Solid-state nanocrystalline dye-sensitized solar cell using 2-mercapto benzimidazole doped poly(ethylene oxide) as a new polymer electrolyte

New composite doped poly (ethylene oxide) polymer electrolyte was developed using 2-mercapto benzimidazole as plasticizer and iodide/triiodide as redox couple. The fabrication of the cell involves Poly(ethylene oxide)/ 2-mercapto benzimidazole / iodide/triiodide as polymer electrolyte in dye-sensitized solar cell fabricated with N3 dye and TiO2 nanoparticles as the photoanode and Platinum coated FTO (fluorine doped SnO2) as counter electrode. The current-volatage characteristics under simulated sunlight AM1.5 shows a short circuit current Isc of 8.7mA and open circuit photovoltage 508 mV. The conductivity measurements for the new polymer electrolyte and the photoelectrochemical measurments were carried out systematically. In 2-mercapto benzimidazole the electron rich sulphur and nitrogen atoms, act as pi-electron donors that form good interaction with iodine which plays a vital role in the performance of the fabricated dye-sensitized solar cells. The resonance effect increases the stability of the cell to a considerable extent. These results suggest that the new composite polymer electrolyte performs as a promising new doped polymer-electrolyte.

Bioactive mesopore-glass microspheres with controllable protein-delivery properties by biomimetic surface modification

Microsphere systems with the ideal properties for bone regeneration need to be bioactive, and at the same time possess the capacity for controlled protein/drug-delivery; however, the current crop of microsphere system fails to fulfill these properties. The aim of this study was to develop a novel protein-delivery system of bioactive mesoporous glass (MBG) microspheres by a biomimetic method through controlling the density of apatite on the surface of microspheres, for potential bone tissue regeneration. MBG microspheres were prepared by using the method of alginate cross-linking with Ca2+ ions. The cellular bioactivity of MBG microspheres was evaluated by investigating the proliferation and attachment of bone marrow stromal cell (BMSC). The loading efficiency and release kinetics of bovine serum albumin (BSA) on MBG microspheres were investigated after coprecipitating with biomimetic apatite in simulated body fluids (SBF). The results showed that MBG microspheres supported BMSC attachment and the Si containing ionic products from MBG microspheres stimulated BMSCs proliferation. The density of apatite on MBG microspheres increased with the length of soaking time in SBF. BSA-loading efficiency of MBG was significantly enhanced by co-precipitating with apatite. Furthermore, the loading efficiency and release kinetics of BSA could be controlled by controlling the density of apatite formed on MBG microspheres. Our results suggest that MBG microspheres are a promising protein-delivery system as a filling material for bone defect healing and regeneration.

Bioactive inorganic materials/alginate composite microspheres with controllable drug-delivery ability

Alginate microspheres are considered a promising material as a drug carrier in bone repair due to excellent biocompatibility, but their main disadvantage is low drug entrapment efficiency and non-controllable release. The aim of this study was to investigate the effect of incorporating mesoporous bioglass (MBG), non-mesoporous bioglass (BG) or hydroxyapatite (HAp) into alginate microspheres on their drug-loading and release properties. X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and atomic emission spectroscopy (AES) were used to analyse the composition, structure and dissolution of bioactive inorganic materials and their microspheres. Dexamethasone (DEX)-loading and release ability of four microspheres were tested in phosphate buffered saline with varying pHs. Results showed that the drug-loading capacity was enhanced with the incorporation of bioactive inorganic materials into alginate microspheres. The MBG/Alginate microspheres had the highest drug loading ability. DEX release from alginate microspheres correlated to the dissolution of MBG, BG and HAp in PBS, and that the pH was an efficient factor in controlling the DEX release; a high pH resulted in greater DEX release, whereas a low pH delayed DEX release. In addition, MBG/alginate, BG/alginate and HAp/alginate microspheres had varying apatite-formation and dissolution abilities, which indicate that the composites would behave differently with respect to bioactivity. The study suggests that microspheres made of a composite of bioactive inorganic materials and alginate have a bioactivity and degradation profile which greatly improves their drug delivery capacity, thus enhancing their potential applications as bioactive filler materials for bone tissue regeneration.

Use of micro-ATR/FTIR imaging to study heterogeneous polymer oxidation by direct solvent casting onto the ATR IRE

A technique is described whereby micro-ATR/FTIR imaging can be used to follow polymer degradation reactions in situ in real time. The internal reflection element (IRE) assembly is removed from the ATR objective and polymer is solvent cast directly onto the IRE surface. The polymer is then subjected to degradation conditions and molecular structural changes monitored by periodically replacing the IRE assembly back in the ATR objective and collecting spectra which can be used to construct images. This approach has the benefit that the same part of the sample is always studied, and that contact by pressure which might damage the polymer surface is not required. The technique is demonstrated using the polymer Topas which was degraded by exposure to UVC light in air.

The return of a forgotten polymer : Polycaprolactone in the 21st century

During the resorbable-polymer-boom of the 1970s and 1980s, polycaprolactone (PCL) was used in the biomaterials field and a number of drug-delivery devices. Its popularity was soon superseded by faster resorbable polymers which had fewer perceived disadvantages associated with long term degradation (up to 3-4 years) and intracellular resorption pathways; consequently, PCL was almost forgotten for most of two decades. Recently, a resurgence of interest has propelled PCL back into the biomaterials-arena. The superior rheological and viscoelastic properties over many of its aliphatic polyester counterparts renders PCL easy to manufacture and manipulate into a large range of implants and devices. Coupled with relatively inexpensive production routes and FDA approval, this provides a promising platform for the production of longer-term degradable implants which may be manipulated physically, chemically and biologically to possess tailorable degradation kinetics to suit a specific anatomical site. This review will discuss the application of PCL as a biomaterial over the last two decades focusing on the advantages which have propagated its return into the spotlight with a particular focus on medical devices, drug delivery and tissue engineering.

Dynamics of in vitro polymer degradation of polycaprolactone-based scaffolds : accelerated versus simulated physiological conditions

The increasing use of biodegradable devices in tissue engineering and regenerative medicine means it is essential to study and understand their degradation behaviour. Accelerated degradation systems aim to achieve similar degradation profiles within a shorter period of time, compared with standard conditions. However, these conditions only partially mimic the actual situation, and subsequent analyses and derived mechanisms must be treated with caution and should always be supported by actual long-term degradation data obtained under physiological conditions. Our studies revealed that polycaprolactone (PCL) and PCL-composite scaffolds degrade very differently under these different degradation conditions, whilst still undergoing hydrolysis. Molecular weight and mass loss results differ due to the different degradation pathways followed (surface degradation pathway for accelerated conditions and bulk degradation pathway for simulated physiological conditions). Crystallinity studies revealed similar patterns of recrystallization dynamics, and mechanical data indicated that the scaffolds retained their functional stability, in both instances, over the course of degradation. Ultimately, polymer degradation was shown to be chiefly governed by molecular weight, crystallinity susceptibility to hydrolysis and device architecture considerations whilst maintaining its thermodynamic equilibrium.

Scaffold development using 3D printing with a starch-based polymer

Rapid prototyping (RP) techniques have been utilised by tissue engineers to produce three-dimensional (3D) porous scaffolds. RP technologies allow the design and fabrication of complex scaffold geometries with a fully interconnected pore network. Three-dimensional printing (3DP) technique was used to fabricate scaffolds with a novel micro- and macro-architecture. In this study, a unique blend of starch-based polymer powders (cornstarch, dextran and gelatin) was developed for the 3DP process. Cylindrical scaffolds of five different designs were fabricated and post-processed to enhance the mechanical and chemical properties. The scaffold properties were characterised by scanning electron microscopy (SEM), differential scanning calorimetry (DSC), porosity analysis and compression tests

Systematic variations in polymer gel dosimeter calibration due to container influence and deviations from water equivalence

There are a number of gel dosimeter calibration methods in contemporary usage. The present study is a detailed Monte Carlo investigation into the accuracy of several calibration techniques. Results show that for most arrangements the dose to gel accurately reflects the dose to water, with the most accurate method involving the use of a large diameter flask of gel into which multiple small fields of varying dose are directed. The least accurate method was found to be that of a long test tube in a water phantom, coaxial with the beam. The large flask method is also the most straightforward and least likely to introduce errors during setup, though, to its detriment, the volume of gel required is much more than other methods.

Comparison of human alveolar osteoblasts cultured on polymer-ceramic composite scaffolds and tissue culture plates

The effects of medical grade polycaprolactone–tricalcium phosphate (mPCL–TCP) (80:20) scaffolds on primary human alveolar osteoblasts (AOs) were compared with standard tissue-culture plates. Of the seeded AOs, 70% adhered to and proliferated on the scaffold surface and within open and interconnected pores; they formed multi-layered sheets and collagen fibers with uniform distribution within 28 days. Elevation of alkaline phosphatase activity occurred in scaffold–cell constructs independent of osteogenic induction. AO proliferation rate increased and significant decrease in calcium concentration of the medium for both scaffolds and plates under induction conditions were seen. mPCL–TCP scaffolds significantly influenced the AO expression pattern of osterix and osteocalcin (OCN). Osteogenic induction down-regulated OCN at both RNA and protein level on scaffolds (3D) by day 7, and up-regulated OCN in cell-culture plates (2D) by day 14, but OCN levels on scaffolds were higher than on cell-culture plates. Immunocytochemical signals for type I collagen, osteopontin and osteocalcin were detected at the outer parts of scaffold–cell constructs. More mineral nodules were found in induced than in non-induced constructs. Only induced 2D cultures showed nodule formation. mPCL–TCP scaffolds appear to stimulate osteogenesis in vitro by activating a cellular response in AO's to form mineralized tissue. There is a fundamental difference between culturing AOs on 2D and 3D environments that should be considered when studying osteogenesis in vitro.

Osteogenic induction of human bone marrow-derived mesenchymal progenitor cells in novel synthetic polymer-hydrogel matrices

The aim of this project was to investigate the in vitro osteogenic potential of human mesenchymal progenitor cells in novel matrix architectures built by means of a three-dimensional bioresorbable synthetic framework in combination with a hydrogel. Human mesenchymal progenitor cells (hMPCs) were isolated from a human bone marrow aspirate by gradient centrifugation. Before in vitro engineering of scaffold-hMPC constructs, the adipogenic and osteogenic differentiation potential was demonstrated by staining of neutral lipids and induction of bone-specific proteins, respectively. After expansion in monolayer cultures, the cells were enzymatically detached and then seeded in combination with a hydrogel into polycaprolactone (PCL) and polycaprolactone-hydroxyapatite (PCL-HA) frameworks. This scaffold design concept is characterized by novel matrix architecture, good mechanical properties, and slow degradation kinetics of the framework and a biomimetic milieu for cell delivery and proliferation. To induce osteogenic differentiation, the specimens were cultured in an osteogenic cell culture medium and were maintained in vitro for 6 weeks. Cellular distribution and viability within three-dimensional hMPC bone grafts were documented by scanning electron microscopy, cell metabolism assays, and confocal laser microscopy. Secretion of the osteogenic marker molecules type I procollagen and osteocalcin was analyzed by semiquantitative immunocytochemistry assays. Alkaline phosphatase activity was visualized by p-nitrophenyl phosphate substrate reaction. During osteogenic stimulation, hMPCs proliferated toward and onto the PCL and PCL-HA scaffold surfaces and metabolic activity increased, reaching a plateau by day 15. The temporal pattern of bone-related marker molecules produced by in vitro tissue-engineered scaffold-cell constructs revealed that hMPCs differentiated better within the biomimetic matrix architecture along the osteogenic lineage.

PLGA-based microparticles for the sustained release of BMP-2

The development of growth factor delivery strategies to circumvent the burst release phenomenon prevalent in most current systems has driven research towards encapsulating molecules in resorbable polymer matrices. For these polymer release techniques to be efficacious in a clinical setting, several key points need to be addressed. This present study has investigated the encapsulation of the growth factor, BMP-2 within PLGA/PLGA-PEG-PLGA microparticles. Morphology, size distribution, encapsulation efficiency and release kinetics were investigated and we have demonstrated a sustained release of bioactive BMP-2. Furthermore, biocompatibility of the PLGA microparticles was established and released BMP-2 was shown to promote the differentiation of MC3T3-E1 cells towards the osteogenic lineage to a greater extent than osteogenic supplements (as early as day 10 in culture), as determined using alkaline phosphatase and alizarin red assays. This study showcases a potential BMP-2 delivery system which may now be translated into more complex delivery systems, such as 3D, mechanically robust scaffolds for bone tissue regeneration applications.

Large-scale fabrication of H2(H2O)Nb2O6 and Nb2O5 hollow microspheres

Hollow micro-sized H2(H2O)Nb2O6 spheres constructed by nanocrystallites have been successfully synthesized via a bubble-template assisted hydrothermal process. In the reaction process, H2O2 acts as a bubble generator and plays a key role in the formation of the hollow structure. An in situ bubble-template mechanism has been proposed for the possible formation of the hollow structure. The spherelike assemblies of these H2(H2O)Nb2O6 nanoparticles have been transformed into their corresponding pseudohexagonal phase Nb2O5 through a moderate annealing dehydration process without destroying the hierarchical structure. Optical properties of the as-prepared hollow spheres were investigated. It is exciting that the absorption edge of the hollow Nb2O5 microspheres shifts about 18 nm to the violet compared with bulk powders in the UV/vis spectra, indicating its superior optical properties.

The hydrogen-bonded coordination polymer tetracesium bis(5-nitroisophthalate) heptahydrate

The coordination polymer complex tetracesium bis(5-nitroisophthalate) heptahydrate [Cs4(C8H3NO6)2 (H2O)7]n has been synthesized and characterized using single-crystal X-ray diffraction. Crystals are monoclinic, space group P21/c, with Z = 4 in a cell with dimensions a = 12.3213(3), b =6.7557(2) c = 36.2020(9) Å, β = 90.548(2)o. The complex is based on a repeating unit comprising four independent and different Cs coordination centres, two 6-coordinate, and two 8-coordinate [Cs-O, range 2.959(5)-3.386(5)Å], and seven water molecules, two of which are monodentate and the other five bridging, while all other oxygen atoms in the structure, including those of the nitro groups form inter-Cs bridges. Extensive water O-H…O hydrogen-bonding interactions give a three-dimensional framework. This structure represents the first of an alkali metal compound of 5-nitroisophthalic acid that has been reported.