Front Cover: Facile Multicomponent Synthesis of Oxazolidinones from Primary Amines and Cesium (Hydrogen)Carbonate (Eur. J. Org. Chem. 27/2023)

A facile multicomponent, catalyst-free oxazolidinone synthesis from primary aliphatic or aromatic amines, dibromoethane (DBE), and the usage of either cesium carbonate or cesium hydrogencarbonate as the simultaneous base and C1 source is reported. The applicability of this technically simple reaction was demonstrated by a broad scope with generally high yields, enabling concise late-stage functionalization of amino groups into N-substituted oxazolidinones. The proposed operating reaction mechanism consists of a first-step nucleophilic substitution reaction between DBE and the primary amine, followed by the formation of a carbamate or carbonate intermediate and subsequent cyclization. Additional versatility of the herein-developed protocol has been showcased in a medicinal chemistry approach by the generation of an oxazolidinone-modified dipeptidyl peptidase 8 (DPP8) inhibitor.     

Development and validation of a quantitative method for the selective determination of tin species in tin octoate by differential pulse polarography

Tin octoate is used as a catalyst in the synthesis of polydimethylsiloxane (PDMS), a room temperature vulcanizing (RTV) silicone rubber. This rubber is largely used in the medical field due to its great biocompatibility. In this framework, a high-speed and costless analytical method for the determination of stannic ions, Sn(IV), in the presence of stannous ions, Sn(II), has been developed.The separation of these two ions was carried out using differential pulse polarography (DPP). For this purpose, the tin species contents in the catalyst is quantitatively extracted under inert condition to avoid any changes in the ratio Sn(IV)/Sn(II). Polarography showed well-shaped oxidation and reduction peaks respectively at −650 and −860 mV for stannous ions. The peak of the stannic ion was well separated and appeared at −1210 mV. Many parameters such as extraction process, extraction time, pH, chelating agents and polarographic conditions were optimized. We have also demonstrated that no oxidation of the stannous ions occurred during the sample preparation.The dosing range considered in this study extends between 10 and 40 μg/mL, corresponding to 6.8% and 27.2% of the degradation product (Sn(IV)) in the catalyst, regarding to the sampling. Finally this method was successfully validated using the total error concept.     

Simultaneous determination of trace amounts of sulfite and thiosulfate in petroleum and its distillates by extraction and differential pulse polarography

Simultaneous determination of sulfite and thiosulfate at sub-ppm levels in petroleum and its distillates was investigated using a convenient, accurate and sensitive procedure. This method involved preliminary extraction of the sample followed by detection via differential pulse polarography (DPP) at a dropping mercury electrode. In this procedure, an appropriate amount of sample was shaken with a recommended volume of 0.25% (w/w) sodium acetate solution. The mixture was filtered in two steps and was then ready for DPP. The method was free from interferences from hydrogen sulfide, elemental sulfur, organic sulfides, and thiophene. Various instrumental factors such as scan rate, pulse height, initial and final potential, and purge time were optimized. The 3σ detection limits were 410 and 125 ng g⁻¹ for sulfite and thiosulfate, respectively. At 5 μg g⁻¹ level in samples, the relative standard deviations (n=4) were 2.51 and 1.15% for sulfite and thiosulfate, respectively. The proposed method was applied to real samples containing input feeds, distillates and fuel oils from Abadan Petroleum Refinery in the south of Iran.     

Near-Field Scattering Enhancement of Perylene Based Aggregates for Random Lasing

Strong near-field scattering enhancement (NFSE) of polyhedral oligomeric silsesquioxanes (POSS) nanoparticles (NPs) aggregates is found through physical simulation. An aggregation of begin{document}$N$end{document}, begin{document}$N'$end{document}-di-[3-(isobutyl polyhedral oligomeric silsesquioxanes) propyl] perylene diimide (DPP) which possesses POSS as scatteres experimentally performs strong NFSE, which confirms the physical simulation results. Moreover, coherent random laser is triggered from the DPP aggregates in carbon disulfide. It is the NFSE of POSS NPs connected to both ends of DPP through covalent bonds and the NFSE of their aggregation thanks to DPP's aggregation that is responsible for the coherent random laser. So, this work develops a method to improve weak scattering of system through construction of molecules, and opens a road to a variety of novel interdisciplinary investigations, involving molecular designing for disordered photonics.     

Diketopyrrolopyrrole‐based polymer fibrils formation by changing molecular conformation during film formation

The microstructure of conjugated polymers film is strongly dependent on factors such as the conformation and the film formation processing. In this article, we show how to induce more planarization conformation of conjugated polymer backbone during film formation processing and finally leading to the fibrils formation of the cast film. The conjugated polymer we used is poly[[2,5‐bis(2‐octyldodecyl)‐2,3,5,6‐tetrahydro‐3,6‐dioxopyrrolo[3,4‐c]pyrrole‐1,4‐diyl]‐alt–[[2,2′‐(2,5‐thiophene)bis‐thieno[3,2‐b]thiophen]‐5,5′‐diyl]] (PDPPTT‐T). The main solvent is chloroform (CF), the aliphatic 1,8‐diiodooctane (DIO) is used as the additives, which has similar solubility parameter to the conjugated polymer side chain, is a bad solvent to the conjugated backbone and has a lower volatility than CF. Thus, during the film formation, chloroform was evaporated faster than the additive. After the chloroform evaporated completely, the side chain was still dissolved in the additive, which decreases the steric hindrance and improves planarization conformation of the conjugated backbone of PDPPTT‐T. Films processed using the aliphatic additives have fibrillar morphology while films cast from the CF solvent were featureless. TEM images reveal that the fibrils were about 30 nm in width and several hundred nanometers in length. The backbones of PDPPTT‐T were parallel to the long axis of fibrils. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1079–1086     

Role of Dipeptidyl Peptidase 4 Inhibitors in Antidiabetic Treatment

In recent years, important changes have occurred in the field of diabetes treatment. The focus of the treatment of diabetic patients has shifted from the control of blood glucose itself to the overall management of risk factors, while adjusting blood glucose goals according to individualization. In addition, regulators need to approve new antidiabetic drugs which have been tested for cardiovascular safety. Thus, the newest class of drugs has been shown to reduce major adverse cardiovascular events, including sodium-glucose transporter 2 (SGLT2) and some glucagon like peptide 1 receptor (GLP1) analog. As such, they have a prominent place in the hyperglycemia treatment algorithms. In recent years, the role of DPP4 inhibitors (DPP4i) has been modified. DPP4i have a favorable safety profile and anti-inflammatory profile, do not cause hypoglycemia or weight gain, and do not require dose escalation. In addition, it can also be applied to some types of chronic kidney disease patients and elderly patients with diabetes. Overall, DPP4i, as a class of safe oral hypoglycemic agents, have a role in the management of diabetic patients, and there is extensive experience in their use.     

Acceptor-donor-acceptor conjugated oligomers based on diketopyrrolopyrrole and thienoacenes with four,five and six rings for organic thin-film transistors

Three acceptor-donor-acceptor(A-D-A) conjugated oligomers, i.e., O1, O2 and O3, have been synthesized using diketopyrrolopyrrole(DPP) as an electron-acceptor unit, and naphtho[1,2-b:5,6-b']dithiophene(NDT), anthra[1,2-b:5,6-b']dithiophene(ADT) or dithieno[3,2-b:3',2'-b']naphtho[1,2-b:5,6-b']dithiophene(DTNDT) as electron-donor unit. These oligomers exhibit identical highest occupied molecular orbital(HOMO) and lowest unoccupied molecular orbital(LUMO) energy levels, which were ca.-5.1 and-3.3 eV, respectively. Upon thermal annealing, all three oligomers formed thin films with ordered microstructures, and their organic thin film transistors(OTFTs) exhibited p-type transport behavior. The mobility was increased with an extension of the size of D-units. O3 showed the best OTFT performance with the mobility of up to 0.20 cm~2·V~(-1)·s~(-1). The film quality of O3 was improved by adding 1 wt% poly(methylmethacrylate)(PMMA). In consequence, the mobility of the O3-based devices was further enhanced to 0.30 cm~2·V~(-1)·s~(-1).     

Discovery of dipeptidyl peptidase Ⅳ(DPP4) inhibitors based on a novel indole scaffold

Dipeptidyl peptidase Ⅳ(DPP4) inhibitors are proven in the treatment of type 2 diabetes.We designed and synthesized a series of novel indole compounds that selectively inhibit the activity of DPP4 over dipeptidyl peptidase 9(DPP9)(200 fold).We further co-crystallized DPP4 with indole sulfonamide(compound 1) to confirm a proposed binding mode.Good metabolic stability of the indole compounds represents another positive attribute for further development.     

Magnetic beads as versatile tools for electrochemical DNA and protein biosensing

Magnetic beads (MBs) are versatile tools in the separation of nucleic acids, proteins and other biomacromolecules, their complexes and cells. In this article recent application of MBs in electrochemical biosensing and particularly in the development of DNA hybridization sensors is reviewed. In these sensors MBs serve not only for separation but also as a platform for optimized DNA hybridization. A hybridization event is detected separately at another surface, which is an electrode. The detection is based either on the intrinsic DNA electroactivity or on various kinds of DNA labeling, including chemical modification, enzyme tags, nanoparticles, electroactive beads, etc., greatly amplifying the signals measured. In addition to DNA hybridization, other kinds of biosensing in combination with MBs, such as DNA-protein interactions, are reviewed.     

Insight into Gentisic Acid Antidiabetic Potential Using In Vitro and In Silico Approaches

Numerous scientific studies have confirmed the beneficial therapeutic effects of phenolic acids. Among them gentisic acid (GA), a phenolic acid extensively found in many fruit and vegetables has been associated with an enormous confirmed health benefit. The present study aims to evaluate the antidiabetic potential of gentisic acid and highlight its mechanisms of action following in silico and in vitro approaches. The in silico study was intended to predict the interaction of GA with eight different receptors highly involved in the management and complications of diabetes (dipeptidyl-peptidase 4 (DPP4), protein tyrosine phosphatase 1B (PTP1B), free fatty acid receptor 1 (FFAR1), aldose reductase (AldR), glycogen phosphorylase (GP), α-amylase, peroxisome proliferator-activated receptor gamma (PPAR-γ) and α-glucosidase), while the in vitro study studied the potential inhibitory effect of GA against α-amylase and α-glucosidase. The results indicate that GA interacted moderately with most of the receptors and had a moderate inhibitory activity during the in vitro tests. The study therefore encourages further in vivo studies to confirm the given results.