Extraction of wood compounds by use of subcritical fluids

A study of the extraction of oak wood compounds with subcritical water-ethanol mixtures as extractant, with an ethanol content between 0-60%, is reported. Identification and characterisation of the extracted compounds have been made by spectrophotometry and gas chromatography with either flame ionisation or mass detectors. Extraction was performed statically manner by use of a single cycle or repeated cycles. All variables affecting the extraction process were studied and optimised. Extraction time and temperature are 60 min and 200ºC, respectively. Comparison of the extract thus obtained with commercial extracts showed the former to be rich in compounds characteristic of the commercial extracts. The method enables manipulation of the extract composition by changing the temperature and water/ethanol ratio used. It is faster than the traditional procedures for obtaining wood extracts

Two-parameter determination in vinegar by a flow injection-pervaporation system

A flow-injection method (FI) for the sequential determination of ethanol and acetic acid in vinegar is reported. The determination of ethanol is based on the oxidation of the pervaporated ethanol by Cr2O7K2. The acetic acid is determined by an acid-base reaction with Thymol Blue as the indicator. Both reactions are monitored photometrically at 600 nm using a single detector. Optimisation studies and assessment of the sequential FI method are also reported. The linear determination range is between 0-12 % (v/v) for ethanol and 0-10 % (grams of acetic acid in 100 ml) for acetic acid. The sample throughput of the sequential manifold is 7 per hour. The new method has been applied to vinegar samples and the results obtained are in excellent agreement with those from the reference methods used in Spain

Semiautomatic flow-injection method for the determination of volatile acidity in wines

A flow-injection (FI) method based on analytical pervaporation was assessed for its routine use in the determination of volatile acidity in winery laboratories. The new method was compared with both the official method and the Mathieu method, which is most often used in Spanish wineries, by testing 30 different wines, including young and aged, and sweet and dry wines from Montilla-Moriles appellation d´origine. The robustness of the new method was established and then all three methods were studied in terms of range of linearity and regression of the calibration curve, repeatability, reproducibility, sensitivity, detection and quantification limits (LOD and LQ, respectively) and time of analysis. The FI method surpasses the Mathieu method in reproducibility and both the Mathieu and official methods in LOD and LQ and sensitivity; it also requires less personnel involvement and shorter analysis time. The statistical criteria established by the “Office International de la Vigne et du Vin” were applied to the data and the results obtained indicated that the differences between the analytical parameters of the 3 methods are not significant and can be applied indistinctly. The correlation of the methods was studied by taking them 2 by 2, and the corresponding equations, coefficients and deviations confirmed the statistical results. Thus, the new method can be used in winery laboratories with clear advantages over its 2 counterparts (the routine and official methods)

Sequential Spectrophotometric determination of methanol and iron in vinegar by a flow injection-pervaporation method

An easily automatable sequential flow-injection-pervaporation method is proposed for the photometric determination of methanol and iron in vinegar. The method is based on separation of the methanol from the sample matrix by pervaporation followed by its oxidation to formaldehyde with permanganate, decolouration of the latter with S2O5-2 and subsequent reaction of formaldehyde with p-rosaniline to yield a violet reaction product with maximum absorption at 567 nm. Iron is determined by an existing method based on reaction with thiocyanate in acidic medium and monitoring at 508 nm. After optimisation by either the univariate or multivariate approaches, as required, the linear range was established for methanol (4-1000 mg L-1) and iron (0.18-20 mg L-1); The proposed method was then compared with reference methods for methanol and iron in terms of repeatability (2.452 mg L-1 and 0.245 mg L-1, respectively), reproducibility (4.435 mg L-1 and 0.356 mg L-1, respectively), detection limit (LOD=82 and 0.234 mg L-1, respectively) and traceability. The throughput was nine samples per hour

Method for the simultaneous determination of total polyphenol and anthocyan indexes in red wines using a flow injection approach

A simultaneous and fast method for the determination of total polyphenol index (t.p.i.) and total anthocyan index (t.a.i.) has been developed by a flow injection approach and a diode array spectrophotometer for monitoring at 280 nm and 520 nm, respectively. Linear ranges were obtained from 20 to 70 index units and from 20 to 500 mg l-1 for t.p.i. and t.a.i., respectively. The results provided by the proposed method agree with those obtained using the polyphenol index at 280 nm and the Ribereau-Gayon method for the determination of total anthocyans. The sample throughput was 25-30 samples per hour. Analytical features such as repeatability, reproducibility and detection and quantification limits as well as the results of a robustness study based on the Steiner-Younden procedure are also given

Determination of ethanol in beverages by flow injection, pervaporation and density measurements

A fast, clean and easy to automate flow injection-pervaporation method for the determination of ethanol in different beverages using density measurements is proposed. The method is based on separation of the ethanol from the sample using a pervaporation module, thus obtaining in the acceptor chamber of the pervaporator a water-alcohol mixture, the density of which is measured. After optimisation by either the univariate or multivariate approach as required, a linear range between 0-40% was established. Then, the assessment of the method versus a reference one was studied in terms of repeatability (0.12% v/v), reproducibility (0.32% v/v), detection limit (0.11% v/v) and traceability. The sample throughput was 15 samples h-1. The method was in agreement with the reference methods used in the European Union

Superheated liquids for the extraction of solid residues from winemaking processes

Solid residues from winemaking process have been subjected to extraction with superheated water-ethanol mixtures. Identification and characterisation of the extracted compounds have been made by spectrophotometry, gas chromatography with either flame ionisation or mass detectors and high performance liquid chromatography with UV detection. The extraction has been performed in a static manner by single or repetitive cycles. All variables affecting the extraction process have been studied and optimised. The extraction time and temperature are 65 min and 210ºC, respectively. Two phases constitute the extract: an aqueous phase, which is rich in phenol compounds and an oily phase, mainly formed by fatty acids. The method allows manipulation of the extract composition by changing the applied pressure, temperature, water-ethanol ratio and pH. The method is faster than the traditional extraction procedures for obtaining valuable compounds from these residues

HySEA model verification for Tohoku 2011 Tsunami. Application for mitigation tsunami assessment

In many aspects Tohoku-Oki 2011 mega tsunami has changed our perception of tsunami risk. The tsunami-HySEA model is used to numerically simulate this event and observed data will we used to verify the model results. Three nested meshes of enhanced resolution (4 arc-min, 32 arc-sec and 2 arc-sec) will be used by the numerical model. The propagation mesh covers all Pacific Ocean with more of 7 million cells. An intermediate mesh with 5 millions cells contains the Japanese archipelago and, finally, two finer meshes, with nearly 8 and 6 millions cells, cover Iwate and Miyagi Prefectures at Tohoku region, the most devastated areas hit by the tsunami. The presentation will focus on the impact of the tsunami wave in these two areas and comparisons with observed data will be performed. DART buoys time series, inundation area and observed runup is used to assess model performance. The arrival time of the leading flooding wave at the vicinity of the Senday airport, as recorded by video cameras, is also used as verification data for the model. After this tsunami, control forests as well as breakwaters has been discussed as suitable mitigation infrastructures. As particular case, we will analyse the evolution of the tsunami in the area around the Sendai airport (Miyagi Prefecture) and its impact on the airport. A second simulation has been performed, assuming the existence of a coastal barrier protecting the area. The role of this barrier in modifying tsunami wave evolution and mitigating flooding effects on the airport area are discussed. The protection effect of the breakwaters near Kamaishi (Iwate Prefecture) is also assessed. The numerical model shows how these structures, although did not provide a full protection to tsunami waves, they helped to largely mitigate its effects in the area.Acknowledgements. This research has been partially supported by the Junta de Andalucía research project TESELA (P11-RNM7069), the Spanish Government Research project DAIFLUID (MTM2012-38383-C02-01) and Universidad de Málaga, Campus de Excelencia Internacional Andalucía Tech. The multi-GPU computations were performed at the Laboratory of Numerical Methods (University of Malaga)

Novel iron-pybisulidine catalysts for the selective aerobic oxidation and C-O/C-C cleavage of organic substrates

The selective oxidation of organic compounds is one of the most attractive transformations for both, industry and academia. Industrial interest stems from the potential application of such oxidation methodologies in the economic, greener synthesis of valuable products, whereas academic research is challenged by the difficulties in achieving specific, direct functionalisation of the “inert” CH bonds in complex molecules. In this Ph. D. thesis, our contribution to the selective oxidation of organic substrates using a novel class of iron catalysts is presented. A general introduction covering the major challenges in the area of iron-catalysed selective oxidation of organic compounds is described in Chapter 1. Chapter 2 covers the design, synthesis and coordination properties of the novel PyBisulidine type ligands, which we have conceived for their potential use in selective oxidation, attempting to overcome some of the limitations of current methods. The efficiency of such PyBisulidine ligands is demonstrated in Chapter 3, where iron-PyBisulidine complexes are used for catalysing the aerobic α-oxidation of functionalised ethers. High catalytic efficiency, very good mass balance and excellent functional group tolerance were achieved with these catalysts under mild conditions. Such advantages stem from an unconventional reaction mechanism, involving the dehydrogenative oxygenation of the ether substrate to give a peroxobisether, followed by the cleavage of the peroxy bond to form two ester molecules. Unlike metalloenzymes and biomimetic iron complexes, H2 is released as the sole byproduct during the catalytic cycle. The oxidation mechanism is discussed in Chapter 4. Like natural dioxygenases, iron-PyBisulidine catalysts were found capable of promoting the aerobic cleavage of aliphatic C-C and C-O bonds. Even though biomimetic complexes are often seen as simplified models to study enzymatic processes, a more synthetic perspective of the selective aerobic cleavage of ethereal C-C and C-O bonds is described in Chapter 5.The great potential of such cleavages in organic synthesis is well exemplified in the iron-PyBisulidine catalysed direct conversion of natural isochromans into biologically active isochromanones with excellent selectivity. The ability of the iron-PyBisulidine complexes in catalysing aerobic C-C cleavages is further expanded in Chapter 6, where the oxidative cleavage of olefinic C=C bonds to carbonyl compounds is demonstrated. The catalytic reactions proceeded efficiently, showing a broad scope and a mechanism that involves the formation of dioxetane intermediates is postulated. Chapter 7 is an extension of Chapter 6, in which iron-PyBisulidine complexes were found to catalyse α-methylstyrene linear dimerisation under an inert atmosphere. Moreover, control in the regioselectivity of the double bond in the dimers can be achieved by modifications in the PyBisulidine ligands. Final conclusions and a perspective of the research covered in this Ph.D. thesis are provided in Chapter 8