Crystal structure of the GDP-bound GTPase Era from Staphylococcus aureus.

GTPase Era from Staphylococcus aureus belongs to the TRAFAC superfamily of the TrmE-Era-EngA-EngB-Septin-like GTPases class and plays a significant role in the vital activity of this pathogenic microorganism as a maturation factor of the 30S ribosome subunit. However, the functions of this protein are not fully understood, making it a promising object for further study. Here, the 2.

Phosphine-Catalyzed Synthesis and Cytotoxic Evaluation of Michael Adducts of the Sesquiterpene Lactone Arglabin.

A general method for chemo- and diastereoselective modification of anticancer natural product arglabin with nitrogen- and carbon-centered pronucleophiles under the influence of nucleophilic phosphine catalysts was developed. The locked s-cis-geometry of α-methylene-γ-butyrolactone moiety of arglabin favors for the additional stabilization of the zwitterionic intermediate by electrostatic interaction between phosphonium and enolate oxygen centers, leading to the unprecedentedly high efficiency of the phosphine-catalyzed Michael additions to this sesquiterpene lactone. Using n-BuP as the catalyst, pyrazole, phthalimide, 2-oxazolidinone, 4-quinazolinone, uracil, thymine, cytosine, and adenine adducts of arglabin were obtained.

α-Umpolung/Michael Addition/Quaternization Tandem Reaction to provide α-Imido-β-phosphonium Propanoates with Broad Spectrum of Biological Activity.

This paper has been supported by the Kazan Federal University Strategic Academic Leadership Program ('PRIORITY-2030'). HRMS data were obtained in the CSF-SAC FRC KSC RAS by support of the State Assignment of the Federal Research Center "Kazan Scientific Center", Russian Academy of Sciences. A.

Linkage of the Dinuclear Gold(I) Complex Luminescence and Origin of Endocyclic Amino Group of Cyclic PN-Bridging Ligands.

Gold(I) complexes of LAuCl composition based on PN ligands, namely 1,5-diaza-3,7-diphosphacyclooctanes, containing ethylpyridyl substituents at the phosphorus atoms and sp- or sp-hybridized endocyclic nitrogen atoms were synthesized. The SCXRD analysis indicated the strong impact of the geometry of the nitrogen atom on the structure and conformational flexibility of the complexes. The -aryl substituted ligand with the planar endocyclic nitrogen atom provides higher flexibility of the complex and an ability to bind the solvent molecules in the "host-guest" mode, whereas that kind of behavior is forbidden for the complex with an -alkyl substituted ligand with a pyramidal nitrogen atom.

An Unusual Rearrangement of Pyrazole Nitrene and Coarctate Ring-Opening/Recyclization Cascade: Formal CH-Acetoxylation and Azide/Amine Conversion without External Oxidants and Reductants.

We report an unusual transformation where the transient formation of a nitrene moiety initiates a sequence of steps leading to remote oxidative C-H functionalization (R-CH to R-CHOC(O)R') and the concomitant reduction of the nitrene into an amino group. No external oxidants or reductants are needed for this formal molecular comproportionation. Detected and isolated intermediates and computational analysis suggest that the process occurs with pyrazole ring opening and recyclization.

Hybrids of Sterically Hindered Phenols and Diaryl Ureas: Synthesis, Switch from Antioxidant Activity to ROS Generation and Induction of Apoptosis.

The utility of sterically hindered phenols (SHPs) in drug design is based on their chameleonic ability to switch from an antioxidant that can protect healthy tissues to highly cytotoxic species that can target tumor cells. This work explores the biological activity of a family of 45 new hybrid molecules that combine SHPs equipped with an activating phosphonate moiety at the benzylic position with additional urea/thiourea fragments. The target compounds were synthesized by reaction of iso(thio)cyanates with C-arylphosphorylated phenols containing pendant 2,6-diaminopyridine and 1,3-diaminobenzene moieties.

Stereoelectronic Effect in the Reaction of α-Methylene Lactones with Tertiary Phosphines and Its Application in Organocatalysis.

The kinetic data indicate that the addition of tertiary phosphines to α-methylene lactones in acetic acid is strongly accelerated in comparison to the reactions of related open-chain esters. Six-membered α-methylene-δ-valerolactone exhibited a more pronounced rate increase than five-membered α-methylene-γ-butyrolactone. The use of α-methylene-γ-butyrolactam as a nitrogen analogue of α-methylene-γ-butyrolactone resulted in a total loss of the reaction acceleration.

Tuning Crystal Packing and Magnetic Properties in a Series of [Dy] Metallocubanes Based on Azobenzene Derivatives of Salicylic Acid.

A series of four new Dy dodecanuclear clusters based on azobenzene derivative ligands of salicylic acid (-) has been synthesized and characterized in the crystalline phase using X-ray diffraction on single crystal and powder, IR spectroscopy, elemental analysis, and DSC-TGA methods. It was revealed that all obtained clusters exhibit the formation of the similar metallic cluster nodes, as vertex-sharing heterocubanes, obtained from four Dy cations, three bridging hydroxyl groups, and O atoms from the salicylic ligands. The coordination geometry around the Dy(III) centers has been carefully analyzed.

Chemical and Electrochemical Reductions of Monoiminoacenaphthenes.

Redox properties of monoiminoacenaphthenes (MIANs) were studied using various electrochemical techniques. The potential values obtained were used for calculating the electrochemical gap value and corresponding frontier orbital difference energy. The first-peak-potential reduction of the MIANs was performed.

Cobalt(II) coordination to an N-acenaphthene-based ligand and its sodium complex.

A new bifunctional N-ligand was obtained the condensation reaction of acenaphthenequinone and 2-picolylamine. A peculiarity of this synthesis is the formation of a new intramolecular C-C bond during the reaction. The structure and redox properties of the ligand were studied.

(2-Hydroxy-3-Methoxybenzylidene)thiazolo[3,2-]pyrimidines: Synthesis, Self-Assembly in the Crystalline Phase and Cytotoxic Activity.

A series of new 2-hydroxy-3-methoxybenzylidenethiazolo[3,2-]pyrimidines with different aryl substituents at the 5 position are synthesized and characterized by H/ C NMR and IR-spectroscopy and mass-spectrometry, as well as single crystal X-ray diffraction (SCXRD). It was demonstrated that the type of hydrogen bonding can play a key role in the chiral discrimination of these compounds in the crystalline phase. The hydrogen bond of the O-H.

Calix[4]arene Polyamine Triazoles: Synthesis, Aggregation and DNA Binding.

Artificial gene delivery systems are in great demand from both scientific and practical biomedical points of view. In this paper, we present the synthesis of a new click chemistry calix[4]arene precursor with free lower rim and new water-soluble calixarene triazoles with 12 amino-groups on the upper rim (one with free phenol hydroxyl groups and two another containing four butyl or tetradecyl fragments). Aggregation in the series of amino-triazole calixarenes of different lipophilicity (calixarene with free phenol hydroxyl groups or butyl and tetradecyl fragments on the lower rim) was studied using dynamic light scattering and fluorescent pyrene probe.

Ferrocene-based -chiral amidophosphinate: stereoselective synthesis and X-ray structural study.

Racemic and enantiopure ferrocene-based -chiral amidophosphinates have been simply and stereoselectively synthesized by -lithiation of - or ()-Ugi's amine and further reaction with amidochlorophenylphosphinate Cl-P(O)(Ph)NEt. This is the first example of an asymmetric reaction of -lithiated Ugi's amine with tetracoordinated phosphorus(V) chlorides. The structures of - and ()-Ugi's amine ferrocenyl(phenyl)phosphinic acid ,-diethylamide have been extensively studied experimentally (NMR, X-ray analysis, electrochemistry).

Emission and Luminescent Vapochromism Control of Octahedral Cu I Complexes by Conformationally Restricted P,N Ligands.

A conformationally restricted P,N-ligand capable of the design of polynuclear copper(I) complexes was synthesized via the reaction of primary pyridylphosphine, paraformaldehyde, and benzhydrylamine. The reaction of the ligand with copper(I) iodide leads to the tetranuclear copper(I) complex with the octahedral type of copper-iodide core. Different orientation of coordination bonds of the ligands relative to the P,N -heterocyclic fragments and to the Cu I cores leads to the existence of two types of conformers of the complex with "compact" or "stretched" geometry of the Cu I cluster.

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite's conformance.

A triferrocenyl trithiophosphite was studied by X-ray single-crystal diffraction. Triferrocenyl trithiophosphite has nine axes of internal rotation: three P-S bonds, three C-S bonds and three Fe-cyclopentadienyl axes. Rotation around the P-S bonds results in a totally asymmetric structure with three ferrocenylthio groups exhibiting different orientations towards the phosphorus lone electron pair (LEP).

Deep-Blue Emissive Copper(I) Complexes Based on P-Thiophenylethyl-Substituted Cyclic Bisphosphines Displaying Photoinduced Structural Transformations of the Excited States.

A synthetic method for a primary 2-(thiophen-2'-yl)ethylphosphine was developed. The reaction of thiophenylethylphosphine with paraformaldehyde and primary arylamines leads to the formation of cyclic bisphosphines, namely, 1,5-di(aryl)-3,7-bis(thiophenylethyl)-1,5-diaza-3,7-diphosphacyclooctane (aryl = phenyl, -tolyl). The obtained bisphosphines form cationic bis-P,P-chelate complexes with copper(I) tetrafluoroborate, which were structurally characterized by NMR spectroscopy, mass spectrometry, and elemental and XRD analyses.

PNP Ligands in Cobalt-Mediated Activation and Functionalization of White Phosphorus.

Transition-metal mediated white phosphorus activation is of high interest as an ecological alternative to P chlorination pathway to the practically useful phosphorus products. Herein, we report a facile approach for P activation, transformation and subsequent functionalization using cobalt complexes bearing PNP ligands. The use of N,N-bis(diphenylphosphino)amine as a ligand allows one to transform P tetrahedron into a zig-zag chain with the formation of complex [Co(Ph PNHP(Ph )PPPPP(Ph )NHPPh )]BF (4).

Thermodynamic vs. Kinetic Control in Synthesis of -Donor 2,5-Substituted Furan and 3,5-Substituted Pyrazole from Heteropropargyl Precursor.

Elaboration of a convenient route towards donor-substituted pyrazoles from heteropropargyl precursors is challenging due to a number of thermodynamically favorable side reactions (e.g., acetylene-allene isomerization and Glaser homocoupling).

Synthesis, biological evaluation and structure-activity relationship of 2-(2-hydroxyaryl)alkenylphosphonium salts with potency as anti-MRSA agents.

Here we report the synthesis, in vitro antimicrobial activity, preliminary toxicity and mechanism study of a new series of 2-(2-hydroxyaryl)alkenylphosphonium salts with the variation of phosphonium moiety obtained by a two-step synthetic method from phosphine oxides. The salts showed pronounced activity against Gram-positive bacteria, including MRSA strains, and some fungi. Mechanism of action against S.

Self-Healing Thiolated Pillar[5]arene Films Containing Moxifloxacin Suppress the Development of Bacterial Biofilms.

Polymer self-healing films containing fragments of pillar[5]arene were obtained for the first time using thiol/disulfide redox cross-linking. These films were characterized by thermogravimetric analysis and differential scanning calorimetry, FTIR spectroscopy, and electron microscopy. The films demonstrated the ability to self-heal through the action of atmospheric oxygen.

Thiacalixarenes with Sulfur Functionalities at Lower Rim: Heavy Metal Ion Binding in Solution and 2D-Confined Space.

Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air-water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative , OS-thiacrown-ether , and OS-bridged thiacalixtube ). The study was conducted in bulk liquid phase and Langmuir monolayers.