Structural and magnetic properties of three novel complexes with the versatile ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one

Conventional reactions of the versatile multidentate ligand 5-methyl-1,2,4-triazolo[1,5-a]pyrimidin-7(4H)-one (HmtpO) with metallic(II) salts lead to three novel multidimensional complexes [Cu(HmtpO)(2)(H(2)O)(3)](ClO(4))(2)·H(2)O (1), {[Cu(HmtpO)(2)(H(2)O)(2)](ClO(4))(2)·2HmtpO}(n) (2) and {[Co(HmtpO)(H(2)O)(3)](ClO(4))(2)·2H(2)O}(n) (3). In each compound, the triazolopyrimidine ligand shows a different and unusual coordination mode, giving rise to structures with diverse topologies and dimensionality. Compound 1 is a monomeric complex, in which HmtpO shows both N3-monodentate and N1,O71-bidentate modes. 2 is a bidimensional framework with the ligand showing a N3,O71 bidentate-bridging mode. The structure of 3 consists of 1D chains, in which HmtpO displays a N1,N3,O71-tridentate-bridging mode. It should be noted that these coordination modes of the HmtpO ligand are unique in the case of compounds 2 and 3. On the other hand, the magnetic properties of the polynuclear complexes 2 and 3 have been studied showing weak ferromagnetic and antiferromagnetic behaviour, respectively.     

Optimized enzymatic synthesis of hesperidin fatty acid esters in a two-phase system containing ionic liquid

Response surface methodology (RSM) based on a five-level, three-variable central composite design (CCD) was employed for modeling and optimizing the conversion yield of the enzymatic acylation of hesperidin with decanoic acid using immobilized Candida antarctica lipase B (CALB) in a two-phase system containing [bmim]BF(4). The three variables studied (molar ratio of hesperidin to decanoic acid, [bmim]BF(4)/acetone ratio and lipase concentration) significantly affected the conversion yield of acylated hesperidin derivative. Verification experiments confirmed the validity of the predicted model. The lipase showed higher conversion degree in a two-phase system using [bmim]BF(4) and acetone compared to that in pure acetone. Under the optimal reaction conditions carried out in a single-step biocatalytic process when the water content was kept lower than 200 ppm, the maximum acylation yield was 53.6%.     

Activators of cylindrical proteases as antimicrobials: identification and development of small molecule activators of ClpP protease

ClpP is a cylindrical serine protease whose ability to degrade proteins is regulated by the unfoldase ATP-dependent chaperones. ClpP on its own can only degrade small peptides. Here, we used ClpP as a target in a high-throughput screen for compounds, which activate the protease and allow it to degrade larger proteins, hence, abolishing the specificity arising from the ATP-dependent chaperones. Our screen resulted in five distinct compounds, which we designate as Activators of Self-Compartmentalizing Proteases 1 to 5 (ACP1 to 5). The compounds are found to stabilize the ClpP double-ring structure. The ACP1 chemical structure was considered to have drug-like characteristics and was further optimized to give analogs with bactericidal activity. Hence, the ACPs represent classes of compounds that can activate ClpP and that can be developed as potential novel antibiotics.     

Enantioselective and regioselective indium(III)-catalyzed addition of pyrroles to isatins

The indium(III)-catalyzed enantioselective and regioselective addition of pyrroles to isatins is described. The effects of metal and solvent on the reactivity and selectivity are compared and discussed, demonstrating that the indium(III)-indapybox complex provides the most effective catalyst. A case of divergent reactivity between pyrroles and indoles is presented.     

Decay estimates for evolution equations with classical and fractional time-derivatives

Using energy methods, we prove some power-law and exponential decay estimates for classical and nonlocal evolutionary equations. The results obtained are framed into a general setting, which comprise, among the others, equations involving both standard and Caputo time-derivative, complex valued magnetic operators, fractional porous media equations and nonlocal Kirchhoff operators.Both local and fractional space diffusion are taken into account, possibly in a nonlinear setting. The different quantitative behaviours, which distinguish polynomial decays from exponential ones, depend heavily on the structure of the time-derivative involved in the equation.     

Dephosphorylation reactions with deferoxamine, a potential chemical nuclease

We report a detailed kinetic and mechanistic study of the reaction of a widely used therapeutic agent, deferoxamine (DFO), which contains three nucleophilic hydroxamate groups, with the model phosphate diester bis-2,4-dinitrophenylphosphate BDNPP. We clarify the mechanism by detecting important phosphorylated intermediates in the model reaction and show that the mechanism can be extended to the reaction with DNA. The effectiveness of DFO in cleaving DNA was examined over a range of pH in the absence and presence of a biologically available metal (Zn(2+)). The results inform and complement ongoing studies involving DFO, which can act as a powerful nucleophile toward DNA and other targets susceptible to nucleophilic attack.     

Phosphorylimidazole derivatives: potentially biosignaling molecules

The phosphorylation of imidazole by two activated phosphate diesters and a triester gives phosphorylimidazole derivatives that are stable enough in aqueous solution to be observed and identified by ESI-MS/MS and NMR. Half-lives ranging from hours to days (in the case of the monoethyl ester) show that it is possible to design molecules with variable half-lives with potential to be used for biological intervention experiments as possible inhibitors of biosignaling processes or as haptens for the generation of antibodies.     

Synthesis of 1,2-dihydroxyindolizidines from 1-(2-pyridyl)-2-propen-1-ol

1-(2-Pyridyl)-2-propen-1-ol, obtained by vinylation of commercially available picolinaldehyde, resulted a good starting material for the synthesis of the indolizidine skeleton. In particular, a simple process involving bromination, reduction, and nucleophilic substitution (via elimination and addition) allowed an easy conversion of the starting material into (±)-lentiginosine in ~27% overall yield.     

Electroanalytical Performance of (SiPy+Cl−/CuTsPc)5 LbL Film for Detecting Promethazine Hydrochloride

A (SiPy⁺Cl^?/CuTsPc)₅ layer‐by‐layer film was employed for the electroanalytical determination of promethazine hydrochloride in BR buffer pH 5.0 with peaks at 0.48 and 0.79 V. After optimisation of the square‐wave parameters (f=100 s^?1, a=40 mV and ΔE_s=2 mV), the peak at 0.79 V was used for quantification and a detection limit of 8.71×10^?9 mol L^?1 and a quantification limit of 9.31×10^?8 were calculated. The applicability of this procedure was tested on commercial formulations of promethazine hydrochloride by observing the stability, specificity, recovery and precision of the procedure in complex samples, without any preliminary treatment.     

Nonlinear viscoelastic dynamics of nanoconfined wetting liquids

The viscoelastic dynamics of nanoconfined wetting liquids is studied by means of atomic force microscopy. We observe a nonlinear viscoelastic behavior remarkably similar to that widely observed in metastable complex fluids. We show that the origin of the measured nonlinear viscoelasticity in nanoconfined water and silicon oil is a strain rate dependent relaxation time and slow dynamics. By measuring the viscoelastic modulus at different frequencies and strains, we find that the intrinsic relaxation time of nanoconfined water is in the range 0.1-0.0001 s, orders of magnitude longer than that of bulk water, and comparable to the dielectric relaxation time measured in supercooled water at 170-210 K.