Production of Furfural from Lignocellulosic Biomass Using Beta Zeolite and Biomass-Derived Solvent

The production of furfural from the C₅ monosaccharides xylose, arabinose and ribose, as well as from real biomass (corn fiber), was studied using H-Beta zeolite as catalyst in a monophasic system with the biomass-derived solvent, gamma-valerolactone. Due to the combination of Brønsted and Lewis acid sites on this catalyst (Brønsted:Lewis ratio = 1.66), H-Beta acts as a bifunctional catalyst, being able to isomerize (Lewis acid) and dehydrate (Brønsted acid) monosaccharides. The combination of Lewis and Brønsted acid functionality of H-Beta was shown to be effective for the isomerization of xylose and arabinose, followed by dehydration. While no advantages were found in the conversion of xylose, higher furfural yields were achieved from arabinose, using H-Beta, 73 %, compared to sulfuric acid (44 %) and Mordenite (49 %). The furfural yields from corn fiber for H-Beta, H-Mordenite and sulfuric acid were 62, 44, and 55 %, respectively, showing that H-Beta is particularly effective for conversion of this biomass feedstock composed of 45 wt% hemicellulose, of which 66 % is xylose and 33 % arabinose.     

Nonribosomal Peptides Produced by Minimal and Engineered Synthetases with Terminal Reductase Domains

Nonribosomal peptide synthetases (NRPSs) use terminal reductase domains for 2-electron reduction of the enzyme-bound thioester releasing the generated peptides as C-terminal aldehydes. Herein, we reveal the biosynthesis of a pyrazine that originates from an aldehyde-generating minimal NRPS termed ATRed in entomopathogenic Xenorhabdus indica. Reductase domains were also investigated in terms of NRPS engineering and, although no general applicable approach was deduced, we show that they can indeed be used for the production of similar natural and unnatural pyrazinones.     

pH‐Cleavable Nucleoside Lipids: A New Paradigm for Controlling the Stability of Lipid‐Based Delivery Systems

Lipid‐based delivery systems are an established technology with considerable clinical acceptance and several applications in human. Herein, we report the design, synthesis and evaluation of novel orthoester nucleoside lipids (ONLs) for the modulation of liposome stability. The ONLs contain head groups with 3′‐orthoester nucleoside derivatives featuring positive or negative charges. The insertion of the orthoester function in the NL structures allows the formation of pH‐sensitive liposomes. ONL‐based liposomes can be hydrolyzed to provide nontoxic products, including nucleoside derivatives and hexadecanol. To allow the release to be tunable at different hydrolysis rates, the charge of the polar head structure is modulated, and the head group can be released at a biologically relevant pH. Crucially, when ONLs are mixed with natural phosphocholine lipids (PC), the resultant liposome evolves toward the formation of a hexadecanol/PC lamellar system. Biological evaluation shows that stable nucleic acid lipid particles (SNALPs) formulated with ONLs and siRNAs can effectively enter into tumor cells and release their nucleic acid payload in response to an intracellular acidic environment. This results in a much higher antitumor activity than conventional SNALPs. The ability to use pH‐cleavable nucleolipids to control the stability of lipid‐based delivery systems represents a promising approach for the intracellular delivery of drug cargos.     

Investigation of crude latex from various Carica papaya varietices for lipid bioconversions

The protein contents in crude latices from various varieties of papaya (Carica papaya) and their catalytic activities in proteolysis, lipolysis, and interesterification reactions were studied with regard to the variety, the geographic location of cultures, and the frequency of fruit tapping. Biocatalytic activities of these raw materials were compared to several commercially available crude and purified preparations of papain. These investigations were carried out in order to have a better physicochemical characterization of these raw materials, to select the adequate papaya latex for protein or lipid bioconversions, and to valorize them on an industrial scale. For the purified preparations of papain, only proteolytic activity was obtained. All crude papaya latices exhibit proteolytic, lipolytic, and interesterification activities, and no relationship between the proteolytic and lipolytic activities was observed. The high multiple correlation coefficient (R) on the order of R=0.93–0.99, obtained from the regression analysis for the lipolytic and interesterification activities for all crude papaya latices investigated suggested that there was a correlation between these enzyme activities. However, for the same lipase preparation, the interesterification activity differed substantially depending on the type of interesterification reaction.     

Analysis of exempt paint solvents by gas chromatography using solid-phase microextraction

Acetone, methyl acetate, and parachlorobenzotrifluoride (PCBTF or Oxsol? 100) have been exempted as VOC solvents by the U.S. Environmental Protection Agency. In measuring coating VOC content, separate methods for determining exempt solvents are required. One such method utilizes solid-phase microextraction (SPME) to sample the headspace of solvent-based coatings to which the surrogates acetone-d6, methyl acetate-d3, and/or metachlorobenzotrifluoride have been added. The sampled exempt coating solvents are thermally desorbed and analyzed using gas chromatography with flame ionization or mass spectral detection. The SPME headspace method has also been used to analyze MEK, butyl acetate, tert-butyl acetate, toluene, and xylene in solventborne coatings, and alcohols in waterborne systems. This paper presents the results obtained for acetone and toluene in a large number of aerosol paints. Additionally, the results from a round-robin study for acetone, methyl acetate, and parachlorobenzotrifluoride in commercial solvent-based coatings are reported.     

Results of an inter-laboratory comparison of methods for quantitative clay analysis

In a comparison of analytical methods in clay mineralogy, two clay samples (from Hennersdorf and Freydegg) of different clay composition were analyzed by 19 laboratories mainly by XRD. Participants used different methods of pre-treatment, preparation, analysis and evaluation.In spite of the diversity of analytical methods applied, reasonable conformity in quantitative results was obtained for the associated minerals (quartz, calcite and dolomite). On the other hand, qualitative identification of the clay minerals showed considerably stronger divergencies, causing a stronger deviation of quantitative data; analysis of the Freydegg sample proved to have been particularly difficult. The evaluation methods of the different participants were examined to determine whether similar methods provided results that could be more easily compared.In addition, the authors calculated the clay mineral composition according to three different recognized methods, using the same diffractograms and same preparation and measuring conditions. In spite of this, different results were obtained.In the next phase of the programme, an inter-laboratory comparison of methods will be achieved under exactly defined conditions of preparation and analysis.     

Studies on the response of ‘Tifblue’ and ‘Woodard’ rabbiteye blueberries to fertilizers

A field study was conducted to investigate the effects of three fertilizer placement methods and 11 fertilizer formulations on plant survival, economics of replanting, yield, and fruit size of two rabbiteye blueberry (Vaccinium ashei Reade) cultivars Tifblue and Woodard. Fertilizer rates were either mixed with the soil under plants (before planting), sidedressed, or half-rate was placed under plants with the other half sidedressed. Fertilizers at planting caused a total of 34% Woodard and 12% Tifblue plants to die as compared to 6% for Woodard and none for Tifblue when no fertilizer was applied. Fertilizer formulas 2-1-1 and 5-10-10 oxide ratios placed under Woodard plants caused 100% mortality whereas Tifblue fertilized with oxide ratios 2-2-2 and 5-10-10 under plants reached the maximum 50% mortality. Splitting fertilizer placement under the side of the plants resulted in less Woodard plant mortality (30%) than placing all the fertilizer under plants (54%). However, plant mortality for the side/under group was not different than sidedressing all fertilizer (23%). A planted hectare in this experiment consisted of 1852 Tifblue and 926 Woodard plants, providing one Woodard plant to pollinate two Tifblue plants. Based on the results obtained, the 5-10-10 fertilizer placed under plants would be expected to cause half the Tifblue (926 plants) and all the Woodard (926 plants) to be replanted. Plant costs alone was estimated to be $2315 with additional replanting costs of $93 for Tifblue and much higher for Woodard. Sidedressing 5-10-10 fertilizer eight weeks after planting would have prevented plant mortality. Placement of various fertilizers under Woodard or Tifblue plants resulted in a significant increase in plant mortality as compared to side placement of fertilizers. Yield loss due to plant mortality increased linearly with the N level of the fertilizers (ranging from 0 to 2) for both cultivars. Woodard fruit size was not affected by fertilizer placement but placing fertilizers under Tifblue plants produced smaller yields with larger fruit than sidedressed plants. Blueberry plants in a virgin acidic soil may experience no reduction in yield if fertilization is completely eliminated.     

Catalytic Deoxygenation of Stearic Acid and Palmitic Acid in Semibatch Mode

The deoxygenation experiments of different reactants, i.e., pure palmitic acid, stearic acid, and a technical grade stearic acid containing a mixture of 59% of palmitic and 40% of stearic acid were successfully performed over 4 wt% Pd/C mesoporous catalyst at 300 °C under 17 bar of 5% H₂ in argon. The main product in catalytic deoxygenation of saturated fatty acids, C16 and C18, were aliphatic chain length hydrocarbons containing one less carbon than the corresponding acid. Additionally it was found that the deoxygenation rates of different reactant were independent on carbon chain length of its fatty acids.     

Prevention of liquid metal embrittlement cracks in resistance spot welds by adaption of electrode geometry

ABSTRACT

Advanced high strength steels are usually coated by a zinc layer for an increased resistance against corrosion. During the resistance spot welding of zinc coated steel grades, liquid metal embrittlement (LME) may occur. As a result, cracking inside and around the spot weld indentation is observable. The extent of LME cracks is influenced by a variety of different factors. In this study, the impact of the used electrode geometry is investigated over a stepwise varied weld time. A spot welding finite element simulation is used to analyse and explain the observed effects. Results show significant differences especially for highly increased weld times. Based on identical overall dimensions, electrode geometries with a larger working plane allow for longer weld times, while still preventing LME within the investigated material and maintaining accessibility.     

Involvement of GPR17 in Neuronal Fibre Outgrowth

Characterization of new pharmacological targets is a promising approach in research of neurorepair mechanisms. The G protein-coupled receptor 17 (GPR17) has recently been proposed as an interesting pharmacological target, e.g., in neuroregenerative processes. Using the well-established ex vivo model of organotypic slice co-cultures of the mesocortical dopaminergic system (prefrontal cortex (PFC) and substantia nigra/ventral tegmental area (SN/VTA) complex), the influence of GPR17 ligands on neurite outgrowth from SN/VTA to the PFC was investigated. The growth-promoting effects of Montelukast (MTK; GPR17- and cysteinyl-leukotriene receptor antagonist), the glial cell line-derived neurotrophic factor (GDNF) and of two potent, selective GPR17 agonists (PSB-16484 and PSB-16282) were characterized. Treatment with MTK resulted in a significant increase in mean neurite density, comparable with the effects of GDNF. The combination of MTK and GPR17 agonist PSB-16484 significantly inhibited neuronal growth. qPCR studies revealed an MTK-induced elevated mRNA-expression of genes relevant for neuronal growth. Immunofluorescence labelling showed a marked expression of GPR17 on NG2-positive glia. Western blot and RT-qPCR analysis of untreated cultures suggest a time-dependent, injury-induced stimulation of GPR17. In conclusion, MTK was identified as a stimulator of neurite fibre outgrowth, mediating its effects through GPR17, highlighting GPR17 as an interesting therapeutic target in neuronal regeneration.