Reduced Ice Adhesion Using Amphiphilic Poly(Ionic Liquid)-Based Surfaces.

Ice build-up on solid surfaces causes significant economic losses for a range of industries. One solution to this problem is the development of coatings with low ice adhesion strength. Amphiphilic poly(ionic liquid) (PIL)-based surfaces have been recently reported for antifogging/antifrosting applications. However, they have possible anti-icing properties through lowering the ice adhesion strength that have yet to be reported. Herein, we designed well-defined triblock copolymers composed of a polydimethylsiloxane component coupled with PIL segments of poly([2 (methacryloyloxy)ethyl] trimethylammonium chloride) (PMETAC), which were subsequently UV-cured with an oligo(ethylene glycol) dimethacrylate (OEGDMA) cross-linker. The structure-property relationships of the resultant semi-interpenetrating polymer networks (SIPNs) were investigated by varying the counterion (i.e., trimethylammonium bis(trifluoromethanesulfonyl)imide (TFSI-)) and the content of the PIL segments and cross-linker. An ice adhesion strength as low as 13.3 ± 8.6 kPa was observed for the coating containing 12.5 wt % of PMETAC segment and 5 wt % of OEGDMA, which is one of the lowest values reported so far for the amphiphilic coatings. Characterization of the coatings in terms of surface features, wettability, and hydration states have enabled the elucidation of different deicing mechanisms. Self-lubrication due to the existence of nonfreezable bound water led to the obtained low ice adhesion strength. This work offers a new approach for the exploration of PIL-based icephobic coatings for practical applications.

Mechanochromophore-Linked Polymeric Materials with Visible Color Changes.

Mechanical force as a type of stimuli for smart materials has obtained much attention in the past decade. Color-changing materials in response to mechanical stimuli have shown great potential in the applications such as sensors and displays. Mechanochromophore-linked polymeric materials, which are a growing sub-class of these materials, are discussed in detail in this review. Two main types of mechanochromophores which exhibit visible color change, summarized herein, involve either isomerization or radical generation mechanisms. This review focuses on their synthesis and incorporation into polymer matrices, the type of mechanical force used, factors affecting the mechanochromic properties, and their applications.

Crosslinked Polypeptide Films via RAFT-Mediated Continuous Assembly of Polymers.

Polypeptide coatings are a cornerstone in the field of surface modification due to their widespread biological potential. As their properties are dictated by their structural features, subsequent control thereof using unique fabrication strategies is important. Herein, we report a facile method of precisely creating densely crosslinked polypeptide films with unusually high random coil content through continuous assembly polymerization via reversible addition-fragmentation chain transfer (CAP-RAFT). CAP-RAFT was fundamentally investigated using methacrylated poly-l-lysine (PLLMA) and methacrylated poly-l-glutamic acid (PLGMA). Careful technique refinement resulted in films up to 36.1±1.1 nm thick which could be increased to 94.9±8.2 nm after using this strategy multiple times. PLLMA and PLGMA films were found to have 30-50 % random coil conformations. Degradation by enzymes present during wound healing reveals potential for applications in drug delivery and tissue engineering.

Spontaneous cervical haematoma caused by extracapsular haemorrhage from a parathyroid carcinoma presenting with acute onset neck swelling and dysphonia.

We present the case of a 69-year-old male patient who presented with progressive neck swelling causing symptoms of dysphonia and dysphagia. Flexible nasendoscopy revealed bruising of the right hemilarynx, hypopharynx and parapharyngeal mucosal consistent with a spontaneous cervical haematoma. After conservative management, the haematoma self-resolved and the source of the haematoma was thought to be a parathyroid adenoma. Surgical excision was completed, and histopathological assessment revealed a parathyroid carcinoma. Spontaneous cervical haematoma can progress to airway obstruction and the initial focus is to observe for any signs of progression and establish a secure airway if required. The subsequent challenge is to establish the origin of the haematoma and as in this case this can be a diagnostic challenge. This case highlights the diagnostic difficulties of spontaneous cervical haematoma, the importance of comprehensive investigation and the possibility of malignancy preoperatively, especially important when complete excision gives the best opportunity for cure.

Irreversible Spoilage Sensors for Protein-Based Food.

Color changing food spoilage sensors for protein-based food products, such as fish and beef, are mostly based on the halochromic behavior of pH indicators. However, due to their reversible halochromic nature, these sensors can be manipulated by chemical treatment, hiding the true history and quality of deteriorated meat. Therefore, there is a need to create an irreversible and reliable food spoilage sensor, which clearly indicates to consumers if any food degradation or improper storage has occurred, and avoid nefarious food processing companies from disguising spoiled meat as fresh meat. Here, a simple, irreversible, and halochromic sensor showing spoilage of seafood and meat products is developed. Specifically, chlorophenol red (CPR)-fatty acid particles are dispersed within an ammonia-permeable polymer matrix to form a nontoxic film sensor that shows obvious halochromic behavior toward bioamine or total volatile basic nitrogen (TVB-N) given off by deteriorated seafood or meat products. After the removal of TVB-N, this sensor does not revert back to its original color due to a loss of π-π stacking of the original sulfonephthalein molecules. These features make this sensor applicable as a novel and reliable spoilage sensor for protein-based food products.

Reversible Nontoxic Thermochromic Microcapsules.

Thermochromic materials exhibit a color change in response to a change in temperature. Creating nontoxic microcapsules containing thermochromic materials for applications in ink and film materials is historically challenging. In this study, we develop a nontoxic chlorophenol red (CPR)-water thermochromic system and its microcapsules with silicone shells via a reaction between water and octadecyltrichlorosilane (OTS) at the interface of a w/o emulsion. The obtained microcapsules exhibit a clear color change with full reversibility and are successfully used as inks by screen printing and as additives in films. Nontoxicity of both microcapsules and films is demonstrated through cell cytotoxicity assays. These features make these novel materials applicable to the next generation of intelligent sensors, coating, and food packaging materials.

Color-Switchable Polar Polymeric Materials.

Spiropyran is an important mechanophore, which has rarely been incorporated as a cross-linker in polar polymer matrices, limiting its applications in innovative mechanochromic devices. Here, three spiropyrans with two- or three-attachment positions were synthesized and covalently bonded in polar poly(hydroxyethyl acrylate) (PHEA), to achieve color-switchable materials, triggered by light and when swollen in water. The negative photochromism in the dark and mechanical activation by swelling in water were investigated. Measurements of negative photochromism were conducted in solution and cross-linked PHEA bulk polymers, with both showing color reversibility when stored in the dark or on exposure to visible light. The force of swelling in water was sufficient to induce the ring-opening reaction of spiropyran. It was found that tri-substituted spiropyran (SP3) was less influenced by the polar matrix but showed the fastest color activation during swelling. SP3 also showed accelerated ring opening to the colored state during the swelling process. Bleaching rates and color switchability were investigated under swollen and dehydrated conditions. The effect of cross-link density on the swelling activation was explored to better understand the interaction between the mechanophore and the polar environment. The results demonstrated that influences from both the polar environment and the mechanochromic nature of spiropyran had an impact on the absorption intensity, rate of change, and the decoloration rate of the materials. This study provides the opportunity to manipulate the properties of spiropyrans to afford materials with a range of color-switching properties under different stimuli.

Combined Fenton and starvation therapies using hemoglobin and glucose oxidase.

Separately, Fenton and starvation cancer therapies have been recently reported as impressive methods for tumor destruction. Here, we introduce natural hemoglobin and glucose oxidase (GOx) for efficient cancer treatment following combined Fenton and starvation therapies. GOx and hemoglobin were encapsulated in zeolitic imidazolate frameworks 8 (ZIF-8) to fabricate a pH-sensitive MOF activated by tumor acidity. In the slightly acidic environment of cancer cells, GOx is released and it consumes d-glucose and molecular oxygen, nutrients essential for the survival of cancer cells, and produces gluconic acid and hydrogen peroxide, respectively. The produced gluconic acid increases the acidity of the tumor microenvironment leading to complete MOF destruction and enhances hemoglobin and GOx release. The Fe ions from the heme groups of hemoglobin also release in the presence of both endogenous and produced H2O2 and generate hydroxyl radicals. The produced OH˙ radical can rapidly oxidize the surrounding biomacromolecules in the biological system and treat the cancer cells. In vitro experiments demonstrate that this novel nanoparticle is cytotoxic to cancer cells HeLa and MCF-7, at very low concentrations (<2 µg mL-1). In addition, the selectivity index values are 5.52 and 11.04 for HeLa and MCF-7 cells, respectively, which are much higher than those of commercial drugs and those of similar studies reported by other research groups. This work thus demonstrates a novel pH-sensitive system containing hemoglobin and GOx for effective and selective cancer treatment using both radical generation and nutrient starvation.

Cancer Treatment through Nanoparticle-Facilitated Fenton Reaction.

Currently, cancer is the second largest cause of death worldwide and has reached critical levels. In spite of all the efforts, common treatments including chemotherapy, photodynamic therapy, and photothermal therapy suffer from various problems which limit their efficiency and performance. For this reason, different strategies are being explored which improve the efficiency of these traditional therapeutic methods or treat the tumor cells directly. One such strategy utilizing the Fenton reaction has been investigated by many groups for the possible treatment of cancer cells. This approach is based on the knowledge that high levels of hydrogen peroxide exist within cancer cells and can be used to catalyze the Fenton reaction, leading to cancer-killing reactive oxygen species. Analysis of the current literature has shown that, due to the diverse morphologies, different sizes, various chemical properties, and the tunable structure of nanoparticles, nanotechnology offers the most promising method to facilitate the Fenton reaction with cancer therapy. This review aims to highlight the use of the Fenton reaction using different nanoparticles to improve traditional cancer therapies and the emerging Fenton-based therapy, highlighting the obstacles, challenges, and promising developments in each of these areas.

Ultrathin Metal-Organic Framework Nanosheets as a Gutter Layer for Flexible Composite Gas Separation Membranes.

Ultrathin metal-organic framework (MOF) nanosheets show great potential in various separation applications. In this study, MOF nanosheets are incorporated as a gutter layer in high-performance, flexible thin-film composite membranes (TFCMs) for CO2 separation. Ultrathin MOF nanosheets (∼3-4 nm) were prepared via a surfactant-assisted method and subsequently coated onto a flexible porous support by vacuum filtration. This produced an ultrathin (∼25 nm), extremely flat MOF layer, which serves as a highly permeable gutter with reduced gas resistance when compared with conventional polydimethylsiloxane gutter layers. Subsequent spin-coating of the ultrathin MOF gutter layer with a polymeric selective layer (Polyactive) afforded a TFCM exhibiting the best CO2 separation performance yet reported for a flexible composite membrane (CO2 permeance of ∼2100 GPU with a CO2/N2 ideal selectivity of ∼30). Several unique MOF nanosheets were examined as gutter layers, each differing with regard to structure and thickness (∼10 and ∼80 nm), with results indicating that flexibility in the ultrathin MOF layer is critical for optimized membrane performance. The inclusion of ultrathin MOF nanosheets into next-generation TFCMs has the potential for major improvements in gas separation performance over current composite membrane designs.

A unique 19F MRI agent for the tracking of non phagocytic cells in vivo.

There is currently intense interest in new methods for understanding the fate of therapeutically-relevant cells, such as mesenchymal stem cells (MSCs). The absence of a confounding background signal and consequent unequivocal assignment makes 19F MRI one of the most attractive modalities for the tracking of injected cells in vivo. We describe here the synthesis of novel partly-fluorinated polymeric nanoparticles with small size and high fluorine content as MRI agents. The polymers, constructed from perfluoropolyether methacrylate (PFPEMA) and oligo(ethylene glycol) methacrylate (OEGMA) have favourable cell uptake profiles and excellent MRI performance. To facilitate cell studies the polymer was further conjugated with a fluorescent dye creating a dual-modal imaging agent. The efficacy of labelling of MSCs was assessed using 19F NMR, flow cytometry and confocal microscopy. The labelling efficiency of 2.6 ± 0.1 × 1012 19F atoms per cell, and viability of >90% demonstrates high uptake and good tolerance by the cells. This loading translates to a minimum 19F MRI detection sensitivity of ∼7.4 × 103 cells per voxel. Importantly, preliminary in vivo data demonstrate that labelled cells can be readily detected within a short acquisition scan period (12 minutes). Hence, these copolymers show outstanding potential for 19F MRI cellular tracking and for quantification of non-phagocytic and therapeutically-relevant cells in vivo.

MOF-Mediated Destruction of Cancer Using the Cell's Own Hydrogen Peroxide.

A novel reduced iron metal-organic framework nanoparticle with cytotoxicity specific to cancer cells is presented. This nanoparticle was prepared via a hydrothermal method, reduced using hydroquinone, and finally conjugated with folic acid (namely, rMOF-FA). The synthesized nanoparticle shows the controlled release of iron in an acidic ex-vivo environment. Iron present on the rMOF-FA and released into solution can react with high levels of hydrogen peroxide found specifically in cancer cells to increase the hydroxyl radical concentration. The hydroxyl radicals oxidize proteins, lipids, and/or DNA within the biological system to decrease cell viability. In vitro experiments demonstrate that this novel nanoparticle is cytotoxic to cancer cells (HeLa) through generation of OH• inside the cells. At low concentrations of rMOF-FA, the cancer cell viability decreases dramatically, with no obvious reduction of normal cell (NIH-3T3) viability. The calculated half-maximum inhibitory concentration value (IC50) was 43 µg/mL for HeLa cells, which was significantly higher than 105 µg/mL for NIH-3T3. This work thus demonstrates a new type of agent for controlled hydroxyl radical generation using the Fenton reaction to kill the tumor cells.

Influence of polymer elasticity on the formation of non-cracking honeycomb films.

Non-planar non-cracking honeycomb (HC) structures are prepared from star polymers with high glass transition temperatures (T(g) ) and relatively low Young's moduli (E). This study demonstrates that the Young's modulus of a polymer is a more important factor than the glass transition temperature for determining the occurrence of cracking during HC film formation on non-planar surfaces.

Balloon dilatation of tracheostomal stenosis with cuffed tracheostomy tube. A novel approach to tracheostomal dilatation.

Postlaryngectomy tracheostomal stenosis is a common complication. Stomal narrowing can be severe, requiring urgent management with dilatation of the stoma. There are numerous ways to achieve this, ranging from forcibly inserting a larger tracheostomy tube, using a graduated dilator, to surgical intervention in the form of a stomaplasty. We describe an alternative technique using a readily available cuffed tracheostomy tube.

Sebaceous lymphadenoma: a case report and review of the literature.

An 80-year-old woman presented with a mass in her left parotid region. An ultrasound-guided core biopsy showed sebaceous glands with lymphoplasmacytic infiltration. Magnetic resonance imaging displayed a well-circumscribed lesion within the left parotid gland. The mass was completely excised, and the patient made a full recovery. Sebaceous lymphadenomas of the salivary glands are rare, benign tumors that are effectively treated by complete excision. The challenge that these tumors present lies in their accurate diagnosis. Because of their histologic similarity to related malignant tumors, such as mucoepidermoid carcinomas and sebaceous lymphadenocarcinomas, misdiagnosis could lead to unnecessarily radical treatment. We highlight the need for careful clinical and histologic diagnosis in tumors of the salivary glands.

Autophobicity-driven surface segregation and patterning of core-shell microgel nanoparticles.

Core-shell microgel (CSMG) nanoparticles, also referred to as core-cross-linked star (CCS) polymers, can be envisaged as permanently cross-linked block copolymer micelles and, as such, afford novel opportunities for chemical functionalization, templating, and encapsulation. In this study, we explore the behavior of CSMG nanoparticles comprising a poly(methyl methacrylate) (PMMA) shell in molten PMMA thin films. Because of the autophobicity between the densely packed, short PMMA arms of the CSMG shell and the long PMMA chains in the matrix, the nanoparticles migrate to the film surface. They cannot, however, break through the surface because of the inherently high surface energy of PMMA. Similar thermal treatment of CSMG-containing PMMA thin films with a polystyrene (PS) capping layer replaces surface energy at the PMMA/air interface by interfacial energy at the PMMA/PS interface, which reduces the energy barrier by an order of magnitude, thereby permitting the nanoparticles to emerge out of the PMMA bulk. This nanoscale process is reversible and can be captured at intermediate degrees of completion. Moreover, it is fundamentally general and can be exploited as an alternative means by which to reversibly pattern or functionalize polymer surfaces for applications requiring responsive nanolithography.

Patterning on nonplanar substrates: flexible honeycomb films from a range of self-assembling star copolymers.

The effect of glass transition temperature, Tg, on the self-assembly of "honeycomb" microstructures on nonplanar substrates was probed by the synthesis of a library of core cross-linked star polymers with different arm compositions. Star polymers based on poly(dimethyl siloxane), poly(ethyl acrylate), poly(methyl acrylate), poly(tert-butyl acrylate), and poly(methyl methacrylate) were synthesized by the "arm first" strategy using atom-transfer radical polymerization. Reaction conditions were optimized, and a series of high molecular weight star polymers were prepared in high yield. The glass transition temperature of the star polymers ranged from -123 to 100 degrees C which allowed the suitability for the formation of porous honeycomb-like films via the "breath figure" technique on nonplanar surfaces to be investigated. All star compositions successfully formed ordered films on flat surfaces. However, only star polymer compositions with a Tg below 48 degrees C could form homogeneous honeycomb coatings on the surface of nonplanar substrates.

Nasal carcinoma--a rare indication for a permanent pacemaker.

Cardiac sinus syncope is a recognised but rare complication of head and neck cancers. Although electrical pacing remains an important treatment to prevent further syncopal episodes related to bradycardia, vasopressor-related syncope remains a more difficult management problem. The article describes the case of a 66-year-old patient with metastatic squamous cell carcinoma of the nose, who presented with syncope and exhibited carotid sinus syncope related to both carotid body invasion and vasopressor mechanisms. Successful management by the insertion of a permanent pacemaker is described, and a review of the literature on this rare complication is given.