Development of preparative and analytical methods of the hop bitter acid oxide fraction and chemical properties of its components

The bitter acids in hops (Humulus lupulus L.) and beer, such as α-, β-, and iso-α-acids, are known to affect beer quality and display various physiological effects. However, these compounds readily oxidize, and the effect of the oxides on the properties of beer or their potential health benefits are not well understood. In this study, we developed a simple preparative method for the bitter acid oxide fraction derived from hops and designated the constituents as matured hop bitter acids (MHBA). HPLC-PDA-ESI/HRMS and MS² revealed that MHBA are primarily composed of α-acid-derived oxides, which possess a common β-tricarbonyl moiety in their structures similar to α-, β-, and iso-α-acids. We also developed a quantitative analytical method of whole MHBA by HPLC, which showed high precision and reproducibility. Using our newly developed method, the concentration of whole MHBA in several commercial beers was evaluated. Our results will promote the study of bitter acid oxides.     

An overview of fungal community diversity in diseased hop plantations

Samples were taken from several hop fields presenting various symptoms. Fifty-nine pure filamentous fungal strains were isolated and identified through genomic DNA preparations, PCR amplification of the ribosomal DNA internal transcribed spacer region and database interrogations. The most frequent genera were Alternaria (16 isolates) and Epicoccum (14 isolates). The ecosystem was shown to be very diverse, since as many as 27 species belonging to 17 genera were recovered. Furthermore, many of the isolated fungi are known to be involved in phytopathogenesis.     

Characterization of hop pectins shows the presence of an arabinogalactan-protein

Hop pectins were extracted from spent hops using acid extraction conditions and were characterized chemically. The acid extraction of spent hops resulted in a yield of 2%, containing 59% of polysaccharides. The hop pectins under investigation had a relatively high molecular weight and an intrinsic viscosity comparable to that of commercially available apple and citrus pectins. The low degree of methyl esterification of these pectins implicates that they are mainly suitable for use in calcium gels. The degree of acetylation and the neutral sugar content were relatively high.

A high molecular weight fraction which contained arabinogalactan-proteins was shown to be present in the hop pectin extract after preparative size-exclusion chromatography. Additionally, a fraction with a lower molecular weight was present containing mainly homogalacturonans. The arabinogalactans in the high molecular weight population consisted of (1→3)- and (1→3,6)-linked galactans highly branched with arabinose and galactose side-chains. The protein part of the arabinogalactan-protein (13%) was found to be rich in cystein, threonin, serinin, alanin, and hydroxyprolin. The molecular weight distribution of the hop pectin after degradation with the enzymes endopolygalacturonase plus pectin methyl esterase suggested that the arabinogalactan-protein present in the hop pectin extract was linked to the pectin and that the arabinogalactan-protein itself had a fairly low molecular weight.     

多效唑（MET）对啤酒花试管苗生长和移栽的影响

在培养基中加入0.1-0.2mg/L浓度的多效唑（MET）,啤酒花试管苗植株矮壮,单株生根数量增加、移栽成活率提高13％。0．5－2．0mg/L时,试管苗基部愈伤组织增多,枝叶失绿,生长受到抑制。初步发现多将唑对啤酒花试管苗的效力与葡萄糖用量呈正相关。     

Humulus lupulus L. cv. Cascade grown in Northern Italy: morphological and phytochemical characterization

Abstract

Several aroma hops (Humulus lupulus L.) were recently introduced in Northern Italy as a small-scale production of excellence. In this preliminary study, the American cultivar Cascade was investigated in a combined morphological and phytochemical survey. Morphological investigation on trichome structure, density and distribution was performed by scanning electron microscopy and light microscopy. Essential oil composition, α/β-acid and polyphenol profiles over 3 years were determined by GC-MS and HPLC analyses. Two types of non-glandular (simple and cystolithic) and glandular (peltate and bulbous) trichomes were observed on leaves and female inflorescences. The peltate trichomes resulted as the main sites of terpene production and accumulation. The essential oil profiles showed myrcene, β-caryophyllene, (E)-β-farnesene and humulene epoxide II as the dominant compounds over the three collection times, although with different relative abundances. The presence of two exclusive compounds, γ-muurolene and trans-γ-cadinene, characterized the investigated cv. Cascade, potentially enhancing herbal, woody and spicy aroma traits of this cultivation in Northern Italy. The bitter acid composition showed quantitative values consistent with literature data only for the second and third monitoring year. Qualitative differences in polyphenol content were also recorded, for the presence of quercetin-3-O-malonylglucoside and kaempferol-3-O-rutinoside, which may characterize this peculiar Italian cultivation.     

Response of Neoseiulus fallacis Garmen and Galendromus occidentalis Nesbitt (Acari: Phytoseiidae) to Tetranychus urticae Koch (Acari: Tetranychidae)-Damaged Hop Humulus lupulus (L.) (Urticales: Cannabaceae)

Abstract 1 The response of Neoseiulus fallacis Garmen and Galendromus occidentalis (Acari: Phytoseiidae) to Tetranychus urticae Koch (Acari: Tetranychidae)‐damaged and undamaged hop, Humulus lupulus (L.), plants was tested using a Y‐tube olfactometer. 2 Neoseiulus fallacis but not G. occidentalis was attracted to volatiles from T. urticae‐damaged hop plants when paired with undamaged plants. 3 The response of N. fallacis to these volatiles was stronger for plants severed at the soil surface than for intact plants. 4 There was no difference in the response of N. fallacis to severed or intact hop plants that had no spider mite damage, indicating that artificial wounding by severing alone does not elicit the production of attractive volatiles detectable to N. fallacis. These results are consistent with the existence of cross‐talk between signalling pathways initiated by feeding damage and artificial wounding that result in elevated levels of predator‐attracting volatiles.     

Application of diffusion‐edited and solvent suppression 1H‐NMR to the direct analysis of markers in valerian‐hop liquid herbal products

Introduction – The rising trend to consume herbal products for the treatment and/or prevention of minor ailments together with their chemical and pharmacological complexity means there is an urgent need to develop new approaches to their quality and stability. Objectives – This work looks at the application of one‐dimensional diffusion‐edited ¹H‐NMR spectroscopy (1D DOSY) and ¹H‐NMR with suppression of the ethanol and water signals to the characterisation of quality and stability markers in multi‐component herbal medicines/food supplements. Material and Methods – The experiments were performed with commercial tinctures of Valeriana officinalis L. (valerian), expired and non‐expired, as well as its combination with Hummulus lupulus L. (hops), which is one of the most popular blends of relaxant herbs. These techniques did not require purification or evaporation of components for the qualitative analysis of the mixture, but only the addition of D₂O and TSP. Results – The best diagnostic signals were found at δ 7 ppm (H‐11, valerenic acid), δ 4.2 ppm (H‐1, hydroxyvalerenic acid) and δ 1.5‐1.8 ppm (methyl groups in prenylated moieties, α‐acids/prenylated flavones). Conclusion – This work concludes on the potential value of 1D DOSY ¹H‐NMR to provide additional assurance of quality in complex natural mixtures. Copyright © 2016 John Wiley & Sons, Ltd.