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In dieser vorliegenden Arbeit wurde der photolytische und photokatalytische Abbau von Lignin untersucht. Eine Charakterisierung des verwendeten Photoreaktors wurde mittels Kalium-Ferrioxalat-Aktinometrie durchgeführt. Zur Analyse der abgebauten Lignine wurde eine Optimierung einer bereits bestehenden Methode zur Bestimmung des Hydroxylgehaltes erarbeitet. Die Bestimmung der Hydroxylgehalte erfolgte demnach bei Raumtemperatur nach einer Acetylierungsdauer von 72 h und zeigte eine Abnahme der Hydroxylgehalte mit andauernder UV-Bestrahlung. Selbige Beobachtung konnte mit Hilfe der ATR-IR-Spektroskopie gemacht werden. Zusätzlich konnte die Bildung von Carbonsäuren und der Abbau von aromatischen Strukturen detektiert werden. Der Abbau aromatischer Strukturen konnte ebenfalls durch UV-VIS-Spektroskopie gezeigt werden. Eine Vermutung, dass es sich bei dem Abbauprozess um einen oxidativen Mechanismus handelt, konnte mit dem Abbau von Hydroxylgruppen über eine Bildung von Carbonsäuren zu Kohlenstoffdioxid bestätigt werden. Eine Freisetzung von Kohlenstoffdioxid konnte durch eine Bestimmung des IC festgestellt werden. Die Ergebnisse der Gel-Permeations-Chromatographie zusammen mit einer TOC-Analyse zeigen einen Abbau der molaren Masse des Lignins auf. Es konnten Fragmente mit einer Molmasse ähnlich der Monomere des Lignins gefunden werden. Der eingesetzte Photokatalysator wurde via Röntgenbeugung untersucht und konnte als das hoch photokatalytisch aktive P25 von Degussa identifiziert werden. Trotz des Einsatzes verschiedener Katalysatorkonzentrationen in einem Bereich von 0-0,5 g L^(-1) konnte kein Einfluss des Photokatalysators auf den Abbauprozess des Lignins beobachtet werden.
Today, more than 70 million tons of lignin are produced by the pulp and paper industry every year. However, the utilization of lignin as a source for chemical synthesis is still limited due to the complex and heterogeneous lignin structure. The purpose of this study was a selective photodegradation of industrially available kraft lignin in order to obtain appropriate fragments and building block chemicals for further utilization, e.g. polymerization. Thus, kraft lignin obtained from soft wood black liquor by acidification was dissolved in sodium hydroxide and irradiated at a wavelength of 254 nm with and without the presence of titanium dioxide in various concentrations. Analyses of the irradiated products via SEC showed decreasing molar masses and decreasing polydispersity indices over time. At the end of the irradiation period the lignin was depolymerised to form fragments as small as the lignin monomers. TOC analyses showed minimal mineralisation due to the depolymerisation process.
The molecular weight properties of lignins are one of the key elements that need to be analyzed for a successful industrial application of these promising biopolymers. In this study, the use of 1H NMR as well as diffusion-ordered spectroscopy (DOSY NMR), combined with multivariate regression methods, was investigated for the determination of the molecular weight (Mw and Mn) and the polydispersity of organosolv lignins (n = 53, Miscanthus x giganteus, Paulownia tomentosa, and Silphium perfoliatum). The suitability of the models was demonstrated by cross validation (CV) as well as by an independent validation set of samples from different biomass origins (beech wood and wheat straw). CV errors of ca. 7–9 and 14–16% were achieved for all parameters with the models from the 1H NMR spectra and the DOSY NMR data, respectively. The prediction errors for the validation samples were in a similar range for the partial least squares model from the 1H NMR data and for a multiple linear regression using the DOSY NMR data. The results indicate the usefulness of NMR measurements combined with multivariate regression methods as a potential alternative to more time-consuming methods such as gel permeation chromatography.
In der vorliegenden Arbeit wurde Kraft-Lignin als Makromonomer für die Synthese von thermoplastischen Polyurethanen mit hoher molarer Masse durch acide Präzipitation aus Schwarzlauge isoliert. Die Charakterisierung des Rohstoffes bezüglich seiner Ausgangsmolmasse erfolgte mittels Gel-Permeations-Chromatographie mit Polystyren-Polymerstandard, welche sich als sehr hilfreiche Analysemethode erwies. Da das Kraft-Lignin die klassische Polyolkomponente bei der Synthese von Polyurethanen ersetzen sollte, war es notwendig, den Hydroxylgehalt des Kraft-Lignins zu bestimmen. Für diesen Zweck wurde eine bereits etablierte Prozedur zur nasschemischen Bestimmung des Hydroxylgehaltes von Polyolen für die Synthese von Polyurethanen einer Adaption unterzogen. Es wurde die Reaktionsdauer bei der Acetylierung des Kraft-Lignins variiert. Das Ergebnis war, dass die Messgenauigkeit durch eine Erhöhung der Reaktionsdauer von 1 h auf 3 h drastisch von 25,5 % auf 3,6 % reduziert werden konnte. Um abschätzen zu können, ob die erzielte Messgenauigkeit im Rahmen einer nasschemischen Prozedur mit manueller Titration liegt, wurden zusätzlich die Hydroxylgehalte von Ethandiol und Saccharose bestimmt. Diese dienten als Referenzsubstanz mit definierten und bekannten Hydroxylgehalten. Die Ermittlung der Hydroxylgehalte mit diesen Substanzen ergab für Ethandiol eine Messgenauigkeit von 2,2 % und für Saccharose eine Messgenauigkeit von 1,4 %. Eine Messgenauigkeit von 3,6 % ist in Anbetracht des Zeitaufwandes akzeptabel.
Für die Synthese von thermoplastischen Polyurethanen wurde Kraft-Lignin mit Methylendiphenyldiisocyanat in Dimethylacetamid mit Zinnoktoat als Katalysator zur Reaktion gebracht. Es wurde das NCO/OH-Verhältnis und die Reaktionsdauer variiert. Die Analyse der synthetisierten Polyurethane erfolgte mittels Ubbelohde-Kapillarviskosimetrie, Fourier-Transformations-Infrarotspektroskopie und Schmelzpunktbestimmung. Die FTIR-Spektren bestätigte eine erfolgreiche Synthese von Polyurethanen aus Kraft-Lignin und Methylendiphenyldiisocyanat und zeigte, dass die Variation des NCO/OH-Verhältnisses und der Reaktionsdauer keinerlei Einflüsse auf die chemische Grundstruktur des Polyurethans hat. Die Ubbelohde-Kapillarviskosimetrie belegte die thermoplastischen Eigenschaften des synthetisierten Polyurethans, die sich in einem thermoplastischen Nassprozess verarbeiten lassen. Sie zeigte auch die Abhängigkeit der Molmasse der synthetisierten Polyurethane von der Reaktionsdauer und vom NCO/OH-Verhältnis. So steigt die Molmasse des Polyurethans mit steigender Reaktionsdauer und sinkendem NCO/OH-Verhältnis. Letztere Beobachtung ist sogar praktisch hinsichtlich der gesundheitsgefährdenden Eigenschaft von Isocyanaten, da so der Einsatz von Isocyanaten reduziert werden kann. Um die schmelzflüssige Verarbeitbarkeit des synthetisierten Polyurethans zu untersuchen, wurden die Schmelzpunkte der Polymere bestimmt. Es konnte in einem Temperaturbereich von 25 °C-410 °C keine Aggregatzustandsänderung, sondern lediglich eine Zersetzungsreaktion beobachtet werden.
Lignocellulose feedstock (LCF) provides a sustainable source of components to produce bioenergy, biofuel, and novel biomaterials. Besides hard and soft wood, so-called low-input plants such as Miscanthus are interesting crops to be investigated as potential feedstock for the second generation biorefinery. The status quo regarding the availability and composition of different plants, including grasses and fast-growing trees (i.e., Miscanthus, Paulownia), is reviewed here. The second focus of this review is the potential of multivariate data processing to be used for biomass analysis and quality control. Experimental data obtained by spectroscopic methods, such as nuclear magnetic resonance (NMR) and Fourier-transform infrared spectroscopy (FTIR), can be processed using computational techniques to characterize the 3D structure and energetic properties of the feedstock building blocks, including complex linkages. Here, we provide a brief summary of recently reported experimental data for structural analysis of LCF biomasses, and give our perspectives on the role of chemometrics in understanding and elucidating on LCF composition and lignin 3D structure.
The antiradical and antimicrobial activity of lignin and lignin-based films are both of great interest for applications such as food packaging additives. The polyphenolic structure of lignin in addition to the presence of O-containing functional groups is potentially responsible for these activities. This study used DPPH assays to discuss the antiradical activity of HPMC/lignin and HPMC/lignin/chitosan films. The scavenging activity (SA) of both binary (HPMC/lignin) and ternary (HPMC/lignin/chitosan) systems was affected by the percentage of the added lignin: the 5% addition showed the highest activity and the 30% addition had the lowest. Both scavenging activity and antimicrobial activity are dependent on the biomass source showing the following trend: organosolv of softwood > kraft of softwood > organosolv of grass. Testing the antimicrobial activities of lignins and lignin-containing films showed high antimicrobial activities against Gram-positive and Gram-negative bacteria at 35 °C and at low temperatures (0-7 °C). Purification of kraft lignin has a negative effect on the antimicrobial activity while storage has positive effect. The lignin release in the produced films affected the activity positively and the chitosan addition enhances the activity even more for both Gram-positive and Gram-negative bacteria. Testing the films against spoilage bacteria that grow at low temperatures revealed the activity of the 30% addition on HPMC/L1 film against both B. thermosphacta and P. fluorescens while L5 was active only against B. thermosphacta. In HPMC/lignin/chitosan films, the 5% addition exhibited activity against both B. thermosphacta and P. fluorescens.
Miscanthus crops possess very attractive properties such as high photosynthesis yield and carbon fixation rate. Because of these properties, it is currently considered for use in second-generation biorefineries. Here we analyze the differences in chemical composition between M. x giganteus, a commonly studied Miscanthus genotype, and M. nagara, which is relatively understudied but has useful properties such as increased frost resistance and higher stem stability. Samples of M. x giganteus (Gig35) and M. nagara (NagG10) have been separated by plant portion (leaves and stems) in order to isolate the corresponding lignins. The organosolv process was used for biomass pulping (80% ethanol solution, 170 °C, 15 bar). Biomass composition and lignin structure analysis were performed using composition analysis, Fourier-transform infrared (FTIR), ultraviolet-visible (UV-Vis) and nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), size exclusion chromatography (SEC) and pyrolysis gas-chromatography/mass spectrometry (Py-GC/MS) to determine the 3D structure of the isolated lignins, monolignol ratio and most abundant linkages depending on genotype and harvesting season. SEC data showed significant differences in the molecular weight and polydispersity indices for stem versus leaf-derived lignins. Py-GC/MS and hetero-nuclear single quantum correlation (HSQC) NMR revealed different monolignol compositions for the two genotypes (Gig35, NagG10). The monolignol ratio is slightly influenced by the time of harvest: stem-derived lignins of M. nagara showed increasing H and decreasing G unit content over the studied harvesting period (December–April).
Miscanthus x giganteus Stem Versus Leaf-Derived Lignins Differing in Monolignol Ratio and Linkage
(2019)
As a renewable, Miscanthus offers numerous advantages such as high photosynthesis activity (as a C4 plant) and an exceptional CO2 fixation rate. These properties make Miscanthus very attractive for industrial exploitation, such as lignin generation. In this paper, we present a systematic study analyzing the correlation of the lignin structure with the Miscanthus genotype and plant portion (stem versus leaf). Specifically, the ratio of the three monolignols and corresponding building blocks as well as the linkages formed between the units have been studied. The lignin amount has been determined for M. x giganteus (Gig17, Gig34, Gig35), M. nagara (NagG10), M. sinensis (Sin2), and M. robustus (Rob4) harvested at different time points (September, December, and April). The influence of the Miscanthus genotype and plant component (leaf vs. stem) has been studied to develop corresponding structure-property relationships (i.e., correlations in molecular weight, polydispersity, and decomposition temperature). Lignin isolation was performed using non-catalyzed organosolv pulping and the structure analysis includes compositional analysis, Fourier transform infradred (FTIR), ultraviolet/visible (UV-Vis), hetero-nuclear single quantum correlation nuclear magnetic resonsnce (HSQC-NMR), thermogravimetric analysis (TGA), and pyrolysis gaschromatography/mass spectrometry (GC/MS). Structural differences were found for stem and leaf-derived lignins. Compared to beech wood lignins, Miscanthus lignins possess lower molecular weight and narrow polydispersities (<1.5 Miscanthus vs. >2.5 beech) corresponding to improved homogeneity. In addition to conventional univariate analysis of FTIR spectra, multivariate chemometrics revealed distinct differences for aromatic in-plane deformations of stem versus leaf-derived lignins. These results emphasize the potential of Miscanthus as a low-input resource and a Miscanthus-derived lignin as promising agricultural feedstock.
When optimizing the process parameters of the acidic ethanolic organosolv process, the aim is usually to maximize the delignification and/or lignin purity. However, process parameters such as temperature, time, ethanol and catalyst concentration, respectively, can also be used to vary the structural properties of the obtained organosolv lignin, including the molecular weight and the ratio of aliphatic versus phenolic hydroxyl groups, among others. This review particularly focuses on these influencing factors and establishes a trend analysis between the variation of the process parameters and the effect on lignin structure. Especially when larger data sets are available, as for process temperature and time, correlations between the distribution of depolymerization and condensation reactions are found, which allow direct conclusions on the proportion of lignin's structural features, independent of the diversity of the biomass used. The newfound insights gained from this review can be used to tailor organosolv lignins isolated for a specific application.
Background: To protect renewable packaging materials against autoxidation and decomposition when substituting harmful synthetic stabilizers with bioactive and bio-based compounds, extracts from Aesculus hippocastanum L. seeds were evaluated. The study objectives were to determine the antioxidant efficacy of bioactive compounds in horse chestnut seeds with regard to different seed fractions, improve their extraction, and to evaluate waste reuse. Methods: Different extraction techniques for field samples were evaluated and compared with extracts of industrial waste samples based on total phenolic content and total antioxidant capacity (2,2’-azino-bis(3-ethylbenzthiazoline-6-sulphonic acid) (ABTS)). The molecular weight distribution and absorbance in ultraviolet range (UV) of seed coat extracts were determined, and the possibility of extracts containing proanthocyanidins was examined. Results: Seed coat extracts show a remarkable antioxidant activity and a high UV absorbance. Passive extractions are efficient and much less laborious. Applying waste product seed coats leads to a reduced antioxidant activity, total phenolic content, and UV absorbance compared to the field sample counterparts. In contrast to peeled seed extracts, all seed coat extracts contain proanthocyanidins. Discussion: Seed coats are a potential source of bioactive compounds, particularly regarding sustainable production and waste reuse. With minimum effort, highly bioactive extracts with high potential as additives can be prepared.