Thermo-chemical behaviour and chemical product formation from Polar seaweeds during intermediate pyrolysis

Fundamental analytical pyrolysis studies of biomass from Polar seaweeds, which exhibit a different biomass composition than terrestrial and micro-algae biomass were performed via thermogravimetric analysis (TGA) and pyrolysis-gas chromatography/mass-spectrometry (Py-GC/MS). The main reason for this study is the adaptation of these species to very harsh environments making them an interesting source for thermo-chemical processing for bioenergy generation and production of biochemicals via intermediate pyrolysis. Several macroalgal species from the Arctic region Kongsfjorden, Spitsbergen/Norway (Prasiola crispa, Monostroma arcticum, Polysiphonia arctica, Devaleraea ramentacea, Odonthalia dentata, Phycodrys rubens, Sphacelaria plumosa) and from the Antarctic peninsula, Potter Cove King George Island (Gigartina skottsbergii, Plocamium cartilagineum, Myriogramme manginii, Hymencladiopsis crustigena, Kallymenia antarctica) were investigated under intermediate pyrolysis conditions. TGA of the Polar seaweeds revealed three stages of degradation representing dehydration, devolatilization and decomposition of carbonaceous solids. The maximum degradation temperatures Prasiola crispa were observed within the range of 220-320 C and are lower than typically obtained by terrestrial biomass, due to divergent polysaccharide compositions. Biochar residues accounted for 33-46% and ash contents of 27-45% were obtained. Identification of volatile products by Py-GC/MS revealed a complexity of generated chemical compounds and significant differences between the species. A widespread occurrence of aromatics (toluene, styrene, phenol and 4-methylphenol), acids (acetic acid, benzoic acid alkyl ester derivatives, 2-propenoic acid esters and octadecanoic acid octyl esters) in pyrolysates was detected. Ubiquitous furan-derived products included furfural and 5-methyl-2-furaldehyde. As a pyran-derived compound maltol was obtained by one red algal species (P. rubens) and the monosaccharide d-allose was detected in pyrolysates in one green algal (P. crispa). Further unique chemicals detected were dianhydromannitol from brown algae and isosorbide from green algae biomass. In contrast, the anhydrosugar levoglucosan and the triterpene squalene was detected in a large number of pyrolysates analysed. © 2013 Elsevier B.V. All rights reserved.

Engineering surface states of carbon dots to achieve controllable luminescence for solid-luminescent composites and sensitive Be2+ detection

Luminescent carbon dots (L-CDs) with high quantum yield value (44.7%) and controllable emission wavelengths were prepared via a facile hydrothermal method. Importantly, the surface states of the materials could be engineered so that their photoluminescence was either excitation-dependent or distinctly independent. This was achieved by changing the density of amino-groups on the L-CD surface. The above materials were successfully used to prepare multicolor L-CDs/polymer composites, which exhibited blue, green, and even white luminescence. In addition, the excellent excitation-independent luminescence of L-CDs prepared at low temperature was tested for detecting various metal ions. As an example, the detection limit of toxic Be2+ ions, tested for the first time, was as low as μM.

Prediction of the equilibrium structures and photomagnetic properties of the Prussian blue analogue RbMn[Fe(CN)6] by density functional theory

A periodic density functional theory method using the B3LYP hybrid exchange-correlation potential is applied to the Prussian blue analogue RbMn[Fe(CN)6] to evaluate the suitability of the method for studying, and predicting, the photomagnetic behavior of Prussian blue analogues and related materials. The method allows correct description of the equilibrium structures of the different electronic configurations with regard to the cell parameters and bond distances. In agreement with the experimental data, the calculations have shown that the low-temperature phase (LT; Fe(2+)(t(6)2g, S = 0)-CN-Mn(3+)(t(3)2g e(1)g, S = 2)) is the stable phase at low temperature instead of the high-temperature phase (HT; Fe(3+)(t(5)2g, S = 1/2)-CN-Mn(2+)(t(3)2g e(2)g, S = 5/2)). Additionally, the method gives an estimation for the enthalpy difference (HT LT) with a value of 143 J mol(-1) K(-1). The comparison of our calculations with experimental data from the literature and from our calorimetric and X-ray photoelectron spectroscopy measurements on the Rb0.97Mn[Fe(CN)6]0.98 x 1.03 H2O compound is analyzed, and in general, a satisfactory agreement is obtained. The method also predicts the metastable nature of the electronic configuration of the high-temperature phase, a necessary condition to photoinduce that phase at low temperatures. It gives a photoactivation energy of 2.36 eV, which is in agreement with photoinduced demagnetization produced by a green laser.

The ecology of algae in relation to river water equality surveillance

The broad objectives of the work were to develop standard methods for the routine biological surveillance of river water quality, using the non-planktonic algae. Studies on sampling methodology indicated that natural substrata should be sampled directly wherever possible, but for routine purposes, only a semi-quantitative approach was found to be feasible. Artificial substrata were considered to be useful for sample collection in deeper waters, and of three different types tested, Polythene strips were selected for further investigation essentially on grounds of practicality. These were tested in the deeper reaches of a wide range of river types and water qualities: 26 pool sites in 14 different rivers were studied over a period of 9 months. At each site, the assemblages developing on 3 strips following a 4, or less commonly, an 3 week immersion period were analysed quantitatively. Where possible, the natural substrata were also sampled semi-quantitatively at each site, and at a nearby riffle. The results of this survey were very fragmentary: many strips failed to yield useful data, and the results were often difficult to interpret, and of limited value for water quality surveillance purposes. In one river, the Churnet, the natural substrata at 14 riffle sites were sampled semi-quantitatively on 14 occasions at intervals of 4 weeks. In this survey, the results were more readily interpreted in relation to water quality, and no special data processing was found to be necessary or helpful. Further studies carried out on the filamentous green alga Cladophora showed that this alga may have some value as a bioaccumulation indicator for metals, and as a bioassay organism for the assessment of the algal growth promoting potential of natural river waters.

Intermediate pyrolysis and product identification by TGA and Py-GC/MS of green microalgae and their extracted protein and lipid components

The thermo-chemical conversion of green microalgae Chlamydomonas reinhardtii wild type (CCAP 11/32C), its cell wall deficient mutant C. reinhardtii CW15 (CCAP 11/32CW15) and Chlorella vulgaris (CCAP 211/11B) as well as their proteins and lipids was studied under conditions of intermediate pyrolysis. The microalgae were characterised for ultimate and gross chemical composition, lipid composition and extracted products were analysed by Thermogravimetric analysis (TG/DTG) and Pyrolysis-gaschromatography/mass-spectrometry (Py-GC/MS). Proteins accounted for almost 50% and lipids 16-22 % of dry weight of cells with little difference in the lipid compositions between the C. reinhardtii wild type and the cell wall mutant. During TGA analysis, each biomass exhibited three stages of decomposition, namely dehydration, devolatilization and decomposition of carbonaceous solids. Py-GC/MS analysis revealed significant protein derived compounds from all algae including toluene, phenol, 4-methylphenol, 1H-indole, 1H-indole-3methyl. Lipid pyrolysis products derived from C. reinhardtii wild type and C. reinhardtii CW15 were almost identical and reflected the close similarity of the fatty acid profiles of both strains. Major products identified were phytol and phytol derivatives formed from the terpenoid chain of chlorophyll, benzoic acid alkyl ester derivative, benzenedicarboxylic acid alkyl ester derivative and squalene. In addition, octadecanoic acid octyl ester, hexadecanoic acid methyl ester and hydrocarbons including heptadecane, 1-nonadecene and heneicosane were detected from C. vulgaris pyrolysed lipids. These results contrast sharply with the types of pyrolytic products obtained from terrestrial lignocellulosic feedstocks and reveal that intermediate pyrolysis of algal biomass generates a range of useful products with wide ranging applications including bio fuels.

Debazzled:a blue and black ship, dressed to deceive

The blue and black dress that “melted the Internet” is thought to have done so because its perceived color depended on people using different prior assumptions about discounting the illuminant. However, this is not the first monochromatic object to have confused the public. For a brief period during WWI, RMS Mauretania was dressed in (dazzle) camouflage shades of blue and black/grey, yet she is sometimes depicted by artists, modelers, and historians in a much showier dress of red, blue, yellow, green, and black. I raise the possibility that this originates from a case of public deception deriving from the momentary misperception of a playful artist who neglected to discount the illuminant, propagating the most (perhaps only) successful application of dazzle camouflage known.

Superior color rendering with a phosphor-converted blue-cyan monolithic light-emitting diode

The future generation of modern illumination should not only be cheap and highly efficient, but also demonstrate high quality of light, light which allows better color differentiation and fidelity. Here we are presenting a novel approach to create a white solid-state light source providing ultimate color rendition necessary for a number of applications. The proposed semi-hybrid device combines a monolithic blue-cyan light emitting diode (MBC LED) with a green-red phosphor mixture. It has shown a superior color rendering index (CRI), 98.6, at correlated color temperature of around 3400 K. The MBC LED epi-structure did not suffer from the efficiency reduction typical for monolithic multi-color emitters and was implemented in the two most popular chip designs: “epi-up” and “flip-chip”. Redistribution of the blue and cyan band amplitudes in the white-light emission spectrum, using the operating current, is found to be an effective tool for fine tuning the color characteristics. (Figure presented.).