The potential of electron beam irradiation for simultaneous surface modification and bioresorption control of PLLA for medical device applications

Bioresorbable polymers have been widely investigated as materials exhibiting significant potential for successful application in the medical fields of bone fixation devices and drug delivery. Further to the ability to control degradation, surface engineering of polymers has been highlighted as a key method central to their development. Previous work has demonstrated the ability of electron beam (e-beam) technology to control the degradation profiles and bioresorption of a number of commercially relevant bioresorbable polymers (poly-l-lactic acid (PLLA), L-lactide/ DL-lactide co-polymer (PLDL) and poly(lactic-co-glycolic acid) (PLGA). This work investigates the further potential of e-beam technology to impart added biofunctionality through the manipulation of polymer (PLLA) surface properties. A Dynamatron Continuous DC e-beam unit (Synergy Health, UK), with beam energies of 0.5, 0.75, and 1.5 MeV, was used for the irradiation of PLLA samples with delivered surface doses of 150 or 500 kGy at each energy level. The chosen conditions reflect the need to achieve a specific surface modification for the control of surface degradation as demonstrated in previous work. Surface characterization was then performed using contact angle analysis, X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy.
Results demonstrated a significant increase in surface wettability post e-beam treatment. In correlation with this, XPS data showed the introduction of oxygen-containing functional groups to the surface of PLLA. Raman spectroscopy indicated chain scission in the near surface region of PLLA. E-beam irradiation did not seem to affect the surface roughness of PLLA as a direct consequence of the treatment. In conclusion electron beam surface modification has been found to modify both the surface-to-bulk bioresorption profile and the surface hydrophilicity. Both could provide benefits in relation to the performance of implantable medical devices.

Excitation rate coefficients for transitions from the ground level of Gd XXXVII

Excitation rate coefficients, for transitions from the ground level to excited levels of Gd XXXVII, have been calculated over the temperature range 5002500 eV using the R-matrix method. It is observed that the contribution of resonances enhances the rates by up to an order of magnitude over the available (non- resonant) results of Hagelstein.

Electron impact excitation of Gd XXXVII and radiative rates for Ni-like ions with 60

Energy levels and radiative rates for transitions among the 107 finestructure levels belonging to the (1s(2)2s(2)2p(6)) 3s(2)3p(6)3d(10), 3s(2)3p(6)3d(9)4l, 3s(2)3p(5)3d(10)4l, and 3s3p(6)3d(10)4l configurations of Ni-like ions with 60 less than or equal to Z less than or equal to 90 have been calculated using the GRASP code. The collision strengths (Omega) have also been computed for transitions in Gd XXXVII at energies below 800 Ryd, using the DARC code. Resonances have been resolved in a fine energy mesh in the threshold region, and excitation rate coefficients have been calculated for transitions from the ground level to excited levels at temperatures below 2500 eV. These have been compared with those available in the literature, and enhancement in the values of rates, due to resonances, has been observed up to an order of magnitude for some of the transitions.

Light emission from scanning tunnelling microscope on polycrystalline Au films - what is happening at the single-grain level?

When operated with a metallic tip and sample the scanning tunnelling microscope constitutes a nanoscale, plasmonic light source yielding broadband emission up to a photon energy determined by the applied bias. The emission is due to tunnelling electron excitation and subsequent radiative decay of localized plasmon modes, which can be on the lateral scale of a single metal grain (similar to 25 nm) or less. For a Au-tip/Au-polycrystalline sample under ambient conditions it is found that the intensity and spectral content of the emitted light are not dependent on the lateral grain dimension, but are predominantly determined by the tip geometry. However, the intensity increases strongly with increasing film thickness (grain depth) up to 20-25 nm or approximately the skin depth of the Au film. Photon maps can show less emissive grains and two classes of this occurrence are distinguished. The first is geometrical in origin - a double-tip structure in this case - while the second is due to a contamination-induced lowering of the local work function that causes the tunnel gap to increase. It is suggested that differences in work-function lowering between grains presenting different crystalline facets, combined with an exponential decay in emitted light intensity with tip - sample distance, leads to grain contrast. These results are relevant to tip-enhanced Raman scattering and the fabrication of micro/nano-scale planar, light-emitting tunnel devices.

Energy levels, radiative rates, and excitation rates for transitions in OIV

Aims. In this paper we report calculations for energy levels, radiative rates, and excitation rates for transitions in O IV. Methods. The grasp (general-purpose relativistic atomic structure package) and FAC (flexible atomic code) were adopted for calculating energy levels and radiative rates, and the Dirac atomic R-matrix code (DARC) used to determine the excitation rates. Results. Oscillator strengths and radiative rates are reported for all E1, E2, M1, and M2 transitions among the lowest 75 levels of O IV. Additionally, lifetimes are reported for all levels and comparisons made with those available in the literature. Finally, effective collision strengths are reported for all transitions over a wide temperature range below 106 K. Comparisons are made with earlier results and the accuracy of the data is assessed.

Energy levels, radiative rates and excitation rates for transitions in Ni XI

Aims. In this paper we report calculations for energy levels, radiative rates and excitation rates for transitions in Ni xi.
Methods. The grasp (General-purpose Relativistic Atomic Structure Package) and fac (Flexible Atomic Code) have been adopted
for calculating energy levels and radiative rates, and the Dirac Atomic R-matrix Code (darc) has been used to determine the excitation
rates.
Results. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest
250 levels of Ni xi. Additionally, lifetimes are also reported for all levels. However, results for excitation rates are presented only for
transitions among the lowest 17 levels.

Anomalous helicon wave absorption and parametric excitation of electrostatic fluctuations in a helicon-produced plasma

The nonlinear nature of the rf absorption in a helicon-produced plasma was recently evidenced by the observation that the helicon wave damping as well as the level of short-scale electrostatic fluctuations excited in the helicon plasma increases with rf power. Correlation methods using electrostatic probes as well as microwave back-scattering at the upper-hybrid resonance allow identifying the fluctuations as ion-sound and Trivelpiece– Gould waves satisfying the frequency and wavenumber matching conditions for the parametric decay instability of the helicon pump wave. Furthermore, the growth rates and thresholds deduced from their temporal growth are in good agreement with theoretical predictions for the parametric decay instability that takes into account realistic damping rates for the decay waves as well as a non-vanishing parallel wavenumber of the helicon pump. The close relationship between the rf absorption and the excitation of the fluctuations was investigated in more detail by performing time- and space-resolved measurements of the helicon wave field and the electrostatic fluctuations.

Energy levels, radiative rates, and electron impact excitation rates for transitions in OVII

Aims.
In this paper we report calculations for energy levels, radiative rates, and electron impact excitation rates for transitions in O vii.
Methods.
The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative
rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) and the
flexible atomic code (fac) are used.
Results.
Oscillator strengths, radiative rates, and line strengths are reported for all E1, E2, M1, and M2 transitions among the lowest
49 levels of O vii. Collision strengths have been averaged over a Maxwellian velocity distribution, and the resulting effective collision
strengths are reported over a wide temperature range below 2 × 106 K. Additionally, lifetimes are also listed for all levels.
Key words.

Low-energy electron attachment to chloroform (CHCl3) molecules: A joint experimental and theoretical study

Results from a joint experimental and theoretical study of electron attachment to chloroform (CHCl3) molecules in the gas phase are reported. In an electron swarm study involving a pulsed Townsend technique with equal gas and electron temperatures, accurate attachment rate coefficients were determined over the temperature range 295-373 K; they show an Arrhenius-type rise with increasing temperature, corresponding to an activation energy of 0.11 (1) eV. In a high resolution electron beam experiment involving two versions of the laser photoelectron attachment method, the relative cross section for Cl- formation from CHCl3 over the energy range 0.001-1.25 eV at the gas temperature T-G = 300 K was measured. It exhibits clear downward cusp structure at the threshold for excitation of one quantum of the vibrational symmetric deformation mode nu(3), indicating that this mode is active in the primary attachment process. With reference to our thermal attachment rate coefficient k(T = 300 K) = 3.9(2) x 10(-9) cm(3) s(-1), a new highly resolved absolute attachment cross section for T-G = 300 K was determined. This cross section is extended to higher energies by measurements, carried out with a pulsed electron beam apparatus which also provided new data for the distinctly weaker fragment anions HCl2- and CCl2-. The resulting total absolute cross section for anion formation is used to calculate the dependence of the attachment rate coefficient k(T-e;T-G) on electron temperature T-e over the range 50-15000 K at the fixed gas temperature T-G = 300 K. In addition, we report the dependence of the relative cross section for Cl- formation on gas temperature T-G = 310-435 K). For comparison with the experimental data, R-matrix calculations have been carried out for the dominant anion channel Cl-. The results recover the main experimental observations and predict the dependence of the DEA cross section on the initial vibrational level nu(3) and on the vibrational temperature. Our results are compared with those of previous electron beam and electron swarm experiments.

Low-Energy Electron Attachment to the Dichlorodifluoromethane (CCl2F2) Molecule

Results from a joint experimental study of electron attachment to dichlorodifluoromethane (CCl2F2) molecules in the gas phase are reported. In a high resolution electron beam experiment involving two versions of the laser photoelectron attachment method, the relative cross section for formation of the dominant anion Cl- wits measured over the energy range 0.001-1.8 eV at the gas temperature T-G = 300 K. It exhibits cusp structure at thresholds for vibrational excitation of the v(3)(a(1)) mode due to interaction with the attachment channels. With reference to the thermal attachment rate coefficient k(T-e;T-G = 300 K) = 2.2(8) x 10(-9) cm(-3) s(-1) (fitted average from several data), a new highly resolved absolute attachment cross section for TG = 300 K was determined. Partial cross sections for formation of the anions Cl-, Cl-2(-), F-, ClF-, and CCl2F- were measured over the range 0-12 eV, using three different electron beam experiments of medium energy resolution. The dependence of the attachment rate coefficient k(T-e;T-G = 300 K) on electron temperature T-e wits calculated over the range 50-15 000 K, based on a newly constructed total cross section for anion formation at T-G = 300 K. R-matrix Calculations for Cl- production have been carried out for comparison with the experimental data. The R-matrix results are in line with the main experimental observations and predict the dependence of the DEA cross section on the initial vibrational level v(3) and on the vibrational temperature. Furthermore, the cross section for I Vibrational excitation of the v(3) mode hits been computed.

Energy levels, radiative rates and electron impact excitation rates for transitions in He-like Li II, Be III, B IV and C V

We report calculations for energy levels, radiative rates and electron impact excitation rates for transitions in He-like Li II, Be III, B IV and C V. grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates. For determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 49 levels of each ion. Collision strengths have been averaged over a Maxwellian velocity distribution and the effective collision strengths so obtained are reported over a wide temperature range up to 10(6) K. Comparisons have been made with similar data obtained from the flexible atomic code (FAC) to highlight the importance of resonances, included in calculations from darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, particularly for weak transitions and at low energies, have also been discussed. Additionally, lifetimes are also listed for all calculated levels of the above four ions.

Energy levels, radiative rates and electron impact excitation rates for transitions in Si XII, Si XIII and Si XIV

In this paper, we report calculations of energy levels, radiative rates and electron impact excitation rates for transitions in Li-like Si XII, He-like Si XIII and H-like Si XIV. The grasp (general-purpose relativistic atomic structure package) is adopted for calculating energy levels and radiative rates, while for determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (darc) is used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 24 levels of Si XII, 49 levels of Si XIII and 25 levels of Si XIV, belonging to the n≤5 configurations. Collision strengths have been averaged over a Maxwellian electron velocity distribution and the effective collision strengths so obtained are reported over a wide temperature range below 107 K. Comparisons have been made with similar data obtained from the flexible atomic code (fac) to highlight the importance of resonances, included in calculations from darc, in the determination of effective collision strengths. Discrepancies between the collision strengths from darc and fac, particularly for weak transitions and at low energies, are also discussed. Additionally, lifetimes are listed for all calculated levels of the above three ions, although no measurements are available with which to compare.

Energy levels, radiative rates and electron impact excitation rates for transitions in H-like N VII, O VIII, F IX, Ne X and Na XI

We report calculations of energy levels, radiative rates and electron impact excitation rates for transitions in H-like N VII, O VIII, F IX, Ne X and Na XI. The general-purpose relativistic atomic structure package (grasp) is adopted for calculating energy levels and radiative rates, while the Dirac atomic R-matrix code (DARC) and the flexible atomic code (FAC) are used for determining the collision strengths and subsequently the excitation rates. Oscillator strengths, radiative rates and line strengths are listed for all E1, E2, M1 and M2 transitions among the lowest 25 levels of the above five ions. Collision strengths have been averaged over a Maxwellian velocity distribution, and the effective collision strengths so obtained are reported over a wide temperature range below 10(7) K. Additionally, lifetimes are also given for all the calculated energy levels of the above five ions.

Energy levels, radiative rates and electron impact excitation rates for transitions in Li-like N V, F VII, Ne VIII and Na IX

In this paper, we report calculations of energy levels, radiative rates and electron impact excitation rates for transitions in Li-like N V, F VII, Ne VIII and Na IX. The general-purpose relativistic atomic structure package (GRASP) is adopted for calculating energy levels and radiative rates, while for determining the collision strengths and subsequently the excitation rates, the Dirac atomic R-matrix code (DARC) and the flexible atomic code (FAC) are used. Oscillator strengths, radiative rates and line strengths are reported for all E1, E2, M1 and M2 transitions among the lowest 24 levels of N V, F VII, Ne VIII and Na IX. Collision strengths have been averaged over a Maxwellian velocity distribution and the effective collision strengths so obtained are reported over a wide temperature range below 10(6.6) K. Additionally, lifetimes are also reported for all calculated levels of the above four ions.