Counter-ion effect on surfactant-DNA gel particles as controlled DNA delivery systems

The ability to entrap drugs within vehicles and subsequently release them has led to new treatments for a number of diseases. Based on an associative phase separation and interfacial diffusion approach, we developed a way to prepare DNA gel particles without adding any kind of cross-linker or organic solvent. Among the various agents studied, cationic surfactants offered particularly efficient control for encapsulation and DNA release from these DNA gel particles. The driving force for this strong association is the electrostatic interaction between the two components, as induced by the entropic increase due to the release of the respective counter-ions. However, little is known about the influence of the respective counter-ions on this surfactant-DNA interaction. Here we examined the effect of different counter-ions on the formation and properties of the DNA gel particles by mixing DNA (either single-(ssDNA) or double-stranded (dsDNA)) with the single chain surfactant dodecyltrimethylammonium (DTA). In particular, we used as counter-ions of this surfactant the hydrogen sulfate and trifluoromethane sulfonate anions and the two halides, chloride and bromide. Effects on the morphology of the particles obtained, the encapsulation of DNA and its release, as well as the haemocompatibility of these particles are presented, using counter-ion structure and DNA conformation as controlling parameters. Analysis of the data indicates that the degree of counter-ion dissociation from the surfactant micelles and the polar/hydrophobic character of the counter-ion are important parameters in the final properties of the particles. The stronger interaction with amphiphiles for ssDNA than for dsDNA suggests the important role of hydrophobic interactions in DNA.

Energy and system-size dependence of two- and four-particle nu(2) measurements in heavy-ion collisions at root S-NN=62.4 and 200 GeV and their implications on flow fluctuations and nonflow

We present STAR measurements of azimuthal anisotropy by means of the two- and four-particle cumulants nu(2) (nu(2){2} and nu(2){4}) for Au + Au and Cu + Cu collisions at center-of-mass energies root S-NN = 62.4 and 200 GeV. The difference between nu(2){2}(2) and nu(2){4}(2) is related to nu(2) fluctuations (sigma(nu 2)) and nonflow (delta(2)). We present an upper limit to sigma(nu 2)/nu 2. Following the assumption that eccentricity fluctuations sigma(epsilon) dominate nu(2) fluctuations nu(2)/sigma nu(2) approximate to epsilon/sigma epsilon we deduce the nonflow implied for several models of eccentricity fluctuations that would be required for consistency with nu(2){2} and nu(2){4}. We also present results on the ratio of nu(2) to eccentricity.

Microhardness of a dental restorative composite resin containing nanoparticles polymerized with argon ion laser

The objective of this study was to compare the microhardness of two resin composites (microhybrid and nanoparticles). Light activation was performed with argon ion laser 1.56J (L) and halogen light 2.6J (H) was used as control. Measurements were taken on the irradiated surfaces and those opposite them, at thicknesses of 1, 2 and 3 mm. To evaluate the quality of polymerization, the percentages of maximum hardness were calculated (PMH). For statistical analysis the ANOVA and Tukey tests were used (p <= 0.05). To microhybrid was shown that the hardness with laser was inferior to the hardness achieved with halogen light, for both the 1 mm and 2 mm. The nanoparticles polymerized with laser, presented lower hardness even on the irradiated surface, than the same surface light activated with halogen light. The microhybrid attained a minimum PMH of 80% up to the thickness of 2 mm with halogen light, and with laser, only up to 1 mm. The nanoparticles attained a minimum PMH of 80% up to 3 mm thickness with halogen light and with laser this minimum was not obtained at any thickness. Based on these results, it could be concluded that light activation with argon ion laser is contra-indicated for the studied nanoparticles. Published by Elsevier GmbH.

Mapping the hydrodynamic response to the initial geometry in heavy-ion collisions

We investigate how the initial geometry of a heavy-ion collision is transformed into final flow observables by solving event-by-event ideal hydrodynamics with realistic fluctuating initial conditions. We study quantitatively to what extent anisotropic flow (nu(n)) is determined by the initial eccentricity epsilon(n) for a set of realistic simulations, and we discuss which definition of epsilon(n) gives the best estimator of nu(n). We find that the common practice of using an r(2) weight in the definition of epsilon(n) in general results in a poorer predictor of nu(n) than when using r(n) weight, for n > 2. We similarly study the importance of additional properties of the initial state. For example, we show that in order to correctly predict nu(4) and nu(5) for noncentral collisions, one must take into account nonlinear terms proportional to epsilon(2)(2) and epsilon(2)epsilon(3), respectively. We find that it makes no difference whether one calculates the eccentricities over a range of rapidity or in a single slice at z = 0, nor is it important whether one uses an energy or entropy density weight. This knowledge will be important for making a more direct link between experimental observables and hydrodynamic initial conditions, the latter being poorly constrained at present.

Exploring the coordination chemistry of isomerizable terpyridine derivatives for successful analyses of cis and trans isomers by travelling wave ion mobility mass spectrometry

The photochemical cis-trans isomerization of the 4-{4-[2-(pyridin-4-yl)ethenyl]phenyl}-2,2': 6',2''-terpyridine ligand (vpytpy) was investigated by UV-vis, NMR and TWIM-MS. Ion mobility mass spectrometry was performed pursuing the quantification of the isomeric composition during photolysis, however an in-source trans-to-cis isomerization process was observed. In order to overcome this inherent phenomenon, the isomerization of the vpytpy species was suppressed by complexation, reacting with iron(II) ions, and forming the [Fe(vpytpy)(2)](2+) complex. The strategy of "freezing" the cis-trans isomerizable ligand at a given geometric conformation was effective, preventing further isomerization, thus allowing the distinction of each one of the isomers in the photolysed mixture. In addition, the experimental drift times were related to the calculated surface areas of the three possible cis-cis, cis-trans and trans-trans iron(II) complex isomers. The stabilization of the ligand in a given conformation also allows us to obtain the cis-cis and cis-trans complexes exhibiting the ligand in the metastable cis-conformation, as well as in the thermodynamically stable trans-conformation.

Ion-Conducting Membranes Based on Gelatin and Containing LiI/I-2 for Electrochromic Devices

Ionic conducting membranes of gelatin plasticized with glycerol and containing LiI/I-2 have been obtained and characterized by X-ray diffraction measurements, UV-Vis-NIR spectroscopy, thermal analysis and impedance spectroscopy. The transparent (80-90% in the visible range) membranes showed ionic conductivity value of 5 x 10(-5) S/cm at room temperature, which increased to 3 x 10(-3) S/cm at 80 degrees C. All the ionic conductivity measurements as a function of temperature showed VTF dependence and activation energy of 8 kJ/mol. These samples also showed low glass transition temperature of -76 degrees C. Moreover the samples were predominantly amorphous. The membranes applied to small electrochromic devices showed 20% of color change from colored to bleached states during more than 70 cronoamperometric cycles.

Low cost ion implantation technique

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is formed and injected energetically into a space held at high negative potential. The technique allows considerable savings both economically and technologically, rendering feasible ion implantation applications that might otherwise not be possible for many researchers and laboratories. Here, we describe the device and the results of tests demonstrating Nb implantation at 90 keV ion energy and dose about 2 x 10(16) cm(-2). (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4768699]

Protomers: formation, separation and characterization via travelling wave ion mobility mass spectrometry

Travelling wave ion mobility mass spectrometry (TWIM-MS) with post-TWIM and pre-TWIM collision-induced dissociation (CID) experiments were used to form, separate and characterize protomers sampled directly from solutions or generated in the gas phase via CID. When in solution equilibria, these species were transferred to the gas phase via electrospray ionization, and then separated by TWIM-MS. CID performed after TWIM separation (post-TWIM) allowed the characterization of both protomers via structurally diagnostic fragments. Protonated aniline (1) sampled from solution was found to be constituted of a ca. 5:1 mixture of two gaseous protomers, that is, the N-protonated (1a) and ring protonated (1b) molecules, respectively. When dissociated, 1a nearly exclusively loses NH3, whereas 1b displays a much diverse set of fragments. When formed via CID, varying populations of 1a and 1b were detected. Two co-existing protomers of two isomeric porphyrins were also separated and characterized via post-TWIM CID. A deprotonated porphyrin sampled from a basic methanolic solution was found to be constituted predominantly of the protomer arising from deprotonation at the carboxyl group, which dissociates promptly by CO2 loss, but a CID-resistant protomer arising from deprotonation at a porphyrinic ring NH was also detected and characterized. The doubly deprotonated porphyrin was found to be constituted predominantly of a single protomer arising from deprotonation of two carboxyl groups. Copyright (C) 2012 John Wiley & Sons, Ltd.

Cell organisation, sulphur metabolism and ion transport-related genes are differentially expressed in Paracoccidioides brasiliensis mycelium and yeast cells

Abstract Background Mycelium-to-yeast transition in the human host is essential for pathogenicity by the fungus Paracoccidioides brasiliensis and both cell types are therefore critical to the establishment of paracoccidioidomycosis (PCM), a systemic mycosis endemic to Latin America. The infected population is of about 10 million individuals, 2% of whom will eventually develop the disease. Previously, transcriptome analysis of mycelium and yeast cells resulted in the assembly of 6,022 sequence groups. Gene expression analysis, using both in silico EST subtraction and cDNA microarray, revealed genes that were differential to yeast or mycelium, and we discussed those involved in sugar metabolism. To advance our understanding of molecular mechanisms of dimorphic transition, we performed an extended analysis of gene expression profiles using the methods mentioned above. Results In this work, continuous data mining revealed 66 new differentially expressed sequences that were MIPS(Munich Information Center for Protein Sequences)-categorised according to the cellular process in which they are presumably involved. Two well represented classes were chosen for further analysis: (i) control of cell organisation – cell wall, membrane and cytoskeleton, whose representatives were hex (encoding for a hexagonal peroxisome protein), bgl (encoding for a 1,3-β-glucosidase) in mycelium cells; and ags (an α-1,3-glucan synthase), cda (a chitin deacetylase) and vrp (a verprolin) in yeast cells; (ii) ion metabolism and transport – two genes putatively implicated in ion transport were confirmed to be highly expressed in mycelium cells – isc and ktp, respectively an iron-sulphur cluster-like protein and a cation transporter; and a putative P-type cation pump (pct) in yeast. Also, several enzymes from the cysteine de novo biosynthesis pathway were shown to be up regulated in the yeast form, including ATP sulphurylase, APS kinase and also PAPS reductase. Conclusion Taken together, these data show that several genes involved in cell organisation and ion metabolism/transport are expressed differentially along dimorphic transition. Hyper expression in yeast of the enzymes of sulphur metabolism reinforced that this metabolic pathway could be important for this process. Understanding these changes by functional analysis of such genes may lead to a better understanding of the infective process, thus providing new targets and strategies to control PCM.

Effect of denture cleansers on metal ion release and surface roughness of denture base materials

Chemical disinfectants are usually associated with mechanical methods to remove stains and reduce biofilm formation. This study evaluated the effect of disinfectants on release of metal ions and surface roughness of commercially pure titanium, metal alloys, and heat-polymerized acrylic resin, simulating 180 immersion trials. Disk-shaped specimens were fabricated with commercially pure titanium (Tritan), nickel-chromium-molybdenum-titanium (Vi-Star), nickel-chromium (Fit Cast-SB Plus), and nickel-chromium-beryllium (Fit Cast-V) alloys. Each cast disk was invested in the flasks, incorporating the metal disk to the heat-polymerized acrylic resin. The specimens (n=5) were immersed in these solutions: sodium hypochlorite 0.05%, Periogard, Cepacol, Corega Tabs, Medical Interporous, and Polident. Deionized water was used as a control. The quantitative analysis of metal ion release was performed using inductively coupled plasma mass spectrometry (ELAN DRC II). A surface analyzer (Surftest SJ-201P) was used to measure the surface roughness (µm). Data were recorded before and after the immersions and evaluated by two-way ANOVA and Tukey's test (α=0.05). The nickel release proved most significant with the Vi-Star and Fit Cast-V alloys after immersion in Medical Interporous. There was a significant difference in surface roughness of the resin (p=0.011) after immersion. Cepacol caused significantly higher resin roughness. The immersion products had no influence on metal roughness (p=0.388). It could be concluded that the tested alloys can be considered safe for removable denture fabrication, but disinfectant solutions as Cepacol and Medical Interporous tablet for daily denture immersion should be used with caution because it caused greater resin surface roughness and greater ion release, respectively.

Surface modification by metal ion implantation forming metallic nanoparticles in insulating matrix.

There is special interest in the incorporation of metallic nanoparticles in a surrounding dielectric matrix for obtaining composites with desirable characteristics such as for surface plasmon resonance, which can be used in photonics and sensing, and controlled surface electrical conductivity. We investigated nanocomposites produced through metallic ion implantation in insulating substrate, where the implanted metal self-assembles into nanoparticles. During the implantation, the excess of metal atom concentration above the solubility limit leads to nucleation and growth of metal nanoparticles, driven by the temperature and temperature gradients within the implanted sample including the beam-induced thermal characteristics. The nanoparticles nucleate near the maximum of the implantation depth profile (projected range), that can be estimated by computer simulation using the TRIDYN. This is a Monte Carlo simulation program based on the TRIM (Transport and Range of Ions in Matter) code that takes into account compositional changes in the substrate due to two factors: previously implanted dopant atoms, and sputtering of the substrate surface. Our study suggests that the nanoparticles form a bidimentional array buried few nanometers below the substrate surface. More specifically we have studied Au/PMMA (polymethylmethacrylate), Pt/PMMA, Ti/alumina and Au/alumina systems. Transmission electron microscopy of the implanted samples showed the metallic nanoparticles formed in the insulating matrix. The nanocomposites were characterized by measuring the resistivity of the composite layer as function of the dose implanted. These experimental results were compared with a model based on percolation theory, in which electron transport through the composite is explained by conduction through a random resistor network formed by the metallic nanoparticles. Excellent agreement was found between the experimental results and the predictions of the theory. It was possible to conclude, in all cases, that the conductivity process is due only to percolation (when the conducting elements are in geometric contact) and that the contribution from tunneling conduction is negligible.

Gold ion implantation into alumina using an “inverted ion source” configuration.

We describe an approach to ion implantation in which the plasma and its electronics are held at ground potential and the ion beam is injected into a space held at high negative potential, allowing considerable savings both economically and technologically. We used an “inverted ion implanter” of this kind to carry out implantation of gold into alumina, with Au ion energy 40 keV and dose (3–9) × 1016 cm−2. Resistivity was measured in situ as a function of dose and compared with predictions of a model based on percolation theory, in which electron transport in the composite is explained by conduction through a random resistor network formed by Au nanoparticles. Excellent agreement is found between the experimental results and the theory.

Stopping power and depth dose profile of H+ and He+ ion beams in hydroxyapatite thin films.

Hadron therapy is a promising technique to treat deep-seated tumors. For an accurate treatment planning, the energy deposition in the soft and hard human tissue must be well known. Water has been usually employed as a phantom of soft tissues, but other biomaterials, such as hydroxyapatite (HAp), used as bone substitute, are also relevant as a phantom for hard tissues. The stopping power of HAp for H+ and He+ beams has been studied experimentally and theoretically. The measurements have been done using the Rutherford backscattering technique in an energy range of 450-2000 keV for H+ and of 400-5000 keV for He+ projectiles. The theoretical calculations are based in the dielectric formulation together with the MELF-GOS (Mermin Energy-Loss Function – Generalized Oscillator Strengths) method [1] to describe the target excitation spectrum. A quite good agreement between the experimental data and the theoretical results has been found. The depth dose profile of H+ and He+ ion beams in HAp has been simulated by the SEICS (Simulation of Energetic Ions and Clusters through Solids) code [2], which incorporates the electronic stopping force due to the energy loss by collisions with the target electrons, including fluctuations due to the energy-loss straggling, the multiple elastic scattering with the target nuclei, with their corresponding nuclear energy loss, and the dynamical charge-exchange processes in the projectile charge state. The energy deposition by H+ and He+ as a function of the depth are compared, at several projectile energies, for HAp and liquid water, showing important differences.

Autoionizing states and their relevance in electron-ion recombination

Atomic physics plays an important role in determining the evolution stages in a wide range of laboratory and cosmic plasmas. Therefore, the main contribution to our ability to model, infer and control plasma sources is the knowledge of underlying atomic processes. Of particular importance are reliable low temperature dielectronic recombination (DR) rate coefficients. This thesis provides systematically calculated DR rate coefficients of lithium-like beryllium and sodium ions via ∆n = 0 doubly excited resonant states. The calculations are based on complex-scaled relativistic many-body perturbation theory in an all-order formulation within the single- and double-excitation coupled-cluster scheme, including radiative corrections. Comparison of DR resonance parameters (energy levels, autoionization widths, radiative transition probabilities and strengths) between our theoretical predictions and the heavy-ion storage rings experiments (CRYRING-Stockholm and TSRHeidelberg) shows good agreement. The intruder state problem is a principal obstacle for general application of the coupled-cluster formalism on doubly excited states. Thus, we have developed a technique designed to avoid the intruder state problem. It is based on a convenient partitioning of the Hilbert space and reformulation of the conventional set of pairequations. The general aspects of this development are discussed, and the effectiveness of its numerical implementation (within the non-relativistic framework) is selectively illustrated on autoionizing doubly excited states of helium.