Wettability and osteoblast cell response modulation through UV laser processing of nylon 6,6

With an ageing population the demand for cheap, efficient implants is ever increasing. Laser surface treatment offers a unique means of varying biomimetic properties to determine generic parameters to predict cell responses. This paper details how a KrF excimer laser can be employed for both laser-induced patterning and whole area irradiative processing to modulate the wettability characteristics and osteoblast cell response following 24 h and 4 day incubation. Through white light interferometry (WLI) it was found that the surface roughness had considerably increased by up to 1.5 μm for the laser-induced patterned samples and remained somewhat constant at around 0.1 μm for the whole area irradiative processed samples. A sessile drop device determined that the wettability characteristics differed between the surface treatments. For the patterned samples the contact angle, θ, increased by up to 25° which can be attributed to a mixed-state wetting regime. For the whole area irradiative processed samples θ decreased owed to an increase in polar component, γ^P. For all samples θ was a decreasing function of the surface energy. The laser whole area irradiative processed samples gave rise to a distinct correlative trend between the cell response, θ and γ^P. However, no strong relationship was determined for the laser-induced patterned samples due to the mixed-state wetting regime. As a result, owed to the relationships and evidence of cell differentiation one can deduce that laser whole area irradiative processing is an attractive technology for employment within regenerative medicine to meet the demands of an ageing population.     

On the effects of using CO2 and F2 lasers to modify the wettability of a polymeric biomaterial

Enhancement of the surface properties of a material by means of laser radiation has been amply demonstrated previously. In this work a comparative study for the surface modification of nylon 6,6 has been conducted in order to vary the wettability characteristics using CO₂ and excimer lasers. This was done by producing 50 μm spaced (with depths between 1 and 10 μm) trench-like patterns using various laser parameters such as varying the laser power for the CO₂ laser and number of pulses for the excimer laser. Topographical changes were analysed using optical microscopy and white light interferometry which indicated that both laser systems can be implemented for modifying the topography of nylon 6,6. Variations in the surface chemistry were evaluated using energy-dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy analysis which showed that the O₂ increased by up to 1.5 at% and decreased by up to 1.6 at% for the CO₂ and F₂ laser patterned samples, respectively. Modification of the wettability characteristics was quantified by measuring the advancing contact angle, which was found to increase in all instances for both laser systems. Emery paper roughened samples were also analysed in the same manner to determine that the topographical pattern played a major role in the wettability characteristics of nylon 6,6. From this, it is proposed that the increase in contact angle for the laser processed samples is due to a mixed intermediate state wetting regime owed to the periodic surface roughness brought about by the laser-induced trench-like topographical patterns.     

Adsorption of sodium bis(2-ethylhexyl) sulfosuccinate and wettability in polytetrafluoroethylene-solution-air system

The role of sodium bis(2-ethylhexyl) sulfosuccinate (AOT) adsorption at water-air and polytetrafluoroethylene-water (PTFE) interfaces in wetting of low energy PTFE was established from measurements of the contact angle of aqueous AOT solutions in PTFE-solution drop-air systems and the aqueous AOT solution surface tension measurements. For calculations of the adsorption at these interfaces the relationship between adhesion tension (γ_LV cos θ) and surface tension (γ_LV), and the Gibbs and Young equations were taken into account. On the basis of the measurements and calculations the slope of the γ_LV cos θ-γ_LV curve was found to be constant and equal −1 over the whole range of surfactant concentration in solution. It means that the amount of surfactant adsorbed at the PTFE-water interface, Γ_SL, is essentially equal to its amount adsorbed at water-air interface, Γ_LV. By extrapolating the linear dependence between γ_LV cos θ and γ_LV to cos θ = 1 the determined value of critical surface tension of PTFE surface wetting, γ_C, was obtained (23.6 mN/m), and it was higher than the surface tension of PTFE (20.24 mN/m). Using the value of PTFE surface tension and the measured surface tension of aqueous AOT solution in Young equation, the PTFE-solution interface tension, γ_SL, was also determined. The shape of the γ_SL-log C curve occurred to be similar to the isotherm of AOT adsorption at water-air interface, and a linear dependence existed between the PTFE-solution interfacial tension and polar component of aqueous AOT solution. The dependence was found to be established by the fact that the work of adhesion of AOT solution to the PTFE surface was practically constant amounting 46.31 mJ/m² which was close to the work of water adhesion to PTFE surface.     

The role of adsorption of dodecylethyldimethylammonium bromide and benzyldimethyldodecylammonium bromide surfactants in wetting of polytetrafluoroethylene and poly(methyl methacrylate) surfaces

The role of adsorption of dodecylethyldimethylammonium bromide (C₁₂(EDMAB)) and benzyldimethyldodecylammonium bromide (BDDAB) at water-air and polytetrafluoroethylene (PTFE)-water and poly(methyl methacrylate) (PMMA)-water interface, in wetting of PTFE and PMMA surface, was established from the measured values of the contact angle (θ) of aqueous C₁₂(EDMAB) and BDDAB solutions in PTFE (PMMA)-solution drop-air system, and from the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions. Adsorption of C₁₂(EDMAB) and BDDAB at water-air interface was determined earlier from the Gibbs equation. Adsorption at solid-water interface was deduced from the Lucassen-Reynders equation based on the relationship between adhesion tension (γ_LV cos θ) and surface tension (γ_LV). The slope of the γ_LV cos θ-γ_LV curve was found to be constant and equal to −1, and about −0.3 for PTFE and PMMA surface, respectively (in the case of both surfactant studied: C₁₂(EDMAB) and BDDAB, and in the whole range of surfactants concentration in solution). It means that the amount of the surfactant adsorbed at the PTFE-water interface, Γ_SL, was essentially equal to its amount adsorbed at water-air interface, Γ_LV. However, Γ_SL at the PMMA-water interface was about three times smaller as compared to that at water-air interface. By extrapolating the linear dependence between γ_LV cos θ-γ_LV and dependence between cos θ-γ_LV and cos θ = 1 we determined the value of the critical surface tension of PTFE and PMMA surface wetting, γ_c. The obtained values of γ_c for PTFE surface were equal 23.4 and 23.8 mN/m, 23.1 and 23.2 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were higher than the surface tension of PTFE (20.24 mN/m). On the other hand, the obtained values of γ_c for PMMA surface were equal 31.4 and 30.9 mN/m, 31.7 and 31.3 mN/m for C₁₂(EDMAB) and BDDAB, respectively and they were smaller than the surface tension of PMMA (39.21 mN/m). Using the values of PTFE and PMMA surface tension and the measured values of the surface tension of aqueous C₁₂(EDMAB) and BDDAB solutions in the Young equation, the PTFE (PMMA)-solution interfacial tension, γ_SL, was also determined. Next, the work of adhesion (W_A) was deduced, and it occurred that the dependence between the W_A and the surface tension (γ_LV) for both studied solids was linear. However, the values of the W_A for PMMA change as a function of log C (C—surfactant concentration) changed from 91.7 to 68.5 mJ/m² and from 91.8 to 65.1 mJ/m² for C₁₂(EDMAB) and BDDAB, respectively. On the other hand, the work of adhesion of both studied surfactants solutions to the PTFE surface was practically constant (an average value was equal 45.8 and 45.4 mJ/m², respectively). These values were close to the value of the work of water adhesion to PTFE surface (45.5 mJ/m²).     

Rovibrational spectrum and potential energy surface of the N2-N2O van der Waals complex

The rovibrational spectrum of the N₂-N₂O van der Waals complex has been recorded in the N₂O ν₁ region (∼1285 cm⁻¹) using a tunable diode laser spectrometer to probe a pulsed supersonic slit jet. The observed transitions together with the data observed previously in the N₂O ν₃ region are analyzed using a Watson S-reduced asymmetric rotor Hamiltonian. The rotational and centrifugal distortion constants for the ground and excited vibrational states are accurately determined. The band-origin of the spectrum is determined to be 1285.73964(14) cm⁻¹. A restricted two-dimensional intermolecular potential energy surface for a planar structure of N₂-N₂O has been calculated at the CCSD(T) level of theory with the aug-cc-pVDZ basis sets and a set of mid-bond functions. With the intermolecular distance fixed at the ground state value R = 3.6926 Å, the potential has a global minimum with a well depth of 326.64 cm⁻¹ at θ_N2 = 11.0° and θ_N2O = 84.3° and has a saddle point with a barrier height of 204.61 cm⁻¹ at θ_N2 = 97.4° and θ_N2O = 92.2°, where θ_N2(θ_N2O) is the enclosed angle between the N-N axis (N-N-O axis) and the intermolecular axis.     

The role of adsorption of sodium bis(2-ethylhexyl) sulfosuccinate in wetting of glass and poly(methyl methacrylate) surface

Advancing contact angles, θ, for aqueous solutions of the anionic surfactant, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) were measured on glass and poly(methyl methacrylate) (PMMA) surface. Using the obtained results we determined the properties of aqueous AOT solutions in wetting of these surfaces. It occurs that the wettability of glass and PMMA by these solutions depends on the concentration of AOT in solution. There is almost linear dependence between the contact angle (θ) and concentration of AOT (log C) in the range from 5 × 10⁻⁴ to 2.5 × 10⁻³ M/dm³ (value of the critical micelle concentration of AOT—CMC) both for glass and PMMA surface. For calculations of AOT adsorption at solid (glass, PMMA)-solution drop-air system interfaces the relationship between the adhesion tension (γ_LV cos θ) and surface tension (γ_LV) and the Gibbs and Young equations were taken into account. From the measurement and calculation results the slope of the γ_LV cos θ − γ_LV curve was found to be constant and equal 0.7 for glass and −0.1 for PMMA over the whole range of AOT concentration in solution. From this fact it can be concluded that if Γ_SV is equal zero then Γ_SL > 0 for the PMMA-solution and Γ_SL < 0 for glass-solution systems. It means that surfactant concentration excess at PMMA-solution interface is considerably lower than at solution-air interface, but this excess of AOT concentration at glass-solution interface is lower than in the bulk phase. By extrapolating the linear dependence between the adhesion and surface tension the value of the critical surface tension (γ_c) of wetting for glass and PMMA was also determined, that equaled 25.9 and 25.6 mN/m for glass and PMMA, respectively. Using the value of the glass and PMMA surface tension as well as the measured surface tension of aqueous AOT solutions in Young equation, the solid-liquid interface tension (γ_SL) was found. There was a linear dependence between the γ_SL and γ_LV both for glass and PMMA, but there were different slope values of the curves for glass and PMMA, i.e. −0.7 and 0.1, respectively. The dependence between the work of adhesion (W_A) and surface tension (γ_LV) was also linear of different slopes for glass and for PMMA surface.     

Nd1.85Ce0.15CuO4－δ单晶c-轴方向电阻的低场行为

采用自助熔剂缓冷法成功地生长出了Nd_1.85Ce_{0. 15}CuO_4-δ单晶，其零场下零电阻温度约为21K. 在0—0.5T范围内分别测量了磁场平行和垂直样品表面的电阻转变曲线以及0.5T不同角度下的电阻转变曲线. 结果显示磁场平行和垂直样品表面时的转变温度T_p随磁场的变化均服从H=H₀(1-T_p(h)/T_p(0))²关系. 0.5T 关键词： 1.85Ce_0.15CuO_4-δ单晶')" href="#">Nd_1.85Ce_0.15CuO_4-δ单晶 输运性质     

Features of Structural Phase Transitions of Aluminum Hydroxides under Laser Processing

The results of the studies of laser processing of alkoxide aluminum hydroxides with micrometer and nanometer particle sizes are presented. It is shown that the pseudo-boehmite processing process and phase composition of formed oxides are controlled by particle packing, laser radiation propagation in powder, and specific energy deposition. The main phases formed upon laser heating are γ, α-Al₂O₃; the content of δ, θ-Al₂O₃ is low. The minimum corundum crystallite size is ～50 nm.     

The (γ, n) reaction on 16O between giant resonance and pion threshold

A new TOF facility has been built for measurements of differential (γ, n) cross sections to discrete final states of light nuclei in the photon energy range between giant resonance and pion threshold. The observed neutron angle θ_n can continuously be varied between 0° and 150°, and additionally measurements at 175° and 180° are possible. Differential cross sections for the reaction ¹⁶O(γ, n₀)¹⁵O are presented for E_γ = 60 MeV (40° ? θ_n ? 149°) and for θ_n = 90° (60 MeV ? E_γ ? 160 MeV). The results, combined with the corresponding (γ, p₀) cross sections, indicate an absorption mechanism of high energy photons by neutron-proton pairs.     

The wettability of polytetrafluoroethylene and polymethylmethacrylate by aqueous solutions of Triton X-100 and short chain alcohol mixtures

Measurements of advancing contact angles (θ) were carried out for aqueous solutions of Triton X-100 (TX-100) and methanol and ethanol mixtures at constant TX-100 concentration equal to 1 × 10⁻⁷, 1 × 10⁻⁶, 1 × 10⁻⁵, 1 × 10⁻⁴, 6 × 10⁻⁴ and 1 × 10⁻³ M, respectively, on polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA). Using measured contact angle values the relationships between cos θ, adhesion tension and surface tension of the solutions were determined, and on their basis the critical surface tension of PTFE and PMMA wetting was calculated. The obtained average value of the critical surface tension of PTFE wetting is lying in the range of the PTFE surface tension values which can be found in the literature, while for PMMA it is even lower than the Lifshitz-van der Waals component of its surface tension. From the relationship between the adhesion and surface tension and Lucassen-Reynders equation it results that in the case of PTFE the adsorption at the PTFE-solution and solution-air interfaces is the same, which was confirmed by a linear relationship between the cos θ and 1/γ_LV and intercept on cos θ axis equal to −1. However, for PMMA the adsorption of the surface active agents at solution-air interface is higher than at PMMA-solution. Using the values of the contact angle the values of the adhesion work of solution to the PTFE and PMMA surface were also determined, which are constant for PTFE, but for PMMA decrease with alcohol concentration increase. Next, using the contact angle values in the Young equation, the PTFE(PMMA)-solution interface tension was also calculated. The obtained values of PTFE-solution interface tension were compared with those evaluated from the Szyszkowski, Connors and Fainerman and Miller equations, and good agreement between these values was observed for all series of TX-100 and alcohol mixtures at a low alcohol concentration.     

Nylon and nylon blend nanotubes and nanorods

Nylon nanorods and nanotubes (200 nm diameter) were fabricated by the membrane wetting technique (solvent and melt wetting) from a range of nylons (6; 6,6; 6,9; 6,10; 6,12; 11; 12, 6(3)T) and nylon blended with different dyes (Nylon Cast Blue, Nylon 6/6 Black) or with molybdenum disulfide (Nylon cast MDS). The 65-μm long nylon nanotubes and nanorods were characterized by scanning electron microscopy. The nanoscale nylon 6,6 served as an effective high surface area alternative to a nylon membrane as a solid support in a chemiluminescent assay for nylon-bound biotinylated nucleic acids based on streptavidin- alkaline phosphatase and chemiluminescent detection of the bound alkaline phosphatase label with the dioxetane substrate, CDP-Star. Layer-by-layer deposition of the cationic polymer (Sapphire-II™; Tropix) onto the nylon 6,6 nanostructures prior to UV-cross-linking with biotinylated DNA resulted in further enhancement of binding and detection of biotinylated DNA.     

A surface tension study of liquid threads

According to symmetry of liquid threads, definitions of surface tension in axial direction and angular direction are given. The formulas of surface tension in axial direction γ_z and surface tension in angular direction γ_θ are derived. A scheme to calculate Δγ = γ_z − γ_θ is designed. We investigate seven different systems (the numbers of molecules N are 1600, 2240, 2880,3360,4000,4800 and 5280) by molecular dynamics simulations. For liquid threads, Δγ increases with the decreasing radius of dividing surface. It shows that there exists surface tension anisotropy for liquid threads. The results obtained by molecular dynamics simulations support that surface tension is dependent on the dividing surface curvature.     

The analyzing power Aγ(θ) for the elastic scattering of 12 MeV neutrons from deuterons

The analyzing power A_γ(θ) was obtained at 10° intervals between 30° (lab) to 120° (lab) for ²H(n, n)²H at 12.0 MeV. The polarized neutron beam employed in the measurement was obtained by using neutrons emitted at 0° from the polarization transfer reaction ${}^2\text{H}\text{(}\text{d}\text{,}\text{n}\text{)}{}^3\text{He}$. The accuracy in the A_γ(θ) values that was achieved ranged from ± 0.006 to ± 0.013. Comparison of the data to A_γ(θ) results obtained at 12 MeV for the charge symmetric reaction ²H(p, p)²H shows that the two A_γ(θ) distributions are equal to within the above accuracy.     

Studies of vibrational surface modes in ionic crystals: III. Vibrational contributions to the surface thermodynamic functions for the (001) face of LiF,MgO, NaF,NaCl, Nal,RbF, and RbCl

The temperature dependence of the vibrational contributions to surface specific heat, surface entropy, surface energy, and surface Helmholtz free energy have been calculated for the (001) face of seven crystals having the rocksalt structure. The calculations assume a perfect, unrelaxed surface and make use of shell models fitted to bulk phonon spectra determined from inelastic neutron scattering. In terms of the bulk zero-temperature Debye temperature θ₀, the surface specific heat C_v^s exhibits an effective power law behavior, T^α, from at least T = 0.02 θ₀ up to 0.05 θ₀ in most cases (and up to 0.07 θ₀ for NaF), with α ≈ 2.5 in most cases — in contrast with the result of α = 2 in a Debye-like model. (Below 0.02 θ₀, results derived for our 15-layer films depart significantly from intrinsic surface effects because of the finite thickness.) C_v^s attains a maximum at a temperature T(C_max^s) ranging from 0.14 θ₀ to 0.20 θ₀, in contrast with the result T(C_max^s) = 0.21 θ₀ for the Debye-like model. The peak value C_max^s ranges from 0.34 k_BA_SUC to 0.41 k_BA_SUC, where A_SUC is the area of the surface unit cell. The shap the peak in C_v^s differs characteristically between that class of crystals in which there is some overlap of the acoustical and optical bulk bands and that class in which there is an appreciable absolute gap between the acoustical and optical bulk bands; in the latter class the peak is flattened on the low side of the maximum, with the maximum pushed to somewhat higher temperature. On those points of comparison with the rather sparse existing data for surface-excess heat capacity in which the value of specific surface area is not required (e.g., the value of T(C^s_max)), the agreement ranges from encouraging to equivocal. On those comparisons which require the surface area of the experimental samples (e.g., the magnitude of C^s_max) the agreement ranges from only fair to bad. Further experimental work is needed, and great care in surface area determinations is necessary.     

Winkelverteilung der Kernphotoreaktion3He (γ,p)2H

The angular distribution of the photonuclear reaction³He(γ,p)²H was measured with an exitation energyE _x=16 to 27 MeV using a 32.5 MeV betatron. In agreement with a theoretical calculation of Böschet al. we found for the coefficients of the distributionf(θ)=b (a/b+sin²θ(1+β·cosθ+γ·cos²θ)) the values:a/b≦0.14; β=0.77 (+0.14; ?0.07); γ≦0.30. This was the first attempt to use spark chambers as a detection device for photonuclear reactions in the low energy range. We found it to be a promising new facility.     

The (γ, p0) reactions in the giant dipole resonance region of 51V and 52Cr nuclei

The differential cross sections at 90° for the ⁵¹V(e, p₀)⁵⁰Ti and ⁵²Cr(e, p₀ + p₁)⁵¹V reactions have been measured over the giant dipole resonance region. These cross sections were used to obtain the differential cross sections of the ⁵¹V(γ, p₀)⁵⁰Ti and ⁵²Cr(γ, p₀ + p₁)⁵¹V reactions. The results show two peaks that appear at the same energies as the main peaks of the (γ, n) and (γ, p) cross section for both nuclei. The angular distributions of protons from the (e, p) reaction have also been measured at several points of the incident electron energy. The coefficients A₂ obtained by fitting with a series of Legendre polynomials, W(θ) = 1 + A₁P₁(cos θ)+A₂P₂(cos θ), varies with excitation energy. These results are discussed in terms of the direct-semidirect process considering isospin effects in the giant dipole resonance.     

Excimer laser processing as a tool for photocatalytic design of sol-gel TiO2 thin films

Nanostructured sol-gel TiO₂ thin films spin coated on silicate glass plates are subjected to excimer (KrF^*) pulsed laser irradiation in order to tailor their structure and photocatalytic properties. The surface morphology of virgin and laser-processed films are followed applying electron optical imaging and atomic force microscopy. The evolution of the surface roughness and pore formation are shown to be accompanied by optical absorption edge shift to infrared wavelength range. Conventional X-ray diffraction analysis and high-resolution transmission electron imaging are applied in order to obtain information on the phase composition. Co-existence of amorphous and anatase TiO₂ phases in nonirradiated sol-gel films is found. It is established that after laser processing the most intense XRD anatase peak is shifted to lower 2θ range. The analysis of high-resolution transmission electron images of film profiles evidences for the laser induced phase transitions. Formation of rutile and brookite TiO₂ accompanied by evolution of oxygen deficient Ti_nO_2n−1 phases are identified in the subsurface region. The contribution of laser processing for increasing the photocatalytic efficiency of laser-modified films toward the oxidation of methylene blue water solution is demonstrated. The results obtained reveal a novel-processing route for designing sol-gel titania films with improved photocatalytical activity.     

The polarization of protons from the 2H(d, p)3H reaction for deuteron energies below 1 MeV

The angular distribution of proton polarization P^γ' (θ) from the ${}^2\text{H}\text{(}\text{d,}\text{p}\text{)}{}^3\text{H}$ reaction has been measured at 975 keV deuteron energy. Moreover, the energy dependence of P^γ′(E_d) was measured at 45°(lab) for deuteron energies between 250 and 975 keV. The values of σ₀(θ)P^γ' (θ) were fitted in terms of an associated Legendre polynomial expansion. The measured energy dependence of P^γ' (E_d) has been analyzed in terms of barrier-penetration parameters.     

An investigation of phase transformation and crystallinity in laser surface modified H13 steel

This paper presents a laser surface modification process of AISI H13 tool steel using 0.09, 0.2 and 0.4 mm size of laser spot with an aim to increase hardness properties. A Rofin DC-015 diffusion-cooled CO₂ slab laser was used to process AISI H13 tool steel samples. Samples of 10 mm diameter were sectioned to 100 mm length in order to process a predefined circumferential area. The parameters selected for examination were laser peak power, overlap percentage and pulse repetition frequency (PRF). X-ray diffraction analysis (XRD) was conducted to measure crystallinity of the laser-modified surface. X-ray diffraction patterns of the samples were recorded using a Bruker D8 XRD system with Cu?K _α (λ=1.5405 Å) radiation. The diffraction patterns were recorded in the 2θ range of 20 to 80°. The hardness properties were tested at 981 mN force. The laser-modified surface exhibited reduced crystallinity compared to the un-processed samples. The presence of martensitic phase was detected in the samples processed using 0.4 mm spot size. Though there was reduced crystallinity, a high hardness was measured in the laser-modified surface. Hardness was increased more than 2.5 times compared to the as-received samples. These findings reveal the phase source of the hardening mechanism and grain composition in the laser-modified surface.     

Laser-induced periodic surface structures on polymers for formation of gold nanowires and activation of human cells

Frequently observed coherent structures in laser-surface processing are ripples, also denoted as laser-induced periodic surface structures (LIPSS). For polyethylene terephthalate (PET) and polystyrene (PS), LIPSS can be induced by irradiation with linearly polarized ns-pulsed UV laser light. Under an angle of incidence of θ, their lateral period is close to the laser wavelength λ divided by (n _eff ? sinθ). Here, n _eff is the effective refractive index which is 1.32 and 1.23 for PET and PS, respectively. We describe potential applications of LIPSS for alignment and activation of human cells cultivated on polymer substrates, as well as for formation of separated gold nanowires which show pronounced surface plasmon resonances, e.g., at 775 nm for PET.