Optoelectronic,Aggregation, and Redox Properties of Double-Rotor Boron Difluoride Hydrazone Dyes

We develop the chemistry of boron difluoride hydrazone dyes (BODIHYs) bearing two aryl substituents and explore their properties. The low-energy absorption bands (λ_max=427–464 nm) of these dyes depend on the nature of the N-aryl groups appended to the BODIHY framework. Electron-donating and extended π-conjugated groups cause a redshift, whereas electron-withdrawing groups result in a blueshift. The title compounds were weakly photoluminescent in solution and strongly photoluminescent as thin films (λ_PL=525–578 nm) with quantum yields of up to 18 % and lifetimes of 1.1–1.7 ns, consistent with the dominant radiative decay through fluorescence. Addition of water to THF solutions of the BODIHYs studied causes molecular aggregation which restricts intramolecular motion and thereby enhances photoluminescence. The observed photoluminescence of BODIHY thin films is likely facilitated by a similar molecular packing effect. Finally, cyclic voltammetry studies confirmed that BODIHY derivatives bearing para-substituted N-aryl groups could be reversibly oxidized (E_ox1=0.62–1.02 V vs. Fc/Fc⁺) to their radical cation forms. Chemical oxidation studies confirmed that para-substituents at the N-aryl groups are required to circumvent radical decomposition pathways. Our findings provide new opportunities and guiding principles for the design of sought-after multifunctional boron difluoride complexes that are photoluminescent in the solid state.     

Integro-differential equations of hyperbolic type with positive definite kernels

The main purpose of this work is to study the damping effect of memory terms associated with singular convolution kernels on the asymptotic behavior of the solutions of second order evolution equations in Hilbert spaces. For kernels that decay exponentially at infinity and possess strongly positive definite primitives, the exponential stability of weak solutions is obtained in the energy norm. It is also shown that this theory applies to several examples of kernels with possibly variable sign, and to a problem in nonlinear viscoelasticity.     

Fluorescent Flavin/PVP-Coated Silver Nanoparticles: Design and Biological Performance

A red-emitting fluorescent Riboflavin (RF)/Polyvinylpyrrolidone (PVP)-coated silver nanoparticles system, λ_em?=?527 nm, Φ?=?0.242, with a diameter of the metallic core of 27.33 nm and a zeta potential of ? 25.05 mV was prepared and investigated regarding its biological activity. We found that PVP has a key role in RF adsorption around the SNPs surface leading to an enhancement of antioxidant properties (～70%), low cytotoxicity (> 90% cell viability, at 50 µL/mL, after 48 h of incubation) as well as to an efficient process of its cellular uptake (～ 60%, after 24 h of incubation) in L929 cells. The results are relevant concerning the involvement of RF and its coenzymes forms in SNPs - based systems, in cellular respiration as well as for future studies as antioxidant marker system on tumoral cells for viewing and monitoring them, by cellular imaging.

     

Antiproliferative activity, antioxidant capacity and tannin content in plants of semi-arid northeastern Brazil

The objective of this study was to evaluate antiproliferative activity, antioxidant capacity and tannin content in plants from semi-arid northeastern Brazil (Caatinga). For this study, we selected 14 species and we assayed the methanol extracts for antiproliferative activity against the HEp-2 (laryngeal cancer) and NCI-H292 (lung cancer) cell lines using the (3-[4,5-dimethylthiazol-2-yl]-2,5-diphenyltetrazole) (MTT) method. In addition, the antioxidant activity was evaluated with the DPPH (2,2-diphenyl-2-picrylhydrazyl) assay, and the tannin content was determined by the radial diffusion method. Plants with better antioxidant activity (expressed in a dose able to decrease the initial DPPH concentration by 50%, or IC50) and with higher levels of tannins were: Poincianella pyramidalis (42.95±1.77 μg/mL IC50 and 8.17±0.64 tannin content), Jatropha mollissima (54.09±4.36μg/mL IC50 and 2.35±0.08 tannin content) and Anadenanthera colubrina (73.24±1.47 μg/mL IC50 and 4.41±0.47 tannin content). Plants with enhanced antiproliferative activity (% living cells) were Annona muricata (24.94±0.74 in NCI-H292), Lantana camara (25.8±0.19 in NCI-H292), Handroanthus impetiginosus (41.8±0.47 in NCI-H292) and Mentzelia aspera (45.61±1.94 in HEp-2). For species with better antioxidant and antiproliferative activities, we suggest future in vitro and in vivo comparative studies with other pharmacological models, and to start a process of purification and identification of the possible molecule(s) responsible for the observed pharmacological activity. We believe that the flora of Brazilian semi-arid areas can be a valuable source of plants rich in tannins, cytotoxic compounds and antioxidant agents.     

Source apportionment of groundwater pollutants in Apulian agricultural sites using multivariate statistical analyses: case study of Foggia province

Background

Ground waters are an important resource of water supply for human health and activities. Groundwater uses and applications are often related to its composition, which is increasingly influenced by human activities.In fact the water quality of groundwater is affected by many factors including precipitation, surface runoff, groundwater flow, and the characteristics of the catchment area. During the years 2004-2007 the Agricultural and Food Authority of Apulia Region has implemented the project “Expansion of regional agro-meteorological network” in order to assess, monitor and manage of regional groundwater quality. The total wells monitored during this activity amounted to 473, and the water samples analyzed were 1021. This resulted in a huge and complex data matrix comprised of a large number of physical-chemical parameters, which are often difficult to interpret and draw meaningful conclusions. The application of different multivariate statistical techniques such as Cluster Analysis (CA), Principal Component Analysis (PCA), Absolute Principal Component Scores (APCS) for interpretation of the complex databases offers a better understanding of water quality in the study region.

Results

Form results obtained by Principal Component and Cluster Analysis applied to data set of Foggia province it’s evident that some sampling sites investigated show dissimilarities, mostly due to the location of the site, the land use and management techniques and groundwater overuse. By APCS method it’s been possible to identify three pollutant sources: Agricultural pollution 1 due to fertilizer applications, Agricultural pollution 2 due to microelements for agriculture and groundwater overuse and a third source that can be identified as soil run off and rock tracer mining.

Conclusions

Multivariate statistical methods represent a valid tool to understand complex nature of groundwater quality issues, determine priorities in the use of ground waters as irrigation water and suggest interactions between land use and irrigation water quality.

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Shape-persistent linear, kinked, and cyclic oligo(phenylene-ethynylene-butadiynylene)s: self-assembled monolayers

Shape-persistent rigid phenylene-ethynylene-butadiynylenes form lamellar self-assembled monolayers (SAMs) at the HOPG/TCB interface, which were studied by scanning tunneling microscopy (STM) with submolecular resolution. Substitution of the terminating acetylene functions with polar cyanopropyldimethylsilyl groups leads to 2D phase separation and defined rod-rod interactions, which determine the packing distances between the rigid rods. The results stimulated the connection of rigid rods via septiarylene clamp units. They covalently link two rigid rod units and define the intramolecular rod-rod distance that matches the alkoxy substituent chain lengths. The systems can be described as half-ring structures of two rigid rods connected via a rotatable joint unit. These acetylene-terminated half-ring structures were also oligomerized under Cu and Pd catalysis to yield defined acyclic and cyclic oligomers. Detailed STM studies decoded the molecular origin of the surface patterning of such systems. The dodecyloxy side chains are adsorbed along the HOPG main axes and, together with the alkoxy backbone angle, determine the adsorption direction of the adlayers.     

Crystallographic recognition controls peptide binding for bio-based nanomaterials

The ability to control the size, shape, composition, and activity of nanomaterials presents a formidable challenge. Peptide approaches represent new avenues to achieve such control at the synthetic level; however, the critical interactions at the bio/nano interface that direct such precision remain poorly understood. Here we present evidence to suggest that materials-directing peptides bind at specific time points during Pd nanoparticle (NP) growth, dictated by material crystallinity. As such surfaces are presented, rapid peptide binding occurs, resulting in the stabilization and size control of single-crystal NPs. Such specificity suggests that peptides could be engineered to direct the structure of nanomaterials at the atomic level, thus enhancing their activity.     

Free-flow isoelectric focusing of proteins remaining in cell fragments following sonication of thyroid carcinoma cells

The method of preparing protein mixtures for electrophoretic analysis of membrane-associated cell proteins was improved. By sonication, about one-half of the proteins of thyroid cells were released into the supernatant, while the other half preferentially comprising membrane proteins still remained in cell fragments, which could be sedimented by centrifugation. After sonication, even those proteins which remained in cell fragments, could completely be dissolved by free-flow isoelectric focusing media. They migrated through the free-flow electrophoresis chamber without forming precipitates. Because of these improvements, it was possible to show that the two thyroid cancer cell lines ML-1 and ONCO-DG1 express cytokeratin 8 at similar rates, but cytokeratins 7 and 18 differently. In addition, the presence of inorganic pyrophosphatase, tubulin-beta-5, and tubulin-beta-1 chains in human thyroid cells was proved for the first time.     

Development of new and robust LC-MS method for simultaneous quantification of polyphenols from Sambucus ebulus fruits

A new and simple LC-MS method for analysis of flavonoids from Sambucus ebulus berry extracts was developed and validated. Successfully were quantitated seven polyphenols: epicatechin, epigallocatechin gallate, rutin, resveratrol, myricetin, quercetin, and kaempferol.

Two detectors, working in parallel, were used: photodiode-array and single quadrupole mass-detector. The mass detection was used for identification and quantification of the analytes, while the diode-array detector was as confirmation tool. The following m/z were tracked: 457.15 (epigallocatechin gallate); 289.06 (epicatechin); 609.13 (rutin); 227.05 (resveratrol); 317.0 (myricetin); 301.02 (quercetin); 285.02 (kaempferol). For optimization the chromatographic separation three wavelengths 205?nm, 305?nm, 272?nm were monitored. The method was capable to detect in one run compounds with no UV or fluorescence chromophore and with very similar structures, such as plant polyphenols. The linearity was from 0.05?mg/L to 50?mg/L (R² 0.9962–0.9987). The recoveries for all tested analytes were between 81.6% and 104.7%.

The method was applied for analysis of crude extract of Sambucus ebulus ripe fruits. Three major polyphenols – epicatechin (0.84?mg/100gFW), quercetin (0.15?mg/100gFW) and kaempferol (0.05?mg/100gFW) were identified and quantified.

The proposed method could be successfully used for routine analysis of epigallocatechin gallate, epicatechin, rutin, resveratrol, myricetin, quercetin, and kaempferol in Sambucus ebulus extracts.     

Elemental labelling combined with liquid chromatography inductively coupled plasma mass spectrometry for quantification of biomolecules: A review

This article reviews novel quantification concepts where elemental labelling is combined with flow injection inductively coupled plasma mass spectrometry (FI-ICP-MS) or liquid chromatography inductively coupled plasma mass spectrometry (LC–ICP-MS), and employed for quantification of biomolecules such as proteins, peptides and related molecules in challenging sample matrices. In the first sections an overview on general aspects of biomolecule quantification, as well as of labelling will be presented emphasizing the potential, which lies in such methodological approaches. In this context, ICP-MS as detector provides high sensitivity, selectivity and robustness in biological samples and offers the capability for multiplexing and isotope dilution mass spectrometry (IDMS). Fundamental methodology of elemental labelling will be highlighted and analytical, as well as biomedical applications will be presented. A special focus will lie on established applications underlining benefits and bottlenecks of such approaches for the implementation in real life analysis. Key research made in this field will be summarized and a perspective for future developments including sophisticated and innovative applications will given.