A dual encapsulation strategy to generate anion-responsive luminescent lanthanide hydrogels.

We report a new method to generate ion-responsive luminescent hydrogels, involving encapsulation of a luminescent lanthanide probe within crosslinked amphiphilic polymer particles and subsequent entrapment within a hydrogel. The resulting hydrogels are capable of reversible bicarbonate sensing, exhibit no leaching, and can be tuned for a range of sensing applications.

Evaluating the impact of a child sponsorship programme on paediatric health and development in Calauan, Philippines: A retrospective audit.

AIM: International child sponsorship programmes comprise a considerable proportion of global aid accessible to the general population. Team Philippines (TP), a health care and welfare initiative run in association with the University of Notre Dame Sydney since 2013, leads a holistic sponsorship programme for 30 children from Calauan, Philippines. To date, empirical research has not been performed into the overall success and impact of the TP child sponsorship programme. As such, this study aims to evaluate its effectiveness in improving paediatric outcomes. METHODS: Study cohorts comprised 30 sponsored and 29 age- and gender-matched non-sponsored children. Data were extracted from the TP Medical Director database and life-style questionnaires for July-November 2019. Outcome measures included anthropometry, markers of medical health, dental health, exercise, and diet. Statistical analyses were performed in SPSS. RESULTS: Sponsorship resulted in fewer medical diagnoses and prescription medications, superior dental health, and improved diet. Further, sponsored children may show a clinically significant trend towards improved physical health. Sponsorship did not affect growth and development metrics, or levels of physical activity. CONCLUSIONS: The TP child sponsorship programme significantly impacts positive paediatric health outcomes in the Calauan community. The strength of the programme lies in its holistic, sustainable, and community-based model, which is enabled by effective international child sponsorship. This study further supports the relationship between supporting early livelihood and improved health in the paediatric population.

Effect of Particle Interactions on the Assembly of Drying Colloidal Mixtures.

The effects of particle interactions on the size segregation and assembly of colloidal mixtures during drying were investigated. A cationic surfactant was added to a binary latex/silica colloidal dispersion that has been shown to self-stratify upon drying at room temperature. Atomic force microscopy was used to show that the change in particle interactions due to the presence of surfactants reduced the degree of stratification and, in some cases, suppressed the effect altogether. Colloidal dispersions containing higher surfactant concentrations can undergo a complete morphology change, resulting instead in the formation of armored particles consisting of latex particles coated with smaller silica nanoparticles. To further prove that armored particles are produced and that stratification is suppressed, cross-sectional images were produced with energy-dispersive X-ray spectroscopy and confocal fluorescence microscopy. The growth of armored particles was also measured using dynamic light scattering. To complement this research, Brownian dynamics simulations were used to model the drying. By tuning the particle interactions to make them more attractive, the simulations showed the presence of armored particles, and the size segregation process was hindered. The prevention of segregation also results in enhanced transparency of the colloidal films. Overall, this research proves that there is a link between particle interactions and size segregation in drying colloidal blends and provides a valuable tool to control the assembly of different film architectures using an extremely simple method.

In Situ Growth of Silver Nanoparticles on Chitosan Matrix for the Synthesis of Hybrid Electrospun Fibers: Analysis of Microstructural and Mechanical Properties.

A viable alternative for the next generation of wound dressings is the preparation of electrospun fibers from biodegradable polymers in combination with inorganic nanoparticles. A poly(vinyl alcohol)-chitosan-silver nanoparticles (PVA-CTS-Ag NPs) system has been developed for antimicrobial and wound healing applications. Here, the preparation of PVA-CTS-Ag electrospun fibers using a two-step process is reported in order to analyze changes in the microstructural, mechanical, and antibacterial properties and confirm their potential application in the biomedical field. The Ag nanoparticles were well-dispersed into the chitosan matrix and their cubic structure after the electrospinning process was also retained. The Ag NPs displayed an average diameter of ~33 nm into the CTS matrix, while the size increased up to 213 nm in the PVA-CTS-Ag(NPs) fibers. It was observed that strong chemical interactions exist between organic (CTS) and inorganic phases through nitrogenous groups and the oxygen of the glycosidic bonds. A defect-free morphology was obtained in the PVA-CTS-Ag NPs final fibers with an important enhancement of the mechanical properties as well as of the antibacterial activity compared with pure PVA-CTS electrospun fibers. The results of antibacterial activity against E. coli and S. aureus confirmed that PVA-CTS-Ag(NPs) fibers can be potentially used as a material for biomedical applications.

Electrospinning of stimuli-responsive polymers for controlled drug delivery: pH- and temperature-driven release.

Stimuli-responsive polymers have attracted academic interest over the last 60 years due to their potential use in developing systems with a range of functionalities that can be activated by external artificial triggers. The diversity of responses and stimuli, which can be achieved through careful polymer selection and processing, opens up applications in nearly every sector. In particular, the use of responsive polymers for the controlled delivery of drugs and bioactive compounds has been heavily researched. This review provides an overview of the recent advancements in electrospinning of temperature- and pH-responsive polymers to create networks of nanofibres with controlled drug delivery profiles for biomedical applications.

Pioneering personalised design of femoropopliteal nitinol stents.

BACKGROUND/MOTIVATION: Percutaneous femoropopliteal artery intervention moves towards personalised therapy, which requires design of unique lesion-specific stents. However, to date, not much progress has been made in the development of personalised stents. OBJECTIVE: This paper aims to design personalised nitinol stents for femoropopliteal arteries based on medical imaging of patients and advanced computational mechanics, which is the first attempt to the authors' best knowledge. METHODS: The design process is based on three objectives: (i) achieving the healthy lumen area; (ii) reducing the stress in the media layer; (iii) improving the lumen shape after stenting. The design parameters include the strut width and thickness, the crown length, the nominal radius and the number of strut units per crown. Using representative unit-cell models, the effects of the five geometric parameters on the stent performance are investigated thoroughly with numerical simulations. Then, design protocols, especially for the circumferentially varying strut size and the oval stent shape, are developed and fully evaluated for an asymmetric stenosis. RESULTS: Using the design protocols, full personalised stents are designed for arteries with diffuse and focal plaques, based on medical imaging of patients. The personalised stent designs provide a double lumen gain, a reduced stress in the media layer and an improved lumen shape compared to a commercial stent. CONCLUSIONS: The suggested protocols prove their high effectiveness in design of personalised stents, and the suggested approach can be applied to development of personalised therapies involving the use of stent technology including percutaneous coronary artery intervention, transcatheter aortic valve implantation, endovascular aneurysm repair and ureteric stenting.

Polymerizable Gd(iii) building blocks for the synthesis of high relaxivity macromolecular MRI contrast agents.

A new synthetic strategy for the preparation of macromolecular MRI contrast agents (CAs) is reported. Four gadolinium(iii) complexes bearing either one or two polymerizable methacrylamide groups were synthesized, serving as monomers or crosslinkers for the preparation of water-soluble, polymeric CAs using Reversible Addition-Fragmentation Chain Transfer (RAFT) polymerization. Using this approach, macromolecular CAs were synthesized with different architectures, including linear, hyperbranched polymers and gels. The relaxivities of the polymeric CAs were determined by NMR relaxometry, revealing an up to 5-fold increase in relaxivity (60 MHz, 310 K) for the linear polymers compared with the clinically used CA, Gd-DOTA. Moreover, hyperbranched polymers obtained from Gd(iii) crosslinkers, displayed even higher relaxivities up to 22.8 mM-1 s-1, approximately 8 times higher than that of Gd-DOTA (60 MHz, 310 K). A detailed NMRD study revealed that the enhanced relaxivities of the hyperbranched polymers were obtained by limiting the local motion of the crosslinked Gd(iii) chelate. The versatility of RAFT polymerization of Gd(iii) monomers and crosslinkers opens the doors to more advanced polymeric CAs capable of multimodal, bioresponsive or targeting properties.

Designing responsive dressings for inflammatory skin disorders; encapsulating antioxidant nanoparticles into biocompatible electrospun fibres.

Inflammatory skin disorders are highly prevalent and current treatments are marred by side-effects. Here, we have designed anti-inflammatory fibrous sheets with the potential to treat low exudate inflammatory skin disorders such as psoriasis or atopic dermatitis. Antioxidant and anti-inflammatory nanoparticles composed of crosslinked poly(propylene sulfide) (PPS) were encapsulated in poly(ethylene oxide) (PEO) fibres via electrospinning from an aqueous suspension. The loading of nanoparticles did not adversely effect the homogenous nature of the electrospun fibres; furthermore, nanoparticles retained their morphology, size and anti-inflammatory character after electrospinning. The PPS-nanoparticle-loaded nanofibres were found to be highly cytocompatible when tested on human dermal fibroblasts. These findings suggest they have significant potential to topically treat inflamed tissues that are characterized by high reactive oxygen species (ROS) levels.

Crosslinker Copolymerization for Property Control in Inverse Vulcanization.

Sulfur is an underused by-product of the petrochemicals industry. Recent research into inverse vulcanization has shown how this excess sulfur can be transformed into functional polymers, by stabilization with organic crosslinkers. For these interesting new materials to realize their potential for applications, more understanding and control of their physical properties is needed. Here we report four new terpolymers prepared from sulfur and two distinct alkene monomers that can be predictively tuned in glass transition, molecular weight, solubility, mechanical properties, and color.

Supine Colonoscopy: An Advantage over Left Lateral in Synchronous Proctological Surgery.

BACKGROUND: Repositioning sedated or anesthetized patients between colonoscopy and further surgical procedures is potentially unsafe and time consuming. We aim to show that colonoscopy performed in the modified lithotomy position offers surgical, anesthetic, and patient advantage. METHODS: Patients presenting for colonoscopy and a synchronous surgical procedure between May 2013 and August 2014 were prospectively included. Colonoscopy duration, cecal intubation rate (CIR), terminal ileum intubation rate, and patient characteristics were recorded. RESULTS: Sixty-eight patients were included in this study. Of them, 24 (35%) were women and mean age was 42.3 years. Mean colonoscopy duration was 7 minutes (2-24 minutes). CIR was 100%. Terminal ileum intubation rate was 92%. Utilization of ancillary colonoscopic maneuvers was easier for the operator/assistant. Overall theatre time was reduced and there was no increase in length of stay. CONCLUSION: The modified lithotomy position offers multiple surgical, anesthetic, theatre, and patient advantage in those undergoing a colonoscopy followed by a further proctological or surgical procedure.

Efficient access to conjugated 4,4'-bipyridinium oligomers using the Zincke reaction: synthesis, spectroscopic and electrochemical properties.

The cyclocondensation reaction between rigid, electron-rich aromatic diamines and 1,1'-bis(2,4-dinitrophenyl)-4,4'-bipyridinium (Zincke) salts has been harnessed to produce a series of conjugated oligomers containing up to twelve aromatic/heterocyclic residues. These oligomers exhibit discrete, multiple redox processes accompanied by dramatic changes in electronic absorption spectra.

Aminomaleimide fluorophores: a simple functional group with bright, solvent dependent emission.

Amino-substituted maleimides form a new class of highly emissive compounds, with large Stokes shifts (>100 nm) and high quantum yields (up to ∼60%). Emission is responsive to the maleimide's environment with both a red-shift, and quenching, observed in protic polar solvents. Aminomaleimides are easily functionalised, providing a versatile fluorescent probe.

Complementary light scattering and synchrotron small-angle X-ray scattering studies of the micelle-to-unimer transition of polysulfobetaines.

AB and ABA di- and triblock copolymers where A is the hydrophilic poly(oligoethylene glycol methacrylate) (POEGMA) block and B is a thermo-responsive sulfobetaine block [2-(methacryloyloxy) ethyl] dimethyl-(3-sulfopropyl) ammonium hydroxide (PDMAPS) were synthesised by aqueous RAFT polymerisation with narrow dispersity (DM ≤ 1.22), as judged by aqueous SEC analysis. The di- and triblock copolymers self-assembled in salt-free water to form micelles with a PDMAPS core and the self-assembly of these polymers was explored by SLS and TEM analysis. The micelles were shown, by DLS analysis, to undergo a micelle-to-unimer transition at a critical temperature, which was dependent upon the length of the POEGMA block. Increasing the length of the third, POEGMA, block decreased the temperature at which the micelle-to-unimer transition occurred as a result of the increased hydrophilicity of the polymer. The dissociation of the micelles was further studied by SLS and synchrotron SAXS. SAXS analysis revealed that the micelle dissociation began at temperatures below that indicated by DLS analysis and that both micelles and unimers coexist. This highlights the importance of using multiple complementary techniques in the analysis of self-assembled structures. In addition the micelle-to-unimer morphology transition was employed to encapsulate and release a hydrophobic dye, Nile Red, as shown by fluorescence spectroscopy.

A multifunctional azobenzene-based polymeric adsorbent for effective water remediation.

The efficient removal of trace carcinogenic organic pollutants, such as polycyclic aromatic hydrocarbons (PAHs) and ionic dyes, from water is an important technical challenge. We report a highly effective recyclable multifunctional azobenzene (AZ)-based silica-supported polymeric adsorbent which can simultaneously remove both PAHs and anionic dyes from water to below parts per billion (ppb) level based on multiple interactions such as the hydrophobic effect, π-π stacking and electrostatic interactions, thus providing a new strategy for designer water remediation materials.

Dual effect of thiol addition on fluorescent polymeric micelles: ON-to-OFF emissive switch and morphology transition.

The morphology transition from micelles to vesicles of a solution-state self-assembled block copolymer, containing a fluorescent dye at the core-shell interface, has been induced by an addition-elimination reaction using a thiol, and has been shown to be coupled to a simultaneous ON-to-OFF switch in particle fluorescence.

Atom-transfer cyclization with CuSO4/KBH4: a formal "activators generated by electron transfer" process also applicable to atom-transfer polymerization.

The 4-exo and 5-exo-trig atom-transfer cyclizations of 1, 8a-e, 9, 12, and 13 can be mediated with as little as 0.05 mol % of Cu(TPMA)SO(4)·5H(2)O in the presence of 2.5 mol % of borohydride salts in 10 min at room temperature in air. This formal "activators generated by electron transfer" (AGET) procedure utilizes a cheap and oxidatively stable copper source (CuSO(4)·5H(2)O) and can be carried out in environmentally benign solvents (EtOH). It is possible to alter the product distribution in the 5-endo radical-polar crossover reactions of 10a,b and 11 by tailoring the amount of borohydride. Cyclization onto alkynes 14 and 15 is also possible in only 20 min. Controlled radical polymerization of styrene, with increased rates over conventional atom-transfer radical polymerization (ATRP), can be carried out in a controlled fashion (Mn, PDI) using either CuBr or CuSO(4)·5H(2)O and Bu(4)NBH(4).

Self-assembly of hydrophilic homopolymers: a matter of RAFT end groups.

Unusual self-assembly behavior is observed for a range of hydrophilic homopolymers. This self-assembly behavior is contrary to the expected behavior of such hydrophilic polymers and instead mimics more commonly reported amphiphilic block copolymers. It is proposed that the unique combination of hydrophobic end groups at both the α and ω chain end accounts for this unusual self-assembly behavior. Complex internal polymer micelles are spontaneously formed when hydrophilic homopolymer polyelectrolytes and neutral polymers (with a weight fraction of the hydrophobic end groups <10 wt%) are directly dissolved in water. The homopolymers, poly[2-(diethylamino)ethyl methacrylate], poly(N-isopropylacrylamide), and poly(ethoxyethylacrylate) are synthesized by reversible addition-fragmentation chain-transfer (RAFT) polymerization using S'-1-dodecyl-(S')-(α,α'-dimethyl-α″-acetic acid) trithiocarbonate (DDMAT) and its derivatives as chain transfer agents (CTAs). A range of polyelectrolyte homopolymers with different terminal groups are designed and synthesized, which under acidic aqueous solution direct the self-assembly to form well-defined nanostructures. This assembly behavior was also observed for neutral polymers, and it was determined that the structure of the hydrophobic end groups (and thus choice of RAFT CTA) are very important in facilitating this unusual self-assembly behavior of hydrophilic homopolymers. It is proposed that the functionality of commonly used CTAs such as DDMAT, can affect the solution association of the resultant homopolymers and can in fact afford ABA' type polymers, which can undergo self-assembly to form higher-order nanostructures.

Synthesis and characterisation of polyamide dendrimers with systematically varying surface functionality.

Remarkable changes of properties result from systematically varying the surface functionality of polyamide dendrimers within a single generation.