Production and characterization of pure and Cr<Superscript>3+</Superscript>-doped hydroxyapatite for biomedical applications as fluorescent probes

Pure and Cr³⁺-doped hydroxyapatite (HAP) were prepared via chemical precipitation route. The XRD measurements revealed that the typical HAP powder pattern was obtained. SEM analysis indicated that aggregates of nanoparticles were formed. EDX analysis indicates that the [Ca]/[P] concentration ratio was higher than the expected values but can be explained by the presence of carbonate groups as dopants. The optical absorption spectra of the doped samples presented absorption bands typical of Cr³⁺ occupying to different crystalline sites. From the position of the bands, it was possible to estimate the crystal field parameters for both sites of Cr³⁺ in the HAP matrix. The emission spectra of the Cr-doped samples were also investigated and typical transitions of the dopant ion, in trivalent state, were identified. The potential use of the Cr³⁺-HAP as fluorescent probes for medical applications was discussed.     

Variability of solar UV-B irradiance: in situ monitoring and model calculation of the vitamin D synthetic capacity of sunlight

The prediction of the biological effects of solar radiation on human health, in particular involving terrestrial level of solar ultraviolet (UV) radiation, requires the development of an adequate methodological strategy for remote sensing. To date, it is well understood that, in appropriate doses, UV radiation is beneficial for people, specifically due to the production of vitamin D₃ in the skin from its precursor 7-dehydrocholesterol. But as far as excessive UV exposure causes acute and chronic health effects, in most cases biological activity of solar UV radiation is calculated by weighting solar UV spectra with International Commission on Illumination (CIE) erythemal action spectrum. Yet the beneficial vitamin D synthetic capacity of sunlight cannot be correctly estimated in this way because of the significant difference between the erythemic and vitamin D synthesis action spectra. With due regard to the essential role of vitamin D₃ for human health, in this article we examine the possibility of simplified estimation in situ of provitamin D₃ photoconversion into previtamin D₃ from the UV absorption spectra of an in vitro model of vitamin D synthesis upon exposure to sunlight. A large-scale linear correlation (R = 0.99) was found on a clear summer day between the concentration of accumulated previtamin D₃ and maximum absorbance decline in the initial provitamin D₃ absorption spectrum. However, long-term observations showed a poorer (R = 0.77) correlation, and a source of ambiguity of such indirect estimation of previtamin D₃ concentration is discussed in detail. In addition, we propose a reliable algorithm for the direct calculation of previtamin D₃ accumulation using solar UV spectra as input data to the reaction model of previtamin D photosynthesis and demonstrate the critical dependence of previtamin D₃ accumulation on stratospheric ozone, season, latitude and cloudiness. The comparison of experimental and simulation data conforms to recent findings on Europe's darker atmosphere in the UV-B and implicates the practical certainty of the presented algorithm for the calculation of the vitamin D synthetic capacity from the remotely sensed solar spectra.     

Relaxation Properties of Pressure-sensitive Adhesives upon Withdrawal of Bonding Pressure

Relaxation properties of pressure-sensitive adhesives (PSA) have been studied with the squeeze-recoil tester used in the regime of parallel-plate dilatometer under conditions imitating the removal of compressive force in the course of adhesive bond formation. The relaxation properties of PSAs are compared with their adhesive behavior measured using the 180-Deg Peel Test. Two classes of PSAs are considered: 1) conventional rubbery adhesives based on the mixtures of styrene-isoprene-styrene (SIS) block copolymer with a tackifier resin and a plasticizer, and butyl rubber plasticized with low-molecular-weight polyisobutylene, and 2) hydrophilic PSAs composed of the blends of high-molecular-weight poly(N-vinyl pyrrolidone) (PVP) with oligomeric polyethylene glycol (PEG). By comparing the adhesive and relaxation behaviors of different PSAs, the relaxation criteria for pressure-sensitive adhesion have been stated. Relaxation behavior of the examined PSAs demonstrates two values of retardation time: the shorter retardation time of 10–70?sec and the longer time of 300–660?sec. These times can be associated, respectively, with small- and large-scale mechanisms of strain recovery. By comparing the relaxation and adhesive properties of PVP-PEG blend (which involves the formation of a hydrogen-bonded network through both terminal hydroxyl groups in PEG short chains) with the properties of covalently crosslinked copolymers of vinyl pyrrolidone (VP) with PEG-diacrylate and comb-like VP copolymers with PEG-monomethacrylate, the contributions of covalent crosslinking and H-bonding network have been characterized.     

Defensive Compounds and Male-Produced Sex Pheromone of the Stink Bug, Agroecus griseus

Agroecus griseus is a serious corn pest in Brazil. Contents of the dorsal abdominal glands (DAGs) in nymphs, and the metathoracic gland (MTG) in adults of this species were characterized and quantified. Compounds found were similar to those of other Pentatomidae species and included aliphatic hydrocarbons, aldehydes, oxo-alkenals, and esters. However, two compounds were found in the MTG that have not been described previously for this family. Mass spectrometry, infrared spectroscopy, and gas chromatographic analysis using coinjection with authentic standards confirmed the identities of the compounds as enantiopure (S)-2-methylbutyl acetate and 3-methyl-2-butenyl acetate. The five nymphal instars showed significantly different ratios of components, mainly between those of the first and later instars. No significant differences were detected in MTG contents between sexes. Gas chromatography (GC) analysis of aeration extracts of males and females showed the presence of a compound released exclusively by males. Gas chromatography – electroantennographic detection (GC-EAD) assays indicated that the male-specific compound is bioactive in females, suggesting the presence of an attractant pheromone. The mass spectrum and infrared data for this compound matched with methyl 2,6,10-trimethyltridecanoate, a sex pheromone component previously detected in the stink bugs, Euschistus heros and E. obscurus. The synthetic standard coeluted with the natural pheromone on two different GC stationary phases, confirming the proposed structure. Y-tube olfactometer assays showed that the synthetic standard was strongly attractive to females, and GC-EAD tests produced responses with antennae from females similar to those of the natural pheromone.     

High-Performance Membrane Chromatography of Small Molecules

High-performance membrane chromatography (HPMC) proved to be a very efficient method for fast protein separations. Recently, it was shown to be applicable also for the isocratic chromatography of plasmid DNA conformations. However, no study about the separation of small molecules has been performed until now. In this work, we investigated the possibility of gradient and isocratic HPMC of small molecules with Convective Interaction Media disks of different chemistries and tried to explain the mechanism that enables their separation. We demonstrated that it is possible to achieve efficient separations of oligonucleotides and peptides in the ion-exchange mode as well as the separation of small hydrophobic molecules in the reversed-phase mode. It was shown that similar peak resolution can be provided in both gradient and isocratic modes.     

Mechanisms of molecular interactions in polybase–polyacid complex formed by copolymers of N,N‐dimethylaminoethylmethacrylate with alkylmethacrylates and methacrylic acid with ethylacrylate

Mechanisms of molecular interaction in the blends of a polybase, a copolymer of N,N‐dimethylaminoethylmethacrylate with methylmethacrylate and butylmethacrylate (PDMAEMA–MMA/BMA), with a polyacid, a copolymer of methacrylic acid with ethylacrylate (PMAA‐co‐EA), and plasticizer, triethylcitrate (TEC), have been investigated with FTIR Spectroscopy and potentiometry. To evaluate the strengths of hydrogen and ionic bonds in the polyelectrolyte complexes, quantum‐chemical calculations were performed. According to this analysis, the energy of ionic and hydrogen bonding diminishes in the order: multi‐component complexes involving protonated aminogroup of DMAEMA (ammonium cation) in the presence of chlorine counterion with ionized or unchanged carboxyl groups and water molecules (690–520 kJ/mol) > ternary H‐bonded acid‐base complexes associated with molecule of water (520–420 kJ/mol) > binary ionic complex of carboxylate anion and ammonium cation (404 kJ/mol) > H‐bonded complex of carboxylate and ammonium ions (257 kJ/mol) > binary H‐bonded complex of uncharged carboxyl group with ammonium cation (114 kJ/mol) > ternary H‐bonded complex of uncharged carboxyl group, aminogroup and water molecule (43 kJ/mol) > binary H‐bonded complex between nonionized carboxyl and amino groups (26 kJ/mol). Proton‐donating capability of functional groups in the studied polyelectrolyte blends diminishes in the order: HN⁺(CH₃)₂ ? > HOOC? > HO? . The proton‐donating capacity can be significantly improved in the presence of Cl^? ions, the effect of which may be appreciably inhibited if Na⁺ cations are available in the blend or solution. Proton‐accepting capability weakens in the order: uncharged aminogroup > carboxylate anion > uncharged carboxyl group > hydroxyl group. The results of quantum chemical calculations facilitate interpretation of FTIR spectra. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Non-visual interaction with graphs assisted with directional-predictive sounds and vibrations: a comparative study

Blind and visually impaired students need special educational and developmental tools to allow them to interact with graphic entities on PDA and desktop platforms. In previous research, stylus movements regarding the hidden graph were sonified with three directional-predictive sound (DPS) signals, taking into account an exploration behavior and the concept of the capture radius. The results indicated that the scanpaths were by 24–40% shorter in length and task completion times decreased by 20–25%. The goal of the study presented in this paper was to measure and compare the subjective performance recorded with directional-predictive vibrations (DPV) regarding the subjective performance achieved when the hidden graphic images were explored with DPS. The study also aimed to find out which kind of feedback cues would require less cognitive efforts in interpreting their meaning. The prototype of vibro-tactile pen with embedded vibration motor was used to produce DPV instead of sounds. The performance of eight blindfolded subjects was investigated in terms of the number of both feedbacks used and the time spent to complete non-visual inspection of the hidden graphs. There was a statistically significant difference between the average number of DPS and vibrations and task completion time taken by the players to discover the features of hidden graphs being explored with different capture radius. The experimental findings confirmed the beneficial use of DPS signals in the task when cross-modal coordination should benefit the user in the absence of visual information when compared with DPV patterns.     

A functional polymeric material based on hybrid electrochemically controlled junctions

A thin film polymeric junction was fabricated which yields a molecular electronic device functionally able to learn, i.e. to respond coherently to an external training signal. The fabricated structure is based upon electrochemical control of electronic current in a conducting polymer in contact with a solid electrolyte polymer. This functional behavior bears some resemblance to simple cases of biological learning processes. We report a comprehensive electronic characterization of the device function. Additional study was performed in order to estimate the possibility of the integration of such kinds of devices in statistical adaptive networks.     

Confinement effects on the kinetics of formation of sequential semi-interpenetrating polymer networks

Summary Peculiarities of formation kinetics of sequential semi-interpenetrating polymer networks based on crosslinked polyurethane with different cross-linking density and linear polystyrene and polybutylmethacrylate have been studied. Polyurethane networks were synthesized differing in molecular mass M_c of the chains between cross-links. Monomeric styrene and butyl methacrylate were introduced into these networks by swelling them in monomers up to equilibrium. The kinetics of polymerization of monomers in swollen networks was investigated. The experimental data show the dependence of the kinetic parameters of polymerization on M_c, this dependence being different for various monomers. Sharp discrepancy in molecular mass distribution of polymers formed in various matrices has been observed. The differences in dependencies of reaction kinetics and molecular mass distribution are supposed to be connected to various dependence of the chain growth and termination of various monomers on the density of network, i.e. on the confinements imposed by the intranetwork space.     

A camera-joystick for sound-augmented non-visual navigation and target acquisition: a case study

This paper presents the results of a comparative study of user input with a camera-joystick and a manual joystick used in a target acquisition task when neither targets nor pointer could be perceived visually. The camera-joystick is an input technique in which each on-screen item is accessible from the center with a predefined vector of head motion. Absolute pointing was implemented with an acceleration factor of 1.7 and a moving average on 5 detected head positions. The underlying assumption was that, in order to provide a robust input for blind users, the interaction technique has to be based on perceptually well-discriminated human movements, which compose a basic framework of an accessible virtual workspace demanding minimum external auxiliary cues. The target spots, having a diameter of 35 mm and a distance between the centers of adjacent spots of 60 mm, were arranged in a rectangular grid of 5 rows by 5 columns. The targets were captured from a distance of 600 mm. The results have shown that the camera input is a promising technique for non-visual human–computer interaction. The subjects demonstrated, more than twice, better performance in the target acquisition task with the camera-joystick versus the manual joystick. All the participants reported that the camera-joystick was a robust and preferable input technique when visual information was not available. Blind interaction techniques could be significantly further improved allowing a user-dependent activation of the navigational cues to better coordinate feedbacks with exploratory behavior.