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Program Book - Master Brewers Association of the Americas

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O-12<br />

Investigations on <strong>the</strong> behavior <strong>of</strong> organic radicals in barley<br />

and malt during <strong>the</strong> malting and mashing process by electronspin-resonance<br />

spectroscopy<br />

FRANK-JUERGEN METHNER (1), Thomas Kunz (1), Naoyuki<br />

Kobayashi (2)<br />

(1) TU Berlin/VLB Berlin, Berlin, Germany; (2) Sapporo Brewery,<br />

Ltd., Shizuoka, Japan<br />

Barley, malt and spent grain as well as <strong>the</strong> malting and mashing<br />

process were investigated by using Electron-Spin-Resonance (ESR)<br />

spectroscopy. For solids a method using a new reference signal was<br />

applied. The ESR spectroscopy is a rapid method for detecting ions<br />

and organic radicals containing unpaired electrons. It can be used for<br />

liquid and solid samples. Besides liquid measurements, ESR-spectroscopy,<br />

using Mn 2+ as an internal standard, has been used in <strong>the</strong><br />

past to control <strong>the</strong> concentration <strong>of</strong> organic radicals in malt or green<br />

malt and <strong>the</strong>ir development during <strong>the</strong> malting process. The new<br />

reference signal is detectable directly besides that <strong>of</strong> organic radicals<br />

in <strong>the</strong> ESR spectrum and allows a better quantitative detection <strong>of</strong><br />

organic radical concentration. Influences on <strong>the</strong> sample also have an<br />

impact on <strong>the</strong> reference signal, because <strong>the</strong> substance responsible for<br />

signal generation is positioned next to <strong>the</strong> sample in <strong>the</strong> spectrometer.<br />

Based on this background, it is possible to analyze <strong>the</strong> radical<br />

concentration in barley, malt and spent grain quantitatively. Besides<br />

low temperature ESR-measurements (77 K) for <strong>the</strong> detection <strong>of</strong> typical<br />

metal ions in malt, <strong>the</strong> new reference signal has been used for <strong>the</strong><br />

investigation <strong>of</strong> organic radical concentration in different fractions<br />

<strong>of</strong> malt samples as well as <strong>the</strong> development <strong>of</strong> organic radicals during<br />

<strong>the</strong> mashing and malting process under different technological conditions,<br />

such as steeping degree, germination time, wi<strong>the</strong>ring and<br />

curing under different atmospheres like oxygen, nitrogen and CO 2 .<br />

The results show different concentrations dependant on certain malt<br />

fractions. The highest concentrations were located in husks, whereas<br />

<strong>the</strong> lowest were found in <strong>the</strong> endosperm. Therefore a correlation<br />

between extract yield and radical concentration in spent grain with<br />

respect to mass was achieved. It could be shown that mashing conditions<br />

also have an impact on <strong>the</strong> concentration <strong>of</strong> stable organic radicals,<br />

because <strong>the</strong>y are able to react partially with organic reactants<br />

during <strong>the</strong> process. Based on this background it is possible to use this<br />

method to investigate spent grain analysis via ESR to observe influences<br />

on mashing, e.g. <strong>the</strong> applied mashing process (temperature,<br />

time, rests) or <strong>the</strong> use <strong>of</strong> sonic waves. Wi<strong>the</strong>ring and kilning have a<br />

major influence on radical generation in malt depending on malting<br />

conditions. A strong increase in radical concentration during wi<strong>the</strong>ring<br />

and kilning shows high stress conditions and intensive oxidation<br />

reactions. Investigations on barley have shown that <strong>the</strong> concentration<br />

<strong>of</strong> organic radicals can vary strongly depending on environmental<br />

and storage conditions (humidity, temperature, drying).<br />

From 1975 to 1981, Frank-Juergen Methner studied brewing science<br />

at <strong>the</strong> Technical University <strong>of</strong> Berlin (TU). After <strong>the</strong>se studies, he<br />

began working as an operating supervisor at <strong>the</strong> Schlosser Brewery.<br />

From 1982 to 1986 he worked as a scientific assistant with teaching<br />

duties at <strong>the</strong> Research Institute for Brewing and Malting Technology<br />

<strong>of</strong> VLB in Berlin. His research projects and Ph.D. <strong>the</strong>sis, “Aroma<br />

Formation <strong>of</strong> Berliner Weissbier with Special Focus on Acids and Esters,”<br />

were additional tasks. For 18 years, starting in 1987, Methner<br />

held a leading position as a director at <strong>the</strong> Bitburg Brewery, Bitburg,<br />

Germany, with responsibilities in fields such as technology and quality<br />

management. Beginning with <strong>the</strong> winter semester 2004/2005, he<br />

took over <strong>the</strong> chair <strong>of</strong> brewing science at TU and is currently <strong>the</strong> head<br />

<strong>of</strong> <strong>the</strong> Research Institute <strong>of</strong> Technology for Brewing and Malting <strong>of</strong><br />

<strong>the</strong> Research and Teaching Institute for Brewing (VLB). Since 2005<br />

he has been vice-chair <strong>of</strong> <strong>the</strong> EBC Brewing Science Group.<br />

70<br />

Technical Session IV: Nutrition and Health<br />

Moderator: Charles Bamforth, University <strong>of</strong> California, Davis, CA<br />

Dr. Charlie Bamforth is chair <strong>of</strong> <strong>the</strong> Department <strong>of</strong> Food Science &<br />

Technology and Anheuser-Busch Endowed Pr<strong>of</strong>essor <strong>of</strong> Malting &<br />

Brewing Sciences at <strong>the</strong> University <strong>of</strong> California, Davis. He has been<br />

part <strong>of</strong> <strong>the</strong> brewing industry for almost 30 years. He formerly was<br />

<strong>the</strong> deputy director-general <strong>of</strong> Brewing Research International and<br />

research manager and quality assurance manager <strong>of</strong> Bass <strong>Brewers</strong>.<br />

He is a special pr<strong>of</strong>essor in <strong>the</strong> School <strong>of</strong> Biosciences at <strong>the</strong> University<br />

<strong>of</strong> Nottingham, England, and was previously visiting pr<strong>of</strong>essor <strong>of</strong><br />

brewing at Heriot-Watt University in Scotland. Charlie is a Fellow <strong>of</strong><br />

<strong>the</strong> Institute <strong>of</strong> Brewing & Distilling and <strong>of</strong> <strong>the</strong> Institute <strong>of</strong> Biology.<br />

Charlie is Editor-in-Chief <strong>of</strong> <strong>the</strong> Journal <strong>of</strong> <strong>the</strong> American Society <strong>of</strong><br />

Brewing Chemists and has published numerous papers, articles, and<br />

books on beer and brewing.<br />

O-13<br />

Hops and health<br />

MARTIN BIENDL (1)<br />

(1) Hopsteiner, Mainburg, Germany<br />

Hops has been declared <strong>the</strong> “German Medicinal Plant <strong>of</strong> <strong>the</strong><br />

Year 2007”. This award makes it obvious that hops is not just a<br />

raw material for beer production but is also a recognized natural<br />

medicinal product. Mankind presumably used hops as a healing<br />

plant for a long time before discovering during <strong>the</strong> Middle Ages that<br />

it has preservation properties as a beer ingredient. Since <strong>the</strong> early<br />

Middle Ages, use <strong>of</strong> hops in folk medicine has been documented.<br />

It served as a remedy for treating a variety <strong>of</strong> diseases, e.g. stomach<br />

complaints, ear infections or toothache. It is noteworthy that<br />

such uses <strong>of</strong> hops were known both in European and in Indian-<br />

Ayurvedic medicine and were also common in a large number<br />

<strong>of</strong> Native American tribes in North America at a time when no<br />

transfer <strong>of</strong> knowledge could have taken place between continents.<br />

Hops continued to be used for healing purposes for centuries.<br />

Today, it is mainly recommended for calming and to aid sleep. The<br />

effectiveness <strong>of</strong> hops is attributed to its many positive constituents,<br />

above all bitter substances and polyphenols. Especially in <strong>the</strong> last<br />

decade, pharmacological research into <strong>the</strong> positive health aspects<br />

<strong>of</strong> hops and hop constituents has been considerably stepped up.<br />

Accordingly, scientific investigations are ongoing worldwide. They<br />

are providing new information continuously that contributes to<br />

an understanding <strong>of</strong> medicinal properties that have been used for<br />

centuries. In <strong>the</strong> case <strong>of</strong> α-acids and β-acids, <strong>the</strong> best known hop<br />

bitter substances, manifold antibacterial, but also anti-inflammatory<br />

and even carcinostatic, properties have been discovered. Mixtures <strong>of</strong><br />

certain hop polyphenols have proved to be effective against bacteria<br />

that cause caries or allergies. The prenylflavonoids in hops seem<br />

to be particularly interesting. They are also classed as polyphenols<br />

but occur relatively rarely in <strong>the</strong> plant world. The best known is<br />

<strong>the</strong> prenylflavonoid xanthohumol, mainly because <strong>of</strong> its cancer<br />

preventive potential, which is <strong>of</strong> exceptional interest. Some <strong>of</strong><br />

<strong>the</strong>se hop constituents with proven positive effects are carried over<br />

unchanged into beer during brewing (e.g. rutin, <strong>the</strong> glycoside <strong>of</strong> <strong>the</strong><br />

potent anti-oxidant quercetin); o<strong>the</strong>rs are converted chemically (e.g.<br />

isomerizations <strong>of</strong> xanthohumol to isoxanthohumol or α-acids to isoα-acids).<br />

A multitude <strong>of</strong> positive effects has also been shown to be<br />

associated with <strong>the</strong>se isomerized compounds, e.g. isoxanthohumol<br />

is effective against osteoporosis and iso-α-acids against diabetes. All<br />

<strong>the</strong>se nutritionally valuable beer ingredients originating from hops<br />

as a brewing raw material promote <strong>the</strong> image <strong>of</strong> beer and provide<br />

some convincing arguments in <strong>the</strong> discussion about beer and health.

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