Protonated niobate/titanate pyrochlores via lead-acid exchange in Pb1.5Nb2O6.5 and Pb2Nb1.33Ti0.67O6.67

Hydrogen-based niobates and niobate-titanates were derived from the pyrochlores Pb_1.5Nb₂O_6.5 (PN) and Pb₂Nb_1.33Ti_0.67O_6.67 (PNT) by ion exchange in acid baths, affording sub-micron size white powders. The niobium sublattice was left intact, as shown by X-ray diffraction. A combination of stripping and thermogravimetric analyses gave the effective formulas H_2.66Pb_0.17Nb₂O_6.5·0.5H₂O (HPN) and H_3.88Pb_0.06Nb_1.33Ti_0.67O_6.67·0.33H₂O (HPNT). The corresponding structural refinements gave good fits to the XRD data. Densities measured by He pycnometry agreed with densities calculated from XRD analyses and the effective formulas. Thermal stability was assessed by TGA, DSC, and XRD. With increasing temperature, HPN and HPNT lost weight (H₂O), becoming amorphous, and then transforming to crystalline phases, with greatly reduced particle size. HPN was more stable than HPNT. The electrical conductivities of powder compacts in wet atmospheres were moderate and attributed mainly to proton conduction; i.e., 10⁻⁶ to 10⁻⁵ S cm⁻¹ for HPN and 10⁻⁷ to 10⁻⁶ S cm⁻¹ for HPNT (from room temperature to 230 °C). Experimental results were interpreted in terms of Nb(V) being a stronger electron acceptor than Ti(IV).     

Studies of a novel conducting polymer by cyclic and square wave voltammetries: Its synthesis and characterization

A novel conducting polymer of polynaphthidine, poly(NAP), was synthesized electrochemically by direct anodic oxidation of naphthidine in aqueous media. The yield of the electropolymerization reaction depends on the temperature and pH of the solution. It was possible to differentiate two working regions: I (for pH < 0.5 and all temperatures) where the film yield tends to zero and II (for approximately 2.0 < pH < 2.8 and temperatures >15 °C) where the film production is maximum. Therefore, the naphthidine electrooxidation mechanism was studied under experimental conditions of region I by cyclic (CV) and square wave voltammetries (SWV) as well as by controlled potential electrolysis.The experimental conditions of region II were chosen to obtain the poly(NAP). The electrochemical response of the film was investigated in pH 1 HClO₄ + 0.1 M NaClO₄ electrolyte solution by CV and SWV. A plot of I_p,n/fvs. f from SW voltammograms showed the so-called “quasi-reversible maximum”. Formal potential, formal rate constant and anodic transfer coefficient for the surface redox process were also evaluated from the SWV.The poly(NAP) is insoluble in common organic solvents and shows electrochromic behaviour. Its probable structure was determined by FTIR spectroscopy.     

Extensions to “virtual reference feedback tuning: A direct method for the design of feedback controllers”

The papers [Campi, Lecchini & Savaresi (2002). Automatica, 38(8), 1337-1346; (2003). European Journal of Control, 9(1), 66-76] present a direct controller synthesis procedure that uses identification algorithms applied to filtered input-output plant data. This contribution discusses variations that, in some cases, may alleviate noise-induced correlation (in the open-loop case) and allow the applicability of the approach to unstable plants. Importantly, it also introduces an invalidation test step based on the available data (i.e., prior to experimental controller testing), to check if the flexibility of the controller parameterisation and the approximations involved are suitable for the design objectives or, on the contrary, the resulting closed loop may be unstable.     

Comparative Assessment of Complex Stabilities of Radiocopper Chelating Agents by a Combination of Complex Challenge and in vivo Experiments

For ⁶⁴Cu radiolabeling of biomolecules to be used as in vivo positron emission tomography (PET) imaging agents, various chelators are commonly applied. It has not yet been determined which of the most potent chelators—NODA‐GA ((1,4,7‐triazacyclononane‐4,7‐diyl)diacetic acid‐1‐glutaric acid), CB‐TE2A (2,2′‐(1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐4,11‐diyl)diacetic acid), or CB‐TE1A‐GA (1,4,8,11‐tetraazabicyclo[6.6.2]hexadecane‐4,11‐diyl‐8‐acetic acid‐1‐glutaric acid)—forms the most stable complexes resulting in PET images of highest quality. We determined the ⁶⁴Cu complex stabilities for these three chelators by a combination of complex challenge and an in vivo approach. For this purpose, bioconjugates of the chelating agents with the gastrin‐releasing peptide receptor (GRPR)‐affine peptide PESIN and an integrin α_vβ₃‐affine c(RGDfC) tetramer were synthesized and radiolabeled with ⁶⁴Cu in excellent yields and specific activities. The ⁶⁴Cu‐labeled biomolecules were evaluated for their complex stabilities in vitro by conducting a challenge experiment with the respective other chelators as challengers. The in vivo stabilities of the complexes were also determined, showing the highest stability for the ⁶⁴Cu–CB‐TE1A‐GA complex in both experimental setups. Therefore, CB‐TE1A‐GA is the most appropriate chelating agent for *Cu‐labeled radiotracers and in vivo imaging applications.     

Stereoselective Synthesis of Pyrroloquinolines by a Brønsted Acid Catalyzed [4+2]‐Heterocyclization of Indole‐7‐Carbaldehydes,Anilines and Electron‐Rich Alkenes

The pyrrolo[3,2,1‐ij]quinoline heterocyclic core is found in the structure of a variety of compounds with interesting applications and then, new efficient and flexible strategies to construct this skeleton are required. Here, a new diastereoselective tetrafluoroboric acid (HBF₄)‐catalyzed three‐component coupling reaction of 1H‐indole‐7‐carbaldehyde derivatives, anilines and electron‐rich alkenes to give pyrrolo[3,2,1‐ij]quinolines is described. The reaction involves an unusual [4+2]‐heterocyclization between an in situ formed imine and an alkene. The new catalytic method, where water is the only by‐product, is efficient, robust and flexible, and allows for multigram‐scale synthesis.

     

Aflatoxin and PAH exposure biomarkers in a U.S. population with a high incidence of hepatocellular carcinoma

The incidence of hepatocellular carcinoma (HCC) is significantly elevated in a Hispanic community in Bexar County, Texas. Chronic exposure to dietary aflatoxins (AFs) is a major risk factor for HCC; increased risk has been linked to polycyclic aromatic hydrocarbon (PAH) co-exposure and hepatitis virus infection. The aims of this study were to assess AF and PAH exposures, investigate dietary factors that may contribute to increased AF exposure, and determine the prevalence of hepatitis virus infection in Bexar Co. Blood and urine samples were collected from 184 volunteers for biomarker analyses and hepatitis screening. Serum AFB₁-lysine adduct, urinary AFM₁ and 1-hydroxypyrene (1-OHP) levels were measured using high-performance liquid chromatography. The average AFB₁-lysine adduct level detected in 20.6% of serums was 3.84 ± 3.11 pg/mg albumin (range 1.01-16.57 pg/mg). AFM₁ was detected in 11.7% of urines, averaging 223.85 ± 250.56 pg/mg creatinine (range 1.89-935.49 pg/mg). AFM₁ detection was associated with increased consumption of corn tortillas (p = 0.009), nuts (p = 0.033) and rice (p = 0.037). A significant difference was observed between mean 1-OHP values of non-smokers (0.07 ± 0.13) and smokers (0.80 ± 0.68) μmol/mol creatinine (p < 0.01). A high hepatitis C virus positivity rate (7.1%) was observed. Findings suggest that the incidence and level of AF and PAH exposure were less than those observed in a high-risk population; however, participants consuming higher amounts of foods prone to AF contamination may be more vulnerable to exposure and interactions with other environmental/biological factors (i.e., HCV).     

Enzymatic production of human milk fat substitutes containing palmitic and docosahexaenoic acids at sn-2 position and oleic acid at sn-1,3 positions

This paper studies the synthesis of structured triacylglycerols (STAGs) rich in palmitic and docosahexaenoic acids (PA and DHA) at sn-2 position and oleic acid (OA) at sn-1,3 positions by a four step process. First, triacylglycerols (TAGs) were obtained with 63–66 mol PA/100 mol total fatty acids and 10 mol DHA/100 mol by acidolysis of tuna oil and commercial PA, catalyzed by the non-positionally specific lipase Novozym 435. Then these TAGs were purified neutralizing the free fatty acids (FFAs) by KOH hydroethanolic solutions and extracting TAGs with hexane; these TAGs were completely recovered as pure TAGs (without FFAs). The third step involved the displacement of fatty acids located at sn-1,3 positions by acidolysis of PA and DHA enriched TAGs with OA rich FFAs, catalyzed by the sn-1,3 specific lipase DF from Rhizopus oryzae, immobilized on Accurel MP-1000; TAGs with 67 mol OA/100 mol at sn-1,3 positions and 52.1 and 15.4 mol PA and DHA, respectively, per 100 mol at sn-2 position were obtained. Both acidolysis reactions were carried out in stirred tank reactors (STRs) with lipase both dispersed in the reaction medium and contained in a cartridge filter attached to the stirrer rod. Finally STAGs were purified and obtained with yields of over 80 mol STAGs/100 mol STAGs in the reaction product (no FFAs were detected).