Luke Hanley

Light and Molecular Ions: The Emergence of Vacuum UV Single-Photon Ionization in MS

Thanks to recent technological advances and single-photon ionizations (SPIs) ability to detect all organics, the technique could become the long-sought universal soft ionization method. (To listen to a podcast about this feature, please go to the Analytical Chemistry Web site at pubs.acs.org/journal/ancham.).

Antibacterial activity of dental composites containing zinc oxide nanoparticles

The resin-based dental composites commonly used in restorations result in more plaque accumulation than other materials. Bacterial biofilm growth contributes to secondary caries and failure of resin-based dental composites. Methods to inhibit biofilm growth on dental composites have been sought for several decades. It is demonstrated here that zinc oxide nanoparticles (ZnO-NPs) blended at 10% (w/w) fraction into dental composites display antimicrobial activity and reduce growth of bacterial biofilms by roughly 80% for a single-species model dental biofilm. Antibacterial effectiveness of ZnO-NPs was assessed against Streptococcus sobrinus ATCC 27352 grown both planktonically and as biofilms on composites. Direct contact inhibition was observed by scanning electron microscopy and confocal laser scanning microscopy while biofilm formation was quantified by viable counts. An 80% reduction in bacterial counts was observed with 10% ZnO-NP-containing composites compared with their unmodified counterpart, indicating a statistically significant suppression of biofilm growth. Although, 20% of the bacterial population survived and could form a biofilm layer again, 10% ZnO-NP-containing composites maintained at least some inhibitory activity even after the third generation of biofilm growth. Microscopy demonstrated continuous biofilm formation for unmodified composites after 1-day growth, but only sparsely distributed biofilms formed on 10% ZnO-NP-containing composites. The minimum inhibitory concentration of ZnO-NPs suspended in S. sobrinus planktonic culture was 50 microg mL(-1). ZnO-NP-containing composites (10%) qualitatively showed less biofilm after 1-day-anaerobic growth of a three-species initial colonizer biofilm after being compared with unmodified composites, but did not significantly reduce growth after 3 days.

Collision‐induced dissociation of aluminum cluster ions: Fragmentation patterns, bond energies, and structures for Al+2–Al+7

Collision‐induced dissociation (CID) of cooled, mass selected aluminum cluster ions (Al+2–7) by xenon, has been studied over an energy range of 0–10 eV (center of mass). These experiments were carried out in a new apparatus which is described in detail. From the product branching ratios and cross section magnitudes we derive qualitative structural information about the cluster ions. The fragmentation thresholds are analyzed to yield dissociation energies, approximate ionization potentials, and further structural information about the cluster ions and their neutral counterparts. Cluster stabilities range from 0.85±0.40 eV for Al+4 to 2.25±0.70 eV for Al+7. The results provide a stringent test for recent calculations on Al2–6.

Preparation and analysis of macroporous TiO2 films on Ti surfaces for bone-tissue implants.

This article describes the preparation and analysis of macroporous TiO2 films on Ti surfaces, for application in bone tissue-Ti implant interfaces. These TiO2 bioceramic films have a macroporous structure consisting of monodisperse, three-dimensional, spherical, interconnected pores adjustable in the micron size range. Micron-sized polystyrene (PS) bead templates are used to precisely define the pore size, creating macroporous TiO2 films with 0.50, 16, and 50 microm diameter pores, as shown by scanning electron microscopy. X-ray photoelectron spectroscopy shows the films to be predominantly composed of TiO2, with approximately 10% carbon. X-ray diffraction reveal rutile as the main phase when fired to the optimal temperature of 950 degrees C. Preliminary experiments find that the in vitro proliferation of human bone-derived cells (HBDC) is similar on all three pore sizes. However, higher [3H]thymidine incorporation by the HBDC is observed when they are grown on 0.50- and 16-microm pores compared to the 50-microm pores, suggesting an enhanced cell proliferation for the smaller pores.

The growth and modification of materials via ion-surface processing

A wide variety of gas phase ions with kinetic energies from 1–10 7 eV increasingly are being used for the growth and modification of state-of-the-art material interfaces. Ions can be used to deposit thin films; expose fresh interfaces by sputtering; grow mixed interface layers from ions, ambient neutrals, and/or surface atoms; modify the phases of interfaces; dope trace elements into interface regions; impart specific chemical functionalities to a surface; toughen materials; and create micron- and nanometer-scale interface structures. Several examples are developed which demonstrate the variety of technologically important interface modification that is possible with gas phase ions. These examples have been selected to demonstrate how the choice of the ion and its kinetic energy controls modification and deposition for several different materials. Examples are drawn from experiments, computer simulations, fundamental research, and active technological applications. Finally, a list of research areas is provided for which ion–surface modification promises considerable scientific and technological advances in the new millennium. 2001 Elsevier Science B.V. All rights reserved.

Thin hydroxyapatite coatings via sol–gel synthesis

Production of hydroxyapatite coatings using an alkoxide-based sol–gel route requires control of solution aging time and heating schedule. 31P nuclear magnetic resonance spectroscopy was used to investigate the changes during aging of the sol and thermal gravimetric analysis employed to study the behavior of the xerogels as a function of temperature, while final products were determined using X-ray diffraction. Results from 31P nuclear magnetic resonance spectroscopy and thermal analysis revealed that sols must be aged for at least 24 h to complete the reaction of the two reactants. Deposition of the sol for coating production will then yield monophasic hydroxyapatite. Coatings produced from sols aged for less than 24 h yielded calcium oxide in addition to hydroxyapatite. Prefiring is necessary to remove most of the residual organic materials. Final heating up to 800°C produces crystallization at 550°C and removal of the remaining organic constituents for the formation of a thin hydroxyapatite layer.

Photolysis of chemisorbed dioxygen on Pd(111): Dependence on photon energy

Photolysis of chemisorbed dioxygen bound in the peroxo and superoxo configurations to Pd(111) has been studied and cross section vs photon energy measurements have been made. Three photoprocesses occur: (1) photodesorption of O2(g); (2) photoconversion between different O2(a) species; and (3) photodissociation to produce O(a). The threshold photon energy for O2(a) photodesorption or photoconversion is 3.4±0.3 eV or lower; for photodissociation of O2(a) to produce O(a), the threshold photon energy is 3.7±0.3 eV. The cross sections for photodissociation and photodesorption of chemisorbed dioxygen on Pd(111) at a photon energy of 5.2 eV are (3.5±1.2)×10−20 and (1.3±0.1)×10−19 cm2 , respectively.

GRGDSP peptide-bound silicone membranes withstand mechanical flexing in vitro and display enhanced fibroblast adhesion.

Mechanobiological studies of cardiac tissue require devices that allow forces to be exerted on cells in vitro. Silicone elastomer is often used in these devices because it is flexible and transparent, permitting optical imaging of the cells. However, native untreated silicone is hydrophobic and is unsuitable for cell culture. Peptides covalently bound to silicone surfaces are examined here for the enhancement of cellular adhesion during in vitro dynamic flexing. A procedure is described for the chemical modification of medical grade silicone membranes with covalently bound GRGDSP peptides. The conditions for mechanical studies of cardiac cell cultures are then duplicated and it is demonstrated that the peptide layers survive 48 h of mechanical flexing in vitro. Specifically, mechanical flexing in vitro of the 30 pmol/cm2 peptide-modified silicone membranes has no significant effect on the amount of peptides that remains bound to the surface. Cardiac fibroblasts display enhanced adhesion to these peptide-bound silicone membranes for at least 24 h of growth, compared with native silicone or tissue culture polystyrene. The effects of serum versus serum-free media on fibroblast growth are also examined.

Oxidation of small boron cluster ions (B+1–13) by oxygen

Absolute cross sections for all ionic products formed in reactions of B+1–13 with oxygen have been measured under single collision conditions, at collision energies from 0.25 to 10 eV. Three main reaction mechanisms appear to be important: oxidative fragmentation, collision induced dissociation, and boron atom abstraction. The dominant oxidation process are exoergic for all cluster sizes, but appear to have bottlenecks or activation barriers for the larger cluster ions. Clusters smaller than B+6 have similar chemistry, then there is a sharp transition in chemistry for clusters larger than B+6 . Correlations are explored between cluster reactivity and cluster stability, and the oxidation chemistry is compared to the similar results found for aluminum cluster ion oxidation.

Classical dynamics simulations of SiMe3+ ion–surface scattering

This paper presents classical dynamics simulations of Si(CD3)3+scattering from a hexanethiolate self-assembled monolayer on Au(111) and from a clean Au(111) surface. Simulations are performed with a united atom model using purely repulsive scattering potentials. These simulations predict the partitioning of the incident ion kinetic energy into the scattered ion kinetic energy and the internal modes of both the surface and the ion. For the organic surface, the simulations predict energy transfer to surface, ion internal, and ion kinetic energies of 0.78, 0.11, and 0.12 of the collision energy. The corresponding transfer efficiencies of 0.12, 0.21, and 0.65 were calculated for the Au(111) surface. These computational results compare well with the experimental results on the same systems which are reported in the preceding paper. The simulations predict near specular scattering for both surfaces. They also demonstrate that the ion penetrates only the topmost two to three layers of Me atoms of the organic sur...