Effect of fermentation processing on the flavor of Baijiu

Among these, the strong-aroma type accounts for about 70% of total liquor. 324 production. Fenjiu in Shanxi province is a typical light-aroma Baijiu t...
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Effect of fermentation processing on the flavor of Baijiu Huilin Liu, and Baoguo Sun J. Agric. Food Chem., Just Accepted Manuscript • DOI: 10.1021/acs.jafc.8b00692 • Publication Date (Web): 11 May 2018 Downloaded from http://pubs.acs.org on May 12, 2018

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Journal of Agricultural and Food Chemistry

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Effect of fermentation processing on the flavor of Baijiu

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Huilin Liu, Baoguo Sun*

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Beijing Advanced Innovation Center for Food Nutrition and Human Health,

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Beijing Key Laboratory of Flavor Chemistry, Beijing Technology and Business

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University, No. 11, Fucheng Road, Beijing, 100048, China.

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*Corresponding Author: Tel.: (+86)10-68984768; Fax: 86-10-68984768; E-mail:

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[email protected].

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Abstract

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Baijiu, otherwise known as the national liquor of China, is a well-known distilled

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spirit that has been produced for over 2,000 years. Baijiu is a clear and transparent

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fermented alcoholic beverage containing more than 1,870 volatile compounds,

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including esters, alcohols, aromatics, ketones, heterocycles, nitrogenous compounds,

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acids, aldehydes, terpenes, sulfur compounds, acetals, and lactones. This perspective

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describes the Baijiu production process, summarizes recent progress in the

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development and study of Baijiu flavor chemistry, discusses the effect of fermentation

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processing on Baijiu flavor, and presents novel development trends in the Baijiu

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industry in the dual directions of flavor and health. Furthermore, the direction of

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research and development for modernization in the Baijiu industry is discussed and

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proposed.

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Keywords: Baijiu, Chinese liquor, Fermentation, Flavor chemistry, Developments

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1. Introduction

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Baijiu, an ancient Chinese liquor, is the national liquor of China and possesses a

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unique position in traditional Chinese culture. Chinese liquor-making has a 9,000-year

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history, with reports as early as seven millennia before Christ (B.C.).1 Baijiu is one of

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the oldest distillates in the world, with a 2,000-year history dating from the Western

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Han dynasty (202 B.C. to 8 A.D.) according to the record of a distiller from the tomb

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of Haihunhou. Baijiu is a clear and transparent fermented alcoholic beverage with a

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high ethanol content ranging from 38 to 65 vol.%.2 Baijiu is also the most consumed

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spirit globally, with over 13 billion liters consumed in 2016, representing a market

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value of approximately $ 97.4 billion. Therefore, Baijiu constitutes a major part of the

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Chinese food industry.

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Baijiu is a world-renowned distilled spirit, alongside brandy, whiskey, vodka, gin,

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and rum. The raw material, production process, composition, and taste of Baijiu are

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very different from those of other famous distilled spirits. Baijiu is normally prepared

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from sorghum alone or a mixture of corn, rice, wheat, peas, millet, and sorghum. For

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Baijiu production, Jiuqu, known as the foundation of Baijiu, is often used as a

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fermentation starter,3 and is mixed with grains to saccharify and ferment

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simultaneously, which produces ethanol and flavor compounds. The fermented

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mixture is then distilled under solid-state conditions to produce fresh Baijiu liquor.

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Baijiu is rich in many flavor components, including organic acids (such as acetic acid,

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lactic acid, malic acid, tartaric acid, and linoleic acid), esters (such as ethyl acetate,

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ethyl lactate, and ethyl hexanoate), lactones, phenols, heterocycles, terpenes, and

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aromatic compounds.4 Furthermore, Baijiu contains potential functional components,

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such as amino acids5 and peptides6, which are beneficial to humans. A tetrapeptide

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(Ala-Lys-Arg-Ala) and tripeptide (Pro-His-Pro) have been successfully identified in

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sesame

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2,2'-azobis(2-methyl-propanimidamidine) dihydrochloride-induced oxidative stress in

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HepG2 cells and antihypertensive activity, respectively.6,7 The first economic history

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book from China, ‘Shi-Huo-Zhi’ by Ban Gu, reported that “Jiu, an alcoholic beverage,

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has long been used as a base for traditional Chinese medicine” since the Eastern Han

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dynasty, which is a good summary of the application of Baijiu in medicine and

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healthcare.8 In the Qiaocheng district of Bozhou, a Gujinggong Baijiu production

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region of China, the longevity of about 500 people that lived for more than 100 years

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has been partly attributed to the habit of drinking a little Baijiu daily. In recent years,

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Bo Xi et al. have shown that light and moderate alcohol intake might have a

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protective effect on all-cause and cardiovascular disease-specific mortality in US

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adults.9 Therefore, drinking Baijiu in moderation might be beneficial to human

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health.10

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2. Baijiu Production

flavor-type

Baijiu

and

showed

preventive

effects

against

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The production of Baijiu is different from that of other distilled liquors because it

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combines the two distinctive processes of fermentation and distillation. During

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fermentation, conversions of starch to sugar and sugar to alcohol take place

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simultaneously. In the production of other distilled liquors, such as whisky and vodka,

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the above two reactions occur stepwise, or conversion of sugar to alcohol takes place

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alone, such as in rum production. Furthermore, most distillation processing is

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performed in the solid state during Baijiu production, for which a special device,

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called the Zeng (Fig. 1), is often used. The Zeng is a conical distiller (approximate

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dimensions: Top diameter, 2 m; bottom diameter, 1.8 m; and height, 1 m) that is

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widely used for distillation. The Zeng is uniquely designed according to the

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characteristics of solid-state fermentation, making it different from other distillation

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units. With scientific advances, the Zeng material has been changed from wood to

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reinforced concrete or stainless steel, and the cooler has been changed from Tianguo

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to straight to improve the cooling efficiency. However, the basic operation of artificial

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labor remains unchanged, with continuous feeding and discharging still not widely

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applied. The Zeng is a special steaming tower in which, under constant heating

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conditions, the alcohol concentration of each layer is also constant. The concentration

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of volatile components decreases layer by layer in the lower section and increases

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layer by layer in the upper section. These volatile components are obtained from t

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alcohol and aroma compounds in the fermented grains of by vaporization,

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condensation, and vaporization again, to achieve multicomponent concentration and

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extraction.

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The general scheme for traditional processing in Baijiu production is shown in

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Fig. 1. Typically, the raw material is mixed uniformly with whole or powdered grains

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before adding hot water. Cooking the starch granules in hot water causes them to

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further absorb, expand, rupture, and gelatinize. Meanwhile, the raw materials are

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sterilized, and some adverse volatile components are eliminated, under high

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temperature. When the temperature is 50–60 °C, the amylase in the raw material

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decomposes starch into dextrin and sugar. When the whole raw material is cooked,

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limited sugar generated by saccharification, but when the raw material is cooked after

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grinding, more sugar is generated. Some glucose will be converted to fructose and

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other ketones. Hexoses, such as glucose and fructose, can be dehydrated to produce 5-

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hydroxymethyl furfural during high-pressure cooking, which then further decomposes

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to a keto acid and formic acid. This reaction process is irreversible and proceeds

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according to the first-order kinetic reaction formula. The mixed grains are then

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steamed with fermented grains and husks to prepare fresh liquor, also called base

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liquor. Distillation is the key step in improving Baijiu flavor. The distillation

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efficiency depends on the steam flow rate, distillation speed, water content, and

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porosity of mixed grains. The Baijiu is then stored and aged in a pottery or

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stainless-steel vessel for months or years depending on the desired final product

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quality. Finally, the stored liquor is blended with water to reduce the alcohol content

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before bottling for sale. A repeated-batch fermentation process is used for

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strong-aroma Baijiu, as denoted by the red square in Fig. 1, where the distilled grains

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are cooled to about 20 °C with fast-air cooling before Jiuqu is added and the mixture

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is placed in a fermentation pit to spontaneously ferment for about 1–3 months at

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28–30 °C. The fermentation pit is a special container (approximate dimensions:

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Length, 3.4 m; width, 1.8 m; and depth, 2.0 m) that is widely used for solid-state

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fermentation. The fermented grains at the bottom of fermentation pit (~1/4, v/v) are

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then distilled to obtain the spirit and discarded, with the same volume of fresh raw

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material added to repeat the batch fermentation. These distilled grains are also called

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the vinasse, which is not used further in Baijiu production, but taken as an important

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source of feed for pigs, cattle, poultry, and others. The process of light-aroma Baijiu

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production includes only two fermentation processes, as denoted by the blue square in

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Fig. 1, where the steamed raw material with Jiuqu is added to a ground cylinder for

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the first fermentation of about one month, then the fermented grains are steamed to

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produce fresh liquor before the distilled grains, with new Jiuqu added, are fermented

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again for about one month. After the second fermentation, these distilled grains

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comprise the vinasse.

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Traditional Baijiu production methods have existed for thousands of years and

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mainly rely on the operation skill and experience of individuals. In recent years, some

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developments in modern biotechnology, automation, and electronic information

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technology have been applied in Baijiu production to improve traditional processing.

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As a result, semi-mechanized processes are widely used in Baijiu production by large

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and medium-sized enterprises to reduce labor intensity, improve the quality and flavor

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of Baijiu, and reduce manual labor. However, this mode of production still faces a

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lack of control and standardization. Some enterprises have attempted to use fully

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mechanized processing for Baijiu production, but this impacts the quality and flavor

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of the resultant Baijiu. However, the development of Baijiu processing technology is

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trending

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simultaneously, to ensure the quality and flavor of Baijiu.

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3. Fermentation Processing of Baijiu

towards

full-mechanization,

automation,

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Sorghum is the main raw material used in Baijiu fermentation and contains starch

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(42.07–68.12%), protein (10.3–15.6%), lipids (3.6–5.2%), water (11.1–13.4%), fiber

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(1.5–2.7%), and ash (1.6–3.1%). Starch is changed into glucose by saccharification

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with Clostridium butyricum or amylases in fermented grains. Glucose is degraded to

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pyruvic acid via fructose 1,6-biphosphate fructose in the Embden–Meyerhof–Parnas

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(EMP) pathway by reaction with Saccharomyces cerevisiae. Pyruvic acid was

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converted into acetaldehyde by the removal of a carbon dioxide molecule in a reaction

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with decarboxylase. Acetaldehyde was then transformed into alcohol by reduction

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with ethanol dehydrogenase. Acids formation result from oxidation during the

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fermentation process. Ethanol forms acetaldehyde by oxidation and is further oxidized

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to acetic acid. At room temperature, lower fatty acids react with ethanol to form esters

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through enzyme catalysis. As esterification is a reversible chemical reaction, when the

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highest esterification rate is reached, the esters will decompose into alcohols and acids,

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which plays a decisive role in the formation of Baijiu flavor. Meanwhile, proteins in

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the raw materials are hydrolyzed into peptides and amino acids by protease catalysis.

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The aromatic components produced by fermentation mainly originate from the raw

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material, microorganisms, intermediates, or certain amino acids and tannins from

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sorghum.

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3.1 Fermentation types

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The main fermentation process for Baijiu, involving simultaneous saccharification

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and spontaneous fermentation in the solid state, is responsible for its rich flavor and

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good taste. This special fermentation process is usually performed in an underground

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fermentation pit for 1–3 months (strong-aroma Baijiu), while some Baijiu processes

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use stacking fermentation above ground before underground fermentation, such as

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Maotai and sesame-aroma Baijiu. The pit mud in the fermentation pit, otherwise

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known as microbial gold, is a complex ecosystem that hosts diverse microbial

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communities, including bacteria, archaea, and fungi, which contribute to the

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production of characteristic flavor compounds, such as ethyl caproate.11 High

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diversity indices of about 16 phyla and 105 genera have been found in pit mud used to

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make Luzhou Laojiao Baijiu.12 The fermentation of light-aroma Baijiu is performed in

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ground cylinders that do not contain pit mud. Repeated-batch fermentation is a

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complex process, as shown in Fig. 1. According to the different fermentation methods,

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there are three main types of fermentation used in Baijiu production, namely

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solid-state fermentation, semi-solid-state fermentation, and liquid-state fermentation.

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Solid-state fermentation technology is commonly used to produce most

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well-known Baijiu beverages with different flavors and characteristics, in which

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microbial cultures are grown on a solid matrix.13 Furthermore, solid-state

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fermentation technology can easily provide Baijiu with acceptable flavors and tastes,

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and has many advantages, including higher fermentation productivity, higher

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end-concentration of products, and higher product stability. However, solid-state

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fermentation technology has some problems, such as low mechanization, high costs,

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and long fermentation times, which result in low production efficiency.

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Semi-solid-state fermentation is used to prepare Baijiu with rice and chi aromas in

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Guangxi and Guangdong provinces of China. This process uses rice as the raw

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material, and Jiuqu as the saccharification and fermentation agents, which are soaked

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in a distillation kettle or altar to achieve semi-solid-state fermentation.14

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Liquid-state fermentation generally uses corn as the raw material to produce

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Baijiu, with all processes performed in the liquid state,15 including saccharification,

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fermentation, distillation, and blending, to give a high production efficiency with

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simple operation and low material consumption, making it easier to achieve full

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automation. However, this process produces fewer flavor components, leading to a

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lower quality, because the only raw material, corn, is fermented with pure species.

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Liquid fermentation is an important direction for the development of Baijiu

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production, but the problem of poor flavor compounds must be solved.

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3.2 Fermentation starters

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Fermentation starters are another major factor affecting fermentation and,

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consequently, Baijiu flavor and taste. Jiuqu contains a variety of microorganisms and

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enzymes that are essential to Baijiu production as saccharification, fermentation, and

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aroma-producing agents. Fermentation starters are divided into Daqu, Xiaoqu, Fuqu,

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and other Jiuqu, according to the preparation process.

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Daqu is one of the oldest and most widely used starters in China, and uses barley,

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wheat, or peas as raw materials. Under certain temperature and humidity conditions,

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Daqu can be formed into a brick shape by adding water, stacking, crushing, stirring,

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pressing, and cultivating in a Qu-house, followed by turning, and storage. Daqu is a

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naturally occurring microbiota in which the main microorganisms are molds, yeasts,

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bacteria, and actinomycetes, such as Mucor racemosus, Aspergillus niger,

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Thermomyces lanuginosus, Candida, Saccharomyces cerevisiae, Bacillus subtilis,

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lactic acid, and acetic acid bacteria.16 Daqu is divided into high-temperature,

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medium-temperature, and low-temperature Daqu according to the cultivation

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temperature. High-temperature Daqu is cultured at 60–70 °C and mainly used for

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sauce-aroma Baijiu production. The main flavor compounds in high-temperature

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Daqu include tetramethylpyrazine, guaiacol, phenylethanol, propanoic acid,

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1,3-butanediol, methyl ester, and acetic acid.17,18 However, high-temperature Daqu

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has a lower capacity for saccharification, liquefaction, and fermentation than

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low-temperature Daqu. Medium-temperature Daqu is formed at 50–60 °C and mainly

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used for strong-aroma Baijiu production. It can be used to improve Baijiu flavor by

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imbuing a more rich and full taste, and by producing more caproic acid and ethyl

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caproate. The main flavor compounds in medium-temperature Daqu include

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tetradecanoic acid ethyl ester, guaiacol, pyrazines, phenylethyl alcohol, and

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caryophyllene.17,19 Low-temperature Daqu is heated to no more than 50 °C and

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mainly used for light-aroma Baijiu production. Microorganisms are abundant in

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low-temperature Daqu, resulting in a better fermentation capacity and higher yields of

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Baijiu. A light flavor and pure taste are formed due to the large amounts of acetic acid,

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lactic acid, and alcohol compounds, in addition to, typically, hexyl acetate, ethyl

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acetate, phenylethyl alcohol, ethyl alcohol, hexanal, (E)-2-octenal, (Z)-2-octen-1-ol,

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nonanoic acid, and pyrazines.16,17

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Xiaoqu, which is widely used in the south of China, is another naturally

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occurring microbiota. However, Xiaoqu is quite different from Daqu, and mainly uses

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rice with some herbs or clay as the raw materials. The main microorganisms in

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Xiaoqu are molds and yeasts, especially Rhizopus sp., Rhizopus oryzae, Rhizopus

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peka, and Saccharomyces cerevisiae. The light flavor is mild with rice, herbal, and

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fragrance aromas. The main flavor compounds include acetic acid, ethyl acetate,

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phenylethyl alcohol, and pyrazines.17,20 Xiaoqu produces a higher yield than Daqu.

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Fuqu is another important fermentation starter with short production, excellent

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saccharification and fermentation capacity, and high utilization.21 Fuqu uses bran as

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the raw material, which is more economical than grains. The main microorganisms in

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Fuqu are molds, such as Rhizopus oryzae and aspergillus. These microorganisms are

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inoculated into the culture medium by artificial inoculation under optimized

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conditions.

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Others microbial enzymes, such as cellulase, amylase, glucoamylase, pectinase,

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and protease, in combination with Daqu, Xiaoqu, and Fuqu can effectively improve

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the liquor fermentation yield, which saves labor and energy.

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Further studies have focused more on the interactions of good and pure strains as

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saccharification and fermentation agents for Baijiu combined with traditional Daqu,

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Xiaoqu, Fuqu, and pure cultures of multiple strains and commercial microbial

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enzymes or active dry yeast. This can compensate for flavor compound deficiencies in

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fermentations using a single strain. Meanwhile, new kinds of microbial enzymes or

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active dry yeast are needed for further research and development, and to explore new

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full-enzymatic brewing processes. Furthermore, Jiuqu production is needed for

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mechanization and automation with modern microbiological and molecular biology

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technology.

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3.3 Raw materials

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The raw materials for Baijiu fermentation are mainly prepared from sorghum

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alone or a mixture of corn, rice, wheat, peas, millet, and sorghum.22 The flavor of

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Baiju is strongly influenced by its raw materials, with large differences noted when

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using different types of raw materials, or the same raw materials from different

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regions. In general, sorghum is widely used as the raw material in Baijiu fermentation

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to produce fragrance flavor and high liquor yields, and is well suited to Baijiu

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brewing owing to its nutritional composition and related physical properties.23

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Sorghum is rich in inorganic elements and vitamins, which provides a foundation for

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the good growth and reproduction of microorganisms. Sorghum also contains tannins,

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which can be transformed into aromatic substances, such as syringic acid, to give a

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special aroma to Baijiu. Rice contains less fat and cellulose than sorghum, which is

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too sticky to ferment easily after cooking, and has a large ethyl hexanoate content that

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produces a soft sweet flavor and clean aftertaste.24 Corn contains more phytic acid,

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which is decomposed into inositol and phosphoric acid during fermentation. Inositol

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produces the sweet flavor in Baijiu. Phosphoric acid can promote the production of

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glycerol in Baijiu to give the liquor a sweet flavor. Owing to their high protein content,

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peas are not a good raw material for Baijiu production. Peas are rich in vanillin and

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other phenolic compounds, which may contribute to the Baijiu aroma.

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The fermentation raw materials need high contents of carbohydrates, and certain

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proteins and tannins, which are suitable for the absorption and utilization of

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microorganisms. The raw material should also be easy to store and have an easily

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controllable moisture content to prevent spoilage. However, this does not mean that

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all high-starch materials are suitable for Baijiu production, such as millet or

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buckwheat, which are in short supply. Multigrain brewing is complementary to Baijiu

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fermentation, and its use is a development trend in Baijiu production. Multigrain

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brewing requires that the various raw materials have reasonable ratios and

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relationships, and that the scientific production process is adapted.

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Fermentation is an important process for taking advantage of microorganisms

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from Jiuqu and the environment for Baijiu production, in which starches or

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carbohydrates, proteins or amino acids, and lipids are transformed into ethanol and

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different flavor components through a series of biochemical reactions. The different

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fermentation methods use different microorganisms and enzymes, which contribute to

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the delicate balance and functions of stability, quality, and productivity, resulting in

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different metabolites in the fermentation process, which produce different Baijiu

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flavors. Other new developments in the Baijiu industry are that solid-state

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fermentation

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fermentation needs to be transferred to ground fermentation, natural fermentation

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needs to artificial temperature control, and the control of large-scale mechanical

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equipment via automation and intelligentization will eventually replace manual labor.

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Traditional industrial techniques will be applied to achieve modernization, which

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could allow Baijiu to be exported and become a more famous distilled beverage

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globally due to high-quality, inexpensive, and high-yielding production.

requires

combination

with

liquid

fermentation,

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4. Baijiu Flavor

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Baijiu is differentiated from other liquors because of its distinctive flavor, taste,

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and production process. Flavor substances in Baijiu are endogenous, produced during

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Jiuqu production, saccharification, fermentation, distillation, and storage processes.

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Owing to the diversity of microorganisms and raw materials, Baijiu compositions can

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vary

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chromatography/time-of-flight mass spectrometry (GC×GC/TOFMS) to identify 528

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compounds in Maotai.25 Recently, Jin et al. reported more than 1,000 volatile

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compounds in Baijiu.17 New compounds continue to emerge with more advanced

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analytical techniques. We have listed and summarized all volatile flavor compounds

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reported between 1990 and 2017. These compounds have been identified by

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techniques

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chromatography-mass spectrometry (GC-MS), GC-olfactometry (GC-O), electronic

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noses, and colorimetric artificial noses. A total of 1,874 kinds of volatile flavor

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compounds were identified in Baijiu during this period, including 506 esters, 235

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alcohols, 166 aromatics, 140 ketones, 132 heterocyclic compounds (including 77

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furans), 129 nitrogenous compounds (including 74 pyrazines), 127 acids, 97

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aldehydes, 78 hydrocarbons, 76 terpenes, 73 sulfur compounds, 44 acetals, 18

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lactones, and 53 other compounds. We have listed and summarized odor thresholds of

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217 aroma compounds of Baijiu in Table S1. A total of 217 kinds of aroma

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compounds were identified in Baijiu, including 61 esters, 20 alcohols, 29 aldehydes,

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18 ketones, 23 acids, 11 pyrazines, 6 furans, 13 phenols, 11 aromatics, 15 sulfur

greatly.

In

including

2007,

Zhu

spectroscopy,

et

al.

gas

used

two-dimensional

chromatography

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gas

gas

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compounds, 4 lactones, and 6 other compounds. These different flavor compounds

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lead to special flavor types. Baijiu consists of four dominant aroma types, namely

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strong, light, sauce, and rice aromas, from which all others derive. At present, there

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are 12 types of representative aroma, including the above four aromas and feng, te,

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sesame, laobaigan, fuyu, herbal, chi, and mixed aromas, which are distributed in

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different provinces of China (Fig. 2). All Chinese regions produce Baijiu, especially

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Sichuan, Guizhou, Shandong, Jiangsu, Anhui, Shanxi, and Henan provinces, which

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comprise more than 90% of total Chinese liquor output.26 Owing to the diversity of

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microorganisms and raw materials, Baijiu compositions can vary greatly. These

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different flavor compounds lead to special flavor types. The representative aromas

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and characteristics of Baijiu are listed in Table 1, which provides an overview of these

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12 types of Baijiu. Typically, the concentration of ethyl hexanoate is higher than that

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of other aroma compounds in strong-aroma-type Baijiu, making it the main flavor

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compound. Similarly, ethyl acetate, ethyl lactate, ethyl acetate and β-phenethyl

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alcohol, and ethyl propionate are the main flavor compounds in light-aroma-type,

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Laobaigan-aroma-type, rice-aroma-type, and sesame-aroma-type Baijiu, respectively.

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Among these, the strong-aroma type accounts for about 70% of total liquor

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production. Fenjiu in Shanxi province is a typical light-aroma Baijiu that is also the

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original Chinese Baijiu, while Maotai, a famous spirit, is a sauce-aroma-type Baijiu.

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The flavor of Baijiu is complicated and can be affected by the fermentation,

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distillation, aging, blending processes, raw materials, Jiuqu, and the environmental

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conditions during production (Fig. 3). Therefore, the diversity in Baijiu flavor arises

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from slight changes in production processing. In recent years, researchers have

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focused on investigating the microorganisms and flavor active compounds, and

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improving Baijiu production processes using modern advanced analytical techniques

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to identify additional unknown compounds in Baijiu.

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Baijiu has been a favorite liquor in China for thousands of years, reflecting its

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cultural heritage and health benefits. We have focused on investigating Baijiu

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production, fermentation, and flavor chemistry to summarize the typical flavor types

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of Baijiu and compare fermentation methods, raw materials, fermentation starters,

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dominant microorganisms, main flavor compounds, and flavor characteristics (Table

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1). Baijiu contains various flavor compounds, most of which are beneficial to humans.

340

Therefore, development trends in Baijiu production should be directed by both flavor

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and health. Another important direction for the development of Baijiu research and

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production is the regulation of saccharification and fermentation processes, and

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improving the contents of characteristic flavor substances and key health factors

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produced by functional microorganisms.

345

AUTHOR INFORMATION

346

Corresponding Authors

347

*Tel.: (+86)10-68984768. Fax: 86-10-68984768. E-mail: [email protected].

348

Funding

349

This work was supported by the National Key R&D Program of China

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(2016YFD0400500), the Advisory Project of the academician of the Chinese

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Academy of Engineering (2018-XY-28), and the National Natural Science Foundation

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of China (No.31701567 and No.L1522022).

353

Notes

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The authors declare no competing financial interest.

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References

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(1) McGovern, P. E.; Zhang, J.; Tang, J.; Zhang, Z.; Hall, G. R.; Moreau, R. A.; Nuñez,

357

A.; Butrym, E. D.; Richards, M. P.; Wang, C.; Cheng, G.; Zhao, Z.; Wang, C.

358

Fermented beverages of pre- and proto-historic China. PNAS 2004, 101,

359

17593-17598.

360

(2) Han, Q.; Shi, J. L.; Zhu, J.; Lv, H. L.; Du, S. K. Enzymes extracted from apple

361

peels have activity in reducing higher alcohols in Chinese liquors. J. Agr. Food Chem.

362

2014, 62, 9529-9538.

363

(3) Zhu, Y.; Tramper, J. Koji-where East meets west in fermentation. Biotechnol. Adv.

364

2013, 31, 1448-1457.

365

(4) Fan, W. L.; Qian, M. C. Characterization of aroma compounds of Chinese

366

“Wuliangye” and “Jiannanchun” liquors by aroma extract dilution analysis. J. Agr.

367

Food Chem. 2006, 54, 2695-2704.

368

(5) Cui, L. Nutrition component of Chinese liquor and its benefit to human health.

369

Liquor Making 2008, 35, 15-18.

370

(6) Wu, J.; Sun, B.; Zhao, M.; Zheng, F.; Sun, J.; Sun, X.; Li, H.; Huang, M.

371

Discovery of a bioactive peptide, an angiotensin converting enzyme inhibitor in

372

Chinese Baijiu. J. Chinese Institute Food Sci. Technol. 2016, 16, (9), 14-20.

373

(7) Wu, J.; Huo, J.; Huang, M.; Zhao, M.; Luo, X.; Sun, B. Structural characterization

374

of a tetrapeptide from sesame flavor-type Baijiu and its preventive effects against

375

AAPH-induced oxidative stress in HepG2 cells. J. Agric. Food Chem. 2017, 65,

376

10495-10504.

ACS Paragon Plus Environment

Journal of Agricultural and Food Chemistry

377

(8) Huang, S. The first economic history of China—Shi-Huo-Zhi. China Economic

378

Press. 1991, 8, 204.

379

(9) Bo, X.; Veeranki, S. P.; Zhao, M.; Ma, C.; Yan, Y.; Mi, J. Relationship of alcohol

380

consumption to all-cause, cardiovascular, and cancer-related mortality in U.S. adults.

381

J. AM. Coll. Cardiol. 2017, 70, 913-922.

382

(10) Sun, B. G.; Li, H. H.; Hu, X. M.; Sun, J. Y.; Dong, W. The development trend of

383

healthy Baijiu. J. Chin. Inst. Food Sci. Tech. 2016, 8, 1-8.

384

(11) Liu, M.; Tang, Y.; Zhao, K.; Liu, Y.; Guo, X.; Ren, D.; Yao, W.; Tian, X.; Gu,

385

Y.; Yi, B.; Zhang, X. Determination of the fungal community of pit mud in

386

fermentation cellars for Chinese strong-flavor liquor, using DGGE and Illumina

387

MiSeq sequencing. Food Res. Int. 2017, 91, 80-87.

388

(12) Liu, M. K.; Tang, Y. M.; Guo, X. J.; Zhao, K.; Tian, X. H.; Liu, Y.; Yao, W. C.;

389

Deng, B.; Ren, D. Q.; Zhang, X. P. Deep sequencing reveals high bacterial 302

390

diversity and phylogenetic novelty in pit mud from Luzhou Laojiao cellars for

391

Chinese strong-flavor Baijiu. Food Res. Int. 2017, 102, 68-76.

392

(13) Barrios-Gonzalez, J. Solid-state fermentation: physiology of solid medium, its

393

molecular basis and applications. Proc. Biochem. 2012, 47, 175-185.

394

(14) Lu, Y.; Li, Y. J.; Huang, J.; Hu, Y.; Zhang, Z. Y. Classification, production

395

process and nutritional value of Chinese liquor. Agr. Eng. Technol. 2007, 1, 21-24.

396

(15) Zhang, H.; Chen, L.; Wang, J. F.; Wang, D. Y. Production techniques of liquid

397

state fermented baijiu. China Pet Chem. Standard Qual. 2013, 24, 82.

398

(16) Zheng, X. W.; Yan, Z.; Nout, M. J. R.; Smid, E. J.; Zwietering, M. H.; Boekhout,

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Page 21 of 33

Journal of Agricultural and Food Chemistry

399

T., Han, J. S.; Han, B. J. Microbiota dynamics related to environmental conditions

400

during the fermentative production of Fen-Daqu, a Chinese industrial fermentation

401

starter. Int. J. Food Microbio. 2014, 182, 57-62.

402

(17) Jin, G.; Zhu, Y.; Xu, Y. Mystery behind Chinese liquor fermentation. Trends

403

Food Sci. Tech. 2017, 63, 18-28.

404

(18) Wang, C. L.; Shi, D. J.; Gong, G. L. Microorganisms in Daqu: A starter culture

405

of Chinese maotai-flavor liquor. World J. Microb. Biotech. 2008, 24, 2183-2190.

406

(19) Wu, X. H.; Zheng, X. W.; Han, B. Z.; Vervoort, J.; Nout, M. J. R.

407

Characterization of Chinese liquor starter, “Daqu”, by flavor type with H-1

408

NMR-based nontargeted analysis. J. Agr. Food Chem. 2009, 57, 11354-11359.

409

(20) Gou, M.; Wang, H. Z.; Yuan, H. W.; Zhang, W. X.; Tang, Y. Q.; Kida, K.

410

Characterization of the microbial community in three types of fermentation starters

411

used for Chinese liquor production. J. Inst. Brewing 2015, 121, 620-627.

412

(21) Zhang, W.; Wu, Z. Y.; Zhang, Q. S.; Wang, R.; Li, H. Combination of newly

413

developed high quality Fuqu with traditional Daqu for Luzhou-flavor liquor brewing.

414

World J Microbiol. Biotechnol. 2009, 25, 1721-1726.

415

(22) Wu, Y.; Liu, S.; Fan, X.; Yang, J.; Jiang, W.; Wang, D.; Li, N. Analysis of

416

Aroma Components of Five Different Cooked Grains Used for Chinese Liquor

417

Production by GC-O-MS. Food Sci. 2016, 37, 94-98.

418

(23) Han, Y.; Song, L.; Liu, S.; Zou, N.; Li, Y.; Qin, Y.; Li, X.; Pan, C. Simultaneous

419

determination of 124 pesticide residues in Chinese liquor and liquor-making raw

420

materials (sorghum and rice hull) by rapid Multi-plug Filtration Cleanup and gas

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chromatography-tandem mass spectrometry. Food Chem. 2018, 241, 258-267.

422

(24) Bryant, R. J.; Mcclung, A. M. Volatile profiles of aromatic and non-aromatic rice

423

cultivars using SPME-GC-MS. Food Chem. 2011, 124, 501-513.

424

(25) Zhu, S.; Lu, X.; Ji, K.; Guo, K.; Li, Y.; Wu, C.; Xu, G. Characterization of flavor

425

compounds in Chinese liquor Moutai by comprehensive two-dimensional gas

426

chromatography/time-of-flight mass spectrometry. Anal. Chim. Acta 2007, 597,

427

340-348.

428

(26) Zheng, X. W.; Han, B. Z. Baijiu (白酒), Chinese liquor: History, classification

429

and manufacture. J. Ethnic Foods. 2016, 3, 19-25.

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FIGURE CAPTIONS

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Fig. 1. Traditional production processing of Baijiu. Raw material is mixed uniformly

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with whole or powdered grains before adding hot water. The mixed grains are then

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fermented and the husks are transferred to the Zeng for distillation. The fresh liquor is

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then stored and aged in a pottery or stainless-steel vessel. After aging for several years,

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the stored liquor is blended to obtain differently graded products.

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Fig. 2. Distribution of well-known Baijiu with different aromas.

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Fig. 3. Generalization of all factors influencing Baijiu flavor formation (raw materials,

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fermentation, and distillation develop the flavor of Baijiu; storage processing

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improves the flavor; and blending processing modifies the flavor).

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Table 1. Representative aromas and characteristics of Baijiu.

441 Represe ntative aroma

Fermentation methods

Raw materials

Fermentation starters

Dominant microorganisms

Main flavor compounds

Flavor characteristics

Strong aroma

Solid-state fermentation

Sorghum with or without glutinous rice, rice, wheat and corn

Mediumand Low-temperature Daqu

Solid-state fermentation

Sorghum

Low-temperature Daqu

Ethyl hexanoate, Ethyl acetate, Ethyl lactate, Ethyl butyrate, Ethyl valerate, Ethyl heptanoate, Hexanoic acid, Butanoic acid, Heptanoic acid, Furfural, Phenylethyl alcohol. Ethyl acetate, Ethyl lactate, Acetic acid, 2-Methylpropanoic acid, β-Damascenone, Terpenoids.

Fragrant flavor, soft mouthfeel, and long aftertaste.

Light aroma

Clostridium kluyveri, Burkholderia, Streptococcus, Lactobacillus, Lactobacillaceae, Saccharomyces cerevisiae, Saccharomycopsis fibuligera, Talaromyces Pichia kudriavzevii, Aspergillus, Rhizopus, Eurotium, Phanerochaete chrysosporium. Pichia, Saccharomyces cerevisiae, Saccharomycopsis, Issatchenkia, Hanseniaspora, Torulaspora, Amylomyces, Lactobacillus, Streptpcoccus, Pediococcus, Aerococcus, Bacillus, Acetobacter, Endomycopsis, Candida, Hansenula, Saccharomyces, Geotrichum, Rhizopus, Absidia, Mucor, Aspergillus, Penicillium, Monascus.

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Pure and mild flavor, mellow sweetness, and refreshing aftertaste.

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Sauce aroma

Stacking fermentation and Solid-state fermentation

Sorghum

High-temperatur e Daqu

Aspergillus, Candida, Cryptococcus, Halomonas, Thermomyces, Thermoascus, Paecilomyces variotii, Zygosaccharomyces bailii, Saccharomyces cerevisiae, Pichia membranifaciens, Schizosaccharomycespombe. Lactobacillus, Bacillus.

Rice aroma

Semi-solid-st ate fermentation

Rice

Xiaoqu

Rhizopus sp., Rhizopus oryzae, Rhizopus peka, Saccharomyces cerevisiae.

Feng aroma

Solid-state fermentation

Sorghum

High-temperatur e Daqu

Lactobacillus, Bacillus, Brevibacilus, sporosarcina, Saccharomyces cerevisiae.

Te aroma

Solid-state fermentation

Rice

Medium-tempera ture Daqu

Saccharomyces, Pichia, Galactomyces, Aspergillus, Brettanomyces, Cladosporium, Galactomyces, Thermoascus.

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Ethyl hexanoate, Hexanoic acid, 3-Methylbutanoic acid, 3-Methylbutanol, Tetramethylpyrazine, Ethyl 2-phenylacetate, 2-Phenylethyl acetate, Ethyl 3-phenylpropanoate, 4-Methylguaiacol, γ-Decalactone. β-Phenethyl alcohol, Ethyl acetate, Ethyl lactate, Ethyl benzenecarboxylate, Diethyl succinate. Ethyl acetate, Ethyl caproate, Isoamyl alcohol. More than 98% esters and alcohols among the total flavor compounds, especially Ethyl acetate and Ethyl caproate.

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Soy sauce, with a full-bodied long-lasting aroma.

Soft sweet flavor and clean aftertaste.

Sweet, mellow, and elegant aftertaste. Harmonious, strong, and light flavor.

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Sesame aroma

Solid-state fermentation

Sorghum, wheat and corn

High-temperatur e Daqu

Bacillus, Saccharomyces cerevisiae, Pantoea, Weissella, Lactobacillus, Rubellimicrobium, Halomonas, Thermoactinomyces, Laceyella, Pediococcus.

Laobaig an aroma

Solid-state fermentation, cylinder,

Sorghum

Medium-tempera ture Daqu

Saccharomyces cerevisiae, Acetobacter pasteurianus, Bacillus cereus, Weissella cibaria.

Fuyu aroma

Solid-state fermentation

Sorghum, rice, wheat, corn and Glutinous rice

Medium-tempera ture Daqu and Xiaoqu

Saccharomyces cerevisiae, Bacillaceae, Deinococcaceae, Microbacteriaceae, Micrococcaceae, Moraxellaceae, Nocardiaceae, Rhodobacteraceae, Xanthomonadaceae.

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Ethyl pentanoate, Ethyl hexanoate, 3-Methylbutanal, Methional, Ethyl butanoate, 3-Methyl-1-butanol, Hexanoic acid, Butanoic acid, Trimethyl pyrazine, 2-Acetyl furan, Ethyl furoate, Methionol. Esters, Alcohols, Aldehydes, Acids, Ketones, Hydrocarbons, Pyrazines, Aromatics, Phenolic compounds. Acids, Alcohols, Ethyl butanoate, Low content of ethyl lactate.

Combining fruity with sweaty, roasted sesame-like, and floral flavors.

Soft mellow characteristics and a rich mouthfeel.

Light, strong, and rice flavor traits.

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Herbal aroma

Solid-state fermentation

Sorghum

Daqu and Xiaoqu

Saccharomyces cerevisiae, Monascus, Rhizopus, Penicillium, Geotrichum candidum, actinomyces.

Chi aroma

Semi-solid-st ate fermentation

rice

Xiaoqu

Mucor, Rhizopus chinensis, Rhizopus oryzae, Surface yeasts, Saccharomyces cerevisiae, Candida utilis.

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Butyric acid, Ethyl hexanoate, Caproic acid, Dimethyl trisulfide, Ethyl butanoate, 2-Phenylethyl alcohol, 3-Methyl butyrate, 4-Methyl phenol, 4-Methyl guaiacol, Beta-damascenone, Ethyl pentanoate, (E,Z)-2,6-Nonadienal, Borneol, Fenchol. (E)-2-octenal, 2-Phenylethanol, 3-(Methylthio)-1-propano l (methionol), Diethyl 1,7-heptanedioate (diethyl pimelate), Diethyl 1,8-octanedioate (diethyl suberate), Diethyl 1,9-nonanedioate (diethyl azelate).

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Herb-like sour aroma.

with

Fermented soybean-like with clean aftertaste.

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Mixed aromas

Solid-state fermentation

Sorghum, wheat, barley, and peas

High-temperatur e Daqu

Bacillus subtilis, Bacillus velezensis, Bacillus amylo-liquefaciens, Bacillus licheniformis, Bacillus methylotrophicus, Saccharomycopsis fibuligera, Beauveria bassiana, Eurotium athecium, Eurotium amstelodami, Aspergillus versicolor, Thermoascus crustaceus, Mycocladus corymbiferus, Paecilomyces variotii.

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Tetramethylpyrazine, 2-Pentyl furan.

Between those of sauce aroma (Maotai) and strong aroma (Luzhou).

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