Influence of water states in hydrogels on the transmissibility and permeability of oxygen in contact lens materials

The properties of water in soft contact lenses such as the water content, free-to-bound water ratio were key determinants of their oxygen transmissibility characteristics. Differential scanning calorimetry (DSC) was used for measuring the different states of water in hydrogel materials. The convenient apparatus was devised for testing the oxygen permeability coefficient of hydrogel membranes. DSC data showed that the content of freezing water in hydrogel increased with growth of N-vinyl pyrrolidone (NVP) percentage, and the non-freezing water in hydrogel increased with growth of 2-hydroxyethylmethacrylate (HEMA) percentages. It was found that the transmissibility and permeability of oxygen in hydrogel could be described according to the solution-diffusion model. The systematic variations in chemical structure and volume fraction of water in polymer bring about significant changes in oxygen permeability coefficients. The permeability of the material was affected by the freezing water in hydrogel rather than by the non-freezing water.     

Model for UV induced formation of gold nanoparticles in solid polymeric matrices

UV irradiation of polymeric PMMA films containing HAuCl₄ followed by annealing at 60-80 °C forms gold nanoparticles directly within the bulk material. The kinetics of nanoparticle formation was traced by extinction spectra of nanocomposite film changes vs annealing time. We propose that UV irradiation causes HAuCl₄ dissociation and thus provides a polymeric matrix with atomic gold. The presence of an oversaturated solid solution of atomic gold in the polymeric matrix leads to Au nanoparticle formation during annealing. This process can be understood as a phase transition of the first order. In this paper we apply several common kinetic models of the phase transition for describing Au nanoparticle formation inside the solid polymer matrix. We compare predictions of these models with the experimental data and show that these models cannot describe the process. We propose that the stabilization effect of the matrix on the growing gold nanoparticles is important. The simplest model introducing some probability for the transition from growing nanoparticle to the non-growing, stabilized form is suggested. It is shown that this model satisfactorily describes the experimentally observed evolution of the extinction spectrum of Au nanoparticles forming in a polymer matrix.     

Third order nonlinear optical studies of bromocresol purple in liquid and solid media

The quest for materials exhibiting high nonlinear refraction and absorption are required for photonic device application. In this paper we report a simplified Z-scan technique, to study the optical nonlinearity of the dye bromocresol purple in methanol and ethanol for different concentration and dye doped polymer film at the wavelength 532 nm of Nd:YAG laser. The experimental results show that the investigated organic dye molecule exhibits saturation absorption and negative nonlinearity. The nonlinear absorption co-efficient and the nonlinear refractive index were measured for the dye doped film, and for dye in methanol and ethanol at the concentration of 0.03 mM and 0.05 mM. The measured third order susceptibility was found to be of the order of 10⁻⁶ e.s.u. in both solid and liquid medium. The result shows that the dye has potential applications in nonlinear optics.     

Combinatorial study of nanoparticle dispersion in surface-grafted macromolecular gradients

Surface-tethered assemblies of polymers with gradually varying molecular weight (MW) and/or grafting density are utilized to control the dispersion of nanosized particles. Using several case studies we show that these gradient polymer specimens represent ideal systems for combinatorial exploration of the parameters that control the distribution of the particles in surface-grafted layers. We demonstrate that the particle distribution is governed by the interplay between the particle size and the grafting density and molecular weight of the polymer brush.     

Protein adsorption resistant surface on polymer composite based on 2D- and 3D-controlled grafting of phospholipid moieties

To prepare the biocompatible surface, a phosphorylcholine (PC) group was introduced on this hydroxyl group generated by surface hydrolysis on the polymer composite composed of polyethylene (PE) and poly (vinyl acetate) (PVAc) prepared by supercritical carbon dioxide. Two different procedures such as two-dimensional (2D) modification and three-dimensional (3D) modification were applied to obtain the steady biocompatible surface. 2D modification was that PC groups were directly anchored on the surface of the polymer composite. 3D modification was that phospholipid polymer was grafted from the surface of the polymer composite by surface-initiated atom transfer radical polymerization (SI-ATRP) of 2-methacryloyloxyethyl phosphorylcholine (MPC). The surfaces were characterized by X-ray photoelectron spectroscopy, dynamic water contact angle measurements, and atomic force microscope. The effects of the poly(MPC) chain length on the protein adsorption resistivity were investigated. The protein adsorption on the polymer composite surface with PC groups modified by 2D or 3D modification was significantly reduced as compared with that on the unmodified PE. Further, the amount of protein adsorbed on the 3D modified surface that is poly(MPC)-grafted surface decreased with an increase in the chain length of the poly(MPC). The surface with an arbitrary structure and the characteristic can be constructed by using 2D and 3D modification. We conclude that the polymer composites of PE/PVAc with PC groups on the surface are useful for fabricating biomedical devices due to their good mechanical and surface properties.     

Determination of the optimal wavelength for temperature independent detection of commercial gasoline with a polymer cladding optical fiber

An influence of temperature variations on transmission of a polymer cladding silica core (PCS) optical fiber was investigated in a wide spectral range covering the first (1710 nm) and the second (1170 nm) vibrational overtone bands of gasoline absorption. Thermo-induced changes of the fiber background transmittance have strong dependence on wavelength. A narrow wavelength band around 1214 nm was found to be almost free from the thermal effects while maintaining sufficient sensitivity for gasoline detection.     

Multimode interference wavelength multi/demultiplexer for 1310 and 1550 nm operation based on BCB 4024-40 photodefinable polymer

A 1310 and 1550 nm coarse wavelength multi/demultiplexer based on benzocyclobutene (BCB 4024-40) polymer is demonstrated for the first time. The device is designed based on a combination of general interference and paired interference mechanisms of multimode interference (MMI). It is fabricated on BK7 glass substrate with a thin layer of SiO₂ as cover. A cost effective chemical etching technique is used in the fabrication process to take advantage of the photosensitive nature of the polymer. The device length was significantly reduced by adopting the restricted multimode interference scheme, lower beat length ratio and cascaded MMI couplers. The measured crosstalk at 1310 nm was 14.4 dB and at 1550 nm was 20.6 dB. The measured insertion loss is around 3.2-3.5 dB for both ports.     

Isotropic photonic bandgap in Penrose textured metallic mircocavity

Photonic microcavity has modified photonic modes that have intense localized electric field, which can couple strongly with the embedded emission centers. In this work, we fabricated 2D photonic microcavities with Penrose quasicrystal pattern with 10-fold symmetry. Organic luminescence material tris(8-hydroxyquinoline) aluminum (Alq₃) was embedded into the microcavity and the angle resolved transmission (ART) and photoluminescence (ARPL) spectra of the microcavity were measured. The results showed that the normal Gaussian photoluminescence spectrum of Alq₃ has been strongly modified by the microcavity dispersion characteristic. In addition, omni-directional photonic band gap exists in the microcavity. The higher symmetry of Penrose quasicrystal pattern means that there was minimal difference in the directional dispersion characteristics.     

Tunable cell membrane mimetic surfaces prepared with a novel phospholipid polymer

A novel method to fabricate and tune cell membrane mimetic surfaces was developed based on the use of an amphiphilic random copolymer bearing phosphorylcholine (PC), stearyl and crosslinkable trimethoxysilylpropyl groups synthesized by free radical copolymerization. The polymer was coated on glass coverslips by dip-coating. The coated films were treated in water allowing reorganization of the surface groups to mimic the structure of cell outer membranes. This structure was fixed by crosslinking of the trimethoxysilylpropyl groups linked to the copolymer chains, as ascertained by dynamic contact angle (DCA) and attenuated total reflectance infrared spectroscopy (ATR-FTIR) measurements. Our results indicate that the surface structure can be tuned to a great extent to obtain a stable outer membrane mimetic surface/interface.     

Ultra fast third-order non-linear response of amino-triazole donor-acceptor derivatives by optical Kerr effect

We report the study of the temporal dependence of the non-linear optical response of novel organic materials in solution. The experimental results of the optical Kerr gate using 70 fs pulses show a quasi-instantaneous response for three derivatives of an amino-triazole donor-acceptor system. The non-linearity of the compounds is identified as arising from the electronic contribution to the third-order non-linear susceptibility. The non-linear parameters of each sample were obtained using the optical Kerr response of CS₂ as reference.     

Effects of metallization and bromination on nonlinear optical properties of diphenylporphyrins

Nonlinear refraction and nonlinear absorption of diphenylporphyrins with bromination and metallization were studied by Z-scan technique in nanosecond and picosecond regimes. Results show that both metallization and bromination of diphenylporphyrins can cause the regular change of magnitude and sign of nonlinear absorption. The transition between saturable absorption and reverse saturable absorption happens as bromine increases and metal ion changes. The effect of bromination on nonlinear refraction is small, the change of nonlinear refraction is mainly attributed to the metallization. Influences of photophysical parameters on nonlinear absorption and nonlinear refraction have been elucidated using five-level models.     

Poly(N-vinyl carbazole)-grafted multiwalled carbon nanotubes: Synthesis via direct free radical reaction and optical limiting properties

In this work, samples of poly(N-vinyl carbazole) (PVK)-grafted multiwalled carbon nanotubes (MWCNTs) were synthesized via free radical reaction. The ready-made PVK was allowed to react directly with MWCNTs at 70 °C in the presence of azo-bis-isobutyronitrile (AIBN). The purified deep grey products, which can dissolve in common organic solvents such as chloroform and 1,2-dichlorobenzene (DCB), were then characterized by FTIR spectra, TEM, TGA, elemental analysis, XPS, UV-vis spectra and Raman spectra. It was confirmed that PVK chains were grafted onto the surface of the carbon nanotubes (CNTs). The optical limiting properties of these PVK-grafted MWCNTs samples were investigated by open-aperture z-scan method. All of the samples of PVK-modified carbon nanotubes in chloroform showed optical limiting behavior better than that of C₆₀ in toluene.     

Theoretical investigation of ethylene/1-butene copolymerization process using constrained geometry catalyst (CpSiH2NH)-Ti-Cl2

The ethylene/1-butene copolymerization using constrained geometry catalyst CpSiH₂-NH-TiCl₂ (CGC) was investigated by the density functional theory and molecular dynamics. Structures and energetics of reactants, π-complexes, transition states, and products during insertion of ethylene and 1-butene monomers into the catalytic reactive site of the CGC were investigated by the density functional theory (DFT) using the software Dmol³, while dynamics of atoms during copolymerization process was investigated by classical molecular dynamics (MD) using the New-Ryudo-CR program. The calculated results were compared with the available experimental and theoretical ones. It was found that the ethylene insertion into Ti-Me active species is energetically more favorable than the butene one and the 2,1-butene insertion is more favorable than 1,2-butene one. Once the initial ethylene insertion has taken place, the further ethylene insertion occurring with a less energy barrier, in good agreement with experimental findings.     

Collagen-grafted temperature-responsive nonwoven fabric for wound dressing

Polypropylene (PP) nonwoven fabric (NWF) was modified by direct current pulsed plasma followed by grafting with acrylic acid (AAc) to improve its surface hydrophilicity and to introduce carboxylic acid group on the surface for further conjugation with bioactive collagen biomolecule. To endow temperature-responsive property, PP-g-collagen NWF was further modified with poly(N-isopropylacrylamide) (PNIPAAm). Experimental results demonstrated that the amount of AAc and collagen grafted were 43.4 nmole/cm², and 35.9 μg/cm², respectively. The amount of PNIPAAm immobilized was 213 μg/cm². The physical properties, surface chemical composition, and microstructure of the NWFs were characterized. From animal study, modified NWFs were found to promote wound healing with bigraft PP-g-collagen-g-PNIPAAm NWF showing the best performance.     

Surface-grafted block copolymer gradients: Effect of block length on solvent response

We outline a method to fabricate gradient combinatorial libraries that explore architectural parameters of surface-grafted block copolymers (BCs). In addition, we demonstrate the utility of such libraries for the rapid, thorough assessment of the response of grafted BCs to solvent exposure. Our fabrication route uses surface-initiated controlled radical polymerization to produce a tethered polymer block with uniform length (in this case, poly(n-butyl methacrylate), PBMA), followed by a graded synthesis that adds a second block that varies in its length over the library (here, poly(2-(N,N′-dimethylamino)ethyl methacrylate), PDMAEMA). Our demonstration study maps the response of PBMA and PDMAEMA blocks to hexane and water, and defines regimes of behavior to this respect. Moreover, our study illuminates a narrow BC composition window that exhibits the strongest possible response to water and hexane treatment.     

Electrostatic spray deposited zinc oxide films for gas sensor applications

In this work, thin films of zinc oxide (ZnO) for gas-sensor applications were deposited on platinum coated alumina substrate, using electrostatic spray deposition (ESD) technique. As precursor solution zinc acetate in ethanol was used. Scanning electron microscopy (SEM) evaluation showed a porous and homogeneous film morphology and the energy dispersive X-ray analysis (EDX) confirmed the composition of the films with no presence of other impurities. The microstructure studied with X-ray diffraction (XRD) and Raman spectroscopy indicated that the ZnO oxide films are crystallized in a hexagonal wurtzite phase. The films showed good sensitivity to 1 ppm nitrogen dioxide (NO₂) at 300 °C while a much lower sensitivity to 12 ppm hydrogen sulphide (H₂S).     

Symmetries of discontinuous flows and the dual Rankine-Hugoniot conditions in fluid dynamics

It has recently been shown that the maximal kinematical invariance group of polytropic fluids, for smooth subsonic flows, is the semidirect product of SL (2, R) and the static Galilei group G. This result purports to offer a theoretical explanation for an intriguing similarity, that was recently observed, between a supernova explosion and a plasma implosion. In this paper we extend this result to discuss the symmetries of discontinuous flows, which further validates the explanation by taking into account shock waves, which are the driving force behind both the explosion and implosion. This is accomplished by constructing a new set of Rankine-Hugoniot conditions, which follow from Noether’s conservation laws. The new set is dual to the standard Rankine-Hugoniot conditions and is related to them through the SL (2, R) transformations. The entropy condition, that the shock needs to satisfy for physical reasons, is also seen to remain invariant under the transformations.     

Structural properties and scaling of the radius of gyration of two-dimensional star-branched polymers grown by diffusion

We built up star-branched polymers, whose morphology is fully determined by diffusion, with p=1,3,6 and 12 branches with a total of 30,000 monomer units. We investigated their structural properties by calculating the monomer-monomer correlation functions. A detailed finite size scaling analysis of the radius of gyration was also performed to determine the exponent and the corrections to scaling. From these results we calculated the fractal dimension of the branched aggregates and obtained: d_f=1.222(7), for the linear chain, d_f=1.2305(8), d_f=1.247(8) and d_f=1.261(8) for the three, six and twelve branches polymer, respectively.     

Strong optical limiting property of a ball-type supramolecular zinc-phthalocyanine in polymer-phthalocyanine composite film

The nonlinear absorption and optical limiting (OL) performance of a supramolecular hexa-phthalocyaninato-hexazinc (II) with hexylthio substituents in solution and in the solid-state have been described using the open-aperture Z-scan technique. The measurements were performed using collimated 4 ns pulses generated from a frequency-doubled Nd:YAG laser at 532 nm wavelength. The results indicated that OL performance of the investigated compound in the polymeric film is much better compared to properties in solution. With the excellent combination of OL parameters the investigated compound in the solid-state is a candidate for the use as optical limiter.     

The effect of polymer coatings on switching behavior and cycling durability of Pd/Mg-Ni thin films

Although Pd-capped Mg-Ni alloy switchable mirror thin films have potential applications in smart windows and optical switches, they degrade quickly and cannot be switched after about 150 cycles. This must be improved for practical use. In this study, we tested several polymer coatings on the surface of Pd/Mg₄Ni switchable mirror thin films as a protective membrane and evaluated the optical switching property and durability. The polymer membrane is able to suppress the oxidization of Mg because it has an excellent gas separation characteristic. Polymer coating extended the switching durability of samples to about 1000 cycles. In addition, the transmittance of the thin film in the transparent state is improved by the coating.