Optical isomer separation of flavanones and flavanone glycosides by nano-liquid chromatography using a phenyl-carbamate-propyl-β-cyclodextrin chiral stationary phase

In this paper a phenyl-carbamate-propyl-β-cyclodextrin stationary phase was employed for the enantioseparation of several flavonoids, including flavanones and methoxyflavanones by using nano-liquid chromatography (nano-LC). The same stationary phase was also used for the diastereoisomeric separation of two flavanone glycosides. The compounds: flavanone, 2′-hydroxyflavanone, 4′-hydroxyflavanone, 6-hydroxyflavanone, 7-hydroxyflavanone, 4′-methoxyflavanone, 6-methoxyflavanone, 7-methoxyflavanone, hesperetin, hesperidin, naringenin and naringin were studied using reversed, polar organic and normal elution modes. The effect of the nature and composition of the mobile phase (organic modifier type, buffer and water content in the reversed phase mode) on the enantioresolution (R_s), retention factor (k) and enantioselectivity (α) were investigated. Baseline resolution of all studied flavonoids, with the exception of 2′-hydroxyflavanone and naringin, was achieved in reversed phase mode using a mixture of MeOH/H₂O at different ratios as mobile phase. Good results, in terms of peak efficiency and short analysis time, were obtained adding 1% triethylammonium acetate pH 4.5 buffer to MeOH/H₂O mixture. The separation of the studied compounds was also performed in polar organic mode. By using 100% of MeOH as mobile phase, the resolution was achieved for the studied analytes, except for 7-hydroxyflavanone, 2′-hydroxyflavanone, naringenin, hesperidin and naringin. Normal mode was tested employing a mixture of EtOH/hexane/TFA as mobile phase achieving the enantiomeric and diastereomeric separation of only hesperetin and hesperidin, respectively. The use of nano-LC technique for the resolution of flavanones optical isomers allowed to achieve good resolutions in shorter analysis time compared to the results reported in literature with conventional HPLC.     

Comparative analysis of the energy levels of planar and core-twisted perylene bisimides in solution and solid state by UV/VIS, CV, and UPS/IPES

The frontier orbital energies of four different functionalized perylene bisimide derivatives, PBI-Ph(iPr)₂, PBI-H₄, PBI-F₂ and PBI-Cl₄, were directly determined by UV-photo electron spectroscopy (UPS) and inverse photo electron spectroscopy (IPES) and are compared to the results from cyclic voltammetry (CV) and optical absorption spectroscopy (UV/VIS). The optical spectra reveal significant differences between monomeric species in solution and assembled molecules in the condensed state for the nearly planar PBI-H₄ and PBI-F₂, which are attributed to significant π–π stacking interactions in the condensed phase. In contrast, for PBIs with bulky substituents or twisted core, i.e. 2,6-isopropylphenyl substituents at the imide positions (PBI-Ph(iPr)₂) or four chlorine substituents at perylene bay positions (PBI-Cl₄), similar spectra are observed in solution and in the condensed state, which suggests the absence of strong intermolecular π–π stacking interactions. An entirely different result is obtained for the HOMO/LUMO energy values obtained from UPS/IPES and CV measurements which do not reveal a significant impact of intermolecular π–π stacking interactions. When comparing CV and UPS/IPES results, an accentuated deviation was observed for the perylene bisimide derivatives as compared to correlations found in the literature.     

Hybrid FBG–LPG sensor for surrounding refractive index and temperature simultaneous discrimination

In this work, we propose a configuration of a hybrid fiber Bragg grating together with a long period grating sensor used for simultaneously detect surrounding refractive index and temperature to be applied in aqueous environment and to reveal pollution. We present the simulation of such sensor and analyze the reflected wavelength and amplitude variations of the fiber Bragg grating spectrum to obtain the temperature and the external refractive index variations, respectively. The results show that the fiber Bragg grating reflected amplitude change depends on the variation of the long period grating transmission spectrum with the surrounding refractive index modification and the reflected wavelength shift depends on the temperature of the aqueous solution.     

Catalysis of diribonucleoside monophosphate cleavage by water soluble copper(II) complexes of calix[4]arene based nitrogen ligands

Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N(3) ligating units were synthesized, and their bi- and trimetallic zinc(II) and copper(II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu(2) act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu(2), which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu(3). Rate accelerations relative to the background brought about by 6-Cu(2) and 8-Cu(3) (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.     

The proteome of lentil (Lens culinaris Medik.) seeds: Discriminating between landraces

Lentil (Lens culinaris Medik.) is one of the most ancient crops of the Mediterranean region used for human nutrition; an extensive differentiation of L. culinaris over millennia has resulted in a number of different landraces. As a consequence of environmental and socio‐economic issues, the disappearance of many of them occurred in more recent times. To investigate the potential of proteomics as a tool in phylogenetic studies, testing the possibility to identify specific markers of different plant landraces, 2‐D gel electrophoretic maps of mature seeds were obtained from seven lentil populations belonging to a local ecotype (Capracotta) and five commercial varieties (Turca Rossa, Canadese, Castelluccio di Norcia, Rascino and Colfiorito). 2‐DE analysis resolved hundreds of protein species in each lentil sample, among which only 122 were further identified by MALDI‐TOF PMF and/or nanoLC‐ESI‐LIT‐MS/MS, probably as a result of the poor information available on L. culinaris genome. A comparison of these maps revealed that 103 protein spots were differentially expressed within and between populations. The multivariate statistical analyses carried out on these variably expressed spots showed that 24 protein species were essential for population discrimination, thus determining their proposition as landrace markers. Besides providing the first reference map of mature lentil seeds, our data confirm previous studies based on morphological/genetic observations and further support the valuable use of proteomic techniques as phylogenetic tool in plant studies.     

Localization of proteins in paint cross-sections by scanning electrochemical microscopy as an alternative immunochemical detection technique

The qualitative identification of proteinaceous substances, as well as their location within a complex paint stratigraphy, is one of the most challenging issues in the characterization of painting materials. Nevertheless, information on paint components represent a crucial task for studies concerning both the ancient painting techniques adopted and the state of conservation, being fundamental investigations for the selection of appropriate conservation actions. The present research was aimed at developing a new detection approach for the immunochemical localization of ovalbumin in paint cross-sections based on the use of scanning electrochemical microscopy (SECM). The immunochemical analyses were performed using an anti-ovalbumin primary antibody and a secondary antibody labelled with horseradish peroxidase (HRP). SECM measurements were performed in feedback mode using benzoquinone (BQ)/hydroquinone (H₂Q) redox couple. In presence of hydrogen peroxide (H₂O₂), HRP catalyzes the re-oxidation of H₂Q to BQ and the increment of BQ concentration in correspondence of the target protein was detected by SECM through the electrochemical reduction of the regenerated BQ at the microelectrode. Indeed, the localization of ovalbumin was possible thanks to a clear discrimination of SECM currents, achieved by the comparison of the measurements recorded before and after H₂O₂ administration, based on the HRP on/off approach. The method was evaluated both on samples from standard mocks-up and on a historical sample, collected from a Renaissance wood painting. The obtained results were promising, foreseeing a wider application of SECM on cultural heritage researches.     

Solvent-dependent release of bromine from bromoquercetins

Quercetin, 6-bromoquercetin (3), and 8-bromoquercetin (4) undergo H/D exchange at 6- and 8-positions, in acetone-d₆ and methanol-d₄, catalyzed by acids and bases. The base-catalyzed process is faster, and in acetone-d₆ the half-lives of H-8 and H-6 are 56.5 and 48.6 h, respectively. A high regioselectivity at the position 8 of quercetin is observed under acid-catalysis in both solvents but in methanol-d₄ regioselectivity is retained even under base-catalysis. On the other hand, 6,8-dibromoquercetin (2), 4 and 6,8-dibromo-2′-hydroxyquercetin (5) manifest the ability of exchanging bromine with hydrogen (or deuterium) under acid-catalysis in acetone and other enolizable ketones (e.g., methyl ethyl ketone, acetylacetone, and isophorone). These bromophenols release bromine from their 8-position only, in a slow bromination process that likely involves their protonated form (arenium ion I) as brominating agent and the enol of the above ketones as Br-acceptor. The arenium ion I of these bromophenols is expected to be a powerful electrophile and its formation is most likely to be rate-determining.     

Solution to An Isotopism Question Concerning Rank 2 Semifields

In [8] Dempwolff gives a construction of three classes of rank two semifields of order , with q and n odd, using Dembowski–Ostrom polynomials. The question whether these semifields are new, i.e. not isotopic to previous constructions, is left as an open problem. In this paper we solve this problem for , in particular we prove that two of these classes, labeled and , are new for , whereas presemifields in family are isotopic to Generalized Twisted Fields for each .     

Assembly of Gold Nanoparticles on Functionalized Si(100) Surfaces through Pseudorotaxane Formation

The assembly of gold nanoparticles (AuNPs) on a hydrogenated Si(100) surface, mediated by a series of hierarchical and reversible complexation processes, is reported. The proposed multi‐step sequence involves a redox‐active ditopic guest and suitable calix[n]arene‐based hosts, used as functional organic monolayers of the two inorganic components. Surface reactions and controlled release of AuNPs have been monitored by application of XPS, atomic force microscopy (AFM), field‐emission scanning electron microscopy (FESEM) and electrochemistry.     

Synthesis,Complexation and Photophysics in Protic Solvents of Lanthanide Complexes of Novel Calix[4]arene Polycarboxylic-2,2′-bipyridine Mixed Ligands

Two novel cone calix[4]arene ligands 11a and 11b bearing two iminodiacetic chelating units and two C 6 or C 5 substituted 2,2'-bipyridine chromophores in diametral position at the lower rim were synthesized. These ligands form complexes with lanthanide ions in methanol solution whose stability (4.5<log K ass <6.2) depends on the substitution pattern (C 6 or C 5 ) of the 2,2'-bipyridine units. Contrary to that observed with other neutral calixarene ligands, the luminescence properties of the Eu 3+ and Tb 3+ complexes are not very much affected by the type of the 2,2'-bipyridine chromophore. Luminescence lifetimes (0.31 ms< <1.1 ms) and quantum yields (0.017< { <0.130) are higher for Terbium compared with the corresponding Europium complexes.