Ozonólise das ligninas organossolve e kraft eucalipto. Parte II: cinética nos meios ácido e básico

Organosolv and kraft lignins were treated with ozone both in basic and acid media and the reaction was studied kinetically. In contrast to reported studies, ozone was more efective in basic medium. Kraft lignin was degraded faster than organosolv lignin in both media but in the basic medium the rate of reaction was very much faster than in the acid one: for kraft lignin, the observed degradation was 93% for 2 min of reaction in the basic medium and 56% for 10 min of reaction in the acid medium; for organosolv lignin, 47% and 25%, respectively, in the same times. Higher phenolic hydroxyl groups contents increase the reaction rate.

Efeito dos ácidos hexenurônicos e da lignina no desempenho da ozonólize, em diferentes pHs da reação

The effect of pH on the performance of the ozonolysis stage in pulp production was evaluated for conventional and acid treated brown and oxygen delignified eucalyptus kraft pulps. The objective was to determine separately the effects of lignin and hexenuronic acid on the performance of the ozonolysis stage. The reaction of ozone with hexenuronic acid is less sensitive to pH than the reaction of ozone with lignin. The efficiency and the selectivity of the reaction of ozone with pulp decreases after removal of hexenuronic acids. Increasing up to 7.0 the pH during the ozonolysis is viable in the sequence Z/D(EOP)D, resulting in savings of H2SO4 (8,5 kg/tsa) and NaOH (5 kg/tsa), but is not recommended in the sequence Z/ED(PO).

Ozonólise: a busca por um mecanismo

The ozonolysis reaction is widely used in the academy and in industry. The first reports about the existence of the ozone molecule were made over 200 years ago. Several ideas and assumptions were made to understand the chemical properties of the ozone molecule and the ozonolysis mechanism. The intent of this paper is not to be an extensive review about ozone chemistry or ozonolysis reactions, but to highlight how the rational process was developed and how conclusions were drawn at a time with limited instrumentation.

Pinic and pinonic acid formation in the reaction of ozone with alpha-pinene

The mechanism of formation of key compounds in atmospheric secondary aerosol (SOA) has been investigated by studying the products of the ozonolysis of an enal derived from alpha-pinene using gas chromatography coupled to mass spectrometry.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory studies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (carbon-carbon double bonds) can reach chemical lifetimes of many hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (< 10(-10) cm(2) s(-1)). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Kinetic multi-layer model of aerosol surface and bulk chemistry (KM-SUB): the influence of interfacial transport and bulk diffusion on the oxidation of oleic acid by ozone

We present a novel kinetic multi-layer model that explicitly resolves mass transport and chemical reaction at the surface and in the bulk of aerosol particles (KM-SUB). The model is based on the PRA framework of gas–particle interactions (P¨oschl et al., 5 2007), and it includes reversible adsorption, surface reactions and surface-bulk exchange as well as bulk diffusion and reaction. Unlike earlier models, KM-SUB does not require simplifying assumptions about steady-state conditions and radial mixing. The temporal evolution and concentration profiles of volatile and non-volatile species at the gas-particle interface and in the particle bulk can be modeled along with surface 10 concentrations and gas uptake coefficients. In this study we explore and exemplify the effects of bulk diffusion on the rate of reactive gas uptake for a simple reference system, the ozonolysis of oleic acid particles, in comparison to experimental data and earlier model studies. We demonstrate how KM-SUB can be used to interpret and analyze experimental data from laboratory stud15 ies, and how the results can be extrapolated to atmospheric conditions. In particular, we show how interfacial transport and bulk transport, i.e., surface accommodation, bulk accommodation and bulk diffusion, influence the kinetics of the chemical reaction. Sensitivity studies suggest that in fine air particulate matter oleic acid and compounds with similar reactivity against ozone (C=C double bonds) can reach chemical lifetimes of 20 multiple hours only if they are embedded in a (semi-)solid matrix with very low diffusion coefficients (10−10 cm2 s−1). Depending on the complexity of the investigated system, unlimited numbers of volatile and non-volatile species and chemical reactions can be flexibly added and treated with KM-SUB. We propose and intend to pursue the application of KM-SUB 25 as a basis for the development of a detailed master mechanism of aerosol chemistry as well as for the derivation of simplified but realistic parameterizations for large-scale atmospheric and climate models.

Highly Sensitive Fluorescent Method for the Detection of Cholesterol Aldehydes Formed by Ozone and Singlet Molecular Oxygen

Cholesterol oxidation gives rise to a mixture of oxidized products. Different types of products are generated according to the reactive species being involved. Recently, attention has been focused on two cholesterol aldehydes, 3 beta-hydroxy-5 beta-hydroxy-B-norcholestane-6 beta-carboxyaldehyde (1a) and 3 beta-hydroxy-5-oxo-5,6-secocholestan-6-al (1b). These aldehydes can be generated by ozone-, as well as by singlet molecular oxygen-mediated cholesterol oxidation. It has been suggested that 1b is preferentially formed by ozone and la is preferentially formed by singlet molecular oxygen. In this study we describe the use of 1-pyrenebutyric hydrazine (PBH) as a fluorescent probe for the detection of cholesterol aldehydes. The formation of the fluorescent adduct between la with PBH was confirmed by HPLC-MS/MS. The fluorescence spectra of PBH did not change upon binding to the aldehyde. Moreover, the derivatization was also effective in the absence of an acidified medium, which is critical to avoid the formation of cholesterol aldehydes through Hock cleavage of 5 alpha-hydroperoxycholesterol. In conclusion, PBH can be used as an efficient fluorescent probe for the detection/quantification of cholesterol aldehydes in biological samples. Its analysis by HPLC coupled to a fluorescent detector provides a sensitive and specific way to quantify cholesterol aldehydes in the low femtomol range.

A new fluorescence method for determination of ozone in ambient air

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Efeito dos ácidos hexenurônicos e da lignina no desempenho da ozonólize, em diferentes pHs da reação

The effect of pH on the performance of the ozonolysis stage in pulp production was evaluated for conventional and acid treated brown and oxygen delignified eucalyptus kraft pulps. The objective was to determine separately the effects of lignin and hexenuronic acid on the performance of the ozonolysis stage. The reaction of ozone with hexenuronic acid is less sensitive to pH than the reaction of ozone with lignin. The efficiency and the selectivity of the reaction of ozone with pulp decreases after removal of hexenuronic acids. Increasing up to 7.0 the pH during the ozonolysis is viable in the sequence Z/D(EOP)D, resulting in savings of H2SO4 (8,5 kg/tsa) and NaOH (5 kg/tsa), but is not recommended in the sequence Z/ED(PO).

Desenvolvimento de método analítico para determinação de ozônio residual em água utilizando a ténica de fluorescência e estudo da viabilidade da construção de um sensor fluorimétrico em uma gota de solução para determinação de ozônio em ar

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Thermoplastic polyesters and Co-polyesters derived from vegetable oil: synthesis and optimization of melt polycondensation for medium and long chain poly(omega-hydroxyfatty acid)s and their ester derivatives

The synthesis of a series of omega-hydroxyfatty acid (omega-OHFA) monomers and their methyl ester derivatives (Me-omega-OHFA) from mono-unsaturated fatty acids and alcohols via ozonolysis-reduction/crossmetathesis reactions is described. Melt polycondensation of the monomers yielded thermoplastic poly(omega-hydroxyfatty acid)s [-(CH2)(n)-COO-](x) with medium (n = 8 and 12) and long (n = 17) repeating monomer units. The omega-OHFAs and Me-omega-OHFAs were all obtained in good yield (>= 80%) and purity (>= 97%) as established by H-1 NMR, Fourier Transform infra-red spectroscopy (FT-IR), mass spectroscopy (ESI-MS) and high performance liquid chromatography (HPLC) analyses. The average molecular size (M-n) and distribution (PDI) of the poly(omega-hydroxyfatty acid)s (P(omega-OHFA)s) and poly(omega-hydroxyfatty ester) s (P(Me-omega-OHFA) s) as determined by GPC varied with organo-metallic Ti(IV) isopropoxide [Ti(OiPr)(4)] polycondensation catalyst amount, reaction time and temperature. An optimization of the polymerization process provided P(omega-OHFA) s and P(Me-omega-OHFA) s with M-n and PDI values desirable for high end applications. Co-polymerization of the long chain (n = 12) and medium chain (n = 8) Me-omega-OHFAs by melt polycondensation yielded poly(omega-hydroxy tridecanoate/omega-hydroxy nonanoate) random co-polyesters (M-n = 11000- 18500 g mol(-1)) with varying molar compositions.

Studies on the application of Myceliophthora thermophila JCP1-4 cellulases cocktail on sugarcane bagasse pretreated by different methods

The hydrolysis step for sugar production in biorefineries is crucial for the sequential processes involved and cellulases cocktails behave differently according to the pretreatment employed. In this study, the application of the cellulases cocktail produced by the fungus Myceliophthora thermophila JCP1-4 was studied on the saccharification of sugarcane bagasse pretreated by ozonolysis and thermic ferric nitrate (TFN), and the results were compared with commercial enzymes (Novozymes Celluclast 1.5L, Novozym 188). The fungal cellulases cocktail hold an activity of FPU:β-glucosidase of 1:4(U/mL); time, temperature, FPU by g of cellulose load and percentage of dry matter (DM) were studied. The analysis of central composite design of TFN pretreated showed that fungal cellulases works better in DM values of 3–3.5% (4.5% for commercial), temperatures higher than 50 °C (<45 °C for commercial) and 15FPU for both; commercial enzymes yielded 7.78 g/L of reducing sugars and the fungal enzymes 5.42 g/L. With the ozone pretreated, the fungal enzymes presented a higher thermostability with faster kinects, being able to produce 5.56 g/L of reducing sugars (60 °C, 8 h), against 5.20 g/L for commercial enzymes (50 °C, 24 h), (10FPU, 3%DM for both). The FPU derivate analysis revels better yields with 7.5FPU, and the increase of DM to 7.5% resulted 13.28 g/L of reducing sugars.

Identifizierung und Quantifizierung von sauren Markersubstanzen für troposphärisches sekundäres organisches Aerosol aus biogenen Kohlenwasserstoffen mittels Kapillar-HPLC-ESI-MS n

Sekundäres organisches Aerosol (SOA) ist ein wichtiger Bestandteil von atmosphärischen Aerosolpartikeln. Atmosphärische Aerosole sind bedeutsam, da sie das Klima über direkte (Streuung und Absorption von Strahlung) und indirekte (Wolken-Kondensationskeime) Effekte beeinflussen. Nach bisherigen Schätzungen ist die SOA-Bildung aus biogenen Kohlenwasserstoffen global weit wichtiger als die SOA-Bildung aus anthropogenen Kohlenwasserstoffen. Reaktive Kohlenwasserstoffe, die in großen Mengen von der Vegetation emittiert werden und als die wichtigsten Vorläufersubstanzen für biogenes SOA gelten, sind die Terpene. In der vorliegenden Arbeit wurde eine Methode entwickelt, welche die Quantifizierung von aciden Produkten der Terpen-Oxidation ermöglicht. Die Abscheidung des größenselektierten Aerosols (PM 2.5) erfolgte auf Quarzfilter, die unter Zuhilfenahme von Ultraschall mittels Methanol extrahiert wurden. Nach Aufkonzentrierung und Lösungsmittelwechsel auf Wasser sowie Standardaddition wurden die Proben mit einer Kapillar-HPLC-ESI-MSn-Methode analysiert. Das verwendete Ionenfallen-Massenspektrometer (LCQ-DECA) bietet die Möglichkeit, Strukturaufklärung durch selektive Fragmentierung der Qasimolekülionen zu betreiben. Die Quantifizierung erfolgte teilweise im MS/MS-Modus, wodurch Selektivität und Nachweisgrenze verbessert werden konnten. Um Produkte der Terpen-Oxidation zu identifizieren, die nicht als Standards erhältlich waren, wurden Ozonolysexperimente durchgeführt. Dadurch gelang die Identifizierung einer Reihe von Oxidationsprodukten in Realproben. Neben schon bekannten Produkten der Terpen-Oxidation konnten einige Produkte erstmals in Realproben eindeutig als Produkte des α Pinens nachgewiesen werden. In den Proben der Ozonolyseexperimente konnten auch Produkte mit hohem Molekulargewicht (>300 u) nachgewiesen werden, die Ähnlichkeit zeigen zu den als Dimeren oder Polymeren in der Literatur bezeichneten Substanzen. Sie konnten jedoch nicht in Feldproben gefunden werden. Im Rahmen von 5 Messkampagnen in Deutschland und Finnland wurden Proben der atmosphärischen Partikelphase genommen. Die Quantifizierung von Produkten der Oxidation von α-Pinen, β-Pinen, 3-Caren, Sabinen und Limonen in diesen Proben ergab eine große zeitliche und örtliche Variationsbreite der Konzentrationen. Die Konzentration von Pinsäure bewegte sich beispielsweise zwischen etwa 0,4 und 21 ng/m³ während aller Messkampagnen. Es konnten stets Produkte verschiedener Terpene nachgewiesen werden. Produkte einiger Terpene eignen sich sogar als Markersubstanzen für verschiedene Pflanzenarten. Sabinen-Produkte wie Sabinsäure können als Marker für die Emissionen von Laubbäumen wie Buchen oder Birken verwendet werden, während Caren-Produkte wie Caronsäure als Marker für Nadelbäume, speziell Kiefern, verwendet werden können. Mit den quantifizierten Substanzen als Marker wurde unter zu Hilfenahme von Messungen des Gehaltes an organischem und elementarem Kohlenstoff im Aerosol der Anteil des sekundären organischen Aerosols (SOA) errechnet, der von der Ozonolyse der Terpene stammt. Erstaunlicherweise konnten nur 1% bis 8% des SOA auf die Ozonolyse der Terpene zurückgeführt werden. Dies steht im Gegensatz zu der bisherigen Meinung, dass die Ozonolyse der Terpene die wichtigste Quelle für biogenes SOA darstellt. Gründe für diese Diskrepanz werden in der Arbeit diskutiert. Um die atmosphärischen Prozesse der Bildung von SOA vollständig zu verstehen, müssen jedoch noch weitere Anstrengungen unternommen werden.

Untersuchungen zur stereokontrollierten Synthese von 3-Mercaptolysinderivaten und Untersuchungen zur Synthese von Ansa-Seco-Steroiden

Untersuchungen zur stereokontrollierten Synthese von 3-Mercaptolysinderivaten: 3-Mercaptolysin und Peptide mit einer 3-Mercaptolysin-Einheit sind als Liganden für Nukleardiagnostika in der Kontrastmittelforschung von großem Interesse. Für das Screening Gewebe-selektiver Diagnostika sollten Mercaptolysinderivate, die sich für den Einbau in Peptide eignen, stereokontrolliert aufgebaut werden. Als Grundlage wurde im Rahmen dieser Arbeit eine sehr effiziente Synthese von Methoxymethyl-(4-oxo-butyl)-carbaminsäure-tert-butylester aus Pent-4-en-1-ol entwickelt. Nach Olefinierung des Aldehyds konnten Auxiliar-substituierte 6-Amino-hexensäure-derivate in guten Ausbeuten erhalten werden. Diese bildeten die Startmaterialien für auxiliargesteuerte Aziridinierungen mit anschließender Ringöffnung durch Schwefel-Nukleophile. Zudem wurden Azidierungen an Auxiliar-bewehrten Substraten, Michael-Additionen von Schwefel-Nukleophilen an Dehydroaminosäuren und viele weitere Reaktionen untersucht. Es galt dabei auf patentrechtlich geschützte Reaktionen zu verzichten, weil die Produkte ggf. in großem Maßstab kommerziell genutzt werden sollen. Dabei konnten alle vier stereoisomeren 2-Acetylamino-6-(tert-butoxycarbonyl-methoxymethyl-amino)-3-(4-methoxy-benzylsulfanyl)-hexansäurementhylester in guter Ausbeute synthetisiert werden. Nach Herstellung größerer Mengen der entsprechenden am Schwefelatom ungeschützten N-Fmoc-Aminosäurederivate sollen alle vier Stereoisomere in Peptide eingebaut und auf ihre Eignung als Liganden in Nukleardiagnostika untersucht werden. Untersuchungen zur Synthese neuartiger Ansa-Steroide: Über die Synthese von Ansa-Seco-Steroiden mittels eine Kaskade von intermolekularer Diels-Alder-Reaktion und anschließender Retro-Diels-Alder-Reaktion an 5,6,7,8-Tetradehydrosteroiden wurde erstmals 1986 von E. Winterfeldt et al. berichtet. Die damit eröffnete Möglichkeit eines völlig neuen Zugangs zu pharmakologisch interessanten Makrolid-Substraten konnte aber bislang nicht effektiv genutzt werden, weil insbesondere im Zusammenhang mit der Diels-Alder-Reaktion erhebliche präparative Probleme auftraten: Brauchbare Reaktivität nur bei sehr wenigen Dienophilen, Regioselektivitätsprobleme, etc. Hier galt es zu untersuchen, inwiefern sich diese Probleme durch die intramolekulare Reaktionsführung der Cycloaddition unterdrücken lassen können. Für die intramolekulare Diels-Alder-Reaktion zwischen der 5,7-Dien-Einheit des Steroids und einer an das Substrat gebundenen Dienophil-Einheit ist die Möglichkeit einer günstigen Anordnung der beiden Reaktanden-Gruppen entscheidend. Dafür wurden umfangreiche Untersuchungen zur alpha-konfigurierten Anbindung eines Dienophils in die 3-Position an 3-Hydroxy-5,6,7,8-Tetradehydrosteroiden durchgeführt: Mitsunobu-Reaktionen, Oxidations-Reduktions-Sequenzen, Oxidations-Ketalisierungs-Sequenzen, etc. Hierbei wurden zahlreiche neue Steroide synthetisiert. Es gelang jedoch nicht, 5,6,7,8-Tetradehydrosteroide mit axial in Position 3 eingebundenen Dienophilen in präparativ nutzbaren Mengen zu synthetisieren. Bei der Untersuchung intermolekularer Diels-Alder-Reaktionen zwischen Ergosterol und Brommaleinsäureanhydrid wurde vorzugsweise die Bildung der Addukte des 7,8,14,15-Tetradehydroisomers des Ergosterols beobachtet.