Heart Failure and PAHs,OHPAHs, and Trace Elements Levels in Human Serum: Results from a Preliminary Pilot Study in Greek Population and the Possible Impact of Air Pollution

Cardiovascular diseases (CVDs) have been associated with environmental pollutants. The scope of this study is to assess any potential relation of polycyclic aromatic hydrocarbons (PAHs), their hydroxylated derivatives, and trace elements with heart failure via their direct determination in human serum of Greek citizens residing in different areas. Therefore, we analyzed 131 samples including cases (heart failure patients) and controls (healthy donors), and the respective demographic data were collected. Significantly higher concentrations (p < 0.05) were observed in cases’ serum regarding most of the examined PAHs and their derivatives with phenanthrene, fluorene, and fluoranthene being the most abundant (median of >50 μg L⁻¹). Among the examined trace elements, As, Cd, Cu, Hg, Ni, and Pb were measured at statistically higher concentrations (p < 0.05) in cases’ samples, with only Cr being significantly higher in controls. The potential impact of environmental factors such as smoking and area of residence has been evaluated. Specific PAHs and trace elements could be possibly related with heart failure development. Atmospheric degradation and smoking habit appeared to have a significant impact on the analytes’ serum concentrations. PCA–logistic regression analysis could possibly reveal common mechanisms among the analytes enhancing the hypothesis that they may pose a significant risk for CVD development.     

H/D Exchange Processes in Flavonoids: Kinetics and Mechanistic Investigations

Several classes of flavonoids, such as anthocyanins, flavonols, flavanols, and flavones, undergo a slow H/D exchange on aromatic ring A, leading to full deuteration at positions C(6) and C(8). Within the flavanol class, H-C(6) and H-C(8) of catechin and epicatechin are slowly exchanged in D₂O to the corresponding deuterated analogues. Even quercetin, a relevant flavonol representative, shows the same behaviour in a D₂O/DMSOd₆ 1:1 solution. Detailed kinetic measurements of these H/D exchange processes are here reported by exploiting the time-dependent changes of their peak areas in the ¹H-NMR spectra taken at different temperatures. A unifying reaction mechanism is also proposed based on our detailed kinetic observations, even taking into account pH and solvent effects. Molecular modelling and QM calculations were also carried out to shed more light on several molecular details of the proposed mechanism.     

A New Approach for the Photosynthetic Antenna–Reaction Center Complex with a Model Organized Around an s‐Triazine Linker

Two new artificial mimics of the photosynthetic antenna‐reaction center complex have been designed and synthesized (BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀). The resulting electron‐donor/acceptor conjugates contain a porphyrin (either in its free‐base form (H₂P) or as Zn‐metalated complex (ZnP)), a boron dipyrrin (BDP), and a fulleropyrrolidine possessing, as substituent of the pyrrolidine nitrogen, an ethylene glycol chain terminating in an amino group C₆₀‐X‐NH₂ (X=spacer). In both cases, the three different components were connected by s‐triazine through stepwise substitution reactions of cyanuric chloride. In addition to the facile synthesis, the star‐type arrangement of the three photo‐ and redox‐active components around the central s‐triazine unit permits direct interaction between one another, in contrast to reported examples in which the three components are arranged in a linear fashion. The energy‐ and electron‐transfer properties of the resulting electron‐donor/acceptor conjugates were investigated by using UV/Vis absorption and emission spectroscopy, cyclic voltammetry, and femtosecond transient absorption spectroscopy. Comparison of the absorption spectra and cyclic voltammograms of BDP‐H₂P‐C₆₀ and BDP‐ZnP‐C₆₀ with those of BDP‐H₂P, BDP‐ZnP and BDP‐C₆₀, which were used as references, showed that the spectroscopic and electrochemical properties of the individual constituents are basically retained, although some appreciable shifts in terms of absorption indicate some interactions in the ground state. Fluorescence lifetime measurements and transient absorption experiments helped to elucidate the antenna function of BDP, which upon selective excitation undergoes a rapid and efficient energy transfer from BDP to H₂P or ZnP. This is then followed by an electron transfer to C₆₀, yielding the formation of the singlet charge‐separated states, namely BDP‐H₂P ^.+‐ C₆₀ ^.? and BDP‐ZnP ^.+‐ C₆₀ ^{. ?}. As such, the sequence of energy transfer and electron transfer in the present models mimics the events of natural photosynthesis.     

Cloning and Characterization of a Biotic-Stress-Inducible Glutathione Transferase from Phaseolus vulgaris

Glutathione transferases (GSTs, EC 2.5.1.18) are ubiquitous proteins in plants that play important roles in stress tolerance and in the detoxification of toxic chemicals and metabolites. In this study, we systematically examined the catalytic diversification of a GST isoenzyme from Phaseolus vulgaris (PvGST) which is induced under biotic stress treatment (Uromyces appendiculatus infection). The full-length cDNA of this GST isoenzyme (termed PvGSTU3-3) with complete open reading frame, was isolated using RACE-RT and showed that the deduced amino acid sequence shares high homology with the tau class plant GSTs. PvGSTU3-3 catalyzes several different reactions and exhibits wide substrate specificity. Of particular importance is the finding that the enzyme shows high antioxidant catalytic function and acts as hydroperoxidase, thioltransferase, and dehydroascorbate reductase. In addition, its K _m for GSH is about five to ten times lower compared to other plant GSTs, suggesting that PvGSTU3-3 is able to perform efficient catalysis under conditions where the concentration of reduced glutathione is low (e.g., oxidative stress). Its ability to conjugate GSH with isothiocyanates may provide an additional role for this enzyme to act as a regulator of the released isothiocyanates from glucosinolates as a response of biotic stress. Molecular modeling showed that PvGSTU3-3 shares the same overall fold and structural organization with other plant cytosolic GSTs, with major differences at their hydrophobic binding sites (H-sites) and some differences at the level of C-terminal domain and the linker between the C- and N-terminal domains. PvGSTU3-3, in general, exhibits restricted ability to bind xenobiotics in a nonsubstrate manner, suggesting that the biological role of PvGSTU3-3, is restricted mainly to the catalytic function. Our findings highlight the functional and catalytic diversity of plant GSTs and demonstrate their pivotal role for addressing biotic stresses in Phaseolus vulgaris.     

Enhancement of the Anti-Inflammatory Activity of NSAIDs by Their Conjugation with 3,4,5-Trimethoxybenzyl Alcohol

The synthesis of derivatives of three nonspecific COX-1 and COX-2 inhibitors, ibuprofen, ketoprofen, naproxen is presented. These acids were connected via an amide bond with an amino acid (L-proline, L-tyrosine, and beta-alanine) used as a linker. The amino acid carboxylic group was esterified with 3,4,5 trimethoxybenzyl alcohol. The activity of the novel derivatives was examined in vivo on carrageenan-induced inflammation, and in vitro, as cyclooxygenase and lipoxygenase inhibitors. It was found that the new compounds were more potent anti-inflammatory agents than the parent drugs. Thus, the ibuprofen (21) and ketoprofen (16) derivatives reduced rat paw edema by 67 and 91% (the reduction by the relevant NSAIDs was 36 and 47%, respectively). They inhibited COX-2 more than the starting drugs (21 by 67%, ibuprofen 46%, 19 by 94%, ketoprofen 49%). Docking of compounds on the active sites of COX-1 and COX-2 reflects their in vitro activity. Thus, 19 adopts an unfavorable orientation for COX-1 inhibition, but it binds effectively in the binding pocket of COX-2, in agreement with the absence of activity for COX-1 and the high inhibition of COX-2. In conclusion, the performed structural modifications result in the enhancement of the anti-inflammatory activity, compared with the parent NSAIDs.     

Enhanced network selections in a cognitive wireless B3G world

A network operator of the wireless beyond the third generation (B3G) era will need to be directing terminals to the most appropriate radio networks of its heterogeneous infrastructure. This requires advanced terminal management functionality for conducting optimal network selections, in a seamless to the user manner. This paper enhances network selection schemes by developing functionality for learning the quality of service (QoS) capabilities of candidate networks and by exploiting the acquired knowledge in the network selection. The resulting scheme selects networks that offer the best QoS, taking into account the user needs, policies, the context of operation, and the knowledge. The advantage is that the reliability of the knowledge-based decisions is increased. This enhances the probability of offering the desired QoS to the user and reduces some of the related operational overheads in the network. The learning functionality is influenced by Bayesian networks. The computational effort for the development of the knowledge is shown to be minimal. Results show the behavior of the scheme in terms of knowledge development, respective computational effort required, and network selections made. In general, the paper contributes to the introduction of cognitive systems in the wireless B3G world.     

MIMO Channel Characterization for Short Range Fixed Wireless Propagation Environments

This paper reports results from wideband MIMO measurements performed in short range fixed wireless environments at 5.2 GHz. The objective is to provide MIMO channel characterization results for the measured environments and contribute to the limited available similar studies. Two kinds of propagation scenarios are investigated, rooftop to rooftop and street to rooftop, at three different sites always under LOS propagation conditions. The analysis of measurement data is performed in the context of non physical modeling, providing insight into the statistics of the measured channels. In particular, the slow time varying nature of the channel is studied and the narrow Doppler spectrum shape is approximated. Furthermore, frequency correlation results are obtained and the typical delay dispersion measures are extracted. Then, the antenna correlation is studied and the error of the Kronecker product approximation is evaluated. Finally, capacity results are provided and the channel measurements are characterized in terms of spatial multiplexing quality and multipath richness through condition number analysis. Nikolaos D. Skentos received his Diploma in Electrical and Computer Engineering from the National Technical University of Athens (NTUA), Greece in October 2000. Since January 2001 he has been a research associate at the Mobile Radio Communications Laboratory at the NTUA, and he is currently working towards the Ph.D. degree. His research interests include channel measurements, MIMO channel characterization, MIMO algorithms and space time processing. He has been active in the IST STINGRAY project, the COST 273 Action and the ACE Network of Excellence. He is also a member of the National Technical Chamber of Greece since 2001. Athanasios G. Kanatas received the Diploma in Electrical Engineering from the National Technical University of Athens, Greece, in 1991, the M.Sc. degree in Satellite Communication Engineering from the University of Surrey, Surrey, UK in 1992, and the Ph.D. degree in Mobile Satellite Communications from the National Technical University of Athens, Greece in February 1997. From 1993 to 1994 he was with National Documentation Center of National Research Institute. In 1995 he joined SPACETEC Ltd. where he was Technical Project Manager for VISA/EMEA VSAT Project in Greece. In 1996 he joined the Mobile Radio Communications Laboratory as a research associate. From 1999 to 2002 he was with the Institute of Communication & Computer Systems. In 2000 he became a member of the Board of Directors of OTESAT S.A. He is an Assistant Professor in the Department of Technology Education and Digital Systems at University of Piraeus. His current research interests include channel characterization and estimation, simulation and modeling for mobile, mobile satellite, and future wireless communication systems. He has been a Senior Member of IEEE since 2002, and is also a member of the Technical Chamber of Greece. In 1999 he was elected Chairman of the Communications Society of the Greek IEEE Section. Panagiotis I. Dallas was born 1967 in Thessaloniki, Greece. He obtained his diploma and Ph.D. degree from the Electrical and Computer Engineering Department of Aristotle University of Thessaloniki, Greece, in 1990 and 1997, respectively. Since 1998 he joined with INTRACOM where he currently is Section Manager of Advanced Communications Technologies branch of Emerging Technologies & Markets department, leading the next generation of broadband wireless access systems for internal and EU projects. He runs the relevant standardization activities (IEEE 802.16 and ETSI/BRAN HIPERMAN) in INTRACOM and he represents the company in WiMAX forum. Finally, he has over 30 publications in international journals and conferences. Philip Constantinou received the Diploma in Physics from the National University of Athens in 1972, the Master of Applied Science in Electrical Engineering from the University of Ottawa, Ontario, Canada in 1976, and the Ph.D. degree in Electrical Engineering in 1983 from Carleton University, Ottawa, Ontario, Canada. From 1976 to 1979 he was with Telesat Canada as a Communications System Engineer. In 1980 he joined the Ministry of Communications in Ottawa, Canada where he was engaged in the area of Mobile Communication. From 1984 to 1989 he was with the National Research Center Demokritos in Athens, Greece where he was involved in several research projects in the area of Mobile Communications. In 1989 he joined the National Technical University of Athens where he is currently a Professor and Director of the Mobile Radio Communications Laboratory. His current research interests include Personal Communications, Mobile Satellite Communications, and Interference Problems on Digital Communications Systems.     

Modelling of discontinuities through dipole distribution

An indirect boundary element method using dipole distribution is employed in order to model discontinuities inside the flow region. The problem of flow under a dam is treated with a sheet-pile in its foundation. The discontinuity across the sheet-pile is demonstrated, a general boundary element procedure for a mixed problem is outlined and the coefficients of the linear system are given in analytical form. Very good agreement with existing analytical results is obtained.