Novel porphyrin-incorporated hydrogels for photoactive intraocular lens biomaterials

Novel surface-modified hydrogel materials have been prepared by binding charged porphyrins TMPyP (tetrakis(4-N-methylpyridyl)porphyrin) and TPPS (tetrakis(4-sulfonatophenyl)porphyrin) to copolymers of HEMA (2-hydroxyethyl methacrylate) with either MAA (methacrylic acid) or DEAEMA (2-(diethylamino)ethyl methacrylate). The charged hydrogels display strong electrostatic interactions with the appropriate cationic or anionic porphyrins to give materials which are intended to be used to generate cytotoxic singlet oxygen (1O2) on photoexcitation and can therefore be used to reduce postoperative infection of the intraocular hydrogel-based replacement lenses that are used in cataract surgery. The UV/vis spectra of TMPyP in MAA:HEMA copolymers showed a small shift in the Soret band and a change from single exponential (161 micros) triplet decay lifetime in solution to a decay that could be fitted to a biexponential fit with two approximately equal components with tau = 350 and 1300 micros. O2 bubbling reduced the decay to a dominant (90%) component with a much reduced lifetime of 3 micros and a minor, longer lived (20 micros) component. With D2O solvent the 1O2 lifetime was measured by 1270 nm fluorescence as 35 micros in MAA:HEMA, compared to 67 mus in solution, although absorbance-matched samples showed similar yield of 1O2 in the polymers and in aqueous solution. In contrast to the minor perturbation in photophysical properties caused by binding TMPyP to MAA:HEMA, TPPS binding to DEAEMA:HEMA copolymers profoundly changed the 1O2 generating ability of the TPPS. In N2-bubbled samples, the polymer-bound TPPS behaved in a similar manner to TMPyP in its copolymer host; however, O2 bubbling had only a very small effect on the triplet lifetime and no 1O2 generation could be detected. The difference in behavior may be linked to differences in binding in the two systems. With TMPyP in MAA:HEMA, confocal fluorescence microscopy showed significant penetration of the porphyrin into the core of the polymer film samples (>150 microm). However, for TPPS in DEAEMA:HEMA copolymers, although the porphyrin bound much more readily to the polymer, it remained localized in the first 20 microm, even in heavily loaded samples. It is possible that the resulting high concentration of TPPS may have cross-linked the hydrogels to such an extent that it significantly reduced the solubility and/or diffusion rate of oxygen into the doped polymers. This effect is significant since it demonstrates that even simple electrostatic binding of charged porphyrins to hydrogels can have an unexpectedly large effect on the properties of the system as a whole. In this case it makes the apparently promising TPPS/DEAEMA:HEMA system a poor candidate for clinical application as a postoperative antibacterial treatment for intraocular lenses while the apparently equivalent cationic system TMPyP/MAA:HEMA displays all the required properties.     

Determination of chemisorbed metals on planar fused-silica surfaces using thermal lens spectrometry

Thermal lens spectrometry was used to determine the surface concentrations of metals on planar fused-silica surfaces modified with the use of vanadium(V) oxochloride, tin(IV) tetrachloride, and titanium(IV) oxochloride after complexation reactions with 4-(2-pyridylazo)resorcinol and 2-thiazolylazopyrocatechol from aqueous solutions. The surface concentrations of vanadium and titanium found from thermal lens experiments (8 × 10^?11 and 6 × 10^?10 mol/cm², respectively) correlate well with those theoretically calculated based on monolayer and bilayer approximations for metal-containing groups, respectively. The coverage uniformity and the concentration of a chemisorbed substance on a glass surface were evaluated.     

Enhancement of surface wettability via the modification of microtextured titanium implant surfaces with polyelectrolytes

Micrometer- and submicrometer-scale surface roughness enhances osteoblast differentiation on titanium (Ti) substrates and increases bone-to-implant contact in vivo. However, the low surface wettability induced by surface roughness can retard initial interactions with the physiological environment. We examined chemical modifications of Ti surfaces [pretreated (PT), R(a) ≤ 0.3 μm; sand blasted/acid etched (SLA), R(a) ≥ 3.0 μm] in order to modify surface hydrophilicity. We designed coating layers of polyelectrolytes that did not alter the surface microstructure but increased surface ionic character, including chitosan (CHI), poly(L-glutamic acid) (PGA), and poly(L-lysine) (PLL). Ti disks were cleaned and sterilized. Surface chemical composition, roughness, wettability, and morphology of surfaces before and after polyelectrolyte coating were examined by X-ray photoelectron spectroscopy (XPS), contact mode profilometry, contact angle measurement, and scanning electron microscopy (SEM). High-resolution XPS spectra data validated the formation of polyelectrolyte layers on top of the Ti surface. The surface coverage of the polyelectrolyte adsorbed on Ti surfaces was evaluated with the pertinent SEM images and XPS peak intensity as a function of polyelectrolyte adsorption time on the Ti surface. PLL was coated in a uniform thin layer on the PT surface. CHI and PGA were coated evenly on PT, albeit in an incomplete monolayer. CHI, PGA, and PLL were coated on the SLA surface with complete coverage. The selected polyelectrolytes enhanced surface wettability without modifying surface roughness. These chemically modified surfaces on implant devices can contribute to the enhancement of osteoblast differentiation.     

“Cell adhesion resistant,UV curable,polymer zinc oxide nanocomposite materials for intraocular lens application”

Foldable acrylic lenses are used for surgical replacement of diseased intraocular lens in treatment of cataract. One of the main postsurgical complications of this treatment method is postcapsular opacification caused by proliferating epithelial cells. The most common approach taken by research community to address this issue has been modification of lens surface with hydrophobic or hydrophilic moieties to manipulate surface cell interaction. In the present study, inherently cell repellent photopolymer resins are presented. Taking advantage of zinc oxide antiproliferative properties, its nanocomposite resins were made and investigated. Hydrophobically modified zinc oxide nanoparticles and poly(phenylethylacrylate‐co‐phenylethyl methacrylate) were made, and their nanocomposite films were prepared by UV polymerization. Films made with 5 wt% ZnO nanoparticles in them resisted fibroblast attachment substantially. In addition, these films filtered harmful UV light and showed other necessary properties like visible light transparency, glass transition temperatures, mechanical strength, and biocompatibility necessary for making intraocular lenses.     

Tunable thermal lens spectrometry utilizing microchannel-assisted thermal lens spectrometry

A tunable thermal lens spectrometry system was developed for microchip analysis. The system utilized a Xe lamp as an excitation source, instead of a laser. The system can measure the absorption spectrum of a turbid solution without disturbance of the light scattering background.     

Calcification resistance of polyisobutylene and polyisobutylene‐based materials

Calcification of implanted biomaterials is highly undesirable and limits clinical applicability. Experiments were carried out to assess the calcification resistance of polyisobutylene (PIB), PIB‐based polyurethane (PIB‐PU), PIB‐PU reinforced with (CH₃)₃N⁺CH₂CH₂CH₂NH₂ I^?‐modified montmorillonite (PIB‐PU/nc), PIB‐based polyurethane urea (PIB‐PUU), PIB‐PU containing S atoms (PIB_S‐PU), PIB_S‐PU reinforced with (CH₃)₃N⁺CH₂CH₂CH₂NH₂ I^?‐modified montmorillonite (PIB_S‐PU/nc), and poly(isobutylene‐b‐styrene‐b‐isobutylene) (SIBS), relative to that of a clinically widely implanted polydimethylsiloxane (PDMS)–based PU, Elast‐Eon (the “control”). Samples were incubated in simulated body fluid for 28 days at 37°C, and the extent of surface calcification was analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy‐dispersive X‐ray spectroscopy (EDX), X‐ray photoelectron spectroscopy (XPS), and Fourier‐transform‐infrared (FT‐IR) spectroscopy. Whereas the PDMS‐based PU showed extensive calcification, PIB and PIB‐PU containing 72.5% PIB, ie, a polyurethane whose surface is covered with PIB, were free of calcification. PIB_S‐PU and PIB‐PUU, ie, polyurethanes that contain S or urea groups, respectively, were slightly calcified. The amine‐modified montmorillonite‐reinforcing agent reduced the extent of calcification. SIBS was found slightly calcified. Evidently, PIB and materials fully coated with PIB are calcification resistant.     

Thermal lens spectrophotometry

A thermal lens effect induced under laser irradiation is useful for the detection of very small absorptions. This forms the basis of a new technique which is becoming increasingly important as a tool for ultratrace analysis.     

Monopolar surfaces

Following the development of a methodology for determining the apolar components as well as the electron donor and the electron acceptor parameters of the surface tension of polar surfaces, surfaces of a number of quite common materials were found to manifest virtually only electron donor properties and no, or hardly, any electron acceptor properties. Such materials may be called monopolar; they can strongly interact with bipolar materials (e.g., with polar liquids such as water); but one single polar parameter of a monopolar material cannot contribute to its energy of cohesion. Monopolar materials manifesting only electron acceptor properties also may exist, but they do not appear to occur in as great an abundance. Among the electron donor monopolar materials are: polymethylmethacrylate, polyvinylalcohol, polyethyleneglycol, proteins, many polysaccharides, phospholipids, nonionic surfactants, cellulose esters, etc. Strongly monopolar materials of the same sign repel each other when immersed or dissolved in water or other polar liquids. The interfacial tension between strongly monopolar surfaces and water has a negative value. This leads to a tendency for water to penetrate between facing surfaces of a monopolar substance and hence, to repulsion between the molecules or particles of such a monopolar material, when immersed in water, and thus to pronounced solubility or dispersibility. Monopolar repulsion energies can far outweigh Lifshitz-van der Waals attractions as well as electrostatic and "steric" repulsions. In aqueous systems the commonly observed stabilization effects, which usually are ascribed to "steric" stabilization, may in many instances be attributed to monopolar repulsion between nonionic stabilizing molecules. The repulsion between monopolar molecules of the same sign can also lead to phase separation in aqueous solutions (or suspensions), where not only two, but multiple phases are possible. Negative interfacial tensions between monopolar surfactants and the brine phase can be the driving force for the formation of microemulsions; such negative interfacial tensions ultimately decay and stabilize at a value very close to zero. Strongly monopolar macromolecules or particles surrounded by oriented water molecules of hydration can still repel each other, albeit to an attenuated degree. This repulsion was earlier perceived as caused by "hydration pressure". A few of the relevant colloid and surface phenomena are reviewed and re-examined in the light of the influence of surface monopolarity on these phenomena.     

Metal-oxide surfaces

Over the past two decades the amount of effort devoted to the study of metal oxides by surface scientists has increased significantly. The general characteristics of the electronic structure of metal-oxide surfaces are now fairly well understood, although transition-metal oxides have been more thoroughly studied than have non-transition-metal oxides. The geometric arrangement of atoms on the surfaces of a variety of metal oxides has also been determined. Extensive studies have been performed of the interaction of both molecules and metal atoms with metal oxides, where point defects are found to play a dominant role. However, our understanding of the surface properties of metal oxides is still much less compete than it is for metals and semiconductors, and there are several areas where more experimental and theoretical effort needs to be concentrated.     

Molecular potential energy surfaces constructed from interpolation of systematic fragment surfaces

A systematic method for approximating the ab initio electronic energy of molecules from the energies of molecular fragments has previously been presented. Here it is shown that this approach provides a feasible, systematic method for constructing a global molecular potential energy surface (PES) for reactions of a moderate-sized molecule from the corresponding surfaces for small molecular fragments. The method is demonstrated by construction of PESs for the reactions of a hydrogen atom with propane and n-pentane.     

Restructuring of hydrophobic surfaces created by surfactant adsorption to mica surfaces

Hydrophobic surfaces created by the adsorption of a monolayer of surfactants, such as CTAB or DODAB, to mica display long-range mutual attraction when placed in water. Initially, this attraction was considered to be due to hydrophobic interaction, but more careful measurements using AFM showed that the surfactant monolayer undergoes rearrangements to produce charged patches on the surface; therefore, the nature of the long-range interaction is due to the electrostatic interaction between patches. The monolayer rearrangement depends on the nature of the surfactant and its counterion. To study possible monolayer rearrangements in molecular detail, we performed detailed molecular dynamics computer simulations on systems containing a monolayer of surfactants RN(CH(3))(3)(+)Cl(-) (R indicates a saturated hydrocarbon chain) adsorbed on a mica surface and immersed in water. We observe that when chain R is 18 carbons long the monolayer rearranges into a micelle but it remains a monolayer when the chain contains 24 carbons.     

Wettability of biodegradable surfaces

The study of the interfacial characteristics of biodegradable polymers/copolymers is of importance from the point of view of both surface science and pharmaceutical/cosmetic applications. Films formed from biodegradable polymers allow systematic wettability studies on surfaces with a wide range of copolymer (chemical) compositions. The possibility of interchanging these drug carrier polymers, if their wetting characteristics are similar, could be beneficial to diverse applications. Low-rate dynamic contact angles on films (solvent cast on polar substrates, i.e. on silicon wafer) of poly(lactic acid), and its copolymers with poly(glycolic acid), (with four different copolymer ratios of 85/15, 75/25, 65/35 and 50/50) were measured by axisymmetric drop shape analysis-profile (ADSA-P) with four liquids: water, formamide, 2,2′-thiodiethanol and 3-pyridylcarbinol. The solid surface tensions, γ_sv, were calculated from the advancing contact angles, θ_A. The surface topography of the polymer films was investigated by atomic force microscopy (AFM). The surface composition of the polymer layers was analyzed by X-ray photoelectron spectroscopy (XPS). The advancing contact angles were found to be independent of the composition of the copolymers, while the receding angles, θ_R, did decrease with increasing ratio of the polar component [poly(glycolic acid)] in the copolymers. The solid surface tensions calculated from the advancing contact angles of the liquids for all homo- and copolymers were the same within the error limit; the mean value being γ_sv=35.6 ± 0.2 mJ/m². The surface roughness, which was obtained from AFM images, increased with increasing poly(glycolic acid) ratio, without affecting the advancing contact angles. The constancy of γ_sv is attributed to the effect of the surface activity of the nonpolar segments of the polymer chains, which oriented to form the outermost layer of the film. This was confirmed by XPS analysis. Received: 06 November 2000 Accepted: 09 May 2001     

Adsorbate-induced restructuring of surfaces

Adsorbed atoms and molecules frequently cause restructuring of single-crystal surfaces, ranging from small atomic relaxations and reconstructions to macroscopic shape modifications. The occurrence of such adsorbate-induced restructuring is reviewed, and the mechanisms and dynamic time scales are discussed. The importance of adsorbate-induced restructuring in a variety of surface processes is stressed. It is proposed that such restructuring can explain the observed “structure insensitivity” of a class of catalytic reactions, and that it could play a major role in most forms of reactivity.     

Nanorubbing of polythiophene surfaces

This work describes a new orientation method for semicrystalline poly(3-hexylthiophene) (P3HT) thin films, coupling nanorubbing and subsequent crystallization. Using the stylus of an atomic force microscope, we align the polymer chains on P3HT surfaces with a spatial and geometrical control of the oriented domains (nanorubbing). These chain-aligned structures can be made permanent thanks to the crystallization process, which propagates the orientation obtained at the surface to the bulk.     

Superwetting of structured surfaces

Superwetting of structured surfaces, sometimes referred to as hemi-wicking, was studied both experimentally and theoretically. Structured substrates with regular arrays of square pillars or frustra were machined from graphite blocks and then treated to render them lyophilic. Liquids spread over these surfaces to produce noncircular wetting areas. If the channels between the features were made shallower or narrower, liquids wicked more and spread over a larger area. The inherent wettability of the graphite was relatively unimportant; large differences in the contact angles had little influence on the spreading. Practically, this means that, to achieve extensive coverage, near-zero contact angles are not required. A combination of the appropriate surface structure and moderate inherent wettability can effectively flatten liquids, spreading them over very large areas.     

Characterization of semiconductor surfaces

Summary Vibrational spectroscopy (HREELS) in conjunction with atomic hydrogen as a marker may be used for the characterization of differently prepared semiconductur surfaces. First reaction steps of Si with atomic hydrogen show passivation of dangling bonds and depletion of surface states. From the well separated stretching mode intensities of Ge- and Si-hydrides, we are able to estimate the surface concentration of Ge- and Si-atoms at Ge/Si-alloys. For InP, direct evidence is given for the cation (anion) being the active site of adsorption at a cleaved (sputtered) surface. As a second step, bond breaking of substrate surface atoms follows. At higher exposures, corrosion is observed. From the measurement of chemical shifts of vibrational H-stretching modes also the identification of different oxidation stages after catalytic reactions with alkali atoms (cesium) is possible.

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Charakterisierung von Halbleiter-Oberflächen

     

Relationship between lens properties and director orientation in a liquid crystal lens

Lenses with a homogeneously aligned liquid crystal having a Fresnel structure have been prepared by using a nematic with a positive dielectric anisotropy. Their focal length can be varied continuously from the value f_e for an extraordinary ray to f _o for an ordinary ray by applying an electric field across the lens cell. The effective refractive index of the lens where the director is aligned perpendicular to the grooves of the Fresnel structure becomes smaller than when the director is aligned parallel to the grooves. Then the liquid crystal lens has a characteristic aberration which could not be observed in a conventional glass lens; that is, the focal length of the lens becomes different according to the incidence of rays on the different parts of the lens. The properties of the liquid crystal lens can be improved by making the director orientation axially symmetric, in the form of a concentric circle, but the polarization component rotated 90° from the incident extraordinary ray appears when the voltage is applied across the lens cell. This phenomenon is discussed in relation to the optical properties and the director orientation in a liquid crystal prism cell.     

Relationship between lens properties and director orientation in a liquid crystal lens

Lenses with a homogeneously aligned liquid crystal having a Fresnel structure have been prepared by using a nematic with a positive dielectric anisotropy. Their focal length can be varied continuously from the value f_e for an extraordinary ray to f_o for an ordinary ray by applying an electric field across the lens cell. The effective refractive index of the lens where the director is aligned perpendicular to the grooves of the Fresnel structure becomes smaller than when the director is aligned parallel to the grooves. Then the liquid crystal lens has a characteristic aberration which could not be observed in a conventional glass lens; that is, the focal length of the lens becomes different according to the incidence of rays on the different parts of the lens. The properties of the liquid crystal lens can be improved by making the director orientation axially symmetric, in the form of a concentric circle, but the polarization component rotated 90° from the incident extraordinary ray appears when the voltage is applied across the lens cell. This phenomenon is discussed in relation to the optical properties and the director orientation in a liquid crystal prism cell.