Investigations into metabolic properties and selected nutritional metabolic byproducts of different non-Saccharomyces yeast strains when producing nonalcoholic beer.

Nonalcoholic beers are becoming increasingly popular, in part due to consumers' awareness of a healthier lifestyle. Additionally, consumers are demanding diversification in the product range, which can be offered by producing nonalcoholic beers using non-Saccharomyces yeasts for fermentation to create a wide variety of flavors. So far, little is known about the nutritionally relevant byproducts that these yeasts release during wort fermentation and whether these yeasts can be considered safe for food fermentations. To gain insights into this, the B vitamins of four different nonalcoholic beers fermented with the yeast species Saccharomycodes ludwigii, Cyberlindnera saturnus (two strains), and Kluyveromyces marxianus were analyzed. Furthermore, a total of 16 beers fermented with different non-Saccharomyces yeast strains were analyzed for biogenic amines. Additionally, stress tolerance tests were performed at 37°C and in synthetic human gastric juice in vitro. B vitamins were found in the four nonalcoholic beers in nutritionally relevant amounts so they could serve as a supplement for a balanced diet. Biogenic amines remained below the limit of determination in all 16 beers, and thus likely had no influence, while the stress tolerance tests gave a first indication that seven yeast strains could possibly tolerate the human gastric juice milieu.

Unique Brewing-Relevant Properties of a Strain of Saccharomyces jurei Isolated From Ash (Fraxinus excelsior).

The successful application of Saccharomyces eubayanus and Saccharomyces paradoxus in brewery fermentations has highlighted the potential of wild Saccharomyes yeasts for brewing, and prompted investigation into the application potential of other members of the genus. Here, we evaluate, for the first time, the brewing potential of Saccharomyces jurei. The newly isolated strain from an ash tree (Fraxinus excelsior) in Upper Bavaria, Germany, close to the river Isar, was used to ferment a 12°P wort at 15°C. Performance was compared directly with that of a reference lager strain (TUM 34/70) and the S. eubayanus type strain. Both wild yeast rapidly depleted simple sugars and thereafter exhibited a lag phase before maltose utilization. This phase lasted for 4 and 10 days for S. eubayanus and S. jurei, respectively. S. eubayanus utilized fully the available maltose but, consistent with previous reports, did not use maltotriose. S. jurei, in contrast, utilized approximately 50% of the maltotriose available, making this the first report of maltotriose utilization in a wild Saccharomyces species. Maltotriose use was directly related to alcohol yield with 5.5, 4.9, and 4.5% ABV produced by Saccharomyces pastorianus, S. jurei, and S. eubayanus. Beers also differed with respect to aroma volatiles, with a high level (0.4 mg/L) of the apple/aniseed aroma ethyl hexanoate in S. jurei beers, while S. eubayanus beers had a high level of phenylethanol (100 mg/L). A trained panel rated all beers as being of high quality, but noted clear differences. A phenolic spice/clove note was prominent in S. jurei beer. This was less pronounced in the S. eubayanus beers, despite analytical levels of 4-vinylguaiacol being similar. Tropical fruit notes were pronounced in S. jurei beers, possibly resulting from the high level of ethyl hexanoate. Herein, we present results from the first intentional application of S. jurei as a yeast for beer fermentation (at the time of submission) and compare its fermentation performance to other species of the genus. Results indicate considerable potential for S. jurei application in brewing, with clear advantages compared to other wild Saccharomyces species.

Influence of 3-DG as a Key Precursor Compound on Aging of Lager Beers.

3-Deoxyglucosone (3-DG) is a Maillard reaction intermediate, which forms known beer aging compounds such as Strecker aldehydes. However, the role of 3-DG in beer aging stability has not been described yet. To investigate the influence of 3-DG toward beer aging stability, different concentrations of 3-DG were added to the freshly brewed beer at the beginning of storage. Analysis of well-known degradation products of 3-DG such as 3-deoxygalactosone (HPLC-UV), 5-hydroxymethylfurfural (HPLC-UV), Strecker aldehydes (GC-MS), and free glycated amino acids (HPLC-MS/MS) during beer aging revealed that a higher initial 3-DG concentration increases the formation of the products. In this study, the significant importance of 3-DG as a key precursor compound in beer aging has been shown, especially the increase of Strecker aldehydes.

MacroEvoLution: A New Method for the Rapid Generation of Novel Scaffold-Diverse Macrocyclic Libraries.

Macrocycles are a structural class bearing great promise for future challenges in medicinal chemistry. Nevertheless, there are few flexible approaches for the rapid generation of structurally diverse macrocyclic compound collections. Here, an efficient method for the generation of novel macrocyclic peptide-based scaffolds is reported. The process, named here as "MacroEvoLution", is based on a cyclization screening approach that gives reliable access to novel macrocyclic architectures. Classification of building blocks into specific pools ensures that scaffolds with orthogonally addressable functionalities are generated, which can easily be used for the generation of structurally diverse compound libraries. The method grants rapid access to novel scaffolds with scalable synthesis (multi gram scale) and the introduction of further diversity at a late stage. Despite being developed for peptidic systems, the approach can easily be extended for the synthesis of systems with a decreased peptidic character.

Bidirectional cross metathesis and ring-closing metathesis/ring opening of a C 2-symmetric building block: a strategy for the synthesis of decanolide natural products.

Starting from the conveniently available ex-chiral pool building block (R,R)-hexa-1,5-diene-3,4-diol, the ten-membered ring lactones stagonolide E and curvulide A were synthesized using a bidirectional olefin-metathesis functionalization of the terminal double bonds. Key steps are (i) a site-selective cross metathesis, (ii) a highly diastereoselective extended tethered RCM to furnish a (Z,E)-configured dienyl carboxylic acid and (iii) a Ru-lipase-catalyzed dynamic kinetic resolution to establish the desired configuration at C9. Ring closure was accomplished by macrolactonization. Curvulide A was synthesized from stagonolide E through Sharpless epoxidation.

Stereoselective synthesis of dienyl phosphonates via extended tethered ring-closing metathesis.

Allylphosphonates of allylic alcohols were converted to conjugated dienyl phosphonates in a one-flask reaction, comprising a ring-closing metathesis (RCM), a base-induced ring-opening, and an alkylation. The ring-opening proceeds with very high diastereoselectivity, giving exclusively the (1Z,3E)-configured dienes. Single diastereomers and mixtures of diastereomers can be used as starting materials without noticeable effect on the diastereoselectivity of the sequence.

Total syntheses of naturally occurring seimatopolide A and its enantiomer from chiral pool starting materials using a bidirectional strategy.

Enantioselective total syntheses of both enantiomers of the recently isolated decanolide natural product seimatopolide A are described. The C(2)-symmetric building blocks (R,R)-hexa-1,5-diene-3,4-diol (derived from D-mannitol) and its enantiomer (derived from l-(+)-tartrate) serve as key starting materials, which are elaborated in a bidirectional way using a selective mono-cross-metathesis, regio- and stereoselective epoxidation, and regioselective reductive epoxide opening to furnish the first fragment. Both enantiomers of the second fragment, 3-hydroxypent-4-enoic acid, were conveniently obtained through a lipase-catalyzed kinetic resolution and merged with the first fragment via Shiina esterification. An E-selective ring-closing metathesis was used to access the 10-membered lactone. A comparison of the specific optical rotations of synthetic seimatopolides with those reported for the natural product suggests that the originally assigned (3R,6R,7R,9S)-configuration should be corrected to (3S,6S,7S,9R).

Total synthesis of (-)-cleistenolide.

The first total synthesis of Cleistenolide, a novel natural product recently isolated from the Annonaceae species Cleistochlamys kirkii Oliver, is described. The synthesis proceeds in six steps and 18% overall yield, starting from an enantiopure C2-symmetric building block and using a Sharpless epoxidation, a selective epoxide opening, and a ring-closing metathesis reaction.

The catalytic performance of Ru-NHC alkylidene complexes: PCy3versus pyridine as the dissociating ligand.

The catalytic performance of NHC-ligated Ru-indenylidene or benzylidene complexes bearing a tricyclohexylphosphine or a pyridine ligand in ring closing metathesis (RCM), cross metathesis, and ring closing enyne metathesis (RCEYM) reactions is compared. While the PCy3 complexes perform significantly better in RCM and RCEYM reactions than the pyridine complex, all catalysts show similar activity in cross metathesis reactions.