A Synthetic Lectin for O‐Linked β‐N‐Acetylglucosamine

Changing employment : Receptor 1 binds β‐N‐acetylglucosaminyl (β‐GlcNAc) up to 100 times more strongly than it does glucose. This synthetic lectin shows affinities similar to wheat germ agglutinin (WGA), a natural lectin used to bind GlcNAc. Remarkably, 1 is more selective than WGA. It favors especially the glycoside unit in glycopeptide 2 , a model of the serine‐O‐GlcNAc posttranslational protein modification.

     

Many-electron self-interaction and spin polarization errors in local hybrid density functionals

Errors for systems with noninteger occupation have been connected to common failures of density functionals. Previously, global hybrids and pure density functionals have been investigated for systems with noninteger charge and noninteger spin state. Local hybrids have not been investigated for either of those systems to the best of our knowledge. This study intends to close this gap. We investigate systems with noninteger charge to assess the many-electron self-interaction error and systems with noninteger spin state to assess the spin polarization error of recently proposed local hybrids and their range-separated variants. We find that long-range correction is very important to correct for many-electron self-interaction error in cations, whereas most full-range local hybrids seem to be sufficient for anions, where long-range-corrected density functionals tend to overcorrect. On the other hand, while all hitherto proposed long-range-corrected density functionals show large spin polarization errors, the Perdew-Staroverov-Tao-Scuseria (PSTS) functional performs best of all local hybrids in this case and shows an outstanding behavior for the dependence of the energy on the spin polarization.     

Porous phosphate heterostructures containing CdS quantum dots: assembly, characterization and photoluminescence

The synthesis and characterization of cadmium sulphide (CdS) quantum dots, conjugated in a porous phosphate heterostructure functionalized with aminopropyl groups is described. The resulting material has fluorescence properties with maximum emission intensity at 575 nm. The fluorescent materials are not soluble in water and exhibit high stability in aqueous solution in the pH ranges from 2 to 9. Energy dispersive X-ray spectroscopy confirmed the qualitative elemental composition of the synthesized materials and X-ray photoelectron spectra showed a surface S/Cd atomic ratio of 1.09. SEM images show that the materials are amorphous, possessing porous with sizes of several tens nanometres, homogeneous and exhibit a layered morphology. The adsorption–desorption analysis by N₂ at 77 K showed the accessibility of the CdS quantum dots onto the pores of the structure. The CdS quantum dots were stabilized by mercaptopropionic acid and bounded to the host materials by amine groups.     

Vanadium oxide-porous phosphate heterostructure catalysts for the selective oxidation of H2S to sulphur

Vanadium oxide–containing mesoporous materials, based on a surfactant expanded zirconium phosphate with silica galleries into the interlayer space, named porous phosphate heterostructure (PPH), were prepared by using TEOS and vanadium oxytripropoxide in n-propanol as sources of Si and V, respectively; with different Si/V molar ratios of 1, 2, 5 and 25; and calcining at 550 °C for 6 h. Using this method, vanadium can be partially incorporated to the structure of the gallery, but the surface area strongly decreases and the appearance of V₂O₅ crystallites increases when increasing the vanadium content. The catalysts were characterized by XRD, XPS, TEM, and Raman, and tested in the selective catalytic oxidation of H₂S using a fixed bed reactor, at atmospheric pressure, at 180–260 °C. The catalysts with high contents of vanadium are very active at 200 °C, showing H₂S conversions of 85–99%, with a high selectivity to elemental sulphur and with a low formation of SO₂. Accordingly V₂O₅ crystallites can be proposed as active and selective although the catalytic behavior is related to the number of accessible V-sites in the surface of the catalyst.     

Cloning and characterization of Escherichia coli DUF299: a bifunctional ADP-dependent kinase - Pi-dependent pyrophosphorylase from bacteria

Background  

Phosphoenolpyruvate synthetase (PEPS; EC 2.7.9.2) catalyzes the synthesis of phosphoenolpyruvate from pyruvate in Escherichia coli when cells are grown on a three carbon source. It also catalyses the anabolic conversion of pyruvate to phosphoenolpyruvate in gluconeogenesis. A bioinformatics search conducted following the successful cloning and expression of maize leaf pyruvate, orthophosphate dikinase regulatory protein (PDRP) revealed the presence of PDRP homologs in more than 300 bacterial species; the PDRP homolog was identified as DUF299.     

Quantum-chemical study on the bioactive conformation of epothilones

Herein, I report a DFT study on the bioactive conformation of epothilone A based on the analysis of 92 stable conformations of free and bound epothilone to a reduced model of tubulin receptor. The equilibrium structures and relative energies were studied using B3LYP and X3LYP functionals and the 6-31G(d) standard basis set, which was considered appropriate for the size of the systems under study. Calculated relative energies of free and bound epothilones led me to propose a new model for the bioactive conformation of epothilone A, which accounts for several structure-activity data.     

Projections and averages of isometries on Lipschitz spaces

We characterize projections on spaces of Lipschitz functions expressed as the average of two and three linear surjective isometries. Generalized bi-circular projections are the only projections on these spaces given as the convex combination of two surjective isometries.     

Polycationic amphiphilic cyclodextrins as gene vectors: effect of the macrocyclic ring size on the DNA complexing and delivery properties

A collection of homologous monodisperse facial amphiphiles consisting of an α-, β- or γ-cyclodextrin (α, β or γCD) platform exposing a multivalent display of cationic groups at the primary rim and bearing hexanoyl chains at the secondary hydroxyls have been prepared to assess the influence of the cyclooligosaccharide core size in their ability to complex, compact and protect pDNA and in the efficiency of the resulting nanocondensates (CDplexes) to deliver DNA into cells and promote transfection in the presence of serum. All the polycationic amphiphilic CDs (paCDs) were able to self-assemble in the presence of the plasmid and produce transfectious nanoparticles at nitrogen/phosphorous ratios ≥5. CDplexes obtained from βCD derivatives generally exhibited higher transfection capabilities, which can be ascribed to their ability to form inclusion complexes with cholesterol, thereby enhancing biological membrane permeability. The presence of thiourea moieties as well as increasing the number of primary amino groups then favour cooperative complexation of the polyphosphate chain, enhancing the stability of the complex and improving transfection. In the α and γCD series, however, only the presence of tertiary amino groups in the cationic clusters translates into a significant improvement of the transfection efficiency, probably by activating endosome escape by the proton sponge mechanism. This set of results illustrates the potential of this strategy for the rational design and optimisation of nonviral gene vectors.     

Comparative study of different methods for the preparation of tetraamidato- and tetracarboxylatodiruthenium compounds. Structural and magnetic characterization

Solvothermal and microwave assisted synthesis were used as green and very useful alternative methods to obtain new chloridotetraamidatodiruthenium compounds, [Ru(2)Cl(μ-NHOCR)(4)](n) [R = Me-o-C(6)H(4) (1), Me-m-C(6)H(4) (2), Me-p-C(6)H(4) (3)]. The analogous tetracarboxylato complexes [Ru(2)Cl(μ-O(2)CR)(4)](n) [R = Me-o-C(6)H(4) (4), Me-m-C(6)H(4) (5), Me-p-C(6)H(4) (6)] have also been obtained. These synthetic methods allow the use of greener solvents like water or ethanol. Moreover, solvothermal synthesis permits the direct crystallization of the desired complexes, which are extremely insoluble in common solvents, during the synthetic process. Therefore, the crystal structure of all of them has been established using single crystal X-ray diffraction. Complex 1 shows a Ru-Cl-Ru angle of 180° and constitutes the first example of a chloridotetraamidatodiruthenium derivative displaying linear chains in the solid state. In contrast, complexes 2·0.5EtOH, and 3-6 show polymeric arrangements with the diruthenium units linked by chloride ligands, forming zigzag chains with Ru-Cl-Ru angles ranging between 117.03(6) and 121.45(3)°. All of the complexes show magnetic moments at room temperature corresponding to three unpaired electrons in agreement with the σ(2)π(4)δ(2)(π*δ*)(3) ground-state configuration, which indicates a similar magnetic behaviour in amidato and carboxylato derivatives. In the linear arrangement of complex 1 there is a better magnetic communication between diruthenium units (antiferromagnetic coupling, zJ = -10.5 or -8.7 cm(-1)) than the one observed in the zigzag 2-6 complexes (zJ = -1.23 to -5.75 cm(-1)).     

Polyanionic N-donor ligands as chelating agents in transition metal complexes: synthesis, structural characterization and antiviral properties against HIV

We describe here the synthesis and characterization of new sulfonated and carboxylated-containing N-donor ligands [Na(4)(edts)]·4H(2)O (2), [Na(2)(dmeddp)]·2H(2)O (3) and [Na(4)(edtp)]·H(2)O (4) (edts = ethylene-diamine- N,N,N',N'-tetraethylenesulfonate ion; dmeddp = dimethyl-ethylene-diamine-N,N,N',N'-tetra-3-propionate ion; edtp = ethylene-diamine-N,N,N',N'-tetra-3-propionate ion) and their corresponding metal (Ni, Co, Cu and Zn) complexes. Mainly, UV-Vis and a computer aided analysis of the EPR spectra provided information on the geometry and structure of the complexes in solution. Some of the metal complexes inhibit HIV replication when treating both pre- and post-infected PBMC cells, and hustle the inhibitory effect compared to the metal salts alone.