MethodologyThe first step of the organic synthesis route began with protected glycerol that was benzylated at sn-3; later, it was deprotected to react with palmitic acid at sn-1, sn-2. To remove the benzyl group, hydrogenation was performed with palladium on carbon (Pd/C); subsequently, the molecule was phosphorylated in sn-3 with phosphorus oxychloride and triethylamine, and the intermediate was hydrolyzed in an acid medium to obtain the final compound. After PE synthesis, apoptosis assessment was performed: apoptosis was induced using exposure to annexin V-FITC/propidium iodide-ECD (PI) and quantified using flow cytometry. The experiments were performed in three NHLF cell lines with different concentrations of PE 10, 100 and 1000 µg/mL for 24 and 48 h. ResultsThe PE obtained by organic synthesis presented a melting point of 190–192 °C, a purity of 95%, and a global yield of 8%. The evaluation of apoptosis with flow cytometry showed that at 24 h, exposure to PE 10, 100, and 1000 µg/mL induces early apoptosis in 19.42%− 25.54%, while late apoptosis was only significant P < 0.05 in cells challenged with 100 µg/mL PE. At 48 h, NHLF exposed to PE 10, 100, and 1000 µg/mL showed decreasing early apoptosis: 28.69–32.16%, 12.59–18.84%, and 10.91–12.61%, respectively. The rest of the NHLF exposed to PE showed late apoptosis: 12.03–16–42%, 11.04–15.94%, and 49.23–51.28%. Statistical analysis showed a significance P < 0.05 compared to the control. ConclusionThe organic synthesis route of PE allows obtaining rac-1,2-O-Dipalmitoyl-glycero-3-phosphoethanolamine (1), which showed an apoptotic effect on NHLF.

High repetition ultrafast laser ablation of graphite and silicon/graphite composite electrodes for lithium-ion batteries

Laser structuring can be applied to composite electrodes of lithium-ion cells to enhance wetting and to facilitate the usage of thick-film electrodes by reducing the lithium-ion diffusion overpotential and the tortuosity of the electrodes or the usage of electrodes containing silicon, where additional porosity is required to compensate the volume expansion during lithium de-/insertion. To integrate the additional laser processing step in the well-established electrode manufacturing route, the laser processing speed must be significantly increased to match with the belt speed, which is dependent on the electrode thickness and the type of manufacturing route. Upscaling can be realized by increasing the average laser power, laser intensity, and/or laser repetition rate. Here, an ultrashort pulsed laser source with an average power of 300 W and a pulse duration of 600 fs was applied. For the first time, the presented research provides detailed laser ablation processing data for thick-film composite anodes associated with high repetition rates ranging from 4.9 to 48.8 MHz. The patterning results are compared depending on the widths, depths, aspect ratios, the total appearance regarding debris and cracks, and the volume ablation rate. In high repetition rate laser patterning, the subsequent laser pulses interact with the material vapor plasma generated by the previous laser pulses, resulting in lower ablation depths and higher ablation widths. The increase in laser peak intensity leads to higher achievable ablation depths. Processing strategies are identified for two different ablation scenarios focusing on the pouch cells of a Volkswagen ID.3 and the Tesla 4680 cell.

CRP2.0: A Fast and Robust Cooperation between Routing and Placement in Advanced Technology Nodes

Traditionally, the placement and routing stages of a physical design are performed separately. Because of the additional complexities arising in advanced technology nodes, they have become more interdependent. Therefore, creating efficient cooperation between the routing and placement steps has become an important topic in Electronic Design Automation (EDA). In this article, a framework that allows cooperation between routing and placement is proposed. The main objective of the proposed framework is to improve the detailed routing solution by combining routing and placement. The core of this framework is the Cooperation between Routing and Placement (CRP2.0)1engine including techniques to combine routing and placement. The key contributions of CRP2.0 include an Integer Linear Programming (ILP)-based Detailed Placement (ILP-DP), net classification, and two Cost and Net Caching techniques. The efficacy of the proposed framework is evaluated on the official ACM/IEEE International Symposium on Physical Design (ISPD) 2018 and 2019 contest benchmarks. In this article, we show that by using the Cost Caching technique, the global routing runtime compared with state-of-the-art algorithms was reduced by 28.56%, on average. Moreover, numerical results show that when working with advanced technology nodes, the proposed framework can improve the detailed routing score by an average of 0.3% while only moving 0.7% of the cells, on average. The proposed engine can be employed as an add-on to the physical design flow between the global routing and detailed routing steps.

Total synthesis of pyrrolo-azepine fused alkaloids: Aspastipuline, portulacatone and related alkaloids via TFAA mediated intramolecular Friedel-Crafts acylation

Aspastipulines and Portulacatone are pyrrolo-azepine containing alkaloids isolated from Asparagus stipularis forssk roots and Portulaca oleracea, respectively that have significant anticancer properties and moderate anti-inflammatory activities. Herein, we report the first total synthesis of five Pyrrolo-azepine containing aspastipuline, portulacatone and related alkaloids from a commercially available starting materials, ethyl 1H-pyrrole-2-carboxylate, via TFAA mediated intramolecular Friedel-Crafts acylation as a key step in concise route with good overall yield.

Jasmonic acid catabolism in Arabidopsis defence against mites

Jasmonates are essential modulators of plant defences but the role of JA-derivatives has been scarcely studied, particularly in the plant-pest interplay. To deepen into the JA catabolism and its impact on plant responses to spider mite infestation, we selected the Arabidopsis JAO2 gene as a key element involved in the first step of the JA-catabolic route. JAO2 is responsible for the hydroxylation of JA into 12-OH-JA, contributes to attenuate JA and JA-Ile content and consequently, determines the formation of other JA-catabolites. JAO2 was up-regulated in Arabidopsis by mite infestation. Mites also induced JA-derivative accumulation in plants. In jao2 mutant lines, and in the triple mutant jaoT (jao2–1, jao3–1, jao4–2), mite feeding produced less leaf damage, minor callose deposition and lower mite fecundity rates than in Col-0 plants. The impairment of JA oxidation in jao2 lines not only diminished the 12-OH-JA levels but turned off further sulfation as shown the significant reduction of 12-HSO4-JA form. Thus, JAO2 acts as a negative modulator of defences to spider mites mediated by changes in the generation of JA catabolic molecules, and the consequent production of defensive metabolites such as glucosinolates or camalexin.

A deep neural architecture for harmonizing 3-D input data analysis and decision making in medical imaging

Harmonizing the analysis of data, especially of 3-D image volumes, consisting of different number of slices and annotated per volume, is a significant problem in training and using deep neural networks in various applications, including medical imaging. Moreover, unifying the decision making of the networks over different input datasets is crucial for the generation of rich data-driven knowledge and for trusted usage in the applications. This paper presents a new deep neural architecture, named RACNet, which includes routing and feature alignment steps and effectively handles different input lengths and single annotations of the 3-D image inputs, whilst providing highly accurate decisions. In addition, through latent variable extraction from the trained RACNet, a set of anchors are generated providing further insight on the network’s decision making. These can be used to enrich and unify data-driven knowledge extracted from different datasets. An extensive experimental study illustrates the above developments, focusing on COVID-19 diagnosis through analysis of 3-D chest CT scans from databases generated in different countries and medical centers.

Modulation of the 5-Lipoxygenase Pathway by Chalcogen-Containing Inhibitors of Leukotriene A4 Hydrolase.

The 5-lipoxygenase (5-LOX) pathway gives rise to bioactive inflammatory lipid mediators, such as leukotrienes (LTs). 5-LOX carries out the oxygenation of arachidonic acid to the 5-hydroperoxy derivative and then to the leukotriene A4 epoxide which is converted to a chemotactic leukotriene B4 (LTB4) by leukotriene A4 hydrolase (LTA4H). In addition, LTA4H possesses aminopeptidase activity to cleave the N-terminal proline of a pro-inflammatory tripeptide, prolyl-glycyl-proline (PGP). Based on the structural characteristics of LTA4H, it is possible to selectively inhibit the epoxide hydrolase activity while sparing the inactivating, peptidolytic, cleavage of PGP. In the current study, chalcogen-containing compounds, 4-(4-benzylphenyl) thiazol-2-amine (ARM1) and its selenazole (TTSe) and oxazole (TTO) derivatives were characterized regarding their inhibitory and binding properties. All three compounds selectively inhibit the epoxide hydrolase activity of LTA4H at low micromolar concentrations, while sparing the aminopeptidase activity. These inhibitors also block the 5-LOX activity in leukocytes and have distinct inhibition constants with recombinant 5-LOX. Furthermore, high-resolution structures of LTA4H with inhibitors were determined and potential binding sites to 5-LOX were proposed. In conclusion, we present chalcogen-containing inhibitors which differentially target essential steps in the biosynthetic route for LTB4 and can potentially be used as modulators of inflammatory response by the 5-LOX pathway.

Hierarchical ‘rose-petal’ ZnO/Si surfaces with reversible wettability reaching complete water repellence without chemical modification

Smart surfaces with externally controlled wettability patterns are ubiquitous building blocks for micro-/nanofluidic and lab-on-chip devices, among others. We develop hierarchical surfaces of ZnO nanorods grown on laser-microstructured silicon with reversible photo-induced and heat-induced wettability. The as-prepared surfaces are superhydrophilic, with very low water contact angles (~ 10°), and transition to a wetting state with high water contact angles (~ 150°) when annealed in vacuum. As the annealing temperature increases to 400 °C, the surfaces become completely water-repellent. Even though the annealed surfaces present high water contact angles, at the same time, they are very adhesive for water droplets, which do not roll off even when tilted at 90° or 180o (rose-petal effect), unlike standard hydrophobic surfaces which typically combine high water contact angles with low roll-off angles. The surfaces return to the superhydrophilic state when irradiated with UV light, which indicates a reversible wettability with external stimuli. Based on this transition, we demonstrate local modification of the wetting state of the surfaces by UV irradiation through a mask, which results in directed liquid motion, useful for microfluidic applications. The high contact angles obtained in this work are usually obtained only after chemical modification of the ZnO surface with organic coatings, which was not necessary for the hierarchical surfaces developed here, reducing the cost and processing steps of the fabrication route. These rose-petal surfaces can be used as “mechanical hands” in several applications, such as no-loss transport of small liquid volumes, precision coatings, spectroscopy, and others. Furthermore, the completely water-repellent surfaces, rarely reported elsewhere, may find important applications in frictionless liquid transport for microfluidic and other devices.

Structural basis of the inhibition of cystathionine γ-lyase from Toxoplasma gondii by propargylglycine and cysteine.

Cystathionine γ-lyase (CGL) is a PLP-dependent enzyme that catalyzes the last step of the reverse transsulfuration route for endogenous cysteine biosynthesis. The canonical CGL-catalyzed process consists of an α,γ-elimination reaction that breaks down cystathionine into cysteine, α-ketobutyrate, and ammonia. In some species, the enzyme can alternatively use cysteine as a substrate, resulting in the production of hydrogen sulfide (H2 S). Importantly, inhibition of the enzyme and consequently of its H2 S production activity, makes multiresistant bacteria considerably more susceptible to antibiotics. Other organisms, such as Toxoplasma gondii, the causative agent of toxoplasmosis, encode a CGL enzyme (TgCGL) that almost exclusively catalyzes the canonical process, with only minor reactivity to cysteine. Interestingly, the substitution of N360 by a serine (the equivalent amino acid residue in the human enzyme) at the active site changes the specificity of TgCGL for the catalysis of cystathionine, resulting in an enzyme that can cleave both the CγS and the CβS bond of cystathionine. Based on these findings and to deepen the molecular basis underlying the enzyme-substrate specificity, we have elucidated the crystal structures of native TgCGL and the variant TgCGL-N360S from crystals grown in the presence of cystathionine, cysteine, and the inhibitor D,L-propargylglycine (PPG). Our structures reveal the binding mode of each molecule within the catalytic cavity and help explain the inhibitory behavior of cysteine and PPG. A specific inhibitory mechanism of TgCGL by PPG is proposed. This article is protected by copyright. All rights reserved.

Investigation on the synthesis of 24-(R)-hydroxycholesterol

A facile and novel strategy has been developed for synthesis of 24-(R)-hydroxycholesterol, a key intermediate of tacalcitol, starting from 24-dehydrocholesterol in seven steps with 48.2% overall yield and high diastereomer ratio. Photocatalytic oxidation of olefins by employing inexpensive Rose Bengal as photosensitizer and air as the sole oxidant for the preparation of Δ5,25-3β-Hydroxycholestadiene-24-one-3-acetate is the key step in this synthetic route. This developed strategy features mild conditions, satisfied total yield and excellent stereoselectivity (24-R/S = 97.7:2.3), providing a novel access to the 24-(R)-hydroxycholesterol.

Biphenyl dicarboxylates from ethene and bifuran dimethyl esters

The substrate scope of the Diels-Alder-Dehydration reaction was expanded to the deactivated bifuran structure. Dimethyl biphenyl-4,4′-dicarboxylate (1) and methyl 5- [4-(methoxycarbonyl)phenyl]-2-furoate (2) were synthesized from dimethyl 2,2′-bifuran-5,5′-dicarboxylate (3) via metal-triflate-catalyzed Diels-Alder-Dehydration reaction with ethene. A 31% yield of (1) was obtained using Sc(OTf)3 catalyst, and a 76.6% yield of (2) was obtained using La(OTf)3 catalyst under moderate reaction conditions. This approach is inherently selective to the 4,4′-dicarboxylates, and bypasses the methyl-group oxidation step of the dimethyl-biphenyl route.

Fujiwara‐Moritani Assisted Synthesis of Conjugated 2,3‐Dihydrofuran Trienes and Corresponding 2,3‐Dihydrobenzofuran Derivative

AbstractPalladium catalysed C−H activation has been carried out on furanoid glycals to afford highly substituted and conjugated 2,3‐dihydrofuran trienes and then its conversion into highly substituted 2,3‐dihydrobenzofuran was achieved starting from commercially available, inexpensive sugar precursor diacetone‐D‐glucose. Claisen‐Schmidt condensation reaction, Fujiwara‐Moritani cross coupling reaction and 6π electro‐cyclisation reaction were utilized as the key steps in this synthetic route. Diacetone‐D‐glucose was converted into dihydrofuran moiety via Claisen Schmidt condensation which was submitted to Fujiwara‐Moritani C−C coupling reaction to afford 2,3‐O‐isopropylidine‐4,5‐disubstituted 2,3‐dihydrofurans. Excellent yields (up to 97 %) were obtained during C−C coupling step which indeed is an accomplishment. Next, two step chemical route was established for conversion of these substituted and conjugated 2,3‐dihydrofuran triene moieties into corresponding substituted 2,3‐dihydrobenzofuran moiety.

Modeling Driver Behavior in Road Traffic Simulation

Driver behavior models are an important part of road traffic simulation modeling. They encompass characteristics such as mood, fatigue, and response to distracting conditions. The relationships between external factors and the way drivers perform tasks can also be represented in models. This article proposes a methodology for establishing parameters of driver behavior models. The methodology is based on road traffic data and determines the car-following model and routing algorithm and their parameters that best describe driving habits. Sequential and parallel implementation of the methodology through the urban mobility simulator SUMO and Python are proposed. Four car-following models and three routing algorithms and their parameters are investigated. The results of the performed simulations prove the applicability of the methodology. Based on more than 7000 simulations performed, it is concluded that in future experiments of the traffic in Plovdiv it is appropriate to use a Contraction Hierarchies routing algorithm with the default routing step and the Krauss car-following model with the default configuration parameters.