Physico-chemical properties of meso-tetrakis(p-methoxyphenyl)porphyrin (TMPP) incorporated into pluronicTM p-123 and f-127 polymeric micelles

The physicochemical properties (solubilization, structural organization and stability) of meso-tetrakis(p-methoxyphenyl)porphyrin (TMPP), a promising photosensitizer for photodynamic therapy, solubilized in polymeric micelles of tri-block copolymers PluronicTM P-123 and F-127, were studied. The formulations obtained by the solid dispersion method led to monomerization of TMPP in these copolymers. Solubility studies showed that P-123 solubilizes double the photosensitizer than F-127. The self-aggregation phenomenon was affected by the [TMPP]/[poloxamer] ratio and medium temperature. The decrease in the temperature of these systems promoted the formation of different kinds of TMPP aggregates intrinsically connected with the structural changes occurring in the micelles.

A INFLUÊNCIA DA LIGAÇÃO DE HIDROGÊNIO EM REAÇÕES QUÍMICAS: REAÇÃO DE PRILESCHAJEW

Theoretical analysis at the BHandHLYP/6-311++G(d,p) level of theory with the support of QTAIM calculations was used to reinvestigate the structure of an intermolecular system formed between ethylene oxide (C2H4O) and formic acid (HCO2H) after the epoxidation known as the Prileschajew reaction. Geometric and infrared vibration results revealed that HO2CH forms a strong hydrogen bond with C2H4O followed by a larger red-shift of the H−O bond. NBO analysis was applied to justify this frequency shift. Finally, QTAIM calculations identified the formation of two hydrogen bonds, namely O···H−O and H···O=C.

EXTRAÇÃO DE POLI(3-HIDROXIBUTIRATO), PRODUZIDO POR Cupriavidus necator, COM CARBONATO DE PROPILENO

The environmental impact of plastic waste has attracted worldwide attention. Amid the current context of increasing concern for the environment, biodegradable plastics have been widely studied as a replacement for synthetic plastics. Poly(3-hydroxybutyrate) (P(3HB)) is a biopolymer stored as an intracellular energy and reserve source in many microorganisms. Because it is an intracellular product, P(3HB) must be extracted from the cells at the end of the culture. The purpose of this study was to investigate the effect of extraction time, heating temperature, first standing time (after filtration and extraction), second standing time (after P(3HB) precipitation) and solvent amount, during the process of extracting P(3HB) from Cupriavidus necator DSM 545, using propylene carbonate as solvent. The extraction kinetic of P(3HB) with propylene carbonate from thermally treated biomass was evaluated at different temperatures. The physical properties of the P(3HB) obtained were also evaluated. In this case, P(3HB) obtained at optimal conditions of recovery (98%) and purity (99%) was used. Results showed that temperature was the most important factor in these responses for the range of values studied (110-150 ºC).

DEGRADAÇÃO MICROBIOLÓGICA E ENZIMÁTICA DE POLÍMEROS: UMA REVISÃO

Polymer recycling has been one of the most important trend in the petrochemical area. Among different technologies, biotechnological (enzymatic and/or microbial) degradation of polymers for the recovery of monomers and oligomers is environmentally-friendly and meet some green chemistry principles. In this work, conditions for the biotechnological degradation of some industrially-relevant polymers (e.g. poly(ethylene terephthalate) and polyethylene) were revised, and the main biocatalysts were identified. In most cases, biodegradation mechanisms are still unclear, thus being necessary more studies to unravel these promising bioprocesses. Polymer biodegradation studies also present considerable importance for other fields, including biomedical and agricultural.

Chiral separations of mandelic acid by HPLC using molecularly imprinted polymers

Styrene is used in a variety of chemical industries. Environmental and occupational exposures to styrene occur predominantly through inhalation. The major metabolite of styrene is present in two enantiomeric forms, chiral R- and S- hydroxy-1-phenyl-acetic acid (R-and S-mandelic acid, MA). Thus, the concentration of MA, particularly of its enantiomers, has been used in urine tests to determine whether workers have been exposed to styrene. This study describes a method of analyzing mandelic acid using molecular imprinting techniques and HPLC detection to perform the separation of diastereoisomers of mandelic acid. The molecularly imprinted polymer (MIP) was prepared by non-covalent molecular imprinting using (+) MA, (-) MA or (+) phenylalanine, (-) phenylalanine as templates. Methacrylic acid (MAA) and ethylene glycol dimethacrylate (EGDMA) were copolymerized in the presence of the template molecules. The bulk polymerization was carried out at 4ºC under UV radiation. The resulting MIP was grounded into 25~44¼m particles, which were slurry packed into analytical columns. After the template molecules were removed, the MIP-packed columns were found to be effective for the chromatographic resolution of (±)-mandelic acid. This method is simpler and more convenient than other chromatographic methods.

Lethal weapons : novel approaches for receptor-targeted cancer cell elimination

The currently used forms of cancer therapy are associated with drug resistance and toxicity to healthy tissues. Thus, more efficient methods are needed for cancer-specific induction of growth arrest and programmed cell death, also known as apoptosis. Therapeutic forms of tumor necrosis factor-related apoptosis-inducing ligand (TRAIL) are investigated in clinical trials due to the capability of TRAIL to trigger apoptosis specifically in cancer cells by activation of cell surface death receptors. Many tumors, however, have acquired resistance to TRAIL-induced apoptosis and sensitizing drugs for combinatorial treatments are, therefore, in high demand. This study demonstrates that lignans, natural polyphenols enriched in seeds and cereal, have a remarkable sensitizing effect on TRAIL-induced cell death at non-toxic lignan concentrations. In TRAIL-resistant and androgen-dependent prostate cancer cells we observe that lignans repress receptor tyrosine kinase (RTK) activity and downregulate cell survival signaling via the Akt pathway, which leads to increased TRAIL sensitivity. A structure-activity relationship analysis reveals that the γ-butyrolactone ring of the dibenzylbutyrolactone lignans is essential for the rapidly reversible TRAIL-sensitizing activity of these compounds. Furthermore, the lignan nortrachelogenin (NTG) is identified as the most efficient of the 27 tested lignans and norlignans in sensitization of androgen-deprived prostate cancer cells to TRAIL-induced apoptosis. While this combinatorial anticancer approach may leave normal cells unharmed, several efficient cancer drugs are too toxic, insoluble or unstable to be used in systemic therapy. To enable use of such drugs and to protect normal cells from cytotoxic effects, cancer-targeted drug delivery vehicles of nanometer scale have recently been generated. The newly developed nanoparticle system that we tested in vitro for cancer cell targeting combines the efficient drug-loading capacity of mesoporous silica to the versatile particle surface functionalization of hyperbranched poly(ethylene imine), PEI. The mesoporous hybrid silica nanoparticles (MSNs) were functionalized with folic acid to promote targeted internalization by folate receptor overexpressing cancer cells. The presented results demonstrate that the developed carrier system can be employed in vitro for cancer selective delivery of adsorbed or covalently conjugated molecules and furthermore, for selective induction of apoptotic cell death in folate receptor expressing cancer cells. The tested carrier system displays potential for simultaneous delivery of several anticancer agents specifically to cancer cells also in vivo.

Effect of ethephon on hardening of Pachystroma longifolium seedlings

Immediately after planting, tree seedlings face adverse environmental and biotic stresses that must be overcome to ensure survival and to yield a desirable growth. Hardening practices in the nursery may help improve seedling stress resistance through reduction of aboveground plant tissues and increased root volume and biomass. We conducted an assay to quantify changes in the morphogenesis following application of ethephon on seedlings of Pachystroma longifolium (Ness) I. M. Johnst.during hardening. The results showed no effect of the ethephon treatments on the number of leaves but a reduction of up to 50% in seedling height increment, and an increase in stem diameter increment of up to 44% with the 600 mg L-1 ethephon treatment, which consequently altered seedling Dickson Quality Index. Our results indicate that ethephon may help to promote desired morphological changes that occur during seedling hardening in nurseries.

Color change and quality response of ‘lane late’ orange submitted to degreening process

This study aimed at evaluating the effects of ethylene on peel color and compositional changes in ‘Lane late’ orange stored under refrigerated and ambient conditions. Physiologically mature, but green-peeled, oranges were exposed to ethylene gas under room temperature and high relative humidity for 24 hours. Storage chamber was ventilated with fresh air after 12 hours to mitigate consequences derived from fruit respiration. Both nondestructive analysis, such as peel color (hue angle, chromaticity, and brightness) and weight loss, and destructive ones (soluble solids, titratable acidity, pH, soluble solids to acidity ratio, and puncture force) were performed upon harvest, after degreening, and every three days during eighteen days in storage. Experiment was carried out using an entirely randomized design with thirty replications for nondestructive and four replications for destructive analyses, in a split plot scheme. Exposure to ethylene ensured a golden yellow peel for both fruit stored under ambient and refrigerated conditions. High relative humidity, associated with low temperature prevented fruit from losing moisture. Fruit exposure to ethylene did not affect weight loss, soluble solids, titratable acidity, pH, soluble solids, acidity ratio, or puncture force.

Survey of transportation of liquid bulk chemicals in the Baltic Sea

This study is made as a part of the Chembaltic (Risks of Maritime Transportation of Chemicals in Baltic Sea) project which gathers information on the chemicals transported in the Baltic Sea. The purpose of this study is to provide an overview of handling volumes of liquid bulk chemicals (including liquefied gases) in the Baltic Sea ports and to find out what the most transported liquid bulk chemicals in the Baltic Sea are. Oil and oil products are also viewed in this study but only in a general level. Oils and oil products may also include chemical-related substances (e.g. certain bio-fuels which belong to MARPOL annex II category) in some cargo statistics. Chemicals in packaged form are excluded from the study. Most of the facts about the transport volumes of chemicals presented in this study are based on secondary written sources of Scandinavian, Russian, Baltic and international origin. Furthermore, statistical sources, academic journals, periodicals, newspapers and in later years also different homepages on the Internet have been used as sources of information. Chemical handling volumes in Finnish ports were examined in more detail by using a nationwide vessel traffic system called PortNet. Many previous studies have shown that the Baltic Sea ports are annually handling more than 11 million tonnes of liquid chemicals transported in bulk. Based on this study, it appears that the number may be even higher. The liquid bulk chemicals account for approximately 4 % of the total amount of liquid bulk cargoes handled in the Baltic Sea ports. Most of the liquid bulk chemicals are handled in Finnish and Swedish ports and their proportion of all liquid chemicals handled in the Baltic Sea is altogether over 50 %. The most handled chemicals in the Baltic Sea ports are methanol, sodium hydroxide solution, ammonia, sulphuric and phosphoric acid, pentanes, aromatic free solvents, xylenes, methyl tert-butyl ether (MTBE) and ethanol and ethanol solutions. All of these chemicals are handled at least hundred thousand tonnes or some of them even over 1 million tonnes per year, but since chemical-specific data from all the Baltic Sea countries is not available, the exact tonnages could not be calculated in this study. In addition to these above-mentioned chemicals, there are also other high volume chemicals handled in the Baltic Sea ports (e.g. ethylene, propane and butane) but exact tonnes are missing. Furthermore, high amounts of liquid fertilisers, such as solution of urea and ammonium nitrate in water, are transported in the Baltic Sea. The results of the study can be considered indicative. Updated information about transported chemicals in the Baltic Sea is the first step in the risk assessment of the chemicals. The chemical-specific transportation data help to target hazard or e.g. grounding/collision risk evaluations to chemicals that are handled most or have significant environmental hazard potential. Data gathered in this study will be used as background information in later stages of the Chembaltic project when the risks of the chemicals transported in the Baltic Sea are assessed to highlight the chemicals that require special attention from an environmental point of view in potential marine accident situations in the Baltic Sea area.

Metabolic evaluation of dairy cows submitted to three different strategies to decrease the effects of negative energy balance in early postpartum

In early lactation dairy cattle suffer metabolic alterations caused by negative energy balance, which predisposes to fatty liver and ketosis. The aim of this study was to evaluate the metabolic condition of high yielding dairy cows subjected to three treatments for preventing severe lipomobilization and ketosis in early lactation. Fifty four multiparous Holstein cows yielding >30 L/day were divided into four groups: control (CN= no treatment), glucose precursor (PG= propylene-glycol), hepatic protector (Mp= Mercepton®), and energy supplement with salts of linolenic and linoleic faty acids (Mg-E= Megalac-E®). Treatments were administrated randomly at moment of calving until 8 weeks postpartum. Blood samples were collected on days 1, 7, 14, 21, 28, 35, 42 and 49 postpartum. Body condition score (BCS) was evaluated at the same periods and milk yield was recorded at 2nd, 4th, 5th, 6th, 7th, and 8th weeks of lactation. Concentrations of non-esterified fatty acids (NEFA), albumin, AST, ß-hydroxybutyrate (BHBA), cholesterol, glucose, total protein, urea and triglycerides were analyzed in blood samples. Cut-off points for subclinical ketosis were defined when BHBA >1.4 mmol/L and NEFA >0.7 mmol/L. General occurrence of subclinical ketosis was 24% during the period. An ascendant curve of cholesterol and glucose was observed from the 1st to the 8th week of lactation, while any tendency was observed with BHBA and NEFA, although differences among treatments were detected (p<0.05). BCS decreased from a mean of 3.85 at 1st week to 2.53 at 8th week of lactation (p=0.001). Milk yield was higher in the Mg-E group compared with the other treatment groups (p<0.05) Compared with the CN group, the treatments with Mp and PG did not show significant differences in blood biochemistry and milk yield. Cows receiving PG and Mg-E showed higher values of BHBA and NEFA (P<0.05), indicating accentuated lipomobilization. Supplementation with Mg-E also resulted in significant higher concentrations of cholesterol, BHBA, urea, AST and lower values of glycemia. This performance may be explained by the highest milk yield observed with this treatment. Treatments with PG and Mp did not improve milk yield, compared with control cows, but did not show metabolic evidence of ketosis, fat mobilization or fatty liver. These results suggest that treatment with Mg-E improves milk production but induces a higher negative energy balance leading to moderated lipomobilization and ketone bodies production, increasing the risk of fatty liver.

Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Functional Genomic Approaches for Deciphering Plant-Virus Interactions

Plant-virus interactions are very complex in nature and lead to disease and symptom formation by causing various physiological, metabolic and developmental changes in the host plants. These interactions are mainly the outcomes of viral hijacking of host components to complete their infection cycles and of host defensive responses to restrict the viral infections. Viral genomes contain only a small number of genes often encoding for multifunctional proteins, and all are essential in establishing a viral infection. Thus, it is important to understand the specific roles of individual viral genes and their contribution to the viral life cycles. Among the most important viral proteins are the suppressors of RNA silencing (VSRs). These proteins function to suppress host defenses mediated by RNA silencing and can also serve in other functions, e.g. in viral movement, transactivation of host genes, virus replication and protein processing. Thus these proteins are likely to have a significant impact on host physiology and metabolism. In the present study, I have examined the plant-virus interactions and the effects of three different VSRs on host physiology and gene expression levels by microarray analysis of transgenic plants that express these VSR genes. I also studied the gene expression changes related to the expression of the whole genome of Tobacco mosaic virus (TMV) in transgenic tobacco plants. Expression of the VSR genes in the transgenic tobacco plants causes significant changes in the gene expression profiles. HC-Pro gene derived from the Potyvirus Y (PVY) causes alteration of 748 and 332 transcripts, AC2 gene derived from the African cassava mosaic virus (ACMV) causes alteration of 1118 and 251transcripts, and P25 gene derived from the Potyvirus X (PVX) causes alterations of 1355 and 64 transcripts in leaves and flowers, respectively. All three VSRs cause similar up-regulation in defense, hormonally regulated and different stress-related genes and down-regulation in the photosynthesis and starch metabolism related genes. They also induce alterations that are specific to each viral VSR. The phenotype and transcriptome alterations of the HC-Pro expressing transgenic plants are similar to those observed in some Potyvirus-infected plants. The plants show increased protein degradation, which may be due to the HC-Pro cysteine endopeptidase and thioredoxin activities. The AC2-expressing transgenic plants show a similar phenotype and gene expression pattern as HC-Pro-expressing plants, but also alter pathways related to jasmonic acid, ethylene and retrograde signaling. In the P25 expressing transgenic plants, high numbers of genes (total of 1355) were up-regulated in the leaves, compared to a very low number of down-regulated genes (total of 5). Despite of strong induction of the transcripts, only mild growth reduction and no other distinct phenotype was observed in these plants. As an example of whole virus interactions with its host, I also studied gene expression changes caused by Tobacco mosaic virus (TMV) in tobacco host in three different conditions, i.e. in transgenic plants that are first resistant to the virus, and then become susceptible to it and in wild type plants naturally infected with this virus. The microarray analysis revealed up and down-regulation of 1362 and 1422 transcripts in the TMV resistant young transgenic plants, and up and down-regulation of a total of 1150 and 1200 transcripts, respectively, in the older plants, after the resistance break. Natural TMV infections in wild type plants caused up-regulation of 550 transcripts and down-regulation of 480 transcripts. 124 up-regulated and 29 down-regulated transcripts were commonly altered between young and old TMV transgenic plants, and only 6 up-regulated and none of the down-regulated transcripts were commonly altered in all three plants. During the resistant stage, the strong down-regulation in translation-related transcripts (total of 750 genes) was observed. Additionally, transcripts related to the hormones, protein degradation and defense pathways, cell division and stress were distinctly altered. All these alterations may contribute to the TMV resistance in the young transgenic plants, and the resistance may also be related to RNA silencing, despite of the low viral abundance and lack of viral siRNAs or TMV methylation activity in the plants.

Methyl and ethyl chloride synthesis in microreactors

Methyl chloride is an important chemical intermediate with a variety of applications. It is produced today in large units and shipped to the endusers. Most of the derived products are harmless, as silicones, butyl rubber and methyl cellulose. However, methyl chloride is highly toxic and flammable. On-site production in the required quantities is desirable to reduce the risks involved in transportation and storage. Ethyl chloride is a smaller-scale chemical intermediate that is mainly used in the production of cellulose derivatives. Thus, the combination of onsite production of methyl and ethyl chloride is attractive for the cellulose processing industry, e.g. current and future biorefineries. Both alkyl chlorides can be produced by hydrochlorination of the corresponding alcohol, ethanol or methanol. Microreactors are attractive for the on-site production as the reactions are very fast and involve toxic chemicals. In microreactors, the diffusion limitations can be suppressed and the process safety can be improved. The modular setup of microreactors is flexible to adjust the production capacity as needed. Although methyl and ethyl chloride are important chemical intermediates, the literature available on potential catalysts and reaction kinetics is limited. Thus the thesis includes an extensive catalyst screening and characterization, along with kinetic studies and engineering the hydrochlorination process in microreactors. A range of zeolite and alumina based catalysts, neat and impregnated with ZnCl2, were screened for the methanol hydrochlorination. The influence of zinc loading, support, zinc precursor and pH was investigated. The catalysts were characterized with FTIR, TEM, XPS, nitrogen physisorption, XRD and EDX to identify the relationship between the catalyst characteristics and the activity and selectivity in the methyl chloride synthesis. The acidic properties of the catalyst were strongly influenced upon the ZnCl2 modification. In both cases, alumina and zeolite supports, zinc reacted to a certain amount with specific surface sites, which resulted in a decrease of strong and medium Brønsted and Lewis acid sites and the formation of zinc-based weak Lewis acid sites. The latter are highly active and selective in methanol hydrochlorination. Along with the molecular zinc sites, bulk zinc species are present on the support material. Zinc modified zeolite catalysts exhibited the highest activity also at low temperatures (ca 200 °C), however, showing deactivation with time-onstream. Zn/H-ZSM-5 zeolite catalysts had a higher stability than ZnCl2 modified H-Beta and they could be regenerated by burning the coke in air at 400 °C. Neat alumina and zinc modified alumina catalysts were active and selective at 300 °C and higher temperatures. However, zeolite catalysts can be suitable for methyl chloride synthesis at lower temperatures, i.e. 200 °C. Neat γ-alumina was found to be the most stable catalyst when coated in a microreactor channel and it was thus used as the catalyst for systematic kinetic studies in the microreactor. A binder-free and reproducible catalyst coating technique was developed. The uniformity, thickness and stability of the coatings were extensively characterized by SEM, confocal microscopy and EDX analysis. A stable coating could be obtained by thermally pretreating the microreactor platelets and ball milling the alumina to obtain a small particle size. Slurry aging and slow drying improved the coating uniformity. Methyl chloride synthesis from methanol and hydrochloric acid was performed in an alumina-coated microreactor. Conversions from 4% to 83% were achieved in the investigated temperature range of 280-340 °C. This demonstrated that the reaction is fast enough to be successfully performed in a microreactor system. The performance of the microreactor was compared with a tubular fixed bed reactor. The results obtained with both reactors were comparable, but the microreactor allows a rapid catalytic screening with low consumption of chemicals. As a complete conversion of methanol could not be reached in a single microreactor, a second microreactor was coupled in series. A maximum conversion of 97.6 % and a selectivity of 98.8 % were reached at 340°C, which is close to the calculated values at a thermodynamic equilibrium. A kinetic model based on kinetic experiments and thermodynamic calculations was developed. The model was based on a Langmuir Hinshelwood-type mechanism and a plug flow model for the microreactor. The influence of the reactant adsorption on the catalyst surface was investigated by performing transient experiments and comparing different kinetic models. The obtained activation energy for methyl chloride was ca. two fold higher than the previously published, indicating diffusion limitations in the previous studies. A detailed modeling of the diffusion in the porous catalyst layer revealed that severe diffusion limitations occur starting from catalyst coating thicknesses of 50 μm. At a catalyst coating thickness of ca 15 μm as in the microreactor, the conditions of intrinsic kinetics prevail. Ethanol hydrochlorination was performed successfully in the microreactor system. The reaction temperature was 240-340°C. An almost complete conversion of ethanol was achieved at 340°C. The product distribution was broader than for methanol hydrochlorination. Ethylene, diethyl ether and acetaldehyde were detected as by-products, ethylene being the most dominant by-product. A kinetic model including a thorough thermodynamic analysis was developed and the influence of adsorbed HCl on the reaction rate of ethanol dehydration reactions was demonstrated. The separation of methyl chloride using condensers was investigated. The proposed microreactor-condenser concept enables the production of methyl chloride with a high purity of 99%.

Chemical derivatization of galactoglucomannan for functional materials

In the framework of the biorefinery concept researchers aspire to optimize the utilization of plant materials, such as agricultural wastes and wood. For most of the known processes, the first steps in the valorisation of biomass are the extraction and purification of the individual components. The obtained raw products by means of a controlled separation can consecutively be modified to result in biofuels or biogas for energy production, but also in value-added products such as additives and important building blocks for the chemical and material industries. Considerable efforts are undertaken in order to substitute the use of oil-based starting materials or at least minimize their processing for the production of everyday goods. Wood is one of the raw materials, which have gained large attention in the last decades and its composition has been studied in detail. Nowadays, the extraction of water-soluble hemicelluloses from wood is well known and so for example xylan can be obtained from hardwoods and O-acetyl galactoglucomannans (GGMs) from softwoods. The aim of this work was to develop water-soluble amphiphilic materials of GGM and to assess their potential use as additives. Furthermore, GGM was also applied as a crosslinker in the synthesis of functional hydrogels for the removal of toxic metals and metalloid ions from aqueous solutions. The distinguished products were obtained by several chemical approaches and analysed by nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), size exclusion chromatography (SEC), thermal gravimetric analysis (TGA), scanning electron microscope SEM, among others. Bio-based surfactants were produced by applying GGM and different fatty acids as starting materials. On one hand, GGM-grafted-fatty acids were prepared by esterification and on the other hand, well-defined GGM-block-fatty acid derivatives were obtained by linking amino-functional fatty acids to the reducing end of GGM. The reaction conditions for the syntheses were optimized and the resultant amphiphilic GGM derivatives were evaluated concerning their ability to reduce the surface tension of water as surfactants. Furthermore, the block-structured derivatives were tested in respect to their applicability as additives for the surface modification of cellulosic materials. Besides the GGM surfactants with a bio-based hydrophilic and a bio-based hydrophobic part, also GGM block-structured derivatives with a synthetic hydrophobic tail, consisting of a polydimethylsiloxane chain, were prepared and assessed for the hydrophobization of surface of nanofibrillated cellulose films. In order to generate GGM block-structured derivatives containing a synthetic tail with distinguished physical and chemical properties, as well as a tailored chain length, a controlled polymerization method was used. Therefore, firstly an initiator group was introduced at the reducing end of the GGM and consecutively single electron transfer-living radical polymerization (SET-LRP) was performed by applying three different monomers in individual reactions. For the accomplishment of the synthesis and the analysis of the products, challenges related to the solubility of the reactants had to be overcome. Overall, a synthesis route for the production of GGM block-copolymers bearing different synthetic polymer chains was developed and several derivatives were obtained. Moreover, GGM with different molar masses were, after modification, used as a crosslinker in the synthesis of functional hydrogels. Hereby, a cationic monomer was used during the free radical polymerization and the resultant hydrogels were successfully tested for the removal of chromium and arsenic ions from aqueous solutions. The hydrogel synthesis was tailored and materials with distinguished physical properties, such as the swelling rate, were obtained after purification. The results generated in this work underline the potential of bio-based products and the urge to continue carrying out research in order to be able to use more green chemicals for the manufacturing of biorenewable and biodegradable daily products.

Note on the germination of Vochysia tucanorum seeds treated with growth regulators

(Note on the germination of Vochysia tucanorum seeds treated with growth regulators). The aim of this work was to evaluate the germination response of Vochysia tucanorum Mart. seeds treated with GA3 and CEPA and germinated under white light or darkness. Newly collected seeds from a Cerrado area were stored for 14 days at two temperatures (25 °C ± 2 and 7 °C ± 1). After the storage period the seeds were pre-treated with distilled water (control), gibberellic acid (GA3), 2-chloroethylphosphonic acid (CEPA) and a mixture of GA3 + CEPA. Following this, the seeds were sown in Petri dishes on filter paper moistened with distilled water and germinated in either darkness or white light. The results suggest that seeds are non-photoblastic and non-dormant, however a photoblastic behavior emerges when the seeds were previously stored at low temperature and imbibed in CEPA and GA3 solutions. In general, there is no difference between the 7 °C and 25 °C storage temperatures. The germination of seeds pre-treated with CEPA and CEPA + GA3 under white light was faster as compared to the distilled water control, and the effect of the CEPA + GA3 mixture was more pronounced than CEPA alone. Thus, the germination rate of V. tucanorum seeds can be improved by treatment with CEPA or CEPA + GA3 under white light.