High-throughput approach for the identification of anilinium-based ionic liquids that are suitable for electropolymerisation

We report the synthesis of new protic ionic liquids (PILs) based on aniline derivatives and the use of high-throughput (HT) techniques to screen possible candidates. In this work, a simple HT method was applied to rapidly screen different aniline derivatives against different acids in order to identify possible combinations that produce PILs. This was followed by repeating the HT process with Chemspeed robotic synthesis platform for more accurate results. One of the successful combinations were then chosen to be synthesised on full scale for further analysis. The new PILs are of interest to the fields of ionic liquids, energy storage and especially, conducting polymers as they serve as solvents, electrolytes and monomers in the same time for possible electropolymerisation (i.e. a self-contained polymer precursor).

Effects of biodiesel chemical composition on the chemical and physical properties of the primary and secondary diesel particulate matter

This thesis improves our insight towards the effects of using biodiesels on the particulate matter emission of diesel engines and contributes to our understanding of their potential adverse health effects. The novelty of this project is the use of biodiesel fuel with controlled chemical composition that enables us to relate changes of physiochemical properties of particles to specific properties of the biodiesel. For the first time, the possibility of a correlation of the volatility and the Reactive Oxygen Species concentration of the particles is investigated versus the saturation, oxygen content and carbon chain length of the fuel.

Fast growth of polycrystalline graphene by chemical vapor deposition of ethanol on copper

High conductive graphene films can be grown on metal foils by chemical vapor deposition (CVD). We here analyzed the use of ethanol, an economic precursor, which results also safer than commonly-used methane. A comprehensive range of process parameters were explored in order to obtain graphene films with optimal characteristics in view of their use in optoelectronics and photovoltaics. Commercially-available and electro-polished copper foils were used as substrates. By finely tuning the CVD conditions, we obtained few-layer (2-4) graphene films with good conductivity (-500 Ohm/sq) and optical transmittance around 92-94% at 550 nm on unpolished copper foils. The growth on electro-polished copper provides instead predominantly mono-layer films with lower conductivity (>1000 Ohm/sq) and with a transmittance of 97.4% at 550 nm. As for the device properties, graphene with optimal properties as transparent conductive film were produced by CVD on standard copper with specific process conditions.

Stochastic linear multistep methods for the simulation of chemical kinetics

In this paper, we introduce the Stochastic Adams-Bashforth (SAB) and Stochastic Adams-Moulton (SAM) methods as an extension of the tau-leaping framework to past information. Using the theta-trapezoidal tau-leap method of weak order two as a starting procedure, we show that the k-step SAB method with k >= 3 is order three in the mean and correlation, while a predictor-corrector implementation of the SAM method is weak order three in the mean but only order one in the correlation. These convergence results have been derived analytically for linear problems and successfully tested numerically for both linear and non-linear systems. A series of additional examples have been implemented in order to demonstrate the efficacy of this approach.

Double diffusive Marangoni convection flow of electrically conducting fluid in a square cavity with chemical reaction

Double diffusive Marangoni convection flow of viscous incompressible electrically conducting fluid in a square cavity is studied in this paper by taking into consideration of the effect of applied magnetic field in arbitrary direction and the chemical reaction. The governing equations are solved numerically by using alternate direct implicit (ADI) method together with the successive over relaxation (SOR) technique. The flow pattern with the effect of governing parameters, namely the buoyancy ratio W, diffusocapillary ratio w, and the Hartmann number Ha, is investigated. It is revealed from the numerical simulations that the average Nusselt number decreases; whereas the average Sherwood number increases as the orientation of magnetic field is shifted from horizontal to vertical. Moreover, the effect of buoyancy due to species concentration on the flow is stronger than the one due to thermal buoyancy. The increase in diffusocapillary parameter, w caus

Efficient simulation of stochastic chemical kinetics with the Stochastic Bulirsch-Stoer extrapolation method

Background Biochemical systems with relatively low numbers of components must be simulated stochastically in order to capture their inherent noise. Although there has recently been considerable work on discrete stochastic solvers, there is still a need for numerical methods that are both fast and accurate. The Bulirsch-Stoer method is an established method for solving ordinary differential equations that possesses both of these qualities. Results In this paper, we present the Stochastic Bulirsch-Stoer method, a new numerical method for simulating discrete chemical reaction systems, inspired by its deterministic counterpart. It is able to achieve an excellent efficiency due to the fact that it is based on an approach with high deterministic order, allowing for larger stepsizes and leading to fast simulations. We compare it to the Euler τ-leap, as well as two more recent τ-leap methods, on a number of example problems, and find that as well as being very accurate, our method is the most robust, in terms of efficiency, of all the methods considered in this paper. The problems it is most suited for are those with increased populations that would be too slow to simulate using Gillespie’s stochastic simulation algorithm. For such problems, it is likely to achieve higher weak order in the moments. Conclusions The Stochastic Bulirsch-Stoer method is a novel stochastic solver that can be used for fast and accurate simulations. Crucially, compared to other similar methods, it better retains its high accuracy when the timesteps are increased. Thus the Stochastic Bulirsch-Stoer method is both computationally efficient and robust. These are key properties for any stochastic numerical method, as they must typically run many thousands of simulations.

A novel near-infrared spectroscopy and chemometrics method for rapid analysis of several chemical components and antioxidant activity of mint (mentha haplocalyx briq.) samples

A novel near-infrared spectroscopy (NIRS) method has been researched and developed for the simultaneous analyses of the chemical components and associated properties of mint (Mentha haplocalyx Briq.) tea samples. The common analytes were: total polysaccharide content, total flavonoid content, total phenolic content, and total antioxidant activity. To resolve the NIRS data matrix for such analyses, least squares support vector machines was found to be the best chemometrics method for prediction, although it was closely followed by the radial basis function/partial least squares model. Interestingly, the commonly used partial least squares was unsatisfactory in this case. Additionally, principal component analysis and hierarchical cluster analysis were able to distinguish the mint samples according to their four geographical provinces of origin, and this was further facilitated with the use of the chemometrics classification methods-K-nearest neighbors, linear discriminant analysis, and partial least squares discriminant analysis. In general, given the potential savings with sampling and analysis time as well as with the costs of special analytical reagents required for the standard individual methods, NIRS offered a very attractive alternative for the simultaneous analysis of mint samples.

Particle emissions from biodiesels with different physical properties and chemical composition

Biodiesels produced from different feedstocks usually have wide variations in their fatty acid methyl ester (FAME) so that their physical properties and chemical composition are also different. The aim of this study is to investigate the effect of the physical properties and chemical composition of biodiesels on engine exhaust particle emissions. Alongside with neat diesel, four biodiesels with variations in carbon chain length and degree of unsaturation have been used at three blending ratios (B100, B50, B20) in a common rail engine. It is found that particle emission increased with the increase of carbon chain length. However, for similar carbon chain length, particle emissions from biodiesel having relatively high average unsaturation are found to be slightly less than that of low average unsaturation. Particle size is also found to be dependent on fuel type. The fuel or fuel mix responsible for higher particle mass (PM) and particle number (PN) emissions is also found responsible for larger particle median size. Particle emissions reduced consistently with fuel oxygen content regardless of the proportion of biodiesel in the blends, whereas it increased with fuel viscosity and surface tension only for higher diesel–biodiesel blend percentages (B100, B50). However, since fuel oxygen content increases with the decreasing carbon chain length, it is not clear which of these factors drives the lower particle emission. Overall, it is evident from the results presented here that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions.

Systematic and Day-to-Day Effects of Chemical-Derived Population Estimates on Wastewater-Based Drug Epidemiology

Population size is crucial when estimating population-normalized drug consumption (PNDC) from wastewater-based drug epidemiology (WBDE). Three conceptually different population estimates can be used: de jure (common census, residence), de facto (all persons within a sewer catchment), and chemical loads (contributors to the sampled wastewater). De facto and chemical loads will be the same where all households contribute to a central sewer system without wastewater loss. This study explored the feasibility of determining a de facto population and its effect on estimating PNDC in an urban community over an extended period. Drugs and other chemicals were analyzed in 311 daily composite wastewater samples. The daily estimated de facto population (using chemical loads) was on average 32% higher than the de jure population. Consequently, using the latter would systemically overestimate PNDC by 22%. However, the relative day-to-day pattern of drug consumption was similar regardless of the type of normalization as daily illicit drug loads appeared to vary substantially more than the population. Using chemical loads population, we objectively quantified the total methodological uncertainty of PNDC and reduced it by a factor of 2. Our study illustrated the potential benefits of using chemical loads population for obtaining more robust PNDC data in WBDE.

Nitrogen-doped graphene films from chemical vapor deposition of pyridine: Influence of process parameters on the electrical and optical properties

Graphene films were produced by chemical vapor deposition (CVD) of pyridine on copper substrates. Pyridine-CVD is expected to lead to doped graphene by the insertion of nitrogen atoms in the growing sp2 carbon lattice, possibly improving the properties of graphene as a transparent conductive film. We here report on the influence that the CVD parameters (i.e., temperature and gas flow) have on the morphology, transmittance, and electrical conductivity of the graphene films grown with pyridine. A temperature range between 930 and 1070 °C was explored and the results were compared to those of pristine graphene grown by ethanol-CVD under the same process conditions. The films were characterized by atomic force microscopy, Raman and X-ray photoemission spectroscopy. The optical transmittance and electrical conductivity of the films were measured to evaluate their performance as transparent conductive electrodes. Graphene films grown by pyridine reached an electrical conductivity of 14.3 × 105 S/m. Such a high conductivity seems to be associated with the electronic doping induced by substitutional nitrogen atoms. In particular, at 930 °C the nitrogen/carbon ratio of pyridine-grown graphene reaches 3%, and its electrical conductivity is 40% higher than that of pristine graphene grown from ethanol-CVD.

Self-assembly of indole-2-carboxylic acid at graphite and gold surfaces

Model systems are critical to our understanding of self-assembly processes. As such, we have studied the surface self-assembly of a small and simple molecule, indole-2-carboxylic acid (I2CA). We combine density functional theory gas-phase (DFT) calculations with scanning tunneling microscopy to reveal details of I2CA assembly in two different solvents at the solution/solid interface, and on Au(111) in ultrahigh vacuum (UHV). In UHV and at the trichlorobenzene/highly oriented pyrolytic graphite (HOPG) interface, I2CA forms epitaxial lamellar structures based on cyclic OH⋯O carboxylic dimers. The structure formed at the heptanoic acid/HOPG interface is different and can be interpreted in a model where heptanoic acid molecules co-adsorb on the substrate with the I2CA, forming a bicomponent commensurate unit cell. DFT calculations of dimer energetics elucidate the basic building blocks of these structures, whereas calculations of periodic two-dimensional assemblies reveal the epitaxial effects introduced by the different substrates.

The influence of the gas environment on morphology and chemical composition of surfaces micro-machined with a femtosecond laser

We investigated the influence of different gas environments on the fabrication of surfaces, homogeneously covered with equally sized and spaced micro-structures. Two types of structures have been successfully micro-machined with a femtosecond laser on titanium surfaces in various atmospheres. The surface chemistry of samples machined in oxygen and helium shows TiO2, while machining in nitrogen leads to an additional share of TiN. The actual surface structure was found to vary significantly as a function of the gas environment. We found that the ablated particles and their surface triggered two consecutive events: The optical properties of the gas environment became non-isotropic which then led to the pulse intensity being redistributed throughout the cross section of the laser beam. Additionally, the effective intensity was further reduced for TiN surfaces due to TiN's high reflectivity. Thus, the settings for the applied raster-scanning machining method had to be adjusted for each gas environment to produce comparable structures. In contrast to previous studies, where only noble gases were found suitable to produce homogeneous patches, we obtained them in an oxygen environment.

Organosolv pretreatment of plant biomass for enhanced enzymatic saccharification

The combination of dwindling petroleum reserves and population growth make the development of renewable energy and chemical resources more pressing than ever before. Plant biomass is the most abundant renewable source for energy and chemicals. Enzymes can selectively convert the polysaccharides in plant biomass into simple sugars which can then be upgraded to liquid fuels and platform chemicals using biological and/or chemical processes. Pretreatment is essential for efficient enzymatic saccharification of plant biomass and this article provides an overview of how organic solvent (organosolv) pretreatments affect the structure and chemistry of plant biomass, and how these changes enhance enzymatic saccharification. A comparison between organosolv pretreatments utilizing broadly different classes of solvents (i.e., low boiling point, high boiling point, and biphasic) is presented, with a focus on solvent recovery and formation of by-products. The reaction mechanisms that give rise to these by-products are investigated and strategies to minimize by-product formation are suggested. Finally, process simulations of organosolv pretreatments are compared and contrasted, and discussed in the context of an industrial-scale plant biomass to fermentable sugar process.

Physio-chemical assessment of beauty leaf (Calophyllum inophyllum) as second-generation biodiesel feedstock

Recently, second-generation (non-vegetable oil) feedstocks for biodiesel production are receiving significant attention due to the cost and social effects connected with utilising food products for the production of energy products. The Beauty leaf tree (Calophyllum inophyllum) is a potential source of non-edible oil for producing second-generation biodiesel because of its suitability for production in an extensive variety of atmospheric condition, easy cultivation, high fruit production rate, and the high oil content in the seed. In this study, oil was extracted from Beauty leaf tree seeds through three different oil extraction methods. The important physical and chemical properties of these extracted Beauty leaf oils were experimentally analysed and compared with other commercially available vegetable oils. Biodiesel was produced using a two-stage esterification process combining of an acid catalysed pre-esterification process and an alkali catalysed transesterification process. Fatty acid methyl ester (FAME) profiles and important physicochemical properties were experimentally measured and estimated using equations based on the FAME analysis. The quality of Beauty leaf biodiesels was assessed and compared with commercially available biodiesels through multivariate data analysis using PROMETHEE-GAIA software. The results show that mechanical extraction using a screw press produces oil at a low cost, however, results in low oil yields compared with chemical oil extraction. High pressure and temperature in the extraction process increase oil extraction performance. On the contrary, this process increases the free fatty acid content in the oil. A clear difference was found in the physical properties of Beauty leaf oils, which eventually affected the oil to biodiesel conversion process. However, Beauty leaf oils methyl esters (biodiesel) were very consistent physicochemical properties and able to meet almost all indicators of biodiesel standards. Overall this study found that Beauty leaf is a suitable feedstock for producing second-generation biodiesel in commercial scale. Therefore, the findings of this study are expected to serve as the basis for further development of Beauty leaf as a feedstock for industrial scale second-generation biodiesel production.

Optical and chemical properties of polyterpenol thin films deposited via plasma-enhanced chemical vapor deposition

The development of novel organic polymer thin films is essential for the advancement of many emerging fields including organic electronics and biomedical coatings. In this study, the effect of synthesis conditions, namely radio frequency (rf) deposition power, on the material properties of polyterpenol thin films derived from nonsynthetic environmentally friendly monomer was investigated. At lower deposition powers, the polyterpenol films preserved more of the original monomer constituents, such as hydroxy functional groups; however, they were also softer and more hydrophilic compared to polymers fabricated at higher power. Enhanced monomer fragmentation and consequent reduction in the presence of the polar groups in the structure of the high-power samples reduced their optical band gap value from 2.95 eV for 10 W to 2.64 eV for 100 W. Regardless of deposition power, all samples were found to be optically transparent with smooth, defect-free, and homogenous surfaces.