Ageing and thermal stability studies on quasi-solid composite electrolytes for Grätzel-type solar cells

Loss of volatile components from two types of quasi-solid gel electrolytes to be used in Grätzel (or dye-sensitized, DSSC)-type alternative solar cells are checked time to time by thermogravimetry (TG) to follow the stability or changes of composites during storage at ambient. One of the gel samples, labeled as P2000 and based on UreaSil 2000, a 3D-cage precursor compound, has been found quite stable, while the related P230 sample based on UreaSil 230 seems to have a bit higher deviation in heterogeneity and some tendencies losing gradually from its volatile content, time to time. In addition, two online coupled evolved gas analytical tools (TG–EGA–FTIR and TG/DTA–EGA–MS) are applied to check the gel electrolytes for thermal vaporization, degradation, and decomposition processes as a function of temperature during dynamic heating in air. Initial minor elimination of ethyl acetate has been detected by both in situ coupled mass spectroscopy and FTIR spectroscopic gas cell. According to both evolved gas analytical systems, the other liquid ingredients, acetic acid (AcOH) and sulfolane are also released in the order of their volatility. Above 300 °C, an oxidative thermal degradation of UreaSil-type host matrices is indicated by the occurrence of, among others, formaldehyde or ammonia for electrolyte samples P2000 and P230, respectively. Evolution of various alkyl iodides with short chain length has only been detected by the mass spectroscopic evolved gas analysis method only.     

Characterization of surface plasmon energy transduction in gold nanoparticle/polymer composites by photo-DSC

In this study, we investigate the formulation and optimization of stimulus-responsive composites consisting of gold nanoparticles in polyethylene glycol diacrylate (PEGDA) matrices, which can be remotely heated through localized surface plasmon resonance (SPR). In these materials, laser radiation is absorbed by the nanoparticles and transduced into thermal energy. Optothermal properties of the polymer/nanoparticle composites are characterized using an adaptation of photo-differential scanning calorimetry (photo-DSC), in which a sample is characterized in isothermal mode in the presence and absence of optical illumination. Au/PEGDA composite samples are determined by photo-DSC to transduce energy from a 532 nm optical source with high efficiencies (>80%). UV/Vis/NIR spectrophotometry is used to characterize the optical properties of the samples. Nanoparticle dispersion and size within composite polymer matrices are characterized using transmission electron microscopy (TEM). It is shown that the magnitude and rate of energy transduction can be tuned by varying both nanoparticle concentration and dispersion.     

Bringing about matrix sparsity in linear-scaling electronic structure calculations

The performance of linear-scaling electronic structure calculations depends critically on matrix sparsity. This article gives an overview of different strategies for removal of small matrix elements, with emphasis on schemes that allow for rigorous control of errors. In particular, a novel scheme is proposed that has significantly smaller computational overhead compared with the Euclidean norm-based truncation scheme of Rubensson et al. (J Comput Chem 2009, 30, 974) while still achieving the desired asymptotic behavior required for linear scaling. Small matrix elements are removed while ensuring that the Euclidean norm of the error matrix stays below a desired value, so that the resulting error in the occupied subspace can be controlled. The efficiency of the new scheme is investigated in benchmark calculations for water clusters including up to 6523 water molecules. Furthermore, the foundation of matrix sparsity is investigated. This includes a study of the decay of matrix element magnitude with distance between basis function centers for different molecular systems and different methods. The studied methods include Hartree–Fock and density functional theory using both pure and hybrid functionals. The relation between band gap and decay properties of the density matrix is also discussed.     

Cadmium telluride nanocrystals as luminescent sensitizers in flow analysis

A fully automated multipumping flow system (MPFS) using water-soluble CdTe quantum dots (QD) as sensitizers is proposed for the chemiluminometric determination of the anti-diabetic drugs gliclazide and glipizide in pharmaceutical formulations. The nanocrystals acted as enhancers of the weak CL emission produced upon oxidation of sulphite by Ce(IV) in acidic medium, thus improving sensitivity and expanding the dynamical analytical concentration range. By interacting with the QD, the two analytes prevented their sensitizing effect yielding a chemiluminescence quenching of the Ce(IV)-SO₃²⁻CdTe QD system. The pulsed flow inherent to MPFS assured a fast and efficient mixing of all solutions inside the flow cell, circumventing the need for a reaction coil and facilitating the monitoring of the short-lived generated chemiluminescent species. QD crystal size, concentration and spectral region for measurement were investigated.     

Size-controllable synthesis of functional heterostructured TiO<Subscript>2</Subscript>–WO<Subscript>3</Subscript> core–shell nanoparticles

Mono and bicomponent TiO₂ and WO₃ nanoparticles were synthesized inside Vycor^® glass pores, by cycles of impregnation of the glass with the respective oxide precursor followed by its thermal decomposition. The impregnation-decomposition cycle (IDC) methodology promoted a linear mass increase of the glass matrix, and allowed tuning the nanoparticle size. X-ray diffraction and Raman spectroscopy data allowed identifying the formation of TiO₂ as anatase phase, while WO₃ is a mixture of the γ-WO₃ (monoclinic) and δ-WO₃ (triclinic) phases. High resolution transmission electron microscopy images revealed that for 3, 5, and 7 IDC, the TiO₂ nanoparticles obtained presented average diameters of 3.4, 4.3, and 5.1 nm, and the WO₃ nanoparticles have 2.9, 4.6, and 5.7 nm sizes. These TiO₂ and WO₃ monocomponent nanoparticles were submitted to IDC with the other oxide precursor, resulting in bicomponent nanoparticles. The broadening and shift of the Raman bands related to titanium and tungsten oxides suggest the formation of hetero-structure core–shell nanoparticles with tunable core sizes and shell thicknesses.     

Quantitative Analysis of Flame Instabilities in a Hele-Shaw Burner

We show in this paper that a Hele-Shaw burner can be used for studying the development of premixed flame instabilities in a quasi-two dimensional configuration. It is possible to ignite a plane flame at the top of the cell, and to measure quantitatively the growth rates of the instability by image analysis. Experiments are performed with propane and methane-air mixtures. It is found that the most unstable wavelength, and the maximum linear growth rate of perturbations, directly measured in the present experiments, have the same order of magnitude as those previously measured on flames propagating freely downwards in wide tubes.     

Biodegradable Nanoparticles Loaded with Levodopa and Curcumin for Treatment of Parkinson’s Disease

Background: Parkinson’s disease (PD) is the second most common age-related neurodegenerative disorder. Levodopa (L-DOPA) remains the gold-standard drug available for treating PD. Curcumin has many pharmacological activities, including antioxidant, anti-inflammatory, antimicrobial, anti-amyloid, and antitumor properties. Copolymers composed of Poly (ethylene oxide) (PEO) and biodegradable polyesters such as Poly (ε-caprolactone) (PCL) can self-assemble into nanoparticles (NPs). This study describes the development of NH₂–PEO–PCL diblock copolymer positively charged and modified by adding glutathione (GSH) on the outer surface, resulting in a synergistic delivery of L-DOPA curcumin that would be able to pass the blood–brain barrier. Methods: The NH₂–PEO–PCL NPs suspensions were prepared by using a nanoprecipitation and solvent displacement method and coated with GSH. NPs were submitted to characterization assays. In order to ensure the bioavailability, Vero and PC12 cells were treated with various concentrations of the loaded and unloaded NPs to observe cytotoxicity. Results: NPs have successfully loaded L-DOPA and curcumin and were stable after freeze-drying, indicating advancing into in vitro toxicity testing. Vero and PC12 cells that were treated up to 72 h with various concentrations of L-DOPA and curcumin-loaded NP maintained high viability percentage, indicating that the NPs are biocompatible. Conclusions: NPs consisting of NH₂–PEO–PCL were characterized as potential formulations for brain delivery of L-DOPA and curcumin. The results also indicate that the developed biodegradable nanomicelles that were blood compatible presented low cytotoxicity.     

Bioactive Platinum(IV) Complexes Incorporating Halogenated Phenylacetates

A new series of cytotoxic platinum(IV) complexes (1–8) incorporating halogenated phenylacetic acid derivatives (4-chlorophenylacetic acid, 4-fluorophenylacetic acid, 4-bromophenylacetic acid and 4-iodophenylacetic acid) were synthesised and characterised using spectroscopic and spectrometric techniques. Complexes 1–8 were assessed on a panel of cell lines including HT29 colon, U87 glioblastoma, MCF-7 breast, A2780 ovarian, H460 lung, A431 skin, Du145 prostate, BE2-C neuroblastoma, SJ-G2 glioblastoma, MIA pancreas, the ADDP-resistant ovarian variant, and the non-tumour-derived MCF10A breast line. The in vitro cytotoxicity results confirmed the superior biological activity of the studied complexes, especially those containing 4-fluorophenylacetic acid and 4-bromophenylacetic acid ligands, namely 4 and 6, eliciting an average GI₅₀ value of 20 nM over the range of cell lines tested. In the Du145 prostate cell line, 4 exhibited the highest degree of potency amongst the derivatives, displaying a GI₅₀ value of 0.7 nM, which makes it 1700-fold more potent than cisplatin (1200 nM) and nearly 7-fold more potent than our lead complex, 56MESS (4.6 nM) in this cell line. Notably, in the ADDP-resistant ovarian variant cell line, 4 (6 nM) was found to be almost 4700-fold more potent than cisplatin. Reduction reaction experiments were also undertaken, along with studies aimed at determining the complexes’ solubility, stability, lipophilicity, and reactive oxygen species production.