Vapor phase synthesis of ferroelectric microislands on PVDF thin films.

The interest in patterned polyvinylidene fluoride (PVDF) surfaces has grown significantly in the recent years due to ability to control the ferroelectric behavior through the size and shape of the surface structures. However, forming micron sized structures on the PVDF surface generally requires laborious lithography based methods or use of templates which complicates the process. In this study, we report spontaneous formation of microislands with ferroelectric response during PVDF growth via initiated chemical vapor deposition. Depositions performed under continuous and no flow conditions show that laminar precursor flow to the surface yield homogenous thin films, whereas no flow conditions of the batch mode result in the growth of surface protrusions (microislands) with higher polar phase content. Formation of these surface instabilities after an incubation time indicates the presence of local stress fields building with time, resulting in formation of the islands with higherßphase fraction to release the stress. Furthermore, the increased mobility of the polymer chains at high temperatures reduces the stress field, leading to lowerß/αphase ratios in smaller microislands.

Coaxial nanotubes of stimuli responsive polymers with tunable release kinetics.

Stimuli responsive polymeric (SRP) nanotubes have great potential as nanocarriers of macromolecules due to their large surface areas and release mechanisms that can be activated externally. In this work, we demonstrate vapor phase synthesis of coaxial nanotubes with layers of different SRP polymers for improved release kinetics. Temperature responsive poly(N-isopropylacrylamide) (pNIPAAm), pH responsive poly(methacrylic acid) (pMAA) and poly(hydroxyethyl methacrylate) (pHEMA) are used to fabricate the responsive coaxial nanotubes and the phloroglucinol dye is used as the model molecule to study the release kinetics. Fastest release is observed with single layer pNIPAAm nanotubes with rates of 0.134 min(-1), whereas introducing pHEMA or pMAA as inner layers slows down the release, enabling tuning of the response. Furthermore, repeating the release studies multiple times shows that the release rates remain similar after each run, confirming the stability of the nanotubes.

Microworm optode sensors limit particle diffusion to enable in vivo measurements.

There have been a variety of nanoparticles created for in vivo uses ranging from gene and drug delivery to tumor imaging and physiological monitoring. The use of nanoparticles to measure physiological conditions while being fluorescently addressed through the skin provides an ideal method toward minimally invasive health monitoring. Here we create unique particles that have all the necessary physical characteristics to serve as in vivo reporters, but with minimized diffusion from the point of injection. These particles, called microworms, have a cylindrical shape coated with a biocompatible porous membrane that possesses a large surface-area-to-volume ratio while maintaining a large hydrodynamic radius. We use these microworms to create fluorescent sodium sensors for use as in vivo sodium concentration detectors after subcutaneous injection. However, the microworm concept has the potential to extend to the immobilization of other types of polymers for continuous physiological detection or delivery of molecules.

Selective determination of an ovarian cancer biomarker at low concentrations with surface imprinted nanotube based chemosensor.

In this study, an electrochemical chemosensor that utilizes a conductive polymer-based molecularly imprinted polymer (MIP) surface for rapid and reliable determination of CA125 was devised. A novel method has been applied to fabricate CA125 imprinted polypyrrole nanotubes (MI-PPy NT) via vapor deposition polymerization (VDP) as a recognition element for highly selective and sensitive determination of CA125. The chemosensor was prepared by immobilizing MI-PPy NT onto screen-printed gold electrodes (Au-SPE) and the performance of the sensor was evaluated by cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) in terms of selectivity, sensitivity, linear dynamic concentration range (LDR) and limit of detection (LOD). The MI-PPy NT@Au-SPE sensor exhibited high sensitivity (68.57 µA per decade) to the CA125 concentration ranging from 0.1 U mL-1 to 100 U mL-1 at an LOD of 0.4 U mL-1 with a correlation coefficient of 0.9922. The developed chemosensors with their novel design combined with a facile fabrication method, prove to be promising as future state-of-the-art biosensors.

Fabrication of a Dual-Drug-Loaded Smart Niosome-g-Chitosan Polymeric Platform for Lung Cancer Treatment.

Changes in weather conditions and lifestyle lead to an annual increase in the amount of lung cancer, and therefore it is one of the three most common types of cancer, making it important to find an appropriate treatment method. This research aims to introduce a new smart nano-drug delivery system with antibacterial and anticancer capabilities that could be applied for the treatment of lung cancer. It is composed of a niosomal carrier containing curcumin as an anticancer drug and is coated with a chitosan polymeric shell, alongside Rose Bengal (RB) as a photosensitizer with an antibacterial feature. The characterization results confirmed the successful fabrication of lipid-polymeric carriers with a size of nearly 80 nm and encapsulation efficiency of about 97% and 98% for curcumin and RB, respectively. It had the Korsmeyer-Peppas release pattern model with pH and temperature responsivity so that nearly 60% and 35% of RB and curcumin were released at 37 °C and pH 5.5. Moreover, it showed nearly 50% toxicity against lung cancer cells over 72 h and antibacterial activity against Escherichia coli. Accordingly, this nanoformulation could be considered a candidate for the treatment of lung cancer; however, in vivo studies are needed for better confirmation.

CVD of polymeric thin films: applications in sensors, biotechnology, microelectronics/organic electronics, microfluidics, MEMS, composites and membranes.

Polymers with their tunable functionalities offer the ability to rationally design micro- and nano-engineered materials. Their synthesis as thin films have significant advantages due to the reduced amounts of materials used, faster processing times and the ability to modify the surface while preserving the structural properties of the bulk. Furthermore, their low cost, ease of fabrication and the ability to be easily integrated into processing lines, make them attractive alternatives to their inorganic thin film counterparts. Chemical vapor deposition (CVD) as a polymer thin-film deposition technique offers a versatile platform for fabrication of a wide range of polymer thin films preserving all the functionalities. Solventless, vapor-phase deposition enable the integration of polymer thin films or nanostructures into micro- and nanodevices for improved performance. In this review, CVD of functional polymer thin films and the polymerization mechanisms are introduced. The properties of the polymer thin films that determine their behavior are discussed and their technological advances and applications are reviewed.

Responsive microgrooves for the formation of harvestable tissue constructs.

Given its biocompatibility, elasticity, and gas permeability, poly(dimethylsiloxane) (PDMS) is widely used to fabricate microgrooves and microfluidic devices for three-dimensional (3D) cell culture studies. However, conformal coating of complex PDMS devices prepared by standard microfabrication techniques with desired chemical functionality is challenging. This study describes the conformal coating of PDMS microgrooves with poly(N-isopropylacrylamide) (PNIPAAm) by using initiated chemical vapor deposition (iCVD). These microgrooves guided the formation of tissue constructs from NIH-3T3 fibroblasts that could be retrieved by the temperature-dependent swelling property and hydrophilicity change of the PNIPAAm. The thickness of swollen PNIPAAm films at 24 °C was approximately 3 times greater than at 37 °C. Furthermore, PNIPAAm-coated microgroove surfaces exhibit increased hydrophilicity at 24 °C (contact angle θ = 30° ± 2) compared to 37 °C (θ = 50° ± 1). Thus PNIPAAm film on the microgrooves exhibits responsive swelling with higher hydrophilicity at room temperature, which could be used to retrieve tissue constructs. The resulting tissue constructs were the same size as the grooves and could be used as modules in tissue fabrication. Given its ability to form and retrieve cell aggregates and its integration with standard microfabrication, PNIPAAm-coated PDMS templates may become useful for 3D cell culture applications in tissue engineering and drug discovery.

Electrospun Nanofibers With pH-Responsive Coatings for Control of Release Kinetics.

Functional and stimuli-responsive nanofibers with an enhanced surface area/volume ratio provide controlled and triggered drug release with higher efficacy. In this study, chemotherapeutic agent Rose Bengal (RB) (4,5,6,7-tetrachloro-2', 4',5',7'-tetraiodofluoresceindisodium)-loaded water-soluble polyvinyl alcohol (PVA) nanofibers were synthesized by using the electrospinning method. A thin layer of poly(4-vinylpyridine-co-ethylene glycol dimethacrylate) p(4VP-co-EGDMA) was deposited on the RB-loaded nanofibers (PVA-RB) via initiated chemical vapor deposition (iCVD), coating the fiber surfaces to provide controllable solubility and pH response to the nanofibers. The uncoated and [p(4VP-co-EGDMA)-PVA] coated PVA-RB nanofiber mats were studied at different pH values to analyze their degradation and drug release profiles. The coated nanofibers demonstrated high stability at neutral and basic pH values for long incubation durations of 72 h, whereas the uncoated nanofibers dissolved in <2 h. The drug release studies showed that the RB release from coated PVA-RB nanofibers was higher at neutral and basic pH values, and proportional to the pH of the solution, whereas the degradation and RB release rates from the uncoated PVA-RB nanofibers were significantly higher and did not depend on the pH of environment. Further analysis of the release kinetics using the Peppas model showed that while polymer swelling and dissolution were the dominant mechanisms for the uncoated nanofibers, for the coated nanofibers, Fickian diffusion was the dominant release mechanism. The biocompatibility and therapeutic efficiency of the coated PVA-RB nanofibers against brain cancer was investigated on glioblastoma multiforme cancer cells (U87MG). The coated PVA nanofibers were observed to be highly biocompatible, and they significantly stimulated the ROS production in cells, increasing apoptosis. These promising results confirmed the therapeutic activity of the coated PVA-RB nanofibers on brain cancer cells, and encouraged their further evaluation as drug carrier structures in brain cancer treatment.

Synthesis of coaxial nanotubes of polyaniline and poly(hydroxyethyl methacrylate) by oxidative/initiated chemical vapor deposition.

Vapor-phase synthesis techniques of polymeric nanostructures offer unique advantages over conventional, solution-based techniques because of their solventless nature. In this work, we report the fabrication of coaxial polymer nanotubes using two different chemical vapor deposition methods. The fabrication process involves the deposition of an outer layer of the conductive polyaniline (PANI) by oxidative chemical vapor deposition, followed by the deposition of the inner layer of poly(2-hydroxyethyl methacrylate) (pHEMA) hydrogel by initiated chemical vapor deposition. The vapor-phase techniques allowed for fine-tuning of the thickness of the individual layers, keeping the functionalities of the polymers intact. The response of the single components and the coaxial nanotubes to changes in humidity was investigated for potential humidity sensor applications. For single-component conductive PANI nanotubes, the resistance changed parabolically with relative humidity because of competing effects of doping and swelling of the PANI polymer under humid conditions. Introducing a hydrogel inner layer increased the overall resistance, and enhanced swelling, which caused the resistance to continuously increase with relative humidity.

Chemical vapor deposition of conformal, functional, and responsive polymer films.

Chemical vapor deposition (CVD) polymerization utilizes the delivery of vapor-phase monomers to form chemically well-defined polymeric films directly on the surface of a substrate. CVD polymers are desirable as conformal surface modification layers exhibiting strong retention of organic functional groups, and, in some cases, are responsive to external stimuli. Traditional wet-chemical chain- and step-growth mechanisms guide the development of new heterogeneous CVD polymerization techniques. Commonality with inorganic CVD methods facilitates the fabrication of hybrid devices. CVD polymers bridge microfabrication technology with chemical, biological, and nanoparticle systems and assembly. Robust interfaces can be achieved through covalent grafting enabling high-resolution (60 nm) patterning, even on flexible substrates. Utilizing only low-energy input to drive selective chemistry, modest vacuum, and room-temperature substrates, CVD polymerization is compatible with thermally sensitive substrates, such as paper, textiles, and plastics. CVD methods are particularly valuable for insoluble and infusible films, including fluoropolymers, electrically conductive polymers, and controllably crosslinked networks and for the potential to reduce environmental, health, and safety impacts associated with solvents. Quantitative models aid the development of large-area and roll-to-roll CVD polymer reactors. Relevant background, fundamental principles, and selected applications are reviewed.