Iodine-mediated electrocatalysis assist Annulation/cyclization via Intramolecular Benzylic C–H Amination: Batch vs Flow Electrochemistry

The access of heterocyclic compounds via direct amination of C-H bonds are of vital interest because of their role in pharmaceutical and natural products. The combination of molecular iodine and electricity activates benzylic C-H bond and facilitates the amination process via intramolecular C-N bond formation. Iodine works as a mediator for the formation of C-N bond via activation of a distance C-H bond through intermediate N-I bond under electrochemical conditions, so iodine can be called electrocatalyst. Under both batch & flow electrochemistry conditions, similar results were obtained in cyclization product with 77 & 78% yields respectively. However, in case of annulation reaction higher yield was obtained with 99% conversion under flow electrochemical conditions using our design of home-made flow microreactor. In both electrochemical transformations, cyclization as well as annulation reaction, no photocatalyst was used. Notably, flow reactions work under safe & environmentally friendly conditions, and continuous products are obtained.

Structure of the Active Nanocomplex of Antiviral and Anti-Infectious Iodine-Containing Drug FS-1

Chromatographic analysis shows that the ionic nanostructured complex of the FS-1 drug contains nanocomplexes of α-dextrin with a size of ~40–48 Å. Based on good agreement between the UV spectra of the model structures and the experimental spectrum of the FS-1 drug, the structure of the active FS-1 nanocomplex is proposed. The structure of the active centers of the drug in the dextrin ring was calculated using the quantum-chemical approach DFT/B3PW91. The active centers, i.e., a complex of molecular iodine with lithium halide (I), a binuclear complex of magnesium and lithium containing molecular iodine, triiodide (II), and triiodide (III), are located inside the dextrin helix. The polypeptide outside the dextrin helix forms a hydrogen bond with dextrin in Complex I and coordinates the molecular iodine in Complex II. It is revealed that the active centers of the FS-1drug can be segregated from the dextrin helix and form complexes with DNA nucleotide triplets. The active centers of the FS-1 drug are only segregated on specific sections of DNA. The formation of a complex between the DNA nucleotide and the active center of FS-1 is a key stage in the mechanisms of anti-HIV, anti-coronavirus (Complex I) and antibacterial action (Complex II).

Electron Scattering Cross-Section Calculations for Atomic and Molecular Iodine

Cross sections for electron scattering from atomic and molecular iodine are calculated based on the R-matrix (close-coupling) method. Elastic and electronic excitation cross sections are presented for both I and I2. The dissociative electron attachment and vibrational excitation cross sections of the iodine molecule are obtained using the local complex potential approximation. Ionization cross sections are also computed for I2 using the BEB model.

Synthesis and Preliminary Anticancer Activity Assessment of N-Glycosides of 2-Amino-1,3,4-thiadiazoles

The addition of 2-amino-1,3,4-thiadiazole derivatives with parallel iodination of differently protected glycals has been achieved using a double molar excess of molecular iodine under mild conditions. The corresponding thiadiazole derivatives of N-glycosides were obtained in good yields and anomeric selectivity. The usage of iodine as a catalyst makes this method easy, inexpensive, and successfully useable in reactions with sugars. Thiadiazole derivatives were tested in a panel of three tumor cell lines, MCF-7, HCT116, and HeLa. These compounds initiated biological response in investigated tumor models in a different rate. The MCF-7 is resistant to the tested compounds, and the cytometry assay indicated low increase in cell numbers in the sub- G1 phase. The most sensitive are HCT-116 and HeLa cells. The thiadiazole derivatives have a pro-apoptotic effect on HCT-116 cells. In the case of the HeLa cells, an increase in the number of cells in the sub-G1- phase and the induction of apoptosis was observed.

In-orbit demonstration of an iodine electric propulsion system

Propulsion is a critical subsystem of many spacecraft1–4. For efficient propellant usage, electric propulsion systems based on the electrostatic acceleration of ions formed during electron impact ionization of a gas are particularly attractive5,6. At present, xenon is used almost exclusively as an ionizable propellant for space propulsion2–5. However, xenon is rare, it must be stored under high pressure and commercial production is expensive7–9. Here we demonstrate a propulsion system that uses iodine propellant and we present in-orbit results of this new technology. Diatomic iodine is stored as a solid and sublimated at low temperatures. A plasma is then produced with a radio-frequency inductive antenna, and we show that the ionization efficiency is enhanced compared with xenon. Both atomic and molecular iodine ions are accelerated by high-voltage grids to generate thrust, and a highly collimated beam can be produced with substantial iodine dissociation. The propulsion system has been successfully operated in space onboard a small satellite with manoeuvres confirmed using satellite tracking data. We anticipate that these results will accelerate the adoption of alternative propellants within the space industry and demonstrate the potential of iodine for a wide range of space missions. For example, iodine enables substantial system miniaturization and simplification, which provides small satellites and satellite constellations with new capabilities for deployment, collision avoidance, end-of-life disposal and space exploration10–14.

Effects of Molecular Iodine/Chemotherapy in the Immune Component of Breast Cancer Tumoral Microenvironment

Molecular iodine (I2) induces apoptotic, antiangiogenic, and antiproliferative effects in breast cancer cells. Little is known about its effects on the tumor immune microenvironment. We studied the effect of oral (5 mg/day) I2 supplementation alone (I2) or together with conventional chemotherapy (Cht+I2) on the immune component of breast cancer tumors from a previously published pilot study conducted in Mexico. RNA-seq, I2 and Cht+I2 samples showed significant increases in the expression of Th1 and Th17 pathways. Tumor immune composition determined by deconvolution analysis revealed significant increases in M0 macrophages and B lymphocytes in both I2 groups. Real-time RT-PCR showed that I2 tumors overexpress T-BET (p = 0.019) and interferon-gamma (IFNγ; p = 0.020) and silence tumor growth factor-beta (TGFβ; p = 0.049), whereas in Cht+I2 tumors, GATA3 is silenced (p = 0.014). Preliminary methylation analysis shows that I2 activates IFNγ gene promoter (by increasing its unmethylated form) and silences TGFβ in Cht+I2. In conclusion, our data showed that I2 supplements induce the activation of the immune response and that when combined with Cht, the Th1 pathways are stimulated. The molecular mechanisms involved in these responses are being analyzed, but preliminary data suggest that methylation/demethylation mechanisms could also participate.

A Facile Synthesis of 2-Aminobenzoxazines Based on Iodine­Catalyzed Desulfurative Cyclization

A facile and environmentally benign access to N-aryl/alkyl-4H-benzoxazin-2-amines is achieved from 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas under transition-metal-free conditions. The conversions occur smoothly in the presence of a catalytic amount of molecular iodine and hydrogen peroxide as the oxidant in tetrahydrofuran at room temperature to afford moderate to good yields (28–90%) of the desired products within 2 hours. This method reports the first examples of the catalytic transformations of 1-[2-(hydroxymethyl)phenyl/alkyl]-3-phenylthioureas into N-aryl/alkyl-4H-benzoxazin-2-amines based on desulfurative cyclization.

A Study of the Possibility of Obtaining Deposited Coatings based on Intermetallic Titanium and Aluminum Compounds using the Chemical Vapor Transport Method

Theoretical and experimental investigations of processes of titanium-aluminum coating formation on refractory wire substrates by the Chemical Vapor Transport Reactions (CVT) method were carried out. Modelling of CVT was based on the thermodynamic analysis of an equilibrium iodide system implying the presence of one of titanium aluminides in the condensed phase, titanium and aluminum iodides in the gas phase, as well as atomic and molecular iodine. The fact that the volatility and stability of various metals are strongly interrelated was considered as a working hypothesis, which made it possible to obtain a number of alloys with the simultaneous decomposition of metal iodides constituting an alloy. Experiments on the deposition of titanium-aluminum coatings were conducted in a quasi-closed reactor, which allowed us to obtain deposited coatings on long-length refractory substrates