Determination of sugars and organic acids in pulp samples by capillary electrophoresis with UV detection

This MSc work was done in the project of BIOMECON financed by Tekes. The prime target of the research was, to develop methods for separation and determination of carbohydrates (sugars), sugar acids and alcohols, and some other organic acids in hydrolyzed pulp samples by capillary electrophoresis (CE) using UV detection. Aspen, spruce, and birch pulps are commonly used for production of papers in Finland. Feedstock components in pulp predominantly consist of carbohydrates, organic acids, lignin, extractives, and proteins. Here in this study, pulps have been hydrolyzed in analytical chemistry laboratories of UPM Company and Lappeenranta University in order to convert them into sugars, acids, alcohols, and organic acids. Foremost objective of this study was to quantify and identify the main and by-products in the pulp samples. For the method development and optimization, increased precision in capillary electrophoresis was accomplished by calculating calibration data of 16 analytes such as D-(-)-fructose, D(+)-xylose, D(+)-mannose, D(+)-cellobiose, D-(+)-glucose, D-(+)-raffinose, D(-)-mannitol, sorbitol, rhamnose, sucrose, xylitol, galactose, maltose, arabinose, ribose, and, α-lactose monohydratesugars and 16 organic acids such as D-glucuronic, oxalic, acetic, propionic, formic, glycolic, malonic, maleic, citric, L-glutamic, tartaric, succinic, adipic, ascorbic, galacturonic, and glyoxylic acid. In carbohydrate and polyalcohol analyses, the experiments with CE coupled to direct UV detection and positive separation polarity was performed in 36 mM disodium hydrogen phosphate electrolyte solution. For acid analyses, CE coupled indirect UV detection, using negative polarity, and electrolyte solution made of 2,3 pyridinedicarboxylic acid, Ca2+ salt, Mg2+ salts, and myristyltrimethylammonium hydroxide in water was used. Under optimized conditions, limits of detection, relative standard deviations and correlation coefficients of each compound were measured. The optimized conditions were used for the identification and quantification of carbohydrates and acids produced by hydrolyses of pulp. The concentrations of the analytes varied between 1 mg – 0.138 g in liter hydrolysate.

Imaging and Characterisation of Dirt Particles in Pulp and Paper

Dirt counting and dirt particle characterisation of pulp samples is an important part of quality control in pulp and paper production. The need for an automatic image analysis system to consider dirt particle characterisation in various pulp samples is also very critical. However, existent image analysis systems utilise a single threshold to segment the dirt particles in different pulp samples. This limits their precision. Based on evidence, designing an automatic image analysis system that could overcome this deficiency is very useful. In this study, the developed Niblack thresholding method is proposed. The method defines the threshold based on the number of segmented particles. In addition, the Kittler thresholding is utilised. Both of these thresholding methods can determine the dirt count of the different pulp samples accurately as compared to visual inspection and the Digital Optical Measuring and Analysis System (DOMAS). In addition, the minimum resolution needed for acquiring a scanner image is defined. By considering the variation in dirt particle features, the curl shows acceptable difference to discriminate the bark and the fibre bundles in different pulp samples. Three classifiers, called k-Nearest Neighbour, Linear Discriminant Analysis and Multi-layer Perceptron are utilised to categorize the dirt particles. Linear Discriminant Analysis and Multi-layer Perceptron are the most accurate in classifying the segmented dirt particles by the Kittler thresholding with morphological processing. The result shows that the dirt particles are successfully categorized for bark and for fibre bundles.

Effect of apparent viscosity on fluidized bed drying process parameters of guava pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of guava pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp rheological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier Ltd. All rights reserved.

Effect of apparent viscosity on the pressure drop during fluidized bed drying of soursop pulp

Pressure drop and minimum fluidization velocity were experimentally studied in a vibro-fluidized bed of inert particles subjected to different vibration intensities during drying of soursop pulp. Maltodextrin was added to the pulp in order to prevent stickiness between particles and the consequent bed collapse. Pulps were initially concentrated, resulting in pastes with different soluble solids content, and a constant fraction of maltodextrin was guaranteed in the final pulp samples. The pulp theological behavior as affected by temperature and total soluble solids content, including maltodextrin, was evaluated and the effect of pulp apparent viscosity on pressure drop and minimum vibro-fluidization velocity were investigated. Two types of inert particles -3.6 mm glass beads and 3 mm Teflon cylinders (length and diameter) - were tested and, due to lower pressure drop presented by Teflon cylinders during operation of the dry vibro-fluidized bed, these particles were adopted for pulp drying process. Increasing pulp apparent viscosity caused a considerable increase in the vibro-fluidized bed pressure drop during pulp drying and, as a consequence resulted in a larger value of minimum vibro-fluidization velocity. on the other hand, the negative effect of increasing apparent viscosity could be attenuated by increasing the fluidized bed vibration intensity, which could prevent stickiness between particles. (c) 2006 Elsevier B.V. All rights reserved.

Estimation of hexenuronic acids and kappa number in kraft pulps of Eucalyptus globulus by Fourier transform near infrared spectroscopy and multivariate analysis

Fourier transform near infrared (FT-NIR) spectroscopy was evaluated as an analytical too[ for monitoring residual Lignin, kappa number and hexenuronic acids (HexA) content in kraft pulps of Eucalyptus globulus. Sets of pulp samples were prepared under different cooking conditions to obtain a wide range of compound concentrations that were characterised by conventional wet chemistry analytical methods. The sample group was also analysed using FT-NIR spectroscopy in order to establish prediction models for the pulp characteristics. Several models were applied to correlate chemical composition in samples with the NIR spectral data by means of PCR or PLS algorithms. Calibration curves were built by using all the spectral data or selected regions. Best calibration models for the quantification of lignin, kappa and HexA were proposed presenting R-2 values of 0.99. Calibration models were used to predict pulp titers of 20 external samples in a validation set. The lignin concentration and kappa number in the range of 1.4-18% and 8-62, respectively, were predicted fairly accurately (standard error of prediction, SEP 1.1% for lignin and 2.9 for kappa). The HexA concentration (range of 5-71 mmol kg(-1) pulp) was more difficult to predict and the SEP was 7.0 mmol kg(-1) pulp in a model of HexA quantified by an ultraviolet (UV) technique and 6.1 mmol kg(-1) pulp in a model of HexA quantified by anion-exchange chromatography (AEC). Even in wet chemical procedures used for HexA determination, there is no good agreement between methods as demonstrated by the UV and AEC methods described in the present work. NIR spectroscopy did provide a rapid estimate of HexA content in kraft pulps prepared in routine cooking experiments.

Determination of methiocarb and Its degradation products, methiocarb sulfoxide and methiocarb sulfone, in bananas using QuEChERS extraction

The present work describes the development of an analytical method for the determination of methiocarb and its degradation products (methiocarb sulfoxide and methiocarb sulfone) in banana samples, using the QuEChERS (quick, easy, cheap, effective, rugged, and safe) procedure followed by liquid chromatography coupled to photodiode array detector (LCPAD). Calibration curves were linear in the range of 0.5−10 mg L−1 for all compounds studied. The average recoveries, measured at 0.1 mg kg−1 wet weight, were 92.0 (RSD = 1.8%, n = 3), 84.0 (RSD = 3.9%, n = 3), and 95.2% (RSD = 1.9%, n = 3) for methiocarb sulfoxide, methiocarb sulfone, and methiocarb, respectively. Banana samples treated with methiocarb were collected from an experimental field. The developed method was applied to the analysis of 24 samples (peel and pulp) and to 5 banana pulp samples. Generally, the highest levels were found for methiocarb sulfoxide and methiocarb. Methiocarb sulfone levels were below the limit of quantification, except in one sample (not detected).

Kuitujen kiharuuteen vaikuttavia tekijöitä sulfaattiselluloosan valmistuksessa

Diplomityön tarkoituksena oli selvittää kuitujen kihartuvuuden profiili koivu- ja havusellulinjalla prosessivaiheiden suhteen. Profiilin perusteella pyrittiin selvittämään kuitulinjojen prosessista kuitujen kiharuuteen voimakkaimmin vaikuttavia tekijöitä. Työn kirjallisuusosassa käsiteltiin kuitujen ominaisuuksia sekä teollisen sellun valmistusprosessin kuituihin aiheuttamia kuituvaurioita ja niiden mahdollisia syitä. Lisäksi käytiin läpi kuituvaurioiden analysointimenetelmiä ja kuituvaurioiden kanssa korreloivia sellun laatuarvoja. Työn kokeellinen osa suoritettiin kuitulinjojen normaalin tuotannon ohessa. Kokeellisen osan massanäytteitä otettiin varsin moninaisista tuotantotilanteista mahdollisimman kattavan kiharuusprofiilin aikaansaamiseksi. Koivusellulinjalla vuokeittimen tuotantotaso vaikutti suuresti valmistettavan sellun ominaisuuksiin. Kuituvaurioiden syntyyn voimakkaimmin vaikuttavaksi tekijäksi osoittautui keittimen pohja-alueen, puskun ja massan pesuvaiheen sakeus. Tämän alueen sakeus muuttui tuotantotason mukaan, tuotantotason kasvun myötä alueen sakeus laski. Sakeuden lasku vähensi kuitujen kiharuutta sekä massan venymää ja paransi vetojäykkyyttä. Tuotantotason kasvu paransi myös keittimestä otettujen massanäytteiden vetojäykkyyspotentiaalia. Havusellulinjalla käytetyn Lo-Solids –keittomallin ja konventionaalisen keittomallin kesken esiintyi varsin merkittäviä laadullisia eroja. Lo-Solids –keittomallilla keitetyt sellukuidut kihartuivat konventionaalisella keittomallilla keitettyjä sellukuituja enemmän. Lo-Solids –keittomallilla keitetyn sellun vetojäykkyys oli konventionaalisella mallilla keitetyn sellun vetojäykkyyttä heikompi.

Topochemistry of physical and chemical pretreatments of biomass as investigated by FE-SEM, XPS and ToF-SIMS

Surface chemistry is of great importance in plant biomass engineering and applications. The surface chemical composition of biomass which includes lignin, carbohydrates and extractives influences its interactions with chemical agents, such as pulp processing/papermaking chemicals, or enzymes for different purposes. In this thesis, the changes in the surface chemical composition of lignocellulosic biomass after physical modification for the improvement of resulting paper properties and chemical treatment for the enhancement of enzymatic hydrolysis were investigated. Low consistency (LC) refining was used as physical treatment of bleached softwood and hardwood pulp samples, and the surface chemistry of refined samples was investigated. The refined pulp was analysed as whole pulp while the fines-free fibre samples were characterized separately. The fines produced in LCrefining contributed to an enlarged surface specific area as well as the change of surface coverage by lignin and extractives, as investigated by X-ray photoelectron spectroscopy (XPS). The surface coverage by lignin of the whole pulp decreased after refining while the surface coverage by extractives increased both for pine and eucalyptus. In the case of pine, the removal of fines resulted in reduction of the surface coverage by extractives, while the surface coverage by lignin increased on fibre sample (without fines). In the case of eucalyptus, the surface coverage by lignin of fibre samples decreased after the removal of fines. In addition, the surface distribution of carbohydrates, lignin and extractives of pine and eucalyptus samples was determined by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). LC-refining increased the amounts of pentose, hexose and extractives on the surface of pine samples. ToF-SIMS also gave clear evidence about xylan deposition and reduction of surface lignin distribution on the fibre of eucalyptus. However, the changes in the surface chemical composition during the physical treatment has led to an increase in the adsorption of fluorescent whitening agents (FWAs) on fibres due to a combination of electro-static forces, specific surface area of fibres and hydrophobic interactions. Various physicochemical pretreatments were conducted on wood and non-wood biomass for enhancing enzymatic hydrolysis of polysaccharides, and the surface chemistry of the pretreated and enzymatically hydrolysed samples was investigated by field emission scanning electron microscopy (FE-SEM), XPS and ToF-SIMS. A hydrotrope was used as a relatively novel pretreatment technology both in the case of wood and non-wood biomass. For comparison, ionic liquid and hydrothermal pretreatments were applied on softwood and hardwood as well. Thus, XPS analysis showed that the surface lignin was more efficiently removed by hydrotropic pretreatment compared to ionic liquid or hydrothermal pretreatments. SEM analysis also found that already at room temperature the ionic liquid pretreatments were more effective in swelling the fibres compared with hydrotropic pretreatment at elevated temperatures. The enzymatic hydrolysis yield of hardwood was enhanced due to the decrease in surface coverage of lignin, which was induced by hydrotropic treatment. However, hydrotropic pretreatment was not appropriate for softwood because of the predominance of guaiacyl lignin structure in this material. In addition, the reduction of surface lignin and xylan during pretreatment and subsequent increase in cellulose hydrolysis by enzyme could be observed from ToF-SIMS results. The characterisation of the non-wood biomass (e.g. sugarcane bagasse and common reed) treated by hydrotropic method, alkaline and alkaline hydrogen peroxide pretreatments were carried out by XPS and ToF-SIMS. According to the results, the action for the removal of the surface lignin of non-wood biomass by hydrotropic pretreatment was more significant compared to alkaline and alkaline hydrogen peroxide pretreatments, although a higher total amount of lignin could be removed by alkaline and alkaline hydrogen peroxide pretreatment. Furthermore, xylan could be remarkably more efficiently removed by hydrotropic method. Therefore, the glucan yield achieved from hydrotropic treated sample was higher than that from samples treated with alkaline or alkaline hydrogen peroxide. Through the use of ToF-SIMS, the distribution and localization of lignin and carbohydrates on the surface of ignocelluloses during pretreatment and enzymatic hydrolysis could be detected, and xylan degradation during enzymatic hydrolysis could also be assessed. Thus, based on the results from XPS and ToF-SIMS, the mechanism of the hydrotropic pretreatment in improving the accessibility of enzymes to fibre and further ameliorating of the enzymatic saccharification could be better elucidated.

Avaliação física e química da polpa de maracujá congelada comercializada na região de Bauru

A indústria de polpa de maracujá tem como objetivo a obtenção de produtos com características sensoriais e nutricionais próximas da fruta in natura. O objetivo deste trabalho foi avaliar as informações nutricionais das embalagens e as características físico-químicas das polpas de maracujá congeladas. Foram analisadas 25 amostras, de 07 marcas diferentes, adquiridas em supermercados de Bauru-SP, e região. Apenas uma das marcas analisadas (14,3%) encontra-se em acordo com a legislação vigente, sendo que as demais apresentam tabelas ultrapassadas ou incompletas. As características físico-químicas diferem entre as marcas comercializadas, principalmente quanto ao teor de ácido ascórbico, sendo que 64,0% das amostras se encontram em desarcordo com o Regulamento Técnico para Fixação dos Padrões de Identidade e Qualidade (PIQ) para polpa de maracujá do Ministério da Agricultura. As variações observadas entre a polpa in natura e a congelada são menores nos itens: densidade, pH, sólidos solúveis totais, acidez em ácido cítrico e ratio, mas altas quanto ao teor de ácido ascórbico.

Lignin chemistry and topochemistry during kraft delignification of Eucalyptus globulus genotypes with contrasting pulpwood characteristics

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Dissolution of porcine incisor pulps in sodium hypochlorite solutions of varying compositions and concentrations

Background: The solubility of dental pulp tissue in sodium hypochlorite has been extensively investigated but results have been inconsistent; due most likely to variations in experimental design, the volume and/or rate of replenishment of the solutions used and the nature of the tissues assessed. Traditionally, the sodium hypochlorite solutions used for endodontic irrigation in Australia have been either Milton or commercial bleach, with Milton being the most common. Recently, a range of Therapeutic Goods Administration (TGA) approved proprietary sodium hypochlorite solutions, which contain surfactant, has become available. Some domestic chlorine bleaches now also contain surfactants. The purpose of this study was to perform new solubility assessments, comparing Milton with new TGA approved products, Hypochlor 1% and Hypochlor 4% forte, and with a domestic bleach containing surfactant (White King). Methods: Ten randomly assigned pulp samples of porcine dental pulp of approximately equal dimensions were immersed in the above solutions, as well as representative concentrations of sodium hydroxide. Time to complete dissolution was measured and assessed statistically. Results: White King 4% showed the shortest dissolution time, closely followed by Hypochlor 4% forte. White King 1% and Hypochlor 1% each took around three times as long to completely dissolve the samples of pulp as their respective 4% concentrations, while Milton took nearly 10 times as long. The sodium hydroxide solutions showed no noticeable dissolution of the pulp samples. Conclusions: The composition and content of sodium hypochlorite solutions had a profound effect on the ability of these solutions to dissolve pulp tissue in vitro. Greater concentrations provided more rapid dissolution of tissue. One per cent solutions with added surfactant and which contained higher concentrations of sodium hydroxide were significantly more effective in dissolution of pulp tissue than Milton.

Microbial Evaluation Of Traumatized Teeth Treated With Triple Antibiotic Paste Or Calcium Hydroxide With 2% Chlorhexidine Gel In Pulp Revascularization.

Revascularization outcome depends on microbial elimination because apical repair will not happen in the presence of infected tissues. This study evaluated the microbial composition of traumatized immature teeth and assessed their reduction during different stages of the revascularization procedures performed with 2 intracanal medicaments. Fifteen patients (7-17 years old) with immature teeth were submitted to the revascularization procedures; they were divided into 2 groups according to the intracanal medicament used: TAP group (n = 7), medicated with a triple antibiotic paste, and CHP group (n = 8), dressed with calcium hydroxide + 2% chlorhexidine gel. Samples were taken before any treatment (S1), after irrigation with 6% NaOCl (S2), after irrigation with 2% chlorhexidine (S3), after intracanal dressing (S4), and after 17% EDTA irrigation (S5). Cultivable bacteria recovered from the 5 stages were counted and identified by means of polymerase chain reaction assay (16S rRNA). Both groups had colony-forming unit counts significantly reduced after S2 (P < .05); however, no significant difference was found between the irrigants (S2 and S3, P = .99). No difference in bacteria counts was found between the intracanal medicaments used (P = .95). The most prevalent bacteria detected were Actinomyces naeslundii (66.67%), followed by Porphyromonas endodontalis, Parvimonas micra, and Fusobacterium nucleatum, which were detected in 33.34% of the root canals. An average of 2.13 species per canal was found, and no statistical correlation was observed between bacterial species and clinical/radiographic features. The microbial profile of infected immature teeth is similar to that of primarily infected permanent teeth. The greatest bacterial reduction was promoted by the irrigation solutions. The revascularization protocols that used the tested intracanal medicaments were efficient in reducing viable bacteria in necrotic immature teeth.

Micromorphology Of The Dental Pulp Is Highly Preserved In Cancer Patients Who Underwent Head And Neck Radiotherapy.

Teeth are often included in the radiation field during head and neck radiotherapy, and recent clinical evidence suggests that dental pulp is negatively affected by the direct effects of radiation, leading to impaired sensitivity of the dental pulp. Therefore, this study aimed to investigate the direct effects of radiation on the microvasculature, innervation, and extracellular matrix of the dental pulp of patients who have undergone head and neck radiotherapy. Twenty-three samples of dental pulp from patients who finished head and neck radiotherapy were analyzed. Samples were histologically processed and stained with hematoxylin-eosin for morphologic evaluation of the microvasculature, innervation, and extracellular matrix. Subsequently, immunohistochemical analysis of proteins related to vascularization (CD34 and smooth muscle actin), innervation (S-100, NCAM/CD56, and neurofilament), and extracellular matrix (vimentin) of the dental pulp was performed. The morphologic study identified preservation of the microvasculature, nerve bundles, and components of the extracellular matrix in all studied samples. The immunohistochemical analysis confirmed the morphologic findings and showed a normal pattern of expression for the studied proteins in all samples. Direct effects of radiotherapy are not able to generate morphologic changes in the microvasculature, innervation, and extracellular matrix components of the dental pulp in head and neck cancer patients.

Sisal organosolv pulp as reinforcement for cement based composites

The present work describes non-conventional sisal (Agave sisalana) chemical (organosolv) pulp from residues of cordage as reinforcement to cement based materials. Sisal organosolv pulp was produced in a 1:1 ethanol/water mixture and post chemically and physically characterized in order to compare its properties with sisal kraft pulp. Cement based composites reinforced with organosolv or kraft pulps and combined with polypropylene (PP) fibres were produced by the slurry de-watering and pressing method as a crude simulation of the Hatschek process. Composites were evaluated at 28 days of age, after exposition to accelerated carbonation and after 100 soak/dry cycles. Composites containing organosolv pulp presented lower mechanical strength, water absorption and apparent porosity than composites reinforced with kraft pulp. The best mechanical performance after ageing was also achieved by samples reinforced with kraft pulp. The addition of PP fibres favoured the maintenance of toughness after ageing. Accelerated carbonation promoted the densification of the composites reinforced with sisal organosolv + PP fibres.

Rheological and functional properties of flours from banana pulp and peel

Unripe banana flour can be an alternative to minimize post-harvest loss and to increase the aggregate value of banana fruit. Flour from unripe banana is rich in phytosterols and resistant starch, being proposed as health food. Flours from unripe banana peel and pulp were evaluated on their composition, phytosterols content, thermal and rheological properties, and pasting profiles. High amounts of beta-sitosterol, campesterol, and stigmasterol were found in flour from banana peel. These samples showed lower viscosity values of pasting profiles, lower energy enthalpy on gelatinization, and higher temperature of gelatinization than those ones from pulp. Anti-oxidant treatment of fruits with citric acid does not change pasting profiles of flours from pulp, but resulted in slight increase in viscosity, suggesting that structure of starch could be modified by acidification.