Speckle reduction in quantitative phase imaging by generating spatially incoherent laser field at electroactive optical diffusers.

We studied quantitative phase imaging (QPI) using coherent laser illumination coupled with static and moving optical diffusers. The spatial coherence of a continuous-wave laser was controlled by tuning the particle size and the diffusion angle of optical diffusers for speckle-reduced 3D phase imaging of transparent objects. We used a common-path QPI configuration to investigate the coherent phase mapping of polystyrene micro-beads and breast cancer cells (MCF-7) under different degrees of coherent speckles. The proposed speckle reduction method could provide an avenue for enhancing lateral resolution and suppressing coherent artifacts of the phase images from QPI.

Femtosecond-Laser-Based 3D Printing for Tissue Engineering and Cell Biology Applications.

Fabrication of 3D cell scaffolds has gained tremendous attention in recent years because of its applications in tissue engineering and cell biology applications. The success of tissue engineering or cell interactions mainly depends on the fabrication of well-defined microstructures, which ought to be biocompatible for cell proliferation. Femtosecond-laser-based 3D printing is one of the solution candidates that can be used to manufacture 3D tissue scaffolds through computer-aided design (CAD) which can be efficiently engineered to mimic the microenvironment of tissues. UV-based lithography has also been used for constructing the cellular scaffolds but the toxicity of UV light to the cells has prevented its application to the direct patterning of the cells in the scaffold. Although the mask-based lithography has provided a high resolution, it has only enabled 2D patterning not arbitrary 3D printing with design flexibility. Femtosecond-laser-based 3D printing is trending in the area of tissue engineering and cell biology applications due to the formation of well-defined micro- and submicrometer structures via visible and near-infrared (NIR) femtosecond laser pulses, followed by the fabrication of cell scaffold microstructures with a high precision. Laser direct writing and multiphoton polymerization are being used for fabricating the cell scaffolds, The implication of spatial light modulators in the interference lithography to generate the digital hologram will be the future prospective of mask-based lithography. Polyethylene glycol diacrylate (PEG-DA), ormocomp, pentaerythritol tetraacrylate (PETTA) have been fabricated through TPP to generate the cell scaffolds, whereas SU-8 was used to fabricate the microrobots for targeted drug delivery. Well-designed and precisely fabricated 3D cell scaffolds manufactured by femtosecond-laser-based 3D printing can be potentially used for studying cell migration, matrix invasion and nuclear stiffness to determine stage of cancer and will open broader horizons in the future in tissue engineering and biology applications.

Polymeric Nanomaterials Based on the Buckybowl Motif: Synthesis through Ring-Opening Metathesis Polymerization and Energy Storage Applications.

Ring-opening metathesis polymerization (ROMP) of buckybowl corannulene-based oxa-norbornadiene monomer is shown to give rise to polymeric nanomaterials with an average pore size of about 1.4 nm and a surface area of 49.2 m2/g. Application in supercapacitor devices show that the corannulene-based nanomaterials exhibit a specific capacitance of 134 F·g-1 (1.0 V voltage window) in a three-electrode cell configuration. Moreover, the electrode assembled from these materials in a symmetric configuration (1.6 V voltage window) exhibits long-term cyclability of 90% capacitance retention after undergoing 10000 cycles. This work demonstrates that ROMP is a valuable method in synthesizing nanostructured corannulene polymers, and that materials based on the nonplanar polycyclic aromatic motif represents an attractive active component for fabrication of devices targeted at electrochemical energy storage applications.

3D Printed Polycaprolactone Carbon Nanotube Composite Scaffolds for Cardiac Tissue Engineering.

Fabrication of tissue engineering scaffolds with the use of novel 3D printing has gained lot of attention, however systematic investigation of biomaterials for 3D printing have not been widely explored. In this report, well-defined structures of polycaprolactone (PCL) and PCL- carbon nanotube (PCL-CNT) composite scaffolds have been designed and fabricated using a 3D printer. Conditions for 3D printing has been optimized while the effects of varying CNT percentages with PCL matrix on the thermal, mechanical and biological properties of the printed scaffolds are studied. Raman spectroscopy is used to characterise the functionalized CNTs and its interactions with PCL matrix. Mechanical properties of the composites are characterised using nanoindentation. Maximum peak load, elastic modulus and hardness increases with increasing CNT content. Differential scanning calorimetry (DSC) studies reveal the thermal and crystalline behaviour of PCL and its CNT composites. Biodegradation studies are performed in Pseudomonas Lipase enzymatic media, showing its specificity and effect on degradation rate. Cell imaging and viability studies of H9c2 cells from rat origin on the scaffolds are performed using fluorescence imaging and MTT assay, respectively. PCL and its CNT composites are able to show cell proliferation and have the potential to be used in cardiac tissue engineering.

Enhanced rare earth photoluminescence in inverse opal photonic crystals and its application for pH sensing.

Concentration quenching effects of identical rare earth (RE) activator ions and energy transfer (ET) between different RE ions often compromise the photoluminescence (PL) quantum efficiency in RE based luminescence materials. Here, we demonstrate that in NaGd(WO4)2:Tb(3+), Eu(3+) inverse opal photonic crystals (IOPCs), the suppression of the emission line located in the photonic stop band (PSB) and a dramatic increase of the lifetimes of Eu(3+) and Tb(3+) ions are observed. More interestingly, the concentration quenching among Eu(3+) ions and ET from Tb(3+) to Eu(3+) is significantly relieved owing to the periodic empty cavity structure of IOPCs. As a consequence, the luminescent quantum efficiency (QE) of the NaGd(WO4)2:Tb(3+), Eu(3+) IOPCs increases ∼2 times more than that of crushed NaGd(WO4)2:Tb(3+), Eu(3+) powder. In addition, a reusable pH sensor with good linear response (pH 5-10) has been designed based on the high surface-to-volume ratio, high connectivity, and enhanced luminescence of NaGd(WO4)2:Tb(3+), Eu(3+)IOPCs, which could be applied to the dynamical detection of pH value.

Polymeric Biomaterials for Medical Implants and Devices.

In this review article, we focus on the various types of materials used in biomedical implantable devices, including the polymeric materials used as substrates and for the packaging of such devices. Polymeric materials are used because of the ease of fabrication, flexibility, and their biocompatible nature as well as their wide range of mechanical, electrical, chemical, and thermal behaviors when combined with different materials as composites. Biocompatible and biostable polymers are extensively used to package implanted devices, with the main criteria that include gas permeability and water permeability of the packaging polymer to protect the electronic circuit of the device from moisture and ions inside the human body. Polymeric materials must also have considerable tensile strength and should be able to contain the device over the envisioned lifetime of the implant. For substrates, structural properties and, at times, electrical properties would be of greater concern. Section 1 gives an introduction of some medical devices and implants along with the material requirements and properties needed. Different synthetic polymeric materials such as polyvinylidene fluoride, polyethylene, polypropylene, polydimethylsiloxane, parylene, polyamide, polytetrafluoroethylene, poly(methyl methacrylate), polyimide, and polyurethane have been examined, and liquid crystalline polymers and nanocomposites have been evaluated as biomaterials that are suitable for biomedical packaging (section 2). A summary and glimpse of the future trend in this area has also been given (section 3). Materials and information used in this manuscript are adapted from papers published between 2010 and 2015 representing the most updated information available on each material.

Long-term in vitro hydrolytic stability of thermoplastic polyurethanes.

Long-term in vitro stability of thermoplastic polyurethanes (TPUs) was studied for up to 52 weeks in phosphate buffer solution at 37, 55, and 80°C. Water uptake, molecular weights, and tensile properties were measured at regular intervals of 4, 8, 16, 32, and 52 weeks. The rate of molecular weight reduction increased with increasing temperature, and after 52 weeks at 80°C, all commercial polycarbonate (Bionate-55D, Quadrathane-80A, and Chronoflex-80A), poly(dimethylsiloxane) (ElastEon-2A) and polyether (Elasthane-55D) TPUs showed significant (43-51%) molecular weight (Mn ) reduction. The polyisobutylene (PIB)-based TPU exhibited a significantly lower decrease in Mn (26%) after 52 weeks at 80°C. For Bionate-55D and ElastEon-2A, at 80°C in dry nitrogen atmosphere substantial thermal degradation was observed, while for the other TPUs the effect of thermal degradation is small. The temperature dependent reduction of molecular weight was interpreted by simple second order kinetics. From the approximately linear Arrhenius plots the activation energies were calculated, which were highest for PIB-PU-020 and lowest for ElastEon-2A. For Elasthane-55D the in vitro molecular weight reduction was compared with that of explanted leads. The molecular weight reduction in vivo was much smaller than that predicted from in vitro data, which may suggest that the in vitro model does not adequately describe the hydrolysis in vivo. In the absence of validation for the other TPUs that in vitro methods closely reproduce in vivo degradation, it is unknown how these results correlate with in vivo performance.

Self-assembled aliphatic chain extended polyurethane nanobiohybrids: emerging hemocompatible biomaterials for sustained drug delivery.

Novel polyurethanes (PUs) have been synthesized using an aliphatic diisocyanate and aliphatic chain extenders with varying chain length. Nanocomposites of PUs have been prepared by dispersing 2-D nanoclay in poly-ol followed by prepolymerization and subsequent chain extension using various chain extenders. Systematic improvement in toughness and adequate enhancement in stiffness in the presence of nanoclay has been observed for PUs with longer chain extenders, and these new classes of nanocomposites exhibit no toughness-stiffness trade-off. Bottom-up self-assembly starting from the molecular level to micron-scale crystallite has been revealed through electronic structure calculation, X-ray diffraction, small-angle neutron scattering, atomic force microscopy and optical images. The role of hydrogen bonding has been revealed for this type of supramolecular assembly, and in the presence of organically modified nanoclay hydrogen bonding contributes to the formation of bigger clusters of nanocomposites. Controlled biodegradation of PU and its nanocomposites has been investigated in enzymatic media. Biocompatibility of these novel nanocomposites has been extensively verified through platelet adhesion, aggregation and hemolysis assay. Sustained drug delivery by biocompatible pristine PU and its nanocomposites has been demonstrated either by controlling the crystallite size of the polyurethane through alteration of the aliphatic chain length of the extender or by incorporating disc-like nanoclay, creating a tortuous path that results in delayed diffusion. Hence, the developed nanohybrids are potential biomaterials for tissue engineering and drug delivery.

Polycaprolactone composites with TiO2 for potential nanobiomaterials: tunable properties using different phases.

TiO(2) nanoparticles of different phases play a key role in property alteration of nanocomposite fibers. Polycaprolactone (PCL)/TiO(2) composite fibers were prepared using the electrospinning method. Pure anatase and rutile phases were synthesized using the sol-gel route for nanocomposite synthesis. The Effect of nanoparticle phases on crystallinity of fibers and interaction with polymer molecules have been studied using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, morphology through SEM, surface properties using BET method and wetting property of fibers commencing from contact angle measurement. Biocompatibility and biodegradation of hybrid materials have been studied in simulated body fluid (SBF) and phosphate buffer (PBS), respectively. The anatase phase with smaller particle dimensions exhibited significant improvement of most of the properties as compared to composites made of the rutile phase. Better interaction between polymer chain and anatase particle PCL-A nanocomposite fibers leads to better mechanical property and biocompatibility vis-à-vis PCL-R and pristine PCL fibers. Biocompatibility of PCL nanocomposite has been testified through proliferation of fibroblast cell and its adhesion; MTT (3-(4,5-dimethythiazol-2-yl)-2,5-diphenyl tetrazolium bromide) assay demonstrates good proliferation rate for cells on PCL-A nanocomposite fibres.

Effects of nanoclay and polyurethanes on inhibition of mild steel corrosion.

Sulfonated polyurethanes (SPU) were used as corrosion inhibitor for mild steel in acidic solution. The sulfonation of the > N-H groups of the urethane linkages was confirmed from Nuclear Magnetic Resonance (NMR) and Fourier Transform Infra Red (FTIR) spectroscopic techniques. The inhibition efficiency of sulfonated polyurethanes, prepared from two different routes, was investigated using different techniques. The effects of microstructure of polyurethane (PU), degree of sulfonation, time of immersion and temperature on the inhibition of corrosion were discussed. The disc-like nanoparticles, so-called nanoclay, either suspended or chemically attached to SPU chains (nanocomposites) dramatically enhanced the inhibition efficiency for mild steel in acidic medium. All the inhibitors retard the corrosion rate by getting themselves adsorbed on the corroding surface by following the Langmuir adsorption isotherm. The surface analysis of inhibited and uninhibited samples was performed using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Among the various inhibitors used, the nanocomposite of polyurethane was the most effective. Molecular modeling helped in determining the extent of packing of the SPU chains leading to better inhibition efficiency.

Nanostructure to microstructure self-assembly of aliphatic polyurethanes: the effect on mechanical properties.

We report the step by step self-assembly from nanostructure to microstructure (bottom-up approach through X-ray diffraction (1.6 nm), small angle neutron scattering (SANS) (11.6 nm), atomic force microscopy (70 nm smaller crystallite from enlarged image and 450 nm greater crystallites), and polarizing optical microscope (2 microm)) of aliphatic polyurethanes (PU) in contrast to aromatic polyurethanes depending on hard segment content (HSC). Polyurethanes of 10 to 80% HSC have been synthesized by using appropriate amount of polyol and chain extender. The effect of self-assembled patterns on mechanical properties both in solid and liquid state has been established exhibiting structure-property relationship of supramolecular polyurethanes. The crystallinity enhances but the degradation temperature decreases with increasing HSC. The characteristic length (measure of gap between lamellar crystallites), as revealed from SANS, gradually decreases with increasing HSC suggesting compactness of the crystallites through extensive hydrogen bonding. The Young's modulus increases with increasing HSC with a percolation threshold of hard segment (50%) while the toughness improves up to 30% HSC followed by gradual decrease in presence of bigger crystallites which promote brittle fracture. The origin of self-assembly in aliphatic PUs has been demonstrated through electronic structure calculations to form a loop structure with minimum intermolecular distance (2.2 A) while that distance is quite large in aromatic polyurethanes (4.6 A) that cannot form hydrogen bonds. The unique splintering of domain structure and its subsequent reformation under dynamic shear experiment has been established.