Azo dyes containing 1,3,4-thiadiazole fragment: synthesis, properties

New 1,3,4-thiadiazole derivatives containing a diazenyl group, as well as simultaneously a diazenyl and an imino group were synthesized and their opticaland thermal properties were investigated. Initially, new azo compounds...

Zhaoshumycins A and B, Two Unprecedented Antimycin-Type Depsipeptides Produced by the Marine-Derived Streptomyces sp. ITBB-ZKa6

Marine actinomycetes are prolific chemical sources of complex and novel natural products, providing an excellent chance for new drug discovery. The chemical investigation of the marine-derived Streptomyces sp. ITBB-ZKa6, from Zhaoshu island, Hainan, led to the discovery of two unique antimycin-type depsipeptides, zhaoshumycins A (1) and B (2), along with the isolation of the four known neoantimycins A (3), F (4), D (5), and E (6). The structures of the new compounds 1 and 2 were elucidated on the basis of the analysis of diverse spectroscopic data and biogenetic consideration. Zhaoshumycins A (1) and B (2) represent a new class of depsipeptides, featuring two neoantimycin monomers (only neoantimycin D or neoantimycins D and E) linked to a 1,4-disubstituted benzene ring via an imino group. Initial toxicity tests of 1–6 in MCF7 human breast cancer cells revealed that compounds 5 and 6 possess weak cytotoxic activity. Further structure–activity relationship analysis suggested the importance of the NH2 group at C-34 in 5 and 6 for cytotoxicity in MCF7 cells.

Chemical shift prediction of RNA imino groups: application toward characterizing RNA excited states

NH groups in proteins or nucleic acids are the most challenging target for chemical shift prediction. Here we show that the RNA base pair triplet motif dictates imino chemical shifts in its central base pair. A lookup table is established that links each type of base pair triplet to experimental chemical shifts of the central base pair, and can be used to predict imino chemical shifts of RNAs to remarkable accuracy. Strikingly, the semiempirical method can well interpret the variations of chemical shifts for different base pair triplets, and is even applicable to non-canonical motifs. This finding opens an avenue for predicting chemical shifts of more complicated RNA motifs. Furthermore, we combine the imino chemical shift prediction with NMR relaxation dispersion experiments targeting both 15N and 1HN of the imino group, and verify a previously characterized excited state of P5abc subdomain including an earlier speculated non-native G•G mismatch.

Synthesis and stability of the dirhenium(III) cluster compounds with isoleucine, serine and proline in aqueous solutions

The previously developed methods for the synthesis of cis-tetrachlorodi--carboxylates of dirhenium(III) were modified, due to which the derivatives of Re26+ with proteinogenic amino acids (AA) isoleucine, serine and proline were synthesized for the first time. The composition and structure of these substances with the general formula cis-[Re2(АA)2Cl4(CH3CN)2]Cl2 were confirmed by elemental analysis, electron adsorption and IR spectroscopy. The presence of a characteristic peak, which corresponds to the *-electronic transition of the Re–Re quadruple bond for compounds with the cis-arrangement of two bridging-coordinated carboxylate groups in the ligand environment of the Re26+ cluster, was showed by using the data on the electronic absorption spectra of solutions of the synthesized compounds. The IR spectrum contains an intense, weakly split band in the region of 1466–1458 cm–1, which is attributed to the s(CO) coordinated carboxyl group and indicates its bridging coordination to the binuclear Re26+ fragment. The spectra exhibited the presence of bands of stretching (NH3+) and bending vibrations (NH3+) of protonated amino groups in complex compounds of isoleucine and serine and the presence of bands of stretching (NH2+) and bending vibrations (NH2+) of the protonated imino group of proline. The stability of the prepared complex compounds in aqueous solutions was investigated. It is shown that the hydrolysis of the synthesized substances occurs within 9–14 days with a decrease in the pH of the reaction solution due to a gradual replacement of labile chloride ligands by OH–-groups at the first stages of interaction with water. The resistance to hydrolysis is an important parameter of biologically active substances; the determination of the resistance to hydrolysis will expand understanding of the possible mechanisms of their specific biological activity.

Quantitative and structural analysis of isotopically labelled natural crosslinks in type I skin collagen using LC-HRMS and SANS

Collagen structure in biological tissues imparts its intrinsic physical properties by the formation of several covalent crosslinks. For the first time, two major crosslinks in the skin dihydroxylysinonorleucine (HLNL) and histidinohydroxymerodesmosine (HHMD), were isotopically labelled and then analysed by liquid-chromatography high-resolution accurate-mass mass spectrometry (LC-HRMS) and small-angle neutron scattering (SANS). The isotopic labelling followed by LC-HRMS confirmed the presence of one imino group in both HLNL and HHMD, making them more susceptible to degrade at low pH. The structural changes in collagen due to extreme changes in the pH and chrome tanning were highlighted by the SANS contrast variation between isotopic labelled and unlabelled crosslinks. This provided a better understanding of the interaction of natural crosslinks with the chromium sulphate in collagen suggesting that the development of a benign crosslinking method can help retain the intrinsic physical properties of the leather. This analytical method can also be applied to study artificial crosslinking in other collagenous tissues for biomedical applications. Graphical abstract

Synthesis of Tris-pillar[5]arene and Its Association with Phenothiazine Dye: Colorimetric Recognition of Anions

A multicyclophane with a core based on tris(2-aminoethyl)amine (TREN) linked by amide spacers to three fragments of pillar[5]arene was synthesized. The choice of the tris-amide core allowed the multicyclophane to bind to anion guests. The presence of three terminal pillar[5]arene units provides the possibility of effectively binding the colorimetric probe N-phenyl-3-(phenylimino)-3H-phenothiazin-7-amine (PhTz). It was established that the multicyclophane complexed PhTz in chloroform with a 1:1 stoichiometry (lgKa = 5.2 ± 0.1), absorbing at 650 nm. The proposed structure of the complex was confirmed by 1H-NMR spectroscopy: the amide group linking the pillar[5]arene to the TREN core forms a hydrogen bond with the PhTz imino-group while the pillararenes surround PhTz. It was established that the PhTz:tris-pillar[5]arene complex could be used as a colorimetric probe for fluoride, acetate, and dihydrogen phosphate anions due to the anion binding with proton donating amide groups which displaced the PhTz probe. Dye displacement resulted in a color change from blue to pink, lowering the absorption band at 650 nm and increasing that at 533 nm.

Imidazole and Azo-Based Schiff Bases Ligands as Highly Active Antifungal and Antioxidant Components

We describe, herein, the synthesis, full characterization, and optical properties of four different ligandsL1-L4which associate an azo group, an imidazole unit, and a Schiff base fragment. The UV-visible absorption bands are characteristic ofπ→π⁎andn→π⁎transitions with an additional charge transfer between the azobenzene moiety and the imino group. Finally the determination of MIC80values against pathogenic fungi such asS. apiospermum,A. fumigatus,andC. albicansrevealed that these ligands have effective antifungal properties with highest activities (MIC80) onC. albicansfor the azole based ligandsL1-L3. DPPH radical scavenging of the studied ligands was also tested.

Selective conformational control by excitation of NH imino vibrational antennas

We provide experimental evidence for the occurrence of selective and reversible conformational control over the SH group by vibrational excitation of remote NH groups. Using an imino group that acts as a molecular antenna has no precedents.

Exploring the potential of imines as antiprotozoan agents with focus on t. Brucei and p. Falciparum

This work focuses on the design, synthesis and evaluation of imine-containing heterocyclic and acyclic compounds with special focus on their bioactivity against parasitic protozoans (P. falciparum and T. brucei) - given the context of drug resistance in the treatment of malaria and Human African sleeping sickness and the fact that several bioactive organic compounds have been reported to possess the imino group. Starting from 2-aminopyridine, novel #-alkylated-5-bromo-7-azabenzimidazoles and substituted 5-bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives were prepared, and their bioactivity against parasitic protozoans was assessed. NMR spectra of the substituted 5- bromo-1-(carbamoylmethy)-7-azabenzimidazole derivatives exhibited rotational isomerism, and a dynamic NMR study was used in the estimation of the rate constants and the free- energies of activation for rotation. The free-energy differences between the two rotamers were determined and the more stable conformations were predicted. Novel 2-phenyl-7-azabenzimidazoles were also synthesised from 2-aminopyridine. A convenient method for the regioselective formylation of 2,3-diaminopyridines into 2-amino- 7-(benzylimino)pyridine analogues of 2-phenyl-7-azabenzimidazole was developed, and some of the resulting imino derivatives were hydrogenated to verify the importance of the imino moiety for bioactivity. The 2-phenyl-7-azabenzimidazoles and the 2-amino-7- (benzylimino)pyridine analogues were screened for their anti-protozoal activity and their cytotoxicity level was determined against the HeLa cell line. In order to validate the importance of the pyridine moiety, novel #-(phenyl)-2- hydroxybenzylimines, #-(benzyl)-2-hydroxybenzylimines and (±)-trans-1,2-bis[2- hydroxybenzylimino]cyclohexanes were also synthesized and screened for activity against the parasitic protozoans and for cytotoxicity against the HeLa cell line. The biological assay results indicated that these compounds are not significantly cytotoxic and a good number of them show potential as lead compounds for the development of new malaria and trypanosomiasis drugs.

Crystal structure and DFT study of the zwitterionic form of 3-{(E)-1-[(4-ethoxyphenyl)iminiumyl]ethyl}-6-methyl-2-oxo-2H-pyran-4-olate

The title Schiff base compound, C16H17NO4, crystallizes as a zwitterion, with the phenolic H atom having been transferred to the imino group. The resulting iminium and hydroxy groups are linked by an intramolecular N—H...O hydrogen bond, enclosing an S(6) ring motif. The conformation about the C=N bond is E and the dihedral angle between the benzene and pyran rings is 70.49 (6)°. In the crystal, molecules are linked by C—H...O hydrogen bonds, forming a three-dimensional supramolecular structure. There are also C—H...π interactions and offset π–π interactions, involving the pyran rings [intercentroid distance = 3.4156 (8) Å], which consolidate the three-dimensional structure. Quantum chemical calculations of the molecule are in good agreement with the solid state keto–amine (NH) form of the title compound.