Hemoabzymes different strategies for obtaining artificial hemoproteins based on antibodies

Besides existing models of chemical or biotechnological origin for hemoproteins like peroxidases and cytochromes P450, catalytic antibod ies (Abs) with a metalloporphyrin cofactor represent a promising alter native route to catalysts tailored for selective oxidation reactions. A brief overview of the literature shows that, until now, the first strategy for obtaining such artificial hemoproteins has been to produce antipor phyrin Abs, raised against various free-base, N-substituted, Sn-,Pd-,or Fe-porphyrins. Four of them exhibited, in the presence of the corre sponding Fe-porphyrin cofactor, a significant peroxidase activity, with k_cat/K_m values of 10² to 5 × 10³/M/s. This value remained low when com pared to that of peroxidases, probably because neither a proximal ligand of the Fe, nor amino acid residues participating in the catalysis of the heterolytic cleavage of the O—O bond of H₂O₂, have been induced in those Abs. This strategy has been shown to be insufficient for the elabo ration of effective models of cytochromes P450, because only one set of Abs, raised againstmeso-tetrakis(para-carboxyvinylphenyl)porphyrin, was reported to catalyze the nonstereoselective oxidation of styrene by iodosyl benzene using a Mn-porphyrin cofactor, and attempts to gener ate Abs having binding sites for both the substrate and the metallopor phyrin cofactor, using as a hapten a porphyrin covalently linked to the substrate, were not successful. A second strategy is then proposed, which involves the chemical labeling of antisubstrate Abs with a metallopor phyrin. As an example, preliminary results are presented on the covalent linkage of an Fe-porphyrin to an antiestradiol Ab, in order to obtain semisynthetic catalytic Abs able to catalyze the selective oxidation of steroids.     

Plate-Like Smart Structures: Reduced Models and Numerical Simulations

In this paper asymptotic models describing the mechanical and electric equilibrium state of two types of smart structures are presented and justified. The first structure consists of an anisotropic elastic thin plate with two surface bonded anisotropic piezoelectric patches and the second one is an anisotropic elastic sandwich thin plate with an inserted anisotropic piezoelectric patch. The two unknowns of the corresponding asymptotic models, the mechanical displacements of the structures and the electric potentials of the patches, are partially decoupled. The former are the solution of modified Kirchhoff-Love plate models, while the latter can be derived as explicit functions of the mechanical displacements. Moreover, different formulas for the electric potential arise as a consequence of diverse electric boundary conditions. We report numerical simulations with these asymptotic models.     

Design of Luminescent,Heteroleptic, Cyclometalated PtII and PtIV Complexes: Photophysics and Effects of the Cyclometalated Ligands

Neutral pentafluorophenyl benzoquinolinyl Pt^II [Pt(bzq)(HC^N−κN)(C₆F₅)] ( 1 a – g ) complexes, bearing nonmetalated N-heterocyclic HC^N ligands [HC^N=2,5-diphenyl-1,3,4-oxadiazole (Hoxd) a , 2-(2,4-difluorophenyl)pyridine (dfppy) b , 2-phenylbenzo[d]thiazole (pbt) c , 2-(4-bromophenyl)benzo[d]thiazole (Br-pbt) d , 2-phenylquinoline (pq) e , 2-thienylpyridine (thpy) f , 1-(2-pyridyl)pyrene (pypy) g ], and heteroleptic bis(cyclometalated) Pt^IV fac-[Pt(bzq)(C^N)(C₆F₅)Cl] ( 2 b – g , bzq: benzo[h]quinolinyl) derivatives, generated by oxidation of 1 b – g with PhICl₂, are reported. The oxidation reaction of 1 a evolved with formation of the bimetallic Pt^IV complex syn-[Pt(bzq)(C₆F₅)Cl(μ-OH)]₂ 3 . The crystal structures of 1 a,d,f , 2 b,d,e and 3 were corroborated by X-ray crystallography. A comparative study of the absorption and photoluminescence properties of the two series of complexes Pt^II ( 1 ) and Pt^IV ( 2 ), supported by time-dependent DFT calculations (TD-DFT), is presented. The low-lying transitions (absorption and emission) of Pt^II complexes 1 a – e [solution and polystyrene (PS) films] were assigned to the IL/MLCT mixture located on the cyclometalated Pt(bzq) unit, with minor IL′/ML′CT/LL′CT contributions involving the non-metalated ligand. Complex 1 g , bearing the more delocalized pyridyl pyrene (Hpypy) as an ancillary ligand, shows dual ¹ππ* and ³ππ* (Hpypy) emission in fluid CH₂Cl₂ and dual ³IL/³MLCT [Pt(bzq)] and [³ππ*, Hpypy] phosphorescence at 77 K. Upon oxidation, Pt^IV complexes 2 b – f display (solution, PS) ligand-based phosphorescence that arises from the bzq in 2 b (³LC) or from the second C^N ligand in 2 c – f (³L′C) with some ³LL′CT in 2 f . Despite metalation of the pyrenyl group, 2 g exhibits dual emission ¹ππ*/³ππ* located on the pypy chromophore.     

On weighted inductive limits of spaces of ultradifferentiable functions and their duals

In the first part of this paper we discuss the completeness of two general classes of weighted inductive limits of spaces of ultradifferentiable functions. In the second part we study their duals and characterize these spaces in terms of the growth of convolution averages of their elements. This characterization gives a canonical way to define a locally convex topology on these spaces and we give necessary and sufficient conditions for them to be ultrabornological. In particular, our results apply to spaces of convolutors for Gelfand–Shilov spaces.     

Fully automated determination of 74 pharmaceuticals in environmental and waste waters by online solid phase extraction-liquid chromatography-electrospray-tandem mass spectrometry

The present work describes the development of a fully automated method, based on on-line solid-phase extraction (SPE)-liquid chromatography-electrospray-tandem mass spectrometry (LC-MS-MS), for the determination of 74 pharmaceuticals in environmental waters (superficial water and groundwater) as well as sewage waters. On-line SPE is performed by passing 2.5 mL of the water sample through a HySphere Resin GP cartridge. For unequivocal identification and confirmation two selected reaction monitoring (SRM) transitions are monitored per compound, thus four identification points are achieved. Quantification is performed by the internal standard approach, indispensable to correct the losses during the solid phase extraction, as well as the matrix effects. The main advantages of the method developed are high sensitivity (limits of detection in the low ng L⁻¹ range), selectivity due the use of tandem mass spectrometry and reliability due the use of 51 surrogates and minimum sample manipulation. As a part of the validation procedure, the method developed has been applied to the analysis of various environmental and sewage samples from a Spanish river and a sewage treatment plant.     

Optimal Tauberian constant in Ingham’s theorem for Laplace transforms

It is well known that there is an absolute constant \(\mathfrak{C}\) > 0 such that if the Laplace transform \(G(s) = \int_0^\infty {\rho (x)} {e^{ - sx}}dx\) of a bounded function ρ has analytic continuation through every point of the segment (?iλ, iλ) of the imaginary axis, then

$$G(s) = |\int_0^\infty {\rho (\mu )} du - G(0)| \leqslant \frac{{\text{C}}}{\lambda }\mathop {limsup}\limits_{x \to \infty } |\rho (x)|$$

The best known value of the constant \(\mathfrak{C}\) was so far \(\mathfrak{C}\) = 2. In this article we show that the inequality holds with \(\mathfrak{C}\) = π/2 and that this value is best possible. We also sharpen Tauberian constants in finite forms of other related complex Tauberian theorems for Laplace transforms.

     

Carotenoids of lettuce (Lactuca sativa L.) grown on soil enriched with spent coffee grounds

The impact of spent coffee grounds on carotenoid and chlorophyll content in lettuce (Lactuca sativa L. var. capitata) was evaluated. A greenhouse pot experiment was conducted with spent coffee amounts ranging from 0% to 20% (v/v). All evaluated pigments increased proportionally to spent coffee amounts. Lutein and β-carotene levels increased up to 90% and 72%, respectively, while chlorophylls increased up to 61%. Biomass was also improved in the presence of 2.5% to 10% spent coffee, decreasing for higher amounts. Nevertheless, all plants were characterized by lower organic nitrogen content than the control ones, inversely to the spent coffee amounts, pointing to possible induced stress. Collected data suggests that plants nutritional features, with regards to these bioactive compounds, can be improved by the presence of low amounts of spent coffee grounds (up to 10%). This observation is particularly important because soil amendment with spent coffee grounds is becoming increasingly common within domestic agriculture. Still, further studies on the detailed influence of spent coffee bioactive compounds are mandatory, particularly regarding caffeine.     

Decorating poly(alkyl aryl-ether) dendrimers with metallacarboranes

A new family of polyanionic poly(alkyl aryl-ether) metallodendrimers decorated with four and eight cobaltabisdicarbollide units have been obtained in high yield by the ring-opening reaction of cyclic oxonium [3,3'-Co(8-(C(2)H(4)O)(2)-1,2-C(2)B(9)H(10))(1',2'-C(2)B(9)H(11))] with alkoxides formed by deprotonation of terminal alcohols in the α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-p-xylene, α,α'-bis[3,5-bis(hydroxymehyl)phenoxy]-m-xylene, α,α'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-p-xylene, and α,α,'-bis[3,5-bis-[3,5-bis(hydroxymethyl)phenoxy]methylen]phenoxy]-m-xylene dendrimers. The crystal structure of the precursor α,α'-bis[3,5-bis(chloromethyl)phenoxy]-p-xylene is also described. Final products are fully characterized by FTIR, NMR, UV-vis spectroscopies and elemental analysis. For metallodendrimers, the UV-vis absorptions have been a good tool for estimating the experimental number of cobaltabisdicarbollide units peripherally attached to the dendrimeric structure and consequently to corroborate the complete functionalization of the dendrimers.