Hanshu Ding*, Feng Xu

Department of Protein Chemistry, Novozymes Inc., Davis, California, USA Corresponding author email: hdin@novozymes. com; fxu@novozymes. com

OUTLINE

Industrial Phytochemicals 353

Overview 353

Colorants (Pigment, Dye, and Ink) 355

Dietary, Nutraceutical, Food or Feed Additives 356

Bioactive or Pharmaceutical Phytochemicals 356

Phytochemicals for Personal Care or Other Uses 358

Production of Industrial Phytochemicals 358

Extraction and Isolation from Specific Plants 358

Coproduction from Processing (Biorefinery) of Staple Crops 358

Production from Cultured Plant Cells 360

Production from Microbial Fermentation 360

Production from Algae via Aquaculture 361

Coproduction of Phytochemicals in Bioenergy

Processes 361

Coproduction from Starch — or Sugar-Based Bioenergy

Processes 361

Coproduction from Plant Oil-Based Bioenergy Processes 361

Coproduction from Lignocellulose (Biomass)-Based Bioenergy Processes 362

Coproduction from Bio-Oil, Syn-Gas, or Algal Bioenergy Processes 362

Colocation of Fermentative Phytochemicals Production with Bioenergy Processes 363

Utilization of Phytochemical Production By-Products for Bioenergy 363

References 363

INDUSTRIAL PHYTOCHEMICALS

Overview

Phytochemicals may be defined as chemicals derived or derivable from plants. Phytochemical sources may include not only unprocessed trees, crops, grains, fruits, nuts, vegetables and legumes, but also processed plant-derived materials such as starch, sugars and oil. Phytochemicals of commercial interest have demon­strated or suspected utilities for dietary, bioactive, therapeutic and industrial technical uses. Based on chemical structure, major groups of phytochemicals include (Figure 20.1) the following:

1. Carotenoids (carotenes or xanthophylls, e. g. a- or b-carotene, b-cryptoxanthin, lycopene, lutein, and zeaxanthin) and homologs (e. g. crocin)

2. Flavonoids (anthocyanins, flavanols, flavanones, flavonols, flavones, and isoflavones), and condensed tannin and xanthones

3. Other phenolic/quinonics (e. g. tocopherols, curcumin, resveratrol, carminic acids, alizarin, purpurin, lignans (dimeric phenyl propanoid), tannic acid, thymol, and capsaicin)

4. Alkaloids (e. g. caffeine, nicotine, quinine, vinblastine, and opiates) and other N-contained compounds (e. g. chlorophylls, flavins, betalain, indole-3-carbinol, galanthamine, and indigo)

Bioenergy Research: Advances and Applications http://dx. doi. org/10.1016/B978-0-444-59561-4.00020-6

FIGURE 20.1 Major groups of phytochemicals. Source: Drawings from ChemSpider and Sigmaaldrich. com are used in this and Figures 20.2—20.4. (For color version of this figure, the reader is referred to the online version of this book.)

5. S-contained compounds (e. g. g-glutamylcysteines, (allyl)cysteine sulfoxides, and isothiocyanates)

6. Phytosterols (e. g. sitosterol, stigmasterol, campesterol or 4-desmethyl sterols), saponin, digoxin, and other terpenoids (e. g. artemisinin, paclitaxel, and camphor)

7. Polymeric carbohydrates (e. g. cellulose, hemicellulose, b-glucan, pectin, gum, inulin, and resistance starch), oligosaccharides (e. g. oligofructose), and lignin

8. Lipids and volatiles such as lecithin, essential oils, and menthol

9. Proteases such as bromelain and papain, as well as protease inhibitors

It is reported that about 8000 phenolics (including ~4000 flavonoids), ~ 20,000 terpenoids, ~ 10,000 alka­loids, ~700 carotenoids, and ~250 phytosterols are known, and many have been shown with various

functions (Watkins and Chaudhry, 2013). Comprehen­sive studies have been carried out on phytochemicals from whole grains, fruits and vegetables (Liu, 2007; Piironen et al., 2000).

Phytochemicals may have different physical, chemical and biological properties, thus suitable for different industrial usages as colorants (pigment, dye, and ink), dietary food/feed additives or nutraceuticals, bioactive/ pharmaceutical ingredients, personal care (cosmetic, perfume) agents, or other useful materials. For instance, carotenoids, polyphenols, flavonoids and tocopherols may be used as antioxidant or antiinflammatory agents; alkaloids may be used as analgesic, antispasmodic or mental disorder-relieving agents; and carotenoids may be used as coloring agents.

Phytochemicals are of great interest for industrial, technical, household, health care or other uses, due to their renewability, performance, safety, environment — friendliness, and diversity in structure and activity. The use of phytochemicals started at the dawn of humanity, has contributed to the civilization, and is reemerging along with the advancement of bioenergy, biobased chemicals, and biorefinery.

Colorants (Pigment, Dye, and Ink)

Many phytochemicals are chromophoric, reflecting lights that cover the visible wavelength range. Ubiqui­tous phytocolorants include chlorophyll (green) and carotenoids (yellow-red) from leaves and stems of plants, while more specific colorants may exist in flowers, fruits or other parts of plants (Figure 20.2). Colorants could also be produced from algae, bacteria, or fungi including the saprophytes (Gupta et al., 2011; Rymbai et al., 2011; Matthews and Wurtzel, 2007; Mortensen, 2006; Dufosse, 2006; Mapari et al., 2005; Adrio and Demain, 2003; Sengupta, 2003).

Colorants are used mostly as dyestuff, food/feed ad­ditives or cosmetic agents. Traditional plant-extracted/ derived dyestuffs include saffron from saffron crocus plant, madder (red) from madder plants (Rubia), and indigo from Indigofera plants (at present chemical synthesis from fossil feedstocks provides most indigo dyes, although microbial route has been explored).

Commonly used food or feed colorants derived from plants include extracts or isolates from specifically grown plants, such as bixin and norbixin (annatto), beta — lains (including betanin), curcumin (turmeric), crocin

(saffron), and carotenoids (including b-carotene, lutein, canthaxanthin and astaxanthin). The colorants also include extracts or isolates from agricultural residues, such as anthocyanins and carotenoids. The colorants may be produced microbially, as exemplified by the carotenoids such as astaxanthin, b-carotene, lutein, and riboflavin (Chattopadhyay et al., 2008).

Some plant-derived colorants, such as lutein and b-carotene, are used as cosmetic agents. In addition to plants, algae also produce colorants of industrial inter­est. For instance, phycobiliproteins have uses as natural dyes, cosmetic agents or food colorants (in addition to health applications) (Spolaore et al., 2006). Phytocolor­ants may also be used for thermoplastic (van den Oever et al., 2004).