Study of Blood Porphyrin Spectral Profile for Diagnosis of Chronic Renal Failure

The progression to end-stage renal failure is independent of the initial pathogenic mechanism. Metabolic acidosis is a common consequence of chronic renal failure that results from inadequate ammonium excretion and decreased tubular bicarbonate reabsorption. Protoporphyrin IX (PpIX) is the immediate metabolic precursor of the heme molecule. The purpose of this study was to evaluate the levels of erythrocytes protoporphyrin IX at an animal model during progressive renal disease. A total of 36 eight-week-old male Wistar rats were divided into six groups: Normal, 4 and 8 weeks after 5/6 nephrectomy (NX). Renal function was evaluated by creatinine clearance and plasma creatinine levels. The autofluorescence of erythrocytes porphyrin of healthy and NX rats was analyzed using fluorescence spectroscopy. Emission spectra were obtained by exciting the samples at 405 nm. Significant differences between normal and NX rats autofluorescence shape occurred in the 600–700 nm spectral region. A correlation was observed between emission band intensity at 635 nm and progression of renal disease.     

The Kalman condition for the boundary controllability of coupled parabolic systems. Bounds on biorthogonal families to complex matrix exponentials

This paper is devoted to prove the controllability to trajectories of a system of n one-dimensional parabolic equations when the control is exerted on a part of the boundary by means of m controls. We give a general Kalman condition (necessary and sufficient) and also present a construction and sharp estimates of a biorthogonal family in L²(0,T;C) to {tje−Λkt}.     

Hierarchical Analysis of Self‐Assembled PEGylated Hexaphenylalanine Photoluminescent Nanostructures

Despite the growing literature about diphenylalanine‐based peptide materials, it still remains a challenge to delineate the theoretical insight into peptide nanostructure formation and the structural features that could permit materials with enhanced properties to be engineered. Herein, we report the synthesis of a novel peptide building block composed of six phenylalanine residues and eight PEG units, PEG₈‐F6. This aromatic peptide self‐assembles in water in stable and well‐ordered nanostructures with optoelectronic properties. A variety of techniques, such as fluorescence, FTIR, CD, DLS, SEM, SAXS, and WAXS allowed us to correlate the photoluminescence properties of the self‐assembled nanostructures with the structural organization of the peptide building block at the micro‐ and nanoscale. Finally, a model of hexaphenylalanine in aqueous solution by molecular dynamics simulations is presented to suggest structural and energetic factors controlling the formation of nanostructures.     

Weighted Shift Operators Which are m-Isometries

We give a characterization of m-isometric operators on a separable Hilbert space. Moreover, we characterize the unilateral weighted shift operators which are m-isometries.     

Overexpression in Catharanthus roseus hairy roots of a truncated hamster 3-hydroxy-3-methylglutaryl-CoA reductase gene

Catharanthus roseus (L.) G. Don hairy roots harboring hamster 3-hydroxy-3-methylglutaryl-CoA reductase (HMGR) (EC 1.1.1.88) cDNA without membrane-binding domain were evaluated by quantifying the levels of sterols and some indol-alkaloids. Clone 236, with the highest hybridization signal, had the lowest soluble and microsomal HMGR activity and produced more ajmalicine and catharanthine than the control but had reduced campesterol concentration. Clone 19, with low hybridization signal, had high soluble HMGR activity and produced high levels of campesterol and five to seven times more serpentine than the control but a low level of ajmalicine and no accumulation of catharanthine. These results suggest a possible role for HMGR in indole alkaloid biosynthesis and a possible cosuppression of both the endogenous and foreign HMGR genes in clone 236.     

Selective and shape-selective Baeyer-Villiger oxidations of aromatic aldehydes and cyclic ketones with Sn-beta zeolites and H2O2

Sn-Beta is used as a heterogeneous catalyst for the Baeyer-Villiger reaction with hydrogen peroxide. Cyclic ketones are transformed into the corresponding lactones, while unsaturated ketones are oxidized to the corresponding unsaturated lactones with very high chemoselectivity. The catalyst is also selective for the oxidation of aromatic aldehydes with H2O2, producing the formate ester or the corresponding hydrolyzed product, that is the alcohol. Shape-selective oxidations are observed for isomeric reactants with different molecular shapes. The catalytic Sn sites have been characterized by 119Sn MAS-NMR spectroscopy, and tetrahedral incorporation into the zeolite framework has been demonstrated. In situ IR spectroscopy and 18O labeling experiments have shown that the oxidation mechanism involves an intermediate of the Criegee type.     

Asymmetric 1,3-dipolar cycloaddition of N-metalated azomethine ylides to methyl (S)-2-(p-tolylsulfinyl)acrylate. Synthesis of optically pure 2,4,5-trisubstituted 2,5-dihydro-1H-pyrroles

The first 1,3-dipolar reaction of azomethine ylides with optically pure vinyl sulfoxide are reported. The presence of the sulfinyl group increase the reactivity of the acrylate moiety as a dipolarophile, and the reactions evolve with complete regio- and endo-selectivities. Nevertheless, mixtures of the two diastereoisomers 4 and 5 (75-88% de) resulting from the anti dipole/s-cis dipolarophile and syn dipole/s-trans dipolarophile approaches, respectively, are obtained. The stereoselectivity can be controlled by using THF or MeCN as solvents or by changing the reaction temperature in MeCN. After separation of the cycloadducts, optically pure 2,5-dihydro-1H-pyrroles are easily obtained by pyrolytic desulfinylation.     

General approach for the stereocontrolled construction of the beta-lactam ring in amino acid-derived 4-alkyl-4-carboxy-2-azetidinones

The first general approach toward the asymmetric synthesis of 4-alkyl-4-carboxy-2-azetidinones derived from amino acids is described. The stereoselective construction of the beta-lactam ring was achieved through base-mediated intramolecular cyclization of the corresponding N(alpha)-chloroacetyl derivatives bearing (+)- or (-)-10-(N,N-dicyclohexylsulfamoyl)isoborneol as chiral auxiliary (ee up to 82%).