Structural Changes of Cellulose Crystallites Induced by Mercerisation in Different Solvent Systems; Determined by Powder X-ray Diffraction Method

The completeness of mercerisation can be evaluated by investigating the changes in the crystalline regions of cellulose from cellulose I (C-I) to cellulose II (C-II) by the X-ray powder diffraction method. Mercerisation experiments in four different solution systems: ethanol/water, acetone, DMSO and xylene, are reported. Also the effect of some additives, external pressure, treatment time and alkalisation temperature were studied. In two-phase solvent systems, structural changes of cellulose crystallites depended primarily on the distribution and solubility of sodium hydroxide in the solvent phases. The sodium hydroxide concentration in the hydrophilic phase must exceed 7–8 w/w-% before complete crystal change from C-I to C-II can occur. The precipitation of sodium hydroxide due to high concentration prevents the successful use of one-phase ethanol/water system in slurry process. On the contrary, the 2-propanol/water/sodium hydroxide system separates into two layers; to the water-rich lower layer and the 2-propanol-rich upper layer, where the sodium hydroxide remains mainly in the water-rich lower layer. This prevents the precipitation of sodium hydroxide and promotes the alkalisation of cellulose. Ammonium chloride and ammonium hydroxide clearly had a positive effect by promoting the crystal changes, however, the urea concentration used in this study was obviously too small. In the advantageous two-phase 2-propanol/water systems, the alkalisation time was only 15 min when the treatment temperature was kept between 0 and 10 °C. Reduced external pressure was found to have a small but still detectable positive effect on cellulose alkalisation while over-pressure prevented crystal changes.     

Thermal and spectroscopic investigation of europium and samarium sulphates hydrates by TG-FTIR and ICP-MS techniques

The investigation of europium(III) sulphate hydrate and samarium(III) sulphate hydrate was performed by thermal analysis (TG-DTG) and simultaneous infrared evolved gas analysis-Fourier transformed infrared (EGA-FTIR) spectroscopy. The TG, DTG and DTA curves were recorded at the 25–1400 °C in the dynamic air atmosphere by TG/DTA analyser. The infrared evolved gas analysis was obtained on the FTIR spectrometer. Eu₂(SO₄)₃·nH₂O (n = 3.97) and Sm₂(SO₄)₃·nH₂O (n = 8.11) were analysed, the dehydration and decomposition steps were investigated and the water content was calculated. The formation of different oxysulphates was studied.

The trace rare earth elements in Eu and Sm sulphates were determined by ICP-MS. The concentration of trace Eu, Sm, La, Gd, Y and Ce ranged from 3.9 × 10⁻⁶ to 1.5 × 10⁻⁴% (m/m).     

Direct analysis of fly ash materials by inductively coupled plasma atomic emission spectrometry using slurry nebulization

Fly ash samples of cement works were analysed using slurry nebulization inductively coupled plasma atomic emission spectrometric (ICP-AES). Because of the influence of the experimental factors on the signal intensity, the optimal conditions of the analysis circumstances were determined. Control analyses (wet digestion followed by ICP-AES, and XRF of dry powders (pressed pellets)) were also carried out to compare the results. Based on the result, it was concluded that the slurry nebulization method using slurry standard of same type reference material for calibration can be applied for rapid but less precise (RSD 5–10%) determination of the elements in fly ash.     

Synthesis, characterization and thermal properties of small R2R2NX-type quaternary ammonium halides

Twenty-one R₂R^′₂N⁺X⁻ -type (R=methyl or ethyl, R^′=alkyl, X=Br or I) quaternary ammonium (QA) halides have been prepared by using a novel one-pot synthetic route in which a formamide (dimethyl-, diethylformamide, etc.) is treated with alkyl halide in the presence of sodium or potassium carbonate. The formation of QA halides was verified with ¹H-NMR, ¹³C-NMR, MS and elemental analysis. The crystal structures of four QA halides (two bromide and two iodide) were determined using X-ray single crystal diffraction, and the powder diffraction method was used to study the structural similarities between the single crystal and microcrystalline bulk material. The thermal properties of all compounds were studied using TG/DTA and DSC methods. The smallest compounds decomposed during or before melting. The decreasing trend of melting points was observed when the alkyl chain length was increased. The liquid ranges of 120-180 °C were observed for compounds with 5-6 carbon atoms in the alkyl chain. The low melting points and wide liquid ranges suggest potential applicability of these compounds for example as ionic liquids precursors.     

Separation of silver from waste waters by ion-exchange resins and concentration by microbial cells

Summary Waste waters of film processing plants are rich with silver. Part of the silver is regenerated electrochemically, but the rest (0.5 g) remains in waste waters and is sent to sewers. This is a bad politic from both the environmental (toxic waste waters) and the economical point of view (a waste of silver). In this work, the silver was isolated by ion-exchange resins and then concentrated by microorganisms. For exchange of silver, Ionenaustauscher I, II and IV were used. The batch method was used to obtain a static equilibrium. Silver elution from exchangers is based on silver transformation to a stable cation or anion complex. By varying the ligands, pH and eluent concentrations, optimum elution is found at 1 mol/l Na₂S₂O₃, 1 mol/l NH₃, 2 mol/l HNO₃ and 1 mol/l (NH₂)₂CO. The concentration of silver in the eluent is about 50 mg/l. The silver ion uptake from solutions after ion exchange by mixed bacterial culture isolated from photographic waste water drain and pure bacterial cultures Escherichia coli 3009 and Bacillus subtilis 3053. was studied. Experiments were carried out in submerse culture at pH 7 with different Ag⁺ concentrations (4, 8 and 40 mg/l) on a rotary shaker (100 rpm) at 37°C. At the lower Ag⁺ concentrations a good growth and simultaneous removal of Ag⁺ from the solutions was achieved. At Ag⁺ concentration of 40 mg/l growth and removal of Ag⁺ by mixed and pure culture differed significantly. Thus mixed bacterial culture grew well and at the same time removed efficiently Ag⁺ (approximately 90%) from medium. Pure bacterial cultures on the contrary were unable to grow at 40 mg/l Ag⁺, though their biomass showed to be an effective biosorbent for Ag⁺ (approximately 80% of Ag⁺ removal).     

Amine-Directed Palladium-Catalyzed C−H Halogenation of Phenylalanine Derivatives

An efficient primary-amine-directed, palladium-catalyzed C−H halogenation (X=I, Br, Cl) of phenylalanine derivatives is reported on a range of quaternary amino acid (AA) derivatives thanks to suitable conditions employing trifluoroacetic acid as additive. The extension of this original native functionality-directed ortho-selective halogenation was even demonstrated with the more challenging native phenylalanine as tertiary AA.     

An optimization approach for communal home meal delivery service: A case study

This paper is the first to discuss the communal home meal delivery problem. The problem can be modelled as a multiple travelling salesman problem with time windows, that is closely related to the well-studied vehicle routing problem with time windows. Experimental results are reported for a real-life case study from Central Finland over several alternative scenarios using the SPIDER commercial solver. The comparison with current practice reveals that a significant savings potential can be obtained using off-the-shelf optimization tools. As such, the potential for supporting real-life communal routing problems can be considered to be important for VRP practitioners.     

Symmetric spaces approach to some fixed point results

In this paper we present a simple and unified approach to the fixed point results on cone symmetric spaces and metric type spaces based on symmetric spaces fixed point theory. We also give a new characterization of semi-metric spaces with open balls.     

Packing dimension and Ahlfors regularity of porous sets in metric spaces

Let X be a metric measure space with an s-regular measure μ. We prove that if A ì X{A\subset X} is r{\varrho} -porous, then dim_p(A) ￡ s-cr^s{{\rm {dim}_p}(A)\le s-c\varrho^s} where dim_p is the packing dimension and c is a positive constant which depends on s and the structure constants of μ. This is an analogue of a well known asymptotically sharp result in Euclidean spaces. We illustrate by an example that the corresponding result is not valid if μ is a doubling measure. However, in the doubling case we find a fixed N ì X{N\subset X} with μ(N) = 0 such that dim_p(A) ￡ dim_p(X)-c(log\tfrac1r)^-1r^t{{\rm {dim}_p}(A)\le{\rm {dim}_p}(X)-c(\log \tfrac1\varrho)^{-1}\varrho^t} for all r{\varrho} -porous sets A ì X\ N{A \subset X{\setminus} N} . Here c and t are constants which depend on the structure constant of μ. Finally, we characterize uniformly porous sets in complete s-regular metric spaces in terms of regular sets by verifying that A is uniformly porous if and only if there is t < s and a t-regular set F such that A ì F{A\subset F} .