Synthesis of β,γ-unsaturated primary amides from α,β-unsaturated acids and investigation of the mechanism

α,β-Unsaturated acids, through their acid chlorides, react with tritylamine in the presence of triethylamine under mild conditions, to afford in high yield and high regioselectivity the corresponding β,γ-unsaturated tritylamides. Detritylation with TFA generates quantitatively β,γ-unsaturated primary amides. An investigation of this deconjugative isomerization was performed.     

Application of an effective medium theory for modeling ultrasound wave propagation in healing long bones

Quantitative ultrasound has recently drawn significant interest in the monitoring of the bone healing process. Several research groups have studied ultrasound propagation in healing bones numerically, assuming callus to be a homogeneous and isotropic medium, thus neglecting the multiple scattering phenomena that occur due to the porous nature of callus. In this study, we model ultrasound wave propagation in healing long bones using an iterative effective medium approximation (IEMA), which has been shown to be significantly accurate for highly concentrated elastic mixtures. First, the effectiveness of IEMA in bone characterization is examined: (a) by comparing the theoretical phase velocities with experimental measurements in cancellous bone mimicking phantoms, and (b) by simulating wave propagation in complex healing bone geometries by using IEMA. The original material properties of cortical bone and callus were derived using serial scanning acoustic microscopy (SAM) images from previous animal studies. Guided wave analysis is performed for different healing stages and the results clearly indicate that IEMA predictions could provide supplementary information for bone assessment during the healing process. This methodology could potentially be applied in numerical studies dealing with wave propagation in composite media such as healing or osteoporotic bones in order to reduce the simulation time and simplify the study of complicated geometries with a significant porous nature.     

Adaptive station grouping: a highly efficient protocol for optical LANs

A new medium access control protocol for wavelength division multiplexing (WDM) Star Networks, which is capable of achieving a high performance under bursty traffic conditions, is introduced. According to the proposed protocol, the access of stations to the wavelengths is based on their grouping. A separate set of groups is maintained for each wavelength within the traffic stream. All the groups are granted permission to transmit on the corresponding wavelength in a round-robin fashion. The main objective of the grouping algorithm is to have in each group exactly one station which is ready to transmit on the corresponding wavelength, at any given time. In this way, idle slots and collisions are minimized and a nearly optimal throughput-delay performance is achieved. The grouping of stations is dynamically modified at each time slot according to the network feedback information. Due to the dynamic nature of the grouping algorithm, the protocol is capable of being adapted to the sharp changes of the stations’ traffic. Extensive simulation results are presented which indicate that the proposed protocol achieves a significantly superior performance than other well-known medium access control protocols for WDM Star Networks.     

Interaction of Cu(II) and Ni(II) with the 63-93 fragment of histone H2B

Chromatin proteins are believed to represent reactive sites for metal ion binding. We have synthesized the 31 amino acid peptide Ac-NSFVNDIFERIAGEASRLAHYNKRSTITSRE-NH2, corresponding to the 63-93 fragment of the histone H2B and studied its interaction with Cu(II) and Ni(II). Potentiometric and spectroscopic studies (UV-vis, CD, NMR and EPR) showed that histidine 21 acts as an anchoring binding site for the metal ion. Complexation of the studied peptide with Cu(II) starts at pH 4 with the formation of the monodentate species CuH2L. At physiological pH values, the 3N complex (N(Im), 2N(-)), CuL is favoured while at basic pH values the 4N (N(Im), 3N(-)) coordination mode is preferred. Ni(II) forms several complexes with the peptide starting from the distorted octahedral NiH2L at about neutral pH, to a square planar complex where the peptide is bound through a (N(Im), 3N(-)) mode in an equatorial plane at basic pH values. These results could be important in revealing more information about the mechanism of metal induced toxicity and carcinogenesis.     

1H NMR determination of hypericin and pseudohypericin in complex natural mixtures by the use of strongly deshielded OH groups

The ¹H NMR spectra of the commercially available compounds hypericin and its derivative pseudohypericin in CD₃OH solutions indicate significantly deshielded signals in the region of 14-15 ppm. These resonances are attributed to the peri hydroxyl protons OH(6), OH(8) and OH(1), OH(13) of hypericins which participate in a strong six-membered ring intramolecular hydrogen bond with CO(7) and CO(14), respectively, and therefore, they are strongly deshielded. In the present work, we demonstrate that one-dimensional ¹H NMR spectra of hypericin and pseudohypericin, in Hypericum perforatum extracts show important differences in the chemical shifts of the hydroxyl groups with excellent resolution in the region of 14-15 ppm. The facile identification and quantification of hypericin and its derivative compound pseudohypericin was achieved, without prior HPLC separation, for two H. perforatum extracts from Greek cultivars and two commercial extracts: a dietary supplement, and an antidepressant medicine. The results were compared with those obtained from UV-vis and LC/MS measurements.     

Lecithin organogels used as bioactive compounds carriers. A microdomain properties investigation

Organogels were obtained by adding small amounts of water to a solution of lecithin in organic solvents. Either isooctane or isopropyl palmitate and isopropyl myristate were used as the continuous organic phase of the gels. EPR spectroscopy using both DSA membrane-sensitive and lipophilic spin probes was applied to define the dynamic structure of the surfactant monolayer and the continuous oil phase of lecithin organogels. It was found that by increasing the water quantity, an increase of the polar head area per lecithin molecule was induced, and as a consequence the total interface expanded. It was found that the use of esters as organic solvents induced a decrease of the size of the dispersed structures. The interconnection of the aqueous microdomains and their dynamics were monitored by both static and time-resolved fluorescence quenching spectroscopy using Ru(bipy)32+ as fluorophore and Fe(CN)63- as quencher. It was found that the rates of inter- and/or intra-micellar exchange of water molecules were very slow because they appeared quite immobilized close to the lecithin polar heads. According to the results of the dynamic studies, appropriate organogels were formulated and used to incorporate model bioactive compounds with medicinal or cosmetic interest such as caffeine and theophylline. When these systems were tested for trans-membrane diffusion, they showed a 24 h permeation of 20% and 35%, respectively.     

A new method for the determination of free L-carnitine in serum samples based on high field single quantum coherence filtering 1H-NMR spectroscopy

The rapid and accurate determination of specific metabolites present in biofluids is a very demanding task which is essential in both medicine and chemistry. l-carnitine (3-hydroxy-4-N-trimethylammonium butyrate) is an important metabolite which participates in a series of biological paths and therefore its determination is of diagnostic importance. A single quantum coherence filtering ¹H NMR methodology was used for the accurate and rapid determination of l-carnitine in human serum samples. The methodology is based on spectral simplification, and specifically on the distinction of the N-methyl proton signal of l-carnitine that is greatly overlapped in the ¹H-NMR spectrum of serum. The quantitative results provided by the proposed method are in excellent agreement with those obtained by the enzymatic method, which is widely used. The proposed method is rapid (~20 min of experimental time), selective, sensitive, and has good analytical characteristics (accuracy, reproducibility). Selected protein precipitation methods were also investigated and sample pretreatment with EtOH is suggested.     

Adjoint wall functions: A new concept for use in aerodynamic shape optimization

The continuous adjoint method for the computation of sensitivity derivatives in aerodynamic optimization problems of steady incompressible flows, modeled through the k–ε turbulence model with wall functions, is presented. The proposed formulation leads to the adjoint equations along with their boundary conditions by introducing the adjoint to the friction velocity. Based on the latter, an adjoint law of the wall that bridges the gap between the solid wall and the first grid node off the wall is proposed and used during the solution of the system of adjoint (to both the mean flow and turbulence) equations. Any high Reynolds turbulence model, other than the k–ε one used in this paper, could also profit from the proposed adjoint wall function technique. In the examined duct flow problems, where the total pressure loss due to viscous effects is used as objective function, emphasis is laid on the accuracy of the computed sensitivity derivatives, rather than the optimization itself. The latter might rely on any descent method, once the objective function gradient has accurately been computed.     

Correlation between structural and electrical properties of heavily lithiated boron oxide solid electrolytes

Infrared and impedance measurements have been carried out on high lithium content boron oxide solid electrolytes xLi₂O–B₂O₃, with x = 3.0–4.5, in order to establish the correlation between their structural and electrical properties. The samples are two-phase materials, in which crystalline islands are scattered throughout the vitreous background phase. The evolution of structural and electrical properties with increasing x exhibits a marked differentiation around x = 4.0, which is associated with increasing crystallization in the material.     

Exponential lower bounds for finding Brouwer fix points

The computation of Brouwer fixed points is a central tool in economic modeling. Although there have been several algorithms for computing a fixed point of a Brouwer map, starting with Scarf's algorithm of 1965, the question of worst-case complexity was not addressed. It has been conjectured that Scarf's algorithm has typical behavior that is polynomial in the dimension. Here we show that any algorithm for computing the Brouwer fixed point of a function based on function evaluations (a class that includes all known general purpose algorithms) must in the worst case perform a number of function evaluations that is exponential in both the number of digits of accuracy and the dimension. Our lower bounds are very close to the known upper bounds.