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A magnetically separable palladium nanocatalyst has been synthesized through the immobilization of palladium onto 3-aminopropylphenanthroline Schiff based functionalized silica coated superparamagnetic Fe3O4 nanoparticles. The nanocatalyst (Fe3O4@SiNSB-Pd) was fully characterized using several spectroscopic techniques, such as FT-IR, HR-SEM, TEM, XRD, ICP, and XPS. The microscopic image of Fe3O4 showed spherical shape morphology and had an average size of 150 nm. The Pd-nanoparticles exhibited an average size 3.5 ± 0.6 nm. The successful functionalization of Fe3O4@SiNSB-Pd was identified by FT-IR spectroscopy and the appearance of palladium species in Fe3O4@SiNSB-Pd was confirmed by XRD analysis. While XPS has been utilized for the determination of the chemical oxidation state of palladium species in Fe3O4@SiNSB-Pd. Several activated and deactivated arene halides and olefines were employed for Mizoroki-Heck cross-coupling reactions in the presence of Fe3O4@SiNSB-Pd, each of which produced the respective cross-coupling products with excellent yields. The Fe3O4@SiNSB-Pd shows good reactivity and reusability for up to seven consecutive cycles.

Here, we report the growth of bioelectret crystal films of L-leucine on conductive substrates and detail the first quantitative measurements of the direct piezoelectric effect in this proteinogenic amino acid. Through extensive electromechanical characterisation, we demonstrate that L-leucine is a promising candidate material for use in non-toxic, biocompatible and biodegradable energy harvesting and sensing devices. The data presented here is among, if not the, largest set of quasi-static, longitudinal piezoelectric measurements on crystalline films of a proteinogenic amino acid to date. We substantiate these measurements using a combination of density functional theory calculations and optical microscopy. Our data provides a further example of the enormous unexploited potential of amino acids and similar biological materials in flexible energy harvesting applications. Their combination of sizeable piezoelectric strain constants and extremely low elastic and dielectric constants makes them ideal as biocompatible replacements for toxic, expensive inorganic piezoelectric materials.

Development of spray drying of biomolecules has proved challenging primarily due to protein instability caused by high drying temperatures and atomization process. This study suggests a two-step approach towards a better understanding of spray drying process of large biomolecules. Using lysozyme as a model biomolecule a full factorial Design of Experiments (DoE) was employed to define the most critical process and formulation parameters. With respect to parameters such as feed rate, outlet temperature (Tout) and feed solid concentration, Tout was determined to be the most significant factor affecting the enzymatic activity. Forced deactivation studies were performed to identify critical points of potential enzymatic degradation during the drying process. Results show that lysozyme in solid form significantly inactivated when heated up to temperatures similar to Tout (70–90 °C). The approaches presented herein provide an improved understanding of the critical process and formulation parameters required for the successful spray drying of biomolecules.

The fabrication of highly customizable scaffolds is a key enabling technology in the development of predictive

peer-reviewed CuZnSe2 (CZSe) is an important ternary semiconductor comprised of earth-abundant elements with a suitable bandgap for visible light absorption and structural/stoichiometric versatility that make it a promising candidate for photovoltaic applications. Here we report the controlled synthesis of the compound copper chalcogenide in nanocrystal form using a colloidal hot injection approach. Furthermore, we demonstrate control over the crystal phase to occur as either wurtzite (WZ) or zinc blende (ZB) as a function of the presence and absence of phosphine-based ligands. A major emission peak was observed at ∼1.7 eV using low-temperature photoluminescence (PL), ranging from 30 to 200 K. Additionally, we demonstrate the ability to extend this synthetic protocol to form a polytype structure comprised of a ZB core with a WZ shell.

peer-reviewed As part of ongoing efforts to develop electroactive polymers (EAPs) which are biodegradable/bioresorbable, we report on the microwave assisted synthesis and characterization of an electrically conducting and electroactive polymer that capitalises on pKa sensitivity to initiate the system’s fracture and breakdown. The system, poly(bis((thiophen-2-yl) methylene) benzene-1,4-diamine), a poly(thiophene-azomethine) co-polymer (PAZO), incorporates hydrolytically sensitive azomethine linkers amongst bithiophene units resulting in one continuously conjugated and redox-active macromolecular framework. Rapid microwave assisted synthesis allowed for facile preparation of the polymer with significantly reduced reaction times when compared to traditional synthetic routes. Electrochemical analysis indicated quasi-reversible electrochemical behaviour with sufficiently high conductivity for in vivo biomedical applications. The polymer displays tunable degradation behaviour whereby the time duration required for polymeric breakdown is a function of the pKa of the acid used to catalyse the reaction resulting in controllable degradation times ranging from 1 h to 6 months. The development of conductive polymeric materials that are fully degradable over pre-defined time periods opens up a portal to the next generation of EAPs for in vivo biomedical applications.

Corn-cobs are an agro-industrial waste and composed of cellulose mostly. In this study cellulose was isolated from the waste corn-cobs and modified to polymeric hydroxamic acid palladium complex 1 and characterized by using a variety of spectroscopic methods such as field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma atomic emission spectroscopy (ICP-AES). The complex 1 exhibited high catalytic activity towards Suzuki and Heck coupling reactions of activated and deactivated aryl halides to give the respective coupling products with high yield. Moreover, the complex 1 was recovered and recycled five times with no considerable loss of catalytic overall performance.

The polymorphic control of the co-crystal carbamazepine–saccharin (CBZ–SAC) metastable form II was achieved by nano-droplet confinement in tandem with droplet surface charging induced by electrospraying the precursor solution. Polymorphic exclusivity is independent of solvent selection. CBZ–SAC co-crystals obtained by electrospraying are compared with supercritical CO2 nano spray-drying, conventional spray-drying and solvent evaporation methods.

Spray drying is increasingly becoming recognized as an efficient drying and formulation technique for pharmaceutical and biopharmaceutical processing. It offers significant economic and processing advantages compared to lyophilisation/freeze-drying techniques even though the optimisation of process parameters is often a costly and time-consuming procedure. Spray Drying has primarily been used in formulating small molecule drugs with low solubility however it is increasingly being applied to the processing of large biomolecules and biopharmaceuticals. This review examines the basics of spray drying process, current technology and various components used in spray drying process. Moreover, it is focused on introducing critical formulation and processing factors in spray drying of small molecule drugs and large biomolecules, their similarities and differences. Finally, it provides an overview of the experimental optimisation strategies designed to achieve optimum spray drying results in the shortest possible timeframe while utilising minimum product.

Mesoporous silica supported adsorbents have been used towards metal ion removal from water due to their thermally stability and good sorption capacity. Thus, mesoporous silica-based methyl acrylate monomer (Silica-APTES-DPNO) was converted into hydroxamic acid (SBHA) by using oximation reaction and all products are analyzed by by FT-IR. The SBHA showed satisfactory binding properties with copper, cobalt, nickel and lead are 242, 206, 195 and 516 mg g−1, respectively, with the batch adsorption system was set to pH 6. The kinetics of metal ions binding obeyed the pseudo-1st-order process up to 60 min. In this study also consider the Langmuir and Freundlich isotherm to find out the sorption behavior. The isotherm study demonstrated the well fit with Freundlich isotherm (R2 > 0.99). Thus, adsorption take place as a multilayer system, therefore, SBHA material is useful for the metal ions removal from water.

This work describes a novel approach to produce high quality release paper at lower cost than traditional methods. The anti-adhesive properties of release paper require the use of expensive machine glazed kraft or &ldquo, Glassine&rdquo, paper as the paper base. A series of polymer coatings including polyvinyl alcohol, carboxymethyl cellulose, polyethylene vinyl acetate, and polystyrene were chemically synthesized and coated onto a low cost pulp paper base. Surface roughness (Sa) and smoothness coefficients (k) were determined by atomic force microscopy (AFM), and the interactions between the polymer coating and base paper were investigated by Raman spectroscopy. Studies show the use of polyethylene vinyl acetate (PEVA) as a pre-coating layer on low cost pulp paper exhibits similar anti-adhesive properties as higher cost paper bases. In low margin markets such as the production of release paper, decreases in cost are critical to industry survival.

peer-reviewed The development of biocompatible membrane materials capable of delivering active pharmaceutical ingredients (APIs) over a fixed time period offers significant advantages to the pharmaceutical and biomedical industries alike. In addition the incorporation of APIs within polymeric materials potentially allows for the formation of amorphous solid dispersions (ASDs), which have shown enhanced bioavailability, increased dissolution profiles and enhanced adsorption into the blood stream. Mixed matrix membranes (MMMs) have been at the forefront of such developments, however manufacturing MMMs with consistent batch to batch physical characteristics has proved challenging thereby significantly impeding the use of such materials by the pharmaceutical sector. This article describes the development, for the first time, of API and molecular sieve loaded mixed matrix membranes (MMMs) via electro spinning techniques. The developed membranes displayed consistent and controllable physical properties and more efficient API release relative to membranes prepared using traditional casting techniques. Mathematical modelling disclosed that the membranes generated via electrospinning show excellent correlation between experimental and predicted API release kinetics thereby paving the way for the development of MMMs for both pharmaceutical and biomedical applications.

A waste material known as palm oil empty fruit bunch (EFB) is used as a source of cellulose for the development of polymeric materials for the removal of metal ions from industrial wastewater. A poly(acrylonitrile)-grafted palm cellulose copolymer was synthesized by a conventional free radical initiating process followed by synthesis of a poly(amidoxime) ligand by oximation reaction. The resulting products were characterized by FT-IR, FE-SEM, EDX, TGA, DSC, and XPS. The poly(amidoxime) ligand was used to coordinate with and extract a series of transition metal ions from water samples. The binding capacity (qe) of the ligand with the metal ions such as copper, iron, cobalt, nickel, and lead were 260, 210, 168, 172, and 272 mg g−1, respectively at pH 6. The adsorption process followed the pseudo-first-order kinetic model (R2 > 0.99) and as well as the Freundlich isotherm model (R2 > 0.99) indicating the occurrence of a multi-layer adsorption process in the amidoxime ligand adsorbent. Results from reusability studies show that the ligand can be recycled for at least 10 cycles without any significant losses to its initial adsorption capacity. The synthesized polymeric ligand was shown to absorb heavy metals from electroplating wastewater with up to 95% efficiency.

peer-reviewed In this work, lignin was spray dried with sodium lauryl sulphate (SLS) in order to improve the compaction properties of lignin. Bulk level and physicochemical properties of spray dried formulations were measured and compared to as-received lignin and lactose which was used as a reference excipient. Single component tablets from individual powders were prepared and the mechanical properties of these powders were investigated by analysing force–displacement curves recorded during tableting, using a series of compaction equations. Moreover, the performance of these excipients in binary blends containing an active pharmaceutical ingredient (API) was investigated. A positive effect of SLS on the mechanical properties and bulk level properties of the spray dried formulations was observed. Spray dried formulations containing SLS showed superior flow properties to pure spray dried lignin while retaining similar particle size distributions. Spray dried formulations containing up to 10 w/w% SLS also showed superior compactibility in binary blends to as-received materials at porosity levels relevant for immediate release tablets. This study highlights the importance of understanding the compaction mechanics of single component powders as a means of predicting their behaviour in multi-component blends.

Heavy metals pollutants are nonbiodegradable and their bioaccumulation results in detrimental environmental consequences. Therefore, it is important to effectively remove toxic heavy metal waste from industrial sewage. Thus, the main goal of this research is to synthesize an ideal cellulose‐based adsorbent from palm‐based waste materials (agro waste) in order to be utilized in real‐life practical applications with low cost as such removing common toxic heavy metals from industrial effluents. A poly(methyl acrylate) grafted palm cellulose was synthesized via a free‐radical initiation process, followed by an oximation reaction to yield poly(hydroxamic acid) ligands. The adsorption capacity (qe) of poly(hydroxamic acid) ligands for metal ions such as copper (Cu2+), iron (Fe3+), and lead (Pb2+) were 325, 220, and 300 mg g−1, respectively at pH 6. In addition, the X‐ray photoelectron spectrometry results are to be proved the binding of metal ions, for instance, Cu(II) ions showed typically significant BEs of 932.7 and 952.0 eV corresponding to the Cu2p3/2 and Cu2p1/2 species. The heavy metal ions adsorption followed a pseudo‐first‐order kinetic model pathway. The adsorption capacity (qm) is also derived from the Langmuir isotherm linear plot, which does not showed good correction coefficients. However, the results were correlated to the Freundlich isotherm model, where the R2 value showed significance (>0.98), indicating that multiple layer adsorption occurs on the synthesized ligand. The synthesized polymeric ligand is an excellent adsorbent for the removal of heavy metals from the industrial wastewater. In addition, the metal analysis results showed that about 98% removal of copper and iron ions from electroplating wastewater including lead, nickel, and chromium can be removed up to 85–97%.

This work exploits the high-affinity of recombinant antibodies and low background electrochemiluminescence (ECL) for cardiac-biomarker detection. The developed assay is capable of fg mL-1 detection limits as well as the detection of C-Reactive Protein (CRP) over a clinically relevant range. The assay demonstrated robust reproducibility, selectivity and stability while also highlighting a novel platform for detection of cardiac biomarkers at low concentrations.

The electrochemiluminescent (ECL) performance of three ruthenium-based metallopolymer platforms with different homogeneous charge transfer diffusion coefficients (DCT) is reported. Significantly, simultaneous detection of light and current in tandem with steady-state photoluminescence studies demonstrate that increasing the rate of Ru3+ production via enhanced charge transport results in a decrease in ECL intensity of up to 82% when the concentration of the co-reactant, sodium oxalate, is low, i.e., sub-mM. Spectroelectrochemical studies demonstrate that for maximum sensitivity to be obtained, the electroactive properties of the polymeric support matrix need to be considered in tandem with luminophore, analyte and co-reactant concentrations. Keywords: Electrochemiluminescence, Chemiluminescence, Quenching, Electroactive polymers, ECL sensor design, [Ru(bpy)3]2+

A design of experiment (DoE) approach was used to investigate the critical formulation and processing parameters in spray drying ternary amorphous solid dispersions (ASDs) of ibuprofen. A range of 16 formulations of ibuprofen, HPMCP-HP55 and Kollidon VA 64 were spray dried. Statistical analysis revealed the interrelation of various spray drying process conditions and formulation factors, namely solution feed rate, inlet temperature, Active Pharmaceutical Ingredient (API)/excipients ratio and dichloromethane (DCM)/methanol (MeOH) ratio. Powder X-ray diffraction analysis (PXRD) showed that all the samples with the lowest API/excipient ratio (1:4) were amorphous, while others were crystalline. Moreover, differential scanning calorimetry (DSC) analysis was employed to investigate ASD formulation more in-depth. The glass transition temperatures (Tg) of all ASDs were in the range 70-79°C, while crystalline formulations displayed an endothermic peak of melting of crystalline ibuprofen in the range of 50-80°C. The high Tg of ASDs was an indication of highly stable ASD formulations as verified via PXRD at zero day and afterward at 1, 1.5, 3 and 6month intervals. The intermolecular interactions between ibuprofen molecule and excipients were studied by Fourier transform infrared spectroscopy (FTIR) and solid-state nuclear magnetic resonance (ssNMR) spectroscopy. FTIR and Carbon-13 ssNMR analysis indicated that hydrogen bond formation involving the carboxyl group in ibuprofen within the ASDs is likely. More importantly, the solubility of ibuprofen in ASD formulations is improved compared to pure ibuprofen. This was due to both the amorphous structure of ibuprofen and of the existence of amphiphilic excipient, Kollidon VA 64, in the formulation.

peer-reviewed This work reported an improved approach to the synthesis of iron oxide nanostructures using iron(III) chloride as the precursor and hexamethylenetetramine (HMTA) as the key auxiliary. A range of iron oxide (alkoxide) nanostructures including nanosheets, hierarchical flowers (assembled by thin nanosheets), mesoporous hollow nanospheres and solid nanospheres were obtained only by altering the reaction temperature from 180 degrees C to 240 degrees C in a single synthetic protocol. Supplementary experiments driven by reaction time were designed in order to further clarify the morphological evolution behaviors of these nanostructures, which discovered that the spherical morphology with the size of about 150-200 nm formed from the inside of micro-scaled flower-like clusters gradually by the condensing and weaving of curled nanosheets, suggesting that the hollow nanospheres were obtained consequently by the further condensation of incompact nanospheres with the assistance of the rearrangement of surfactant micelles, followed by the oriented attachment assembly and Ostwald ripening. PUBLISHED peer-reviewed

BODIPY (4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) fluorophores are widely used in bioimaging to label proteins, lipids and nucleotides, but in spite of their attractive optical properties they tend to be prone to self-quenching because of their notably small Stokes shift. Herein, we compare two BODIPY compounds from a recently developed family of naphthyridine substituted BODIPY derivatives, one a visible emitting derivative (BODIPY-VIS) and one a near-infrared emitting fluorophore with a Stokes shift of approximately 165 nm as contrast reagents for live mammalian cells and murine brain tissue. The compounds were rendered water soluble by their conjugation to polyethylene glycol (PEG). Both PEGylated compounds exhibited good cell uptake compared with their parent compounds and confocal fluorescence microscopy revealed all dyes explored to be nuclear excluding, localizing predominantly within the lipophilic organelles; the endoplasmic reticulum and mitochondria. Cytotoxicity studies revealed that these BODIPY derivatives are modestly cytotoxic at concentrations exceeding 10 μM where they induce apoptosis and necrosis. Although the quantum yield of emission of the visible emitting fluorophore was over an order of magnitude greater than the Mega-Stokes shifted probe, the latter showed considerably reduced tendency to self quench and less interference from autofluorescence. The near-infrared probe also showed good penetrability and staining in live tissue samples. In the latter case similar tendency to exclude the nucleus and to localize in the mitochondria and endoplasmic reticulum was observed as in live cells. This to our knowledge is the first demonstration of such a Mega-Stokes BODIPY probe applied to cell and tissue imaging.

Amorphous solid dispersion (ASD) is one of the most promising strategies for improving the solubility of active pharmaceutical ingredients (APIs) with low aqueous solubility. Solvent-based techniques such as electrospinning (ES), spray-drying (SD) and rotary evaporation (RE), have all previously been shown to be effective techniques for formulating ASDs. To date however, the effect of these processing techniques on the physicochemical properties and ASD homogeneity or "quality of ASD" produced remains largely unexplored. This work uses ibuprofen (IBU) as a model BCS class II API with two cellulosic excipients, HPMCAS and HPMCP-HP55 to produce ASDs by employing ES, SD and RE processing techniques. The physicochemical, morphological and dissolution properties of each sample were evaluated and the ASD forming strengths of each of the polymers were assessed using Differential Scanning Calorimetry (DSC). Principal |Component Analysis (PCA) of Raman spectra of crystalline and amorphous IBU was employed for qualitative analysis of ASD homogeneity and subsequent ASD stability during long-term storage. Results show that while ASD formation is predominantly dependent on API:excipient ratio, the ASD homogeneity is highly dependent on processing technique. Dissolution studies show that electrospun samples had the highest API release rate due to their fibrous morphology and higher specific surface area. However, these samples were the least homogenous of all ASDs produced thereby potentially influencing sample stability during long term storage. In addition, the higher melting point depression, higher Tg, and increased abundance of functional groups suitable for hydrogen bonding, show HPMCAS to be a significantly better ASD co-former when compared with HPMCP-HP55.

The electrochemiluminescent (ECL) properties of a luminescent metal centre, [Ru(bpy)(3)](2+), can be significantly modulated through its electronic interaction with neighbouring centres and the polymer backbone used to confine it on an electrode surface. From the perspective of ECL based sensing devices, an increase in the ECL efficiency of a metallopolymer film can result in enhanced sensor sensitivity and selectivity. This work probes the ECL properties of both conjugated, [Ru(bpy)(2)(PPyBBIM)(10)](2+), and non-conjugated, [Ru(bpy)(2)(PVP)(10)](2+), ruthenium based metallopolymer films based on a well documented reaction with sodium oxalate, where bpy is 2,2'-bipyridyl, PPYBBIM is poly[2-(2-pyridyl)-bibenzimidazole] and PVP is poly(4-vinylpyridine). Through a combination of ground state electrochemical studies and ECL measurements, the ECL efficiency for each film is determined. This study reveals that despite a dramatic influence in charge transfer rates between metal centres, as observed for the conducting polymer, mediated through the conducting polymer backbone, a corresponding increase in ECL efficiency is not always observed. The degree of communication between the adjacent excited state metal centres are an important consideration for ECL enhancement however self quenching, luminophore distribution and film porosity must also be considered.

peer-reviewed Epoxy resin (ER) thermosetting adhesives provide highly cross-linked 3-dimensional structures leading to highly stable and strong mechanical/physical performance in a wide range of bonding applications. However, such excellent physical attributes pose a significant challenge with respect to disassembly of the bonded adherends and previous disassembly methods have resulted in damage to the adherends. Hence, this paper presents a specifically engineered re-workable nanocomposite adhesive, created by embedding dielectric sensitive Fe3O4 hollow nanospheres (HNSs) in epoxy resin. This nanocomposite adhesive can be completely degraded by dielectric heating, resulting in facile disassembly of bonded adherends. FESEM and 3D Micro-CT characterisation demonstrates good dispersibility of the HNSs in cured ER, while the dielectric degradation performance and hardness/modulus were investigated by FESEM and nanoindentation. Results show that the Fe3O4 HNSs can effectively convert the microwave energy into thermal energy to significantly degrade the mechanical properties of the adhesive modulus and hardness by 83.4% and 90%, respectively. FESEM and HRTEM imaging attributes the reduction in nanocomposite adhesive properties to the formation of spatial voids nucleating from the embedded nanomaterials. Prior to dielectric heating, tensile loaded single lap-shear bonded joint tests indicated that the nanocomposite adhesive was 19.3% stronger than its neat ER adhesive counterpart due a nano-reinforcement toughening mechanism. However, after 3 minutes of dielectric heating exposure, the nanocomposite adhesive joint strength was reduced by 96.3% compared to just 18.7% for the neat ER adhesive, demonstrating the excellent re-workable performance of our new nanocomposite adhesive. PUBLISHED peer-reviewed

The photophysical and electrochemical properties of a novel metallopolymer containing [Re(bpy)(CO)3]+ moieties coordinated to a poly(4-vinylpyridine) polymer chain are reported. Significantly, the release of the metal complexes can be triggered by oxidation or reduction of the rhenium complex. Solvent rapidly binds to the vacant coordination site to give a luminescent product. The redox and photophysical properties of the parent metallopolymer and the released solvated complex are compared. Along with photoemission, the metallopolymer generates significant electrogenerated chemiluminescence upon reduction in the presence of benzoyl peroxide as coreactant.

We have presented novel surface plasmon-coupled emission (SPCE) based on solid-state electrochemiluminescence (ECL) of Nafion films containing tris(2,2′-bipyridyl)ruthenium(II). This approach combines the advantages of ECL, efficient emission in the absence of an external light source, with the highly directional emission of SPCE. We described theoretical calculations and optimal Nafion film thickness to get SPCE based on solid-state ECL. We confirmed the SPCE and dose-dependent SPCE response from the concentration range of 0.05–0.5% (w/v) [Ru(bpy)3]2+ in the Nafion film. SPCE based on solid-state ECL can be used as a useful platform for the analysis of chemical and biomolecular interactions.

A biosensor for the determination of urea in human serum was fabricated using a combination of inkjet printed polyaniline nanoparticles and inkjet printed urease enzyme deposited sequentially onto screen-printed carbon paste electrodes. Chronocoulometry was used to measure the decomposition of urea via the doping of ammonium at the polyaniline-modified electrode surface at -0.3 V vs. Ag/AgCl. Ammonium could be measured in the range from 0.1 to 100 mM. Urea could be measured by the sensor in the range of 2-12 mM (r(2)=0.98). The enzyme biosensor was correlated against a spectrophotometric assay for urea in 15 normal human serum samples which yielded a correlation coefficient of 0.85. Bland-Altman plots showed that in the range of 5.8-6.6 mM urea, the developed sensor had an average positive experimental bias of 0.12 mM (2% RSD) over the reference method.

Immobilisation of a luminescent material on an electrode surface is well known to substantially modulate its photophysical and electrochemical properties. Here a positively charged ruthenium metal complex ([Ru(bpy)(3)](2+)) is immobilised on all electrode surface by ion paring with a sulfonated conducting polymer poly(2-methoxyaniline-5-sulfonic acid), (PMAS). Significantly, our study reveals that the electron transport between the ruthenium metal centres can be greatly enhanced due to the interaction with the conducting polymer when both are surface confined. Charge transfer diffusion rates in the present system are an order of magnitude faster than those found where the metal centre is immobilised within a non-conducting polymeric matrix. Electron transport appears to be mediated through the PMAS conjugated structure, contrasting with the electron hopping process typically observed in non-conducting metallopolymers. This increased regeneration rate causes the ruthenium-based electrochemiluminescence (ECL) efficiency to be increased. The impact of these observations on the ECL detection of low concentrations of disease biomarkers is discussed. (c) 2007 Published by Elsevier Ltd.

This contribution examines the application of near infra-red (NIR) quantum dot (QD) containing films for cholesterol detection. Water-soluble, 2-(dimethylamino) ethanthiol (DAET) protected 800 nm CdSeTe/ZnS core-shell QDs were prepared and incorporated into a chitosan film. The NIR electrogenerated chemiluminescence (ECL) of the QD/chitosan films upon reaction with H2O2 co-reactant (produced as a by-product of cholesterol oxidase-catalysed oxidation of cholesterol) gave a strong ECL signal at −1.35 V vs. Ag/AgCl. The sensor displayed a linear response over the clinically relevant range (0.25 ≤ [cholesterol] ≤ 5 mM) allowing the rapid detection of cholesterol and providing a platform for future development. Significantly, this NIR emission has been shown to exhibit excellent penetrability through biological samples, and will likely be at the forefront of development in the biosensing and imaging fields for the foreseeable future.

The electrochemical and photochemical properties of [Ru(bpy)2dcb]Cl2 monolayers and their subsequent use for the detection of amino acids, e.g., proline, is reported; dcb is 4,4′-dicarboxy-2,2′-bipyridine and bpy is 2,2′-bipyridine. The ability of such a complex to form stable monolayers enables its utilization for the detection of oxalate and several amino acids, producing significant ECL. The electrochemical response of the Ru2+/3+ couple is electrochemically reversible and the monolayers show excellent stability with the response decreasing by less than 8% after continuous scanning over 4 h. The ECL and current responses increase linearly with increasing analyte concentration 0.2 ⩽ [Proline] ⩽ 1 nM while for hydroxy-proline the dynamic range is from 1 to 10 nM. The ECL signal was monitored at ∼644 nm, representing the λmax for the [Ru(bpy)2dcb]Cl2 monolayers. This wavelength is shifted by approximately 28 nm compared to the photoexcited λmax for the same system. This technique is simple, rapid, selective and sensitive, and shows potential for the high-throughput quantitation of amino acids if adapted with other techniques such as FIA or LC systems. Keywords: Electrochemiluminescence, Monolayer, Monolayer emission, Amino acid, Electroanalysis, Luminescence

Steady state luminescence and measurements of the luminescent lifetime as well as cyclic voltammetry have been used to elucidate the mechanism and dynamics of interaction between a luminescent ruthenium metal center and two different fractions of poly(2-methoxyaniline-5-sulfonic acid) (PMAS). The two fractions, high molecular weight (HMWT) PMAS and low molecular weight (LMWT) PMAS oligomer, showed significantly distinctive influences on the luminophore. The HMWT PMAS, confirmed to be an emeraldine salt by its characteristic redox chemistry, greatly impacted the diffusion coefficient of the Ru2+/3+ within the composite film, increasing the diffusion coefficient, DCT, by 2 orders of magnitude. The HMWT PMAS also resulted in quenching of the ruthenium-based emission. Significantly, these results indicate that quenching involves both static and dynamic processes, with the static quenching being the dominant process, suggesting that the metal center and polymer backbone were strongly associated. In stark contrast, the LMWT PMAS did not influence the electrochemical properties of the ruthenium metal center; however, it did double the emission observed from the ruthenium metal center. The insensitivity of the luminescence lifetime does suggest that, as with the HMWT PMAS, LWMT PMAS is strongly associated with the ruthenium metal center. The enhanced luminescence may allow for many potential sensor developments based on the luminescent ruthenium metal center, while the HMWT PMAS quenching could be utilized within quenching-based strategies or electrochemical devices.

Emission spectroscopy and electrochemistry has been used to probe the electronic communication between adjacent metal centres and the conjugated backbone within a family of imidazole based metallopolymers, [Ru(bpy)(2)(PPyBBIM)(n)](2+), in the ground and excited states, bpy is 2,2'-bipyridyl, PPyBBIM is poly[2-(2-pyridyl)-bibenzimidazole] and n = 3, 10 or 20. Electronic communication in the excited state is not efficient and upon optical excitation dual emission is observed, i.e., both the polymer backbone and the metal centres emit. Coupling the ruthenium moiety to the imidazole backbone results in a red shift of approximately 50 nm in the emission spectrum. Luminescent lifetimes of up to 120 ns were also recorded. Cyclic voltammetry was also utilized to illustrate the distance dependence of the electron hopping rates between adjacent metal centres with ground state communication reduced by up to an order of magnitude compared to previously reported results when the metal to backbone ratio was not altered. D(CT) and D(e) values of up to 3.96 × 10(-10) and 5.32 × 10(-10) cm(2) S(-1) were observed with corresponding conductivity values of up to 2.34 × 10(-8) S cm(-1).

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