The efficiency of encapsulation within surface rehydrated polymersomes

The key to the use of polymersomes as effective molecular delivery systems is in the ability to design processing routes that can efficiently encapsulate the molecular payload. We have evaluated various surface rehydration mechanisms for encapsulation, in each case characterizing the morphologies formed using DLS and confocal microscopy as well as determining the encapsulation efficiency for the hydrophilic dye Rhodamine B. In contrast to bulk methods, where the encapsulation efficiencies are low, we find that higher efficiencies can be obtained by the rehydration of thin films. We relate these results to the non-equilibrium mechanisms that underlie vesicle formation and discuss how an understanding of these mechanisms can help optimize encapsulation efficiencies. Our conclusion is that, even considering the good encapsulation efficiency, surface methods are still unsuitable for the massive scale-up needed when applied to commercial mass market molecular delivery scenarios. However, targeting more specialized applications for high value ingredients (like pharmaceuticals) might be more feasible.

Synthetic analogues of protein-lipid complexes

Hypercoiling poly(styrene-alt-maleic anhydride) (PSMA) is known to undergo conformational transition in response to environmental stimuli. The association of PSMA with lipid 2-dilauryl-sn-glycero-3-phosphocholine (DLPC) produces polymer-lipid complex analogues to lipoprotein assemblies found in lung surfactant. These complexes represent a new bio-mimetic delivery vehicle with applications in the cosmetic and pharmaceutical industries. The primary aim of this study was to develop a better understanding of PSMA-DLPC association by using physical and spectroscopic techniques. Ternary phase diagrams were constructed to examine the effects of various factors, such as molecular weight, pH and temperature on PSMA-DLPC association. 31P-NMR spectroscopy was used to investigate the polymorphic changes of DLPC upon associating with PSMA. The Langmuir Trough technique and surface tension measurement were used to explore the association behaviour of PSMA both at the interface and in the bulk of solution, as well as its interaction with DLPC membranes. The ultimate aim of this study was to investigate the potential use of PSMA-DLPC complexes to improve the bioavailability and therapeutic efficacy of a range of drugs. Typical compounds of ophthalmic interest range from new drugs such as Pirenzepine, which has attracted clinical interest for the control of myopia progression, to the well-established family of non-steroid anti-inflammatory drugs. These drugs have widely differing structures, sizes, solubility profiles and pH-sensitivities. In order to understand the ways in which these characteristics influence incorporation and release behaviour, the marker molecules Rhodamine B and Oil Red O were chosen. PSMA-DLPC complexes, incorporated with marker molecules and Pirenzepine, were encapsulated in hydrogels of the types used for soft contact lenses. Release studies were conducted to examine if this smart drug delivery system can retain such compounds and deliver them at a slow rate over a prolonged period of time.

Complementary methods to investigate the development of clogging within a horizontal sub-surface flow tertiary treatment wetland

A combination of experimental methods was applied at a clogged, horizontal subsurface flow (HSSF) municipal wastewater tertiary treatment wetland (TW) in the UK, to quantify the extent of surface and subsurface clogging which had resulted in undesirable surface flow. The three dimensional hydraulic conductivity profile was determined, using a purpose made device which recreates the constant head permeameter test in-situ. The hydrodynamic pathways were investigated by performing dye tracing tests with Rhodamine WT and a novel multi-channel, data-logging, flow through Fluorimeter which allows synchronous measurements to be taken from a matrix of sampling points. Hydraulic conductivity varied in all planes, with the lowest measurement of 0.1 md1 corresponding to the surface layer at the inlet, and the maximum measurement of 1550 md1 located at a 0.4m depth at the outlet. According to dye tracing results, the region where the overland flow ceased received five times the average flow, which then vertically short-circuited below the rhizosphere. The tracer break-through curve obtained from the outlet showed that this preferential flow-path accounted for approximately 80% of the flow overall and arrived 8 h before a distinctly separate secondary flow-path. The overall volumetric efficiencyof the clogged system was 71% and the hydrology was simulated using a dual-path, dead-zone storage model. It is concluded that uneven inlet distribution, continuous surface loading and high rhizosphere resistance is responsible for the clog formation observed in this system. The average inlet hydraulic conductivity was 2 md1, suggesting that current European design guidelines, which predict that the system will reach an equilibrium hydraulic conductivity of 86 md1, do not adequately describe the hydrology of mature systems.

The expression of P-glycoprotein does influence the distribution of novel fluorescent compounds in solid tumour models

Solid tumours display a complex drug resistance phenotype that involves inherent and acquired mechanisms. Multicellular resistance is an inherent feature of solid tumours and is known to present significant barriers to drug permeation in tumours. Given this barrier, do acquired resistance mechanisms such as P-glycoprotein (P-gp) contribute significantly to resistance? To address this question, the multicellular tumour spheroid (MCTS) model was used to examine the influence of P-gp on drug distribution in solid tissue. Tumour spheroids (TS) were generated from either drug-sensitive MCF7WT cells or a drug-resistant, P-gp-expressing derivative MCF7Adr. Confocal microscopy was used to measure time courses and distribution patterns of three fluorescent compounds; calcein-AM, rhodamine123 and BODIPY-taxol. These compounds were chosen because they are all substrates for P-gp-mediated transport, exhibit high fluorescence and are chemically dissimilar. For example, BODIPY-taxol and rhodamine 123 showed high accumulation and distributed extensively throughout the TSWT, whereas calcein-AM accumulation was restricted to the outermost layers. The presence of P-gp in TSAdr resulted in negligible accumulation, regardless of the compound. Moreover, the inhibition of P-gp by nicardipine restored intracellular accumulation and distribution patterns to levels observed in TSWT. The results demonstrate the effectiveness of P-gp in modulating drug distribution in solid tumour models. However, the penetration of agents throughout the tissue is strongly determined by the physico-chemical properties of the individual compounds.

Synthesis of CuS and CuS/ZnS core/shell nanocrystals for photocatalytic degradation of dyes under visible light

High quality CuS and CuS/ZnS core/shell nanocrystals (NCs) were synthesized in a large quantity using a facile hydrothermal method at low temperatures of 60 C and evaluated in the photodegradation of Rhodamine B (RhB) under visible light irradiation. Synthesis time plays an important role in controlling the morphology, size and photocatalytic activity of both CuS and CuS/ZnS core/shell NCs which evolve from spherical shaped particles to form rods with increasing reaction time, and after 5 h resemble "flower" shaped morphologies in which each "flower" is composed of many NCs. Photocatalytic activity originates from photo-generated holes in the narrow bandgap CuS, with encapsulation by large bandgap ZnS layers used to form the core/shell structure that improves the resistance of CuS towards photocorrosion. Such CuS/ZnS core/shell structures exhibit much higher photocatalytic activity than CuS or ZnS NCs alone under visible light illumination, and is attributed to higher charge separation rates for the photo-generated carriers in the core/shell structure. © 2013 Elsevier B.V.

Influence of La-doping on phase transformation and photocatalytic properties of ZnTiO3 nanoparticles synthesized via modified sol-gel method

Non-doped and La-doped ZnTiO3 nanoparticles were successfully synthesized via a modified sol–gel method. The synthesized nanoparticles were structurally characterized by PXRD, UV-vis DRS, FT-IR, SEM-EDS, TEM, Raman and photoluminescence spectroscopy. The results show that doping of La into the framework of ZnTiO3 has a strong influence on the physico-chemical properties of the synthesized nanoparticles. XRD results clearly show that the non-doped ZnTiO3 exhibits a hexagonal phase at 800 °C, whereas the La-doped ZnTiO3 exhibits a cubic phase under similar experimental conditions. In spite of the fact that it has a large ionic radius, the La is efficiently involved in the evolution process by blocking the crystal growth and the cubic to hexagonal transformation in ZnTiO3. Interestingly the absorption edge of the La-doped ZnTiO3 nanoparticles shifted from the UV region to the visible region. The photocatalytic activity of the La-doped ZnTiO3 nanoparticles was evaluated for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity was obtained for 2 atom% La-doped ZnTiO3, which is much higher than that of the non-doped ZnTiO3 as well as commercial N-TiO2. A possible mechanism for the degradation of Rhodamine B over La-doped ZnTiO3 was also discussed by trapping experiments. More importantly, the reusability of these nanoparticles is high. Hence La-doped ZnTiO3 nanoparticles can be used as efficient photocatalysts for environmental applications.

Synthesis of Cr and La-codoped SrTiO3 nanoparticles for enhanced photocatalytic performance under sunlight irradiation

In this study, we report a facile polymeric citrate strategy for the synthesis of Cr,La-codoped SrTiO3 nanoparticles. The synthesized samples were well characterized by various analytical techniques. The UV-vis DRS studies reveal that the absorption edge shifts towards the visible light region after doping with Cr, which is highly beneficial for absorbing the visible light in the solar spectrum. More attractively, codoping with La exhibits greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The optimum photocatalytic activity at 1 atom% of Cr,La-codoped SrTiO3 nanoparticles is almost 6 times higher than that of pure SrTiO3 nanoparticles and 3 times higher than that of Cr-doped SrTiO3 nanoparticles. The high photocatalytic performance in the present photocatalytic system is due to codoping with La, which acts as a most effective donor for stabilizing Cr3+ in Cr,La-codoped SrTiO3 nanoparticles. More importantly, the synthesized photocatalysts possess high reusability. A proposed mechanism for the enhanced photocatalytic activity of Cr,La-codoped SrTiO3 nanoparticles was also investigated by trapping experiments. Therefore, our results not only demonstrate the highly efficient visible light photocatalytic activity of the Cr,La-codoped SrTiO3 photocatalyst, but also enlighten the codoping strategy in the design and development of advanced photocatalytic materials for energy and environmental applications.

Cost-effective and eco-friendly synthesis of novel and stable N-doped ZnO/g-C3N4 core-shell nanoplates with excellent visible-light responsive photocatalysis

N-doped ZnO/g-C3N4 hybrid core–shell nanoplates have been successfully prepared via a facile, cost-effective and eco-friendly ultrasonic dispersion method for the first time. HRTEM studies confirm the formation of the N-doped ZnO/g-C3N4 hybrid core–shell nanoplates with an average diameter of 50 nm and the g-C3N4 shell thickness can be tuned by varying the content of loaded g-C3N4. The direct contact of the N-doped ZnO surface and g-C3N4 shell without any adhesive interlayer introduced a new carbon energy level in the N-doped ZnO band gap and thereby effectively lowered the band gap energy. Consequently, the as-prepared hybrid core–shell nanoplates showed a greatly enhanced visible-light photocatalysis for the degradation of Rhodamine B compare to that of pure N-doped ZnO surface and g-C3N4. Based on the experimental results, a proposed mechanism for the N-doped ZnO/g-C3N4 photocatalyst was discussed. Interestingly, the hybrid core–shell nanoplates possess high photostability. The improved photocatalytic performance is due to a synergistic effect at the interface of the N-doped ZnO and g-C3N4 including large surface-exposure area, energy band structure and enhanced charge-separation properties. Significantly, the enhanced performance also demonstrates the importance of evaluating new core–shell composite photocatalysts with g-C3N4 as shell material.

In situ growth strategy for highly efficient Ag2CO3/g-C3N4 hetero/nanojunctions with enhanced photocatalytic activity under sunlight irradiation

Developing novel heterojunction photocatalysts is a powerful strategy for improving the separation efficiency of photogenerated charge carriers, which is attracting the intense research interest in photocatalysis. Herein we report a highly efficient hetero/nanojunction consisting of Ag2CO3 nanoparticles grown on layered g-C3N4 nanosheets synthesized via a facile and template free in situ precipitation method. The UV–vis diffuse reflectance studies revealed that the synthesized Ag2CO3/g-C3N4 hetero/nanojunctions exhibit a broader and stronger light absorption in the visible light region, which is highly beneficial for absorbing the visible light in the solar spectrum. The optimum photocatalytic activity of Ag2CO3/g-C3N4 at a weight content of 10% Ag2CO3 for the degradation of Rhodamine B was almost 5.5 and 4 times as high as that of the pure Ag2CO3 and g-C3N4, respectively. The enhanced photocatalytic activity of the Ag2CO3/g-C3N4 hetero/nanojunctions is due to synergistic effects including the strong visible light absorption, large specific surface area, and high charge transfer and separation efficiency. More importantly, the high photostability and low use of the noble metal silver which reduces the cost of the material. Therefore, the synthesized Ag2CO3/g-C3N4 hetero/nanojunction photocatalyst is a promising candidate for energy storage and environment protection applications.

Surface plasmon resonance-induced photocatalysis by Au nanoparticles decorated mesoporous g-C3N4 nanosheets under direct sunlight irradiation

In recent years, surface plasmon-induced photocatalytic materials with tunable mesoporous framework have attracted considerable attention in energy conversion and environmental remediation. Herein we report a novel Au nanoparticles decorated mesoporous graphitic carbon nitride (Au/mp-g-C3N4) nanosheets via a template-free and green in situ photo-reduction method. The synthesized Au/mp-g-C3N4 nanosheets exhibit a strong absorption edge in visible and near-IR region owing to the surface plasmon resonance effect of Au nanoparticles. More attractively, Au/mp-g-C3N4 exhibited much higher photocatalytic activity than that of pure mesoporous and bulk g-C3N4 for the degradation of rhodamine B under sunlight irradiation. Furthermore, the photocurrent and photoluminescence studies demonstrated that the deposition of Au nanoparticles on the surface of mesoporous g-C3N4 could effectively inhibit the recombination of photogenerated charge carriers leading to the enhanced photocatalytic activity. More importantly, the synthesized Au/mp-g-C3N4 nanosheets possess high reusability. Hence, Au/mp-g-C3N4 could be promising photoactive material for energy and environmental applications.

Fe-doped and -mediated graphitic carbon nitride nanosheets for enhanced photocatalytic performance under natural sunlight

Herein, we demonstrate the synthesis of highly efficient Fe-doped graphitic carbon nitride (g-C3N4) nanosheets via a facile and cost effective method. The synthesized Fe-doped g-C3N4 nanosheets were well characterized by various analytical techniques. The results revealed that the Fe exists mainly in the +3 oxidation state in the Fe-doped g-C3N4 nanosheets. Fe doping of g-C3N4 nanosheets has a great influence on the electronic and optical properties. The diffuse reflectance spectra of Fe-doped g-C3N4 nanosheets exhibit red shift and increased absorption in the visible light range, which is highly beneficial for absorbing the visible light in the solar spectrum. More significantly, the Fe-doped g-C3N4 nanosheets exhibit greatly enhanced photocatalytic activity for the degradation of Rhodamine B under sunlight irradiation. The photocatalytic activity of 2 mol% Fe-doped g-C3N4 nanosheets is almost 7 times higher than that of bulk g-C3N4 and 4.5 times higher than that of pure g-C3N4 nanosheets. A proposed mechanism for the enhanced photocatalytic activity of Fe-doped g-C3N4 nanosheets was investigated by trapping experiments. The synthesized photocatalysts are highly stable even after five successive experimental runs. The enhanced photocatalytic performance of Fe-doped g-C3N4 nanosheets is due to high visible light response, large surface area, high charge separation and charge transfer. Therefore, the Fe-doped g-C3N4 photocatalyst is a promising candidate for energy conversion and environmental remediation.

g-C3N4/NaTaO3 organic–inorganic hybrid nanocomposite:high-performance and recyclable visible light driven photocatalyst

Novel g-C3N4/NaTaO3 hybrid nanocomposites have been prepared by a facile ultrasonic dispersion method. Our results clearly show the formation of interface between NaTaO3 and g-C3N4 and further loading of g-C3N4 did not affect the crystal structure and morphology of NaTaO3. The g-C3N4/NaTaO3 nanocomposites exhibited enhanced photocatalytic performance for the degradation of Rhodamine B under UV–visible and visible light irradiation compared to pure NaTaO3 and Degussa P25. Interestingly, the visible light photocatalytic activity is generated due to the loading of g-C3N4. A mechanism is proposed to discuss the enhanced photocatalytic activity based on trapping experiments of photoinduced radicals and holes. Under visible light irradiation, electron excited from the valance band (VB) to conduction band (CB) of g-C3N4 could directly inject into the CB of NaTaO3, making g-C3N4/NaTaO3 visible light driven photocatalyst. Since the as-prepared hybrid nanocomposites possess high reusability therefore it can be promising photocatalyst for environmental applications.

Hierarchical ZnO “rod like” architecture synthesized via reverse micellar route for improved photocatalytic activity

Hierarchical ZnO “rod like” architecture was successfully synthesized via reverse micellar route and characterized by various techniques. The FESEM studies show controlled decomposition of zinc oxalate into ZnO “rod like” architecture at 500 °C with slow heat rate at 1°/min. Interestingly, improved photocatalytic activity was observed for the degradation of Rhodamine B, due to the self assembly of hexagonal nanoparticles of zinc oxide forming hierarchical ZnO “rod like” architecture which can greatly enhance the light utilization rate due to its special architecture and enlarge the specific surface area, providing more reaction sites and promoting mass transfer. More importantly, the reusability studies of this architecture were most economical.

Synthesis of magnetically separable and recyclable g‑C3N4−Fe3O4 hybrid nanocomposites with enhanced photocatalytic performance under visible-light irradiation

Herein we demonstrate a facile, reproducible, and template-free strategy to prepare g-C3N4–Fe3O4 nanocomposites by an in situ growth mechanism. The results indicate that monodisperse Fe3O4 nanoparticles with diameters as small as 8 nm are uniformly deposited on g-C3N4 sheets, and as a result, aggregation of the Fe3O4 nanoparticles is effectively prevented. The as-prepared g-C3N4–Fe3O4 nanocomposites exhibit significantly enhanced photocatalytic activity for the degradation of rhodamine B under visible-light irradiation. Interestingly, the g-C3N4–Fe3O4 nanocomposites showed good recyclability without loss of apparent photocatalytic activity even after six cycles, and more importantly, g-C3N4–Fe3O4 could be recovered magnetically. The high performance of the g-C3N4–Fe3O4 photocatalysts is due to a synergistic effect including the large surface-exposure area, high visible-light-absorption efficiency, and enhanced charge-separation properties. In addition, the superparamagnetic behavior of the as-prepared g-C3N4–Fe3O4 nanocomposites also makes them promising candidates for applications in the fields of lithium storage capacity and bionanotechnology.