JFS Special Issue: 75 Years of Advancing Food Science, and Preparing for the Next 75

Byung Hee Kim and Casimir C. Akoh

Abstract: Structured lipids (SLs) are lipids that have been chemically or enzymatically modified from their natural biosynthetic form. Because SLs are made to possess desired nutritional, physicochemical, or textural properties for various applications in the food industry, many research activities have been aimed at their commercialization. The production of SLs by enzymatic procedures has a great potential in the future market because of the specificity of lipases and phospholipases used as the biocatalysts. The aim of this review is to provide concise information on the recent research trends on the enzymatic synthesis of SLs of commercial interest, such as medium- and long-chain triacylglycerols, human milk fat substitutes, cocoa butter equivalents, trans-free or low-trans plastic fats (such as margarines and shortenings), low-calorie fats/oils, health-beneficial fatty acid-rich fats/oils, mono- or diacylglycerols, and structurally modified phospholipids. This limited review covers 108 research articles published between 2010 and 2014 which were searched in Web of Science. Keywords: enzymatic reaction, lipase, phospholipase, structured lipids

Introduction Structured lipids (SLs) are lipids that have been modified from their natural biosynthetic form (Akoh and Kim 2008). The scope of “lipids” includes acylglycerols, such as triacylglycerols (TAGs) which are the most common types of food lipids, diacylglycerols (DAGs), and monoacylglycerols (MAGs) as well as phospholipids. The term “modified” means any alteration in the structure (including composition and positional distribution of fatty acids [FAs]) of the native state. Such structural changes, consequently, endow the SLs with specific, desired nutritional, physicochemical, or textural attributes, which are partially or totally different from those of their corresponding natural form. Therefore, for the last few decades SLs have received much attention as one of the important classes of functional foods and nutraceuticals or “tailor-made” fats and oils satisfying consumers’ particular demands. SLs can be prepared chemically or enzymatically. The use of enzymes as biocatalysts has several advantages over chemical methods, thereby providing alternative and possible routes for the chemical catalysts in the synthesis of SLs for a variety of different applications. The most remarkable feature of enzymes is selectivity or specificity, which cannot be achieved by chemical catalysts, resulting in a few or no formation of byproducts. Second, enzymatic reactions are performed under mild conditions, leading to a reduction in the loss of original attributes of temperature-sensitive substrates and products (namely, SLs). Finally, the use of enzymes reduces the use of energy and deleterious reagents and makes it easy to recover products, resulting in a more environment-friendly and safer alternative for these applications. MS 20150308 Submitted 2/23/2015, Accepted 5/28/2015. Author Kim is with Dept. of Food Science and Technology, Chung-Ang Univ., Anseong, 456-756, Republic of Korea. Author Akoh is with Dept. of Food Science and Technology, The Univ. of Georgia, Food Science Building, Athens, GA, 30602-2610, U.S.A. Direct inquiries to author Akoh (E-mail: [email protected]).

R  C 2015 Institute of Food Technologists

doi: 10.1111/1750-3841.12953 Further reproduction without permission is prohibited

In the enzymatic synthesis of SLs, lipases and phospholipases are preferable as the biocatalysts. Lipases (EC 3.1.1.3) are enzymes used to hydrolyze TAGs. Lipases can catalyze the reverse of hydrolysis, that is, esterification under a hydrophobic environment. They can be used as the biocatalyst in the hydrolysis and esterification of TAGs. Thus, TAGs in the presence of free FAs (acidolysis), FA alkyl esters (interesterification), and other TAGs (interesterification), reaction of TAGs with alcohols (alcoholysis), such as glycerol (glycerolysis) and ethanol (ethanolysis), and esterification of glycerol with free FAs (direct esterification) and FA alkyl esters (transesterification) for producing SLs. Lipases can also catalyze the modification of phospholipids by acting on acyl ester bonds of the phospholipids. Lipases are commonly classified into 2 major groups according to their positional specificity: sn-1,3-specific and nonspecific lipases. The sn-1,3-specific lipases show marked preference for the acyl ester bonds at the 1st and 3rd positions of the acylglycerols, whereas the nonspecific lipases do not show distinct specificity with respect to the position of the acyl ester group on the glycerol backbone. Phospholipases are the enzymes that hydrolyze the ester bonds present in phospholipids. Similar to lipases, they can catalyze the esterification, which is basically favored in organic solvents. The most important types of phospholipases which are used as the biocatalyst for the modification of phospholipids include phospholipases A1 (PLA1; EC 3.1.1.32) and phospholipases A2 (PLA2; EC 3.1.1.4) which specifically act on the 1st and 2nd acyl ester bonds of phospholipids, respectively. Although lipases and phospholipases have several advantages over chemical catalysts for the SLs synthesis, their industrial application has been slow because of their high cost. The use of immobilized enzymes helps to overcome much of this economic problem because it allows easy recovery and several reuses of the enzymes. Researchers and manufacturers of SLs prefer to use commercial immobilized lipases of which the catalytic behaviors and properties are well-known in several reaction systems. The representative examples of the commercial products include Vol. 80, Nr. 8, 2015 r Journal of Food Science C1713

C: Food Chemistry

Recent Research Trends on the Enzymatic Synthesis of Structured Lipids

Research trends in the SLs synthesis . . .

C: Food Chemistry

Lipozyme RM IM (Rhizomucor miehei lipase immobilized on a macroporous anion exchange resin, sn-1,3-specific), Lipozyme TL IM (Thermomyces lanuginosus lipase immobilized on silica gel, sn-1,3-specific), and Novozym 435 (Candida antarctica lipase B immobilized on a macroporous acrylic resin, sn-1,3-specific or nonspecific depending on the substrates) from Novozymes (Denmark, Bagsvaerd, Denmark). On the contrary, there are few commercial immobilized phospholipases. Accordingly, several researchers have attempted to immobilize commercial free phospholipases (for example, Lecitase Ultra, PLA1 from Novozymes) as well as commercial free lipases and lipases developed independently in their laboratories and use the resulting immobilized enzymes as the biocatalyst for the synthesis of SLs. A continuous process employing a packed-bed reactor (PBR) is the most desirable and feasible technology for the industrial production of SLs using immobilized lipases and phospholipases as the biocatalyst (Kim and Akoh 2006). The potential for reutilization of immobilized enzymes is much higher in the PBRs as compared with stirred-batch reactors because rupture of the supporting materials for an immobilized enzyme can be avoided in the PBRs. Furthermore, the ratio of substrate to enzyme is much lower in a PBR than is the case with a stirred-batch reactor during reactions, resulting in higher reaction efficiency in the former (Mu and others 1998). The aim of this review is to provide concise information on the recent research trends on the enzymatic synthesis of SLs of commercial interest in the food industry using lipases and phospholipases as the biocatalysts. The specialty SLs dealt with in this review include medium- and long-chain TAGs (MLCTs), human milk fat substitutes (HMFSs), cocoa butter equivalents (CBEs), trans-free plastic fats (margarines and shortenings), low-calorie fats/oils, health-beneficial FA-rich fats/oils, monoacylglycerols (MAGs)/diacylglycerols (DAGs), and structurally modified phospholipids. This review covers 108 research articles published in the last 5 y (2010–2014) which were searched in the Web of Science, an online subscription-based scientific citation indexing service maintained by Thomson-Reuters Corp. (New York, N.Y., U.S.A.).

MLCTs Long-chain TAGs (LCTs) are the predominant form of common edible oils and serve as a source of long-chain FAs (LCFAs) including essential FAs (EFAs). However, LCTs are metabolized slowly and mostly tend to be deposited in human adipose tissue. In contrast, medium-chain TAGs (MCTs) provide quick delivery of energy via oxidation of the more hydrophilic medium-chain FAs (MCFAs) and have lower tendencies to be deposited in the adipose tissue because of their direct transportation via the portal vein to the liver rather than through the lymphatic system. However, MCTs have the problem of EFA deficiencies. This has created the need for the development of specific SLs retaining the benefits of both LCTs and MCTs, called medium- and long-chain TAGs (MLCTs) (Akoh and Kim 2008). There are 4 different types of FA arrangement on the glycerol backbone of MLCTs, namely MLM, MML, LML, and LLM. Among them, MLM-type MLCTs of which MCFAs are esterified at the sn-1,3 positions and LCFAs at the sn-2 position are considered to be the desired structure of MLCTs because they can act as an efficient carrier of LCFAs compared with other types of MLCTs. That is, the 2-MAGs retaining LCFAs are produced by pancreatic lipase digestion during metabolism of C1714 Journal of Food Science r Vol. 80, Nr. 8, 2015

MLM-type MLCTs and are well absorbed through the intestinal wall (Jandacek and others 1987). Table 1 shows that one fourth of 108 recently published studies searched in Web of Science have dealt with the enzymatic preparation of MLCTs, indicating that MLCTs is one of the major topics in the field of SLs synthesis. sn-1,3-Specific lipase-catalyzed acidolysis of LCTs with MCFAs has been and now is the best approach to prepare MLM-type MLCTs. Many of recent studies have produced MLM-type MLCTs from diverse kinds of plant oils (mainly soybean, corn, olive, canola, rice bran, avocado, mustard, borage, echium, and pine nut oils and palm olein) and MCFAs, such as caprylic (8:0) and capric acids (10:0). These published studies employed free or immobilized sn-1,3-specific lipases developed in laboratories of Kim and others (2010), Nunes and others (2012), Ifeduba and Akoh (2014), and Qin and others (2014a), as well as commercial immobilized sn-1,3-specific lipases, such as Lipozyme RM IM and Lipozyme TL IM (Jennings and others 2010; Ozturk and others 2010; Sengupta and Ghosh 2011; Chnadhapuram and Sunkireddy 2012; Choi and others 2012; Savaghebi and others 2012; Wang and others 2012; Gokce and others 2013; Caballero and others 2014; Silroy and others 2014). In particular, the use of PBRs is preferred in the enzymatic preparation of MLM-type MLCTs because rupture of the supporting materials for immobilized lipases, which facilitates acyl migration that causes the formation of other types of MLCT species can be avoided in these reactors (Xu 2000). However, only 4 out of 18 published studies on the MLM-type MLCTs synthesis employed PBR systems (Hamam and Budge 2010; Jennings and others 2010; Sengupta and Ghosh 2011; Choi and others 2012). Although many research activities have been toward the industrial production of MLM-type MLCTs, to the best of our knowledge they are not yet commercially available. Rather, typical commercial MLCTs (for example, Healthy Resseta from Nisshin Oillio, Yokohama, Kanagawa, Japan) are a mixture of MLM, MML, LML, and LLM. The reason is because they are generally produced through lipase-catalyzed interesterification of plant oils (usually soybean, rapeseed, and cottonseed oils) with MCTs (such as coconut and palm kernel oil). In similar manners to the industrial production of MLCTs, several recent studies have attempted to produce nonMLM-type MLCTs via interesterification of LCTs with MCTs using sn-1,3-specific or nonspecific lipases as the biocatalyst (Bai and others 2013; Khodadadi and others 2013; Perignon and others 2013; Yang and others 2014a; Khodadadi and Kermasha 2014a,b). Non-MLM-type MLCTs were also obtained through acidolysis of LCTs with MCFAs (Casas-Godoy and others 2013) or direct esterification of glycerol with a mixture of LCFAs and MCFAs in the presence of a nonspecific lipase (Yang and others 2014b) or acidolysis of LCTs with a mixture of LCFAs and MCFAs using an sn-1,3-specific lipase as the biocatalyst (Kocak and others 2011).

HMFSs Human milk fat is the main energy source supplying about 50% of dietary calories for infants and an important constituent in human milk providing EFAs and fat-soluble vitamins. A typical human milk fat is mainly composed of palmitic (16:0) and oleic acids (18:1n-9), which constitute about 25% w/w and 40% w/w of the total FAs, respectively. Palmitic acid is predominantly esterified at the sn-2 position (55% w/w), whereas the sn-1,3 position is mainly occupied by unsaturated FAs (USFAs), such as oleic acid (45% w/w) (Tomarelli and others 1968). Thus, 1,3-dioleoyl-2palmitoyl-glycerol (OPO) is one of the major TAG species present

Research trends in the SLs synthesis . . . Table 1–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of medium- and long-chain triacylglycerols (MLCTs). Product type

Reaction scheme

Reaction type

Enzyme

Reactor type

Caballero and others (2014) Ifeduba and Akoh (2014)

MLM-type

Avocado oil + 8:0

Acidolysis

RM IM or TL IM

Cylindrical glass vessel

MLM-type

High-stearidonic soybean oil + 8:0

Acidolysis

Batch (undefined)

Qin and others (2014a) Silroy and others (2014) Gokce and others (2013) Chen and others (2012)

MLM-type

Soybean oil + 8:0

Acidolysis

Rhizomucor miehei lipase (immobilized on Celite powder, prepared in the laboratory) Geobacillus sp. T1 lipase (free)

MLM-type

Mustard oil + 10:0

Acidolysis

TL IM

Batch (undefined)

MLM-type

Echium oil + 12:0

Acidolysis

RM IM

30-mL reactor flask

MLM-type

Tricaprin + marine n-3 FA ethyl ester concentrate Palm olein + 8:0 and 10:0 Step 1: Redistribution of FAs in pine nut oil Step 2: FAs-redistributed pine nut oil + 10:0

Interesterification

RM IM

100-mL round bottom flask

Acidolysis

RM IM

Intraesterification (for step 1)

N 435 (for step 1)

Batch (undefined; vacuum) 50-mL Erlenmeyer flask (for step 1)

Acidolysis (for step 2)

RM IM (for step 2)

Case 1: Olive oil + 8:0

Acidolysis (for both cases)

MLM-type

Case 2: Olive oil + 10:0 Canola oil + 8:0

Rhizopus oryzae heterologous lipase (immobilized on Eupergit C or Lewatit VP OC 1600, prepared in the laboratory)

Acidolysis

TL IM

Flask

MLM-type

Canola oil + 8:0

Acidolysis

RM IM

MLM-type

Mustard oil + 10:0

Acidolysis

TL IM

Silroy and Ghosh (2011)

MLM-type

Acidolysis (for all cases)

N 435

Foresti and Ferreira (2010) Hamam and Budge (2010)

MLM-type

Case 1: Rice bran oil + 10:0 Case 2: Ground nut oil + 10:0 Case 3: Mustard oil + 10:0 Tripalmitin + 10:0

25-mL round bottom flask PBR (column dimension: 50 cm × 10 mm i.d.) Stirred-tank reactor

Acidolysis

RM IM

10-mL vial

MLM-type

Fish oil + 10:0

Acidolysis

RM IM

Jennings and others (2010)

MLM-type

Rice bran oil + 8:0

Acidolysis

RM IM

Kim and others (2010)

MLM-type

Borage oil + 8:0

Acidolysis

Ozturk and others (2010) Yang and others (2014a)

MLM-type

Corn oil + 8:0

Acidolysis

RM IM or lipase from Pichia lynferdii NRRL Y-7723 (free) TL IM

PBR (column dimension: 16.2 × 2.5 cm2 i.d.) PBR (column dimension: 50 × 4.7 cm2 i.d.) 25-mL Erlenmeyer flask

Non-MLM-type

Soybean oil + MCTs

Interesterification

TL IM

Yang and others (2014b)

Non-MLM-type

Glycerol + 8:0, 10:0, and 18:1n-9

Direct esterification

N 435

Khodadadi and Kermasha (2014a) Khodadadi and Kermasha (2014b) Bai and others (2013)

Non-MLM-type

Flaxseed oil + tricaprylin Flaxseed oil + tricaprylin Tricaprylin + trilinolenin

Interesterification

TL IM

50-mL round bottom flask PBR (column dimension: 20 cm × 11.5 mm i.d.) 250-mL three necked round bottom flask (vacuum) 30-mL reactor flask

Interesterification

N 435

30-mL reactor flask

Interesterification

RM IM or N 435

50-mL Erlenmeyer flask

Chnadhapuram and Sunkireddy (2012) Choi and others (2012)

Nunes and others (2012)

Savaghebi and others (2012) Wang and others (2012) Sengupta and Ghosh (2011)

MLM-type MLM-type

MLM-type

Non-MLM-type Non-MLM-type

Batch (undefined)

PBR (column dimension: 7.62 cm × 4.8 mm i.d.; for step 2) Cylindrical glass vessel

30-mL Reaction flask

(Continued) Vol. 80, Nr. 8, 2015 r Journal of Food Science C1715

C: Food Chemistry

Study

Research trends in the SLs synthesis . . . Table 1–Continued. Study Casas-Godoy and others (2013)

Product type Non-MLM-type

Reaction scheme Case 1: Olive oil + 8:0

C: Food Chemistry

Case 2: Olive oil + 10:0 Flaxseed oil + tricaprylin

Reaction type

Enzyme

Reactor type

Acidolysis (for both cases)

Yarrowia lipolytica lipase 2 (immobilized on Accurel MP1000, prepared in the laboratory)

Cylindrical glass tube

Interesterification

RM IM, TL IM, N 435 or Amano DF (free Rhizopus oryzae lipase, Amano, Japan) Thermomyces lanuginosus lipase (immobilized on Immobead 150, Sigma–Aldrich, U.S.A.) or Candida antarctica lipase B (immobilized on macroporous resin, Sigma–Aldrich, U.S.A.) RM IM

30-mL reactor flask

Khodadadi and others (2013)

Non-MLM-type

Perignon and others (2013)

Non-MLM-type

Tricaprylin + trimyristin

Interesterification

Kocak and others (2011)

Non-MLM-type

Terebinth fruit oil + 8:0 and 18:0

Acidolysis

Batch (undefined)

Batch (undefined)

Abbreviations: FAs, fatty acids; MCTs, medium-chain triacylglycerols; MLM, medium-, long-, and medium-chain; N 435, Novozym 435; PBR, packed-bed reactor; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

in human milk fat. The unique FA distribution of human milk fat gives several health benefits to infants, such as improved fat (especially palmitic acid) absorption, improved mineral (especially calcium) absorption, softer stools, and less constipation (Tomarelli and others 1968; Takeuchi 2010). However, although human milk is the preferred choice of nutrition for the infants, infant formulas have been chosen to partially or wholly replace human milk in certain cases. HMFSs are SLs resembling human milk fat in terms of FA composition and distribution, which are made for use in infant formulas. Typical commercial HMFSs (for example, Betapol from Loders Croklaan, Channahon, IL, The Netherlands) have been prepared by acidolysis of tripalmitin-rich fats (such as palm stearin) with oleic acid (free FAs obtained from high-oleic sunflower oil). The reaction is commonly performed in a PBR using an immobilized sn-1,3-specific lipase (such as Lipozyme RM IM). Table 2 lists 22 different examples of recently published studies to prepare HMFSs. Similar to the industrial manufacturing procedure of HMFSs, 10 studies have produced HMFSs through acidolysis of palmitic acid-rich fats, such as tripalmitin, palm stearin, lard, and milk fats with oleic acid or free FAs obtained from oleic acid-rich plant oils, such as olive, rapeseed, sunflower, hazelnut, and camellia oils, although most of the studies employed a batch-type reaction system (Sorensen and others 2010; Tecelao and others 2010; Ilyasoglu and others 2011; Qin and others 2011, 2014b; Zou and others 2011, 2012; Yuksel and Yesilcubuk 2012; Pande and others 2013b; Zhang and others 2013). Intake of polyunsaturated FAs (PUFAs), including arachidonic acid (20:4n-6), EPA (20:5n-3), and DHA (22:6n-3), plays a crucial role in proper growth and development of infants. A typical human milk fat and conventional commercial HMFSs contain small quantities of the PUFAs or their precursors (i.e., EFAs), such as linoleic (18:2n-6) and αlinolenic acids (18:3n-3). Many of the recent research activities have been towards the production of HMFSs enriched in arachidonic acid, EPA, or DHA as well as stearidonic acid (18:4n-3) which can be more efficiently converted into EPA as compared with α-linolenic acid in the human body (Tecelao and others 2010; Nagachinta and Akoh 2012; Teichert and Akoh 2012; Turan and others 2012; Yuksel and Yesilcubuk 2012; Pande and others 2013a,b; Brys and others 2014; Li and others 2014; Simoes and C1716 Journal of Food Science r Vol. 80, Nr. 8, 2015

others 2014; Zou and others 2014b). Such studies have utilized fish oils, algal oils (for example, DHASCO, DHA-rich oil from Martek, Columbia, MD, U.S.A.), fungal oils (such as ARASCO, arachidonic acid-rich oil from Martek), plant oils (echium oil, stearidonic acid-rich oil), and oils derived from genetically modified crops (high-stearidonic soybean oil from Monsanto, St. Louis, MO, U.S.A.) as the PUFA source. Recently, some researchers have attempted to prepare MCFA-rich HMFSs using palm kernel or camphor oil as the MCFA source (Zou and others 2011, 2012, 2014a).

CBEs Cocoa butter is the main component of chocolate. It is composed predominantly of symmetric monounsaturated TAGs, such as 1,3-dipalmitoyl-2-oleoyl-glycerol (POP, 15–19 w/w%), 1palmitoyl-2-oleoyl-3-stearoyl-rac-glycerol (POS, 36–41 w/w%), and 1,3-distearoyl-2-oleoyl-glycerol (SOS, 25–31 w/w%) (Yamada and others 2005). CBEs are SLs with similar TAG composition to cocoa butter, but are produced from low-cost plant oils. They are used as an alternative to natural cocoa butter during chocolate manufacturing because of high cost and fluctuations in the supply and demand for cocoa butter. CBEs can be blended with cocoa butter in any proportion without altering the physical properties of cocoa butter. The European Union Chocolate Directive allows replacement of cocoa butter with CBEs at up to 5% in products that are called “chocolate” (Stewart and Kristott 2004). Commercial CBEs (such as Melano from Fuji Oil, TsukubamiraiCity, Japan) are generally produced by blending POP-rich fats with fats rich in SOS. The palm mid-fraction, which is obtained by fractional crystallization of palm olein, is commonly used as a POP source for preparing CBEs. SOS-rich fats are prepared by fractional crystallization of tropical fats (such as shea butter) containing a significant amount of SOS, or interesterification of triolein-rich plant oils, such as high-oleic sunflower oil with stearic acid ethyl esters using an sn-1,3-specific lipase as the biocatalyst. Unlike conventional procedures for producing CBEs, recent studies on CBE manufacturing have focused on the preparation of POS-rich fats for formulating CBEs with weight ratios among POP, POS, and SOS that are similar to those of cocoa butter (Table 3). The POS-rich fats were produced by acidolysis of

Research trends in the SLs synthesis . . . Table 2–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of human milk fat substitutes (HMFSs).

Brys and others (2014) Li and others (2014) Simoes and others (2014)

Qin and others (2014b)

Zou and others (2014a) Zou and others (2014b) Pande and others (2013a) Pande and others (2013b) Turan and others (2013) Zhang and others (2013)

Reaction scheme

Reaction type

Case 1: Lard + rapeseed oil + fish oil Case 2: Milk fat + rapeseed oil + fish oil Olive oil + 16:0 and DHA Lard + fish oil Fas

Interesterification (for both cases)

RM IM

Enzyme

Flask

Reactor type

Acidolysis Acidolysis

Test tube 20-mL cylindrical glass reactor

Step 1: Lard + camellia oil FAs → SLs Step 2: Blending SLs with coconut oil, soybean oil, flaxseed oil, and sunflower oil Camphor oil + 18:1n-9 Lard + sunflower oil + canola oil + palm kernel oil + palm oil + algal oil + microbial oil Olive oil + tripalmitin + ARASCO FAs + DHASCO FAs Tripalmitin + olive oil FAs and DHA Case 1: Hazelnut oil + 16:0 Case 2: Hazelnut oil + 16:0 ethyl ester Case 1: Tripalmitin + 18:1n-9 Case 2: Palm oil + 18:1n-9

Acidolysis (for step 1)

N 435 RM IM, TL IM, N 435 or Rhizopus oryzae lipase (immobilized on Accurel MP1000, prepared in the laboratory) RM IM

Acidolysis Interesterification

RM IM RM IM

50-mL flask 50-mL round bottom flask

Interesterification + acidolysis Acidolysis Acidolysis (for case 1) Interesterification (for case 2) Acidolysis (for both cases)

N 435 + TL IM

Erlenmeyer flask

TL IM N 435

Erlenmeyer flask Test tube

RM IM

25-mL Erlenmeyer flask

Batch (undefined)

Palm olein + DHASCO FAs and ARASCO FAs Step 1: High-stearidonic soybean oil + tripalmitin → SLs Step 2: SLs + 18:3n-6 or DHA Step 1: hazelnut oil + 16:0 ethyl ester → 16:0-rich SLs Step 2: 16:0-rich SLs + ARASCO and DHASCO Tripalmitin + hazelnut oil FAs and FAs from commercial oil mixture containing echium oil and algal oil Palm stearin + 14:0, 18:0, rapeseed oil FAs, sunflower oil FAs, and palm kernel oil FAs

Acidolysis

N 435

Test tube

Interesterification (for step 1) Acidolysis (for step 2) Interesterification (for both steps)

N 435 or TL IM (for step 1) TL IM (for step 2) N 435 (for step 1)

1-L stirred batch reactor

da Silva and others (2011)

Nagachinta and Akoh (2012) Teichert and Akoh (2012) Turan and others (2012)

RM IM (for step 2)

Batch (undefined, for step 1) Test tube (for step 2)

Acidolysis

TL IM

Flask

Acidolysis

RM IM

Lard + soybean oil

Interesterification

RM IM

Ilyasoglu and others (2011) Qin and others (2011)

Tripalmitin + hazelnut oil Fas Fractionated lard + camellia oil FAs

Acidolysis Acidolysis

RM IM RM IM

Zou and others (2011)

Chemically interesterified palm stearin + 14:0, 18:0, rapeseed oil FAs, sunflower oil FAs, and palm kernel oil FAs Tripalmitin-rich fraction from palm stearin + 18:1n-9 ethyl ester Butterfat + soybean oil FAs and rapeseed oil FAs

Acidolysis

RM IM

PBR (column dimension: 24 cm × 20 mm i.d.) PBR (column dimension: 34 × 2 cm2 i.d.) Batch (undefined) 25-mL cylindrical flask 25-mL round bottom flask

Interesterification

TL IM

Acidolysis

RM IM

Acidolysis (for both cases)

RM IM, N 435 or Candida parapsilosis lipase/ acyltransferase (immobilized on Accurel MP1000, prepared in the laboratory)

Yuksel and Yesilcubuk (2012) Zou and others (2012)

Lee and others (2010) Sorensen and others (2010) Tecelao and others (2010)

Case 1: Tripalmitin + 18:1n-9

Case 2: Tripalmitin + n-3 FAs from a marine oil

250-mL Erlenmeyer flask PBR (column dimension: 95 × 5 cm2 i.d.) 20-mL cylindrical batch reactor

Abbreviations: CLA, conjugated linoleic acid; FAs, fatty acids; N 435, Novozym 435; PBR, packed-bed reactor; RM IM, Lipozyme RM IM; SLs, structured lipids; TL IM, Lipozyme TL IM.

Vol. 80, Nr. 8, 2015 r Journal of Food Science C1717

C: Food Chemistry

Study

Research trends in the SLs synthesis . . . Table 3–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of cocoa butter equivalents (CBEs). Study Kadivar and others (2014) Kim and others (2014)

C: Food Chemistry

Mohamed (2013) Ray and others (2013)

Mohamed (2012) Chae and others (2011) Pacheco and others (2010)

Reaction scheme

Reaction type

Enzyme

Reactor type

High-oleic sunflower oil + 16:0 and 18:0 High-oleic sunflower oil + 16:0 ethyl ester and 18:0 ethyl ester Palm-mid fraction + 16:0 and 18:0 High-oleic sunflower oil + 16:0 and 18:0

Acidolysis

RM IM

Cylindrical glass vessel

Interesterification

RM IM

Acidolysis Acidolysis

High-oleic sunflower oil + 16:0 and 18:0 High-oleic sunflower oil + fully hydrogenated soybean oil Sunflower oil + 16:0 and 18:0

Acidolysis

TL IM Rhizopus oryzae lipase (immobilized on Accurel EP-100, Loders Croklaan, Netherlands) RM IM

PBR (column dimension: 4.9 cm × 2.6 mm i.d.) 50-mL Erlenmeyer flask 1-L cylindrical round bottom glass vessel

Interesterification

TL IM

Acidolysis

RM IM

Batch (undefined) PBR (column dimension: 7.62 cm × 4.8 mm i.d.) Test tube

Abbreviations: PBR, packed-bed reactor; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

POP-rich fats, namely, the palm mid-fraction with mixtures of palmitic and stearic acids (Mohamed 2013), acidolysis of trioleinrich oils, namely, high-oleic sunflower oil with mixtures of palmitic and stearic acids (Mohamed 2012; Ray and others 2013; Kadivar and others 2014), or interesterification of high-oleic sunflower oil with mixtures of palmitic and stearic acid ethyl esters (Kim and others 2014) using commercial immobilized sn-1,3specific lipases, such as Lipozyme RM IM and Lipozyme TL IM. Only 2 out of 7 published studies shown in the table employed a small-scale PBR system for the CBEs production (Chae and others 2011; Kim and others 2014).

low-trans or trans-free margarines, thereby giving more desirable textural attributes to the products. By using a similar strategy, some recent studies have added butterfat, coconut, or palm kernel oil into the blends of high-saturated fats and high-unsaturated plant oils and used the resultant oil/fat blends as the substrates for the lipase-catalyzed production of low-trans or trans-free margarines (Adhikari and others 2010a, 2012b; Shin and others 2010; Soares and others 2013; Ruan and others 2014). Most of the published studies mentioned above employed a batch-type reaction system, except the studies of Li and Others (2010) and Soares and others (2013).

Low-Trans or Trans-Free Plastic Fats

Low-Calorie Fats/Oils

Conventional plastic fats (margarines and shortenings) contain high levels of trans FAs which are formed during partial hydrogenation of the plant oils that are used as the main ingredients of the products. Intake of trans FAs is now associated with increased risk of coronary heart disease because it raises blood total and lowdensity lipoprotein cholesterol levels and lowers the blood highdensity lipoprotein cholesterol level (Mensink and Katan 1990). Since the early 2000s, plastic fat manufacturers and researchers have been developing several alternatives to the partial hydrogenation process to reduce or completely remove trans FAs in their products, resulting in low-trans or trans-free margarines and shortenings. The lipase-catalyzed interesterification of high-saturated fats with high-unsaturated plant oils is one of the most successful alternatives to obtain plastic fats with intermediate characteristics. For example, NovaLipid (from ADM, Decatur, IL, U.S.A.) is a commercial low-trans shortening that is produced through lipasecatalyzed interesterification of soybean oil with fully hydrogenated soybean and cottonseed oils. Table 4 shows that 8 out of 19 recent studies also prepared low-trans or trans-free margarines and shortenings in similar ways to the manufacturing process of NovaLipid. That is, they employed the lipase-catalyzed interesterification of solid fats (palm stearin, fully hydrogenated soybean oil, and beef tallow) with liquid oils (soybean, high-stearidonic soybean, high-oleic sunflower, pine nut, and akebia oils) using a commercial immobilized nonspecific lipase such as Novozym 435 as well as Lipozyme RM IM and Lipozyme TL IM (Adhikari and others 2010b; Li and others 2010; Segura and others 2011; Pande and Akoh 2012; Otero and others 2013; Pacheco and others 2013; Zhao and others 2014; Zhu and others 2014). Kim and others (2008) reported that additional incorporation of MCFA-rich oils into the substrates for the interesterification increases the diversity in the FA profile of resulting

Short-chain FAs containing 2–4 carbons are useful substrates in the synthesis of low-calorie SLs because their calorie values are significantly lower than that of typical LCFAs (9 kcal/g). For example, acetic (2:0), propionic (3:0), and butyric acids (4:0) possess calorie values of 3.5, 5.0, and 6.0 kcal/g, respectively (Akoh and Kim 2008). Very LCFAs (VLCFAs) with a chain length of equal to or more than 22 carbons are also commonly used as the substrates for the preparation of low-calorie SLs because they are poorly absorbed in human bodies (Akoh and Kim 2008). There have been several kinds of commercial low-calorie SLs containing SCFAs (for example, Benefat from Cultor Food Science, New York, NY, U.S.A.) or VLCFAs (for example, Caprenin from Procter & Gamble, Cincinnati, OH, U.S.A.) which are made by chemical methods. Benefat consists of at least one SCFA (acetic, propionic, or butyric acid) and at least one LCFA (predominantly stearic acid, 18:0), and it is produced by base-catalyzed interesterification of fully hydrogenated canola or soybean oil with TAGs of the SCFAs. Caprenin contains behenic acid (22:0) along with caprylic and capric acids because it is produced through chemically catalyzed direct esterification of glycerol with the FA mixtures which are obtained from coconut, palm kernel, and rapeseed oils. Unlike the success in the industrial application of chemical methods for the synthesis of low-calorie SLs, so far there has not been an example of enzymatic production of the low-calorie SLs commercially. However, several researchers have steadily been studying the lipase-catalyzed production of several different types of low-calorie SLs. Table 5 shows that recent studies employed lipase-catalyzed direct esterification, interesterification, or acidolysis for the production of low-calorie SLs containing acetic acid (Cao and others 2013; Lei and others 2013) or behenic acid (Bebarta and others 2013; Kanjilal and others 2013) from different edible lipid sources including soybean, sunflower, and camellia

C1718 Journal of Food Science r Vol. 80, Nr. 8, 2015

Research trends in the SLs synthesis . . . Table 4–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of low-trans or trans-free plastic fats.

Ruan and others (2014) Zhao and others (2014) Zhu and others (2014) Otero and others (2013) Pacheco and others (2013) Pande and Akoh (2013) Soares and others (2013)

Adhikari and others (2012a) Adhikari and others (2012b) Lee and others (2012) Mounika and Reddy (2012) Palla and others (2012)

Pande and Akoh (2012) Tang and others (2012) Segura and others (2011) Adhikari and others (2010a) Adhikari and others (2010b) Li and others (2010)

Shin and others (2010)

Reaction scheme

Reaction type

Trans-free margarines

Product type

Camellia oil + palm stearin + coconut oil

Interesterification

TL IM

Batch (undefined)

Trans-free plastic fats

Akebia oil + palm stearin

Interesterification

TL IM

250-mL Erlenmeyer flask

Low-trans fats

Pine nut oil + palm stearin

Interesterification

TL IM

1-L glass batch reactor

Semisolid fats

Pine nut oil + fully hydrogenated soybean oil

Interesterification

RM IM, TL IM, or N 435

50-mL flask

Plastic fats

Fully hydrogenated soybean oil + soybean oil

Interesterification

RM IM or TL IM

Test tube

Trans-free margarines

High-stearic soybean oil + palm stearin

Interesterification

TL IM or N 435

Test tube

Trans-free margarines

Palm stearin + palm kernel oil + olive oil

Interesterification

RM IM or TL IM

Trans-free Margarines and shortenings Margarines and shortenings

Soybean oil + palm stearin + conjugated linoleic acid

Interesterification + acidolysis

TL IM

100-mL cylindrical glass reactorPBR (column dimension: 10 × 2 cm2 i.d.) 2-L round bottom flask

Rice bran oil + fully hydrogenated soybean oil + coconut oil Palm stearin + pomegranate seed oil FAs Case 1: Palm stearin + 10:0 and 22:0Case 2: Palm stearin + 10:0

Interesterification

TL IM

250-mL Erlenmeyer flask

Acidolysis

TL IM

Acidolysis (for both cases)

RM IM

250-mL Erlenmeyer flask Batch (undefined)

Test tube

Hard fats

Enzyme

Reactor type

Trans-free shortenings and salad dressing oils Plastic fats

Sunflower oil + 16:0 and 18:0

Acidolysis

Trans-free margarines

High-stearidonic soybean oil + high-stearic soybean oil

Interesterification

Rhizomucor miehei lipase (immobilized on alkylated chitosan microspheres, prepared in the laboratory) TL IM or N 435

Trans-free margarines and shortenings Low trans hard fats

Camphor oil + palm stearin

Interesterification

TL IM

Batch (undefined)

Beef tallow + high-oleic sunflower oil

Interesterification

TL IM

Test tube

Trans-free margarines

Rice bran oil + palm stearin + coconut oil

Interesterification

TL IM

Erlenmeyer flask

Trans-free margarines

Palm stearin + pine nut oil

Interesterification

TL IM

Batch (undefined)

Trans-free shortenings

High-oleic sunflower oil + fully hydrogenated soybean oil

Interesterification

TL IM

Low-trans spreadable fats

Butterfat + flaxseed oil + palm stearin

Interesterification

RM IM or N 435

Erlenmeyer flaskPBR (column dimension: 53 × 3.5 cm2 i.d.) 250-mL cylindrical flask

Test tube

Abbreviations: CLA, conjugated linoleic acid; FAs, fatty acids; N 435, Novozym 435; PBR, packed-bed reactor; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

Vol. 80, Nr. 8, 2015 r Journal of Food Science C1719

C: Food Chemistry

Study

Research trends in the SLs synthesis . . . Table 5–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of low-calorie fats/oils. Study

C: Food Chemistry

Product type

Reaction scheme

Bebarta and others (2013)

SLs containing MCFA and VLCFA

Cao and others (2013)

SLs containing SCFA

Kanjilal and others (2013)

SLs containing VLCFA

Lei and others (2013)

SLs containing SCFA and MCFA(MSM-type)

Case 1: Kokum fats + 10:0, 12:0, and 22:0 Case 2: Sal fats + 10:0, 12:0, and 22:0 Case 3: Mango fats + 10:0, 12:0, and 22:0 Triacetin + camellia oil FA methyl esters Case 1: Sunflower oil + 22:0 ethyl ester Case 2: Soybean oil + 22:0 ethyl ester Step 1: glycerol + 8:0 → 1,3dicapryloylglycerol Step 2: 1,3dicapryloylglycerol + acetic anhydride (under reflux)

Reaction type

Enzyme

Reactor type

Acidolysis (for all cases)

RM IM

Batch (undefined, vacuum)

Interesterification

RM IM or N 435

Interesterification (for both cases)

TL IM

5-L round bottom flask Batch (undefined)

Direct esterification (for both steps)

RM IM (for step 1)

Round bottom flask (vacuum, for step 1) 5-mL round bottom flask (for step 2)

Abbreviations: FA, fatty acid; MCFA, medium-chain fatty acid; MSM, medium-, short-, and medium-chain; N 435, Novozym 435; RM IM, Lipozyme RM IM; SCFA, short-chain fatty acid; SLs, structured lipids; TL IM, Lipozyme TL IM; VLCFA, very long-chain fatty acid.

Table 6–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of particular fatty acid-rich fats/oils. Study

Product type

Reaction scheme

Reaction type

Enzyme

Reactor type

Bispo and others (2014) Farfan and others (2013)

n-3 FA-rich oil n-3 FA-rich oil

Glycerol + sardine oil FAs Linseed oil + palm stearin

Direct esterification Interesterification

RM IM TL IM

Yang and others (2013)

n-3 FA-rich oil

Interesterification

TL IM

Bilgic and Yesilcubuk (2012)

n-3 FA-rich oil

Acidolysis

TL IM

Test tube

Kleiner and others (2012)

n-3 FA-rich oil

Acidolysis

TL IM or N 435

Test tube

Chopra and others (2011) de Araujo and others (2011)

n-3 FA-rich oil n-3 FA-rich oil

Acidolysis Acidolysis

RM IM RM IM

Nagao and others (2011)

n-3 FA-rich oil

Direct esterification

RM IM

Batch (undefined) 50-mL cylindrical flask 10-mL flask

Sengupta and Ghosh (2011)

n-3 FA-rich oil

Grape seed oil + perilla oil Olive oil + echium oil FAs High-stearidonic soybean oil + fractionated high-stearidonic soybean oil Fas Rice bran oil + 18:3n-3 Soybean oil + sardine oil FAs Glycerol + FAs generated in the selective hydrolysis of tuna oil with a lipase that acts weakly on DHA for producing DHA Mustard oil + fish oil

Test tube Batch (undefined, vacuum) 250-mL flask

Interesterification

TL IM

Mitra and others (2010)

n-3 FA-rich oil

Interesterification (for both cases)

RM IM

Yang and others (2012)

Conjugated FA-rich oil Conjugated FA-rich oil

Case 1: Soybean oil + perilla oilCase 2: Corn oil + perilla oil Soybean oil + conjugated linoleic acid ethyl esters Corn oil + bitter gourd seed oil (conjugated linolenic acid-rich oil) FAs

Interesterification

RM IM

Acidolysis

TL IM

Elibal and others (2011)

PBR (column dimension: 50 cm × 10 mm i.d.) 50-mL vial 25-mL cylindrical flask 30-mL reaction flask

Abbreviations: FA, fatty acid; N 435, Novozym 435; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

oils and tropical fats. The calorie value of SCFAs is not affected by their sn position and VLCFAs are poorly absorbed regardless of their sn position. Thus, for the enzymatic synthesis of this type of SLs, both sn-1,3-specific and nonspecific lipases have been used as the biocatalysts as shown in the table. All these published studies employed a batch-type reaction system for the production of SLs.

C1720 Journal of Food Science r Vol. 80, Nr. 8, 2015

Health-Beneficial FA-Rich Fats /Oils A variety of FAs has been used as the substrates in the lipasecatalyzed synthesis of SLs enriched in the FAs, to attain particular health-beneficial purposes for different applications. The representative FAs, which have received much attention are: conjugated FAs (such as conjugated linoleic acid) for anti-carcinogenic

Research trends in the SLs synthesis . . . Table 7–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of monoacylglycerols (MAGs) and diacylglycerols (DAGs). Product type

Compton and others (2014) Wang and others (2014a) Wang and others (2014b) Cervera and others (2013) Compton and others (2013) Wang and others (2013) Wang and others (2013)

2-MAGs

Castor oil + ethanol

Ethanolysis

N 435

Batch (undefined)

2-MAGs

Arachidonic acid-rich fungal oil + ethanol High-oleic sunflower oil + ethanol Echium oil or Marinol (DHA-rich oil) Soybean oil + ethanol

Ethanolysis

N 435

Batch (undefined)

Ethanolysis

N 435

Batch (undefined)

Hydrolysis

Flask

Ethanolysis

Porcine pancreatic lipase (free) N 435

Transesterification

N 435

Batch (undefined)

Direct esterification (for step 1)

N 435 (for step 1)

Batch (undefined)

Dhara and Singhal (2014) Meng and others (2014) Sanchez and others (2014) Yeoh and others (2014) Baeza-Jimenez and others (2013) Jin and others (2011)

1,3-DAGs

Glycerol + 16:0 vinyl ester Step 1: 1,2-acetonide glycerol + 16:0 → 1,2acetonide-3-palmitoyl glycerol Step 2: An acid-catalyzed cleavage of 1,2aceonide-3-palmitoyl glycerol Glycerol + sunflower oil

Glycerolysis

TL IM

1,3-DAGs

Glycerol + 18:1n-9

Direct esterification

RM IM

1,3-DAGs

Glycerol + 10:0

Direct esterification

RM IM

Batch (undefined, vacuum) 100-mL round bottom flask 10-mL flask

DAGs

Glycerol + palm olein

Glycerolysis

TL IM

2-L batch reactor

DAGs

Glycerol + fish oil

Glycerolysis

N 435

25-mL glass vessel

DAGs

MAGs + 18:1n-9 ethyl ester

Transesterification

Lipase PS (free Pseudomonas cepacia lipase, Amano, Japan), Lipase PS-D (Lipase PS immobilized on diatomaceous earth, Amano, Japan) or RM IM

Batch (undefined)

2-MAGs 2-MAGs 2-MAGs MAGs 1-MAGs

Reaction scheme

Reaction type

Enzyme

Reactor type

Batch (undefined)

Abbreviations: N 435, Novozym 435; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

(Kelley and others 2007) and anti-obesity effects (Kennedy and others 2010); and n-3 FAs (such as α-linolenic acid, EPA, and DHA) for hypocholesterolemic effect (Bang and others 1978) and normal function of the retina and brain in premature infants (Carlson and others 1986). DHA-rich SLs (such as, Marinol D-40 from Loders Croklaan) is a good example of this type. This product is produced by selective hydrolysis of fish oil TAGs using C. rugosa lipase that weakly acts on DHA. Unlike the industrial process for the preparation of n-3 FA-rich SLs, recent studies employed lipase-catalyzed direct esterification, interesterification, or acidolysis for the preparation of n-3 FA-rich SLs (Table 6). The researchers prepared the SLs from α-linolenic acid-rich plant oils, such as perilla and linseed oils (Mitra and others 2010; Farfan and others 2013; Yang and others 2013), stearidonic acid-rich plant oils (Bilgic and Yesilcubuk 2012; Kleiner and others 2012) such as high-stearidonic soybean and echium oils, and fish oils, such as from tuna and sardines (de Araujo and others 2011; Nagao and others 2011; Sengupta and Ghosh 2011; Bispo and others 2014) or their free FA fractions using Lipozyme RM IM, Lipozyme TL IM, or Novozym 435. The table also shows that some researchers have produced conjugated FA-rich SLs using conjugated linoleic acid ethyl esters or free FAs obtained from bitter gourd seed oil, which is rich in conjugated linolenic acid, as

the substrates (Elibal and others 2011; Yang and others 2012). All the published studies employed a batch-type reaction system for the production of SLs except the study of Sengupta and Ghosh (2011).

MAGs/DAGs MAGs have usually been used as the principal food-grade emulsifiers. MAGs can occur as 2 different types of positional isomers: 1-MAGs and 2-MAGs. 2-MAGs, retaining particular FAs at the sn-2 position, can be used as an efficient carrier of the FAs because they are well absorbed through the intestinal wall. As shown in Table 7, recent studies have focused on the enzymatic preparation of 2-MAGs mainly containing USFAs (oleic, arachidonic, or stearidonic acids) through ethanolysis of several different kinds of TAG oils using Novozym 435 as the biocatalyst (Compton and others 2013, 2014; Wang and others 2014aa, b). Novozym 435 commonly acts as a nonspecific lipase, but it exhibits the strict sn-3 specificity for ethanolysis of TAGs. DAGs have been used by the food industry as emulsifiers in mixture form with MAGs. Besides such conventional applications of DAGs, in late 1990s the specialty commercial SLs (DAG oils such as Enova from Kao, Japan, and from ADM, U.S.A.) were developed for the purpose of obtaining physiological benefits, particularly Vol. 80, Nr. 8, 2015 r Journal of Food Science C1721

C: Food Chemistry

Study

Research trends in the SLs synthesis . . . Table 8–Recent studies (published between 2010 and 2014) on the enzymatic synthesis of structured phospholipids. Study

C: Food Chemistry

Reaction type

Enzyme

Reactor type

Li and others (2014)

n-3 FA-rich phosphatidylcholine

Product type

Soy phosphatidylcholine + DHA ethyl ester and EPA ethyl ester

Reaction scheme

Interesterification

25-mL cylindrical flask

Kim and Yoon (2014)

MCFA-rich phosphatidylcholine

Phosphatidylcholine + 8:0

Acidolysis

Zhao and others (2014)

n-3 FA-rich phosphatidylcholine

Soy phosphatidylcholine + fish oil FAs

Acidolysis

Ochoa and others (2013)

MCFA-rich phosphatidylcholine

Soy phosphatidylcholine + MCFA from Original Thin Oil

Acidolysis

Cabezas and others (2011)

Lysophosphatidylcholine

Sunflower lecithin

Hydrolysis

Hong and others (2011)

Lysophosphatidylcholine

l-α-Glycerylphosphorylcholine + conjugated linoleic acid

Direct esterification

Lecitase Ultra (PLA1 , immobilized on D380, prepared in the laboratory) PLA2 (free) Mucor javanicus lipase (free) Lecitase Ultra (PLA1 , immobilized on Lewatit VP OC 1600, prepared in the laboratory) Lecitase Ultra, PLA1 (immobilized on Duolite A568, prepared in the laboratory) Lecitase 10L (PLA2 , free) Novozym 435

Flask 50-mL glass vessel

Erlenmeyer flask

Batch (undefined) 50-mL glass vessel (vacuum)

Abbreviations: FAs, fatty acids; MCFA, medium-chain fatty acid; N 435, Novozym 435; PLA1, phospholipase A1; PLA2, phospholipase A2; RM IM, Lipozyme RM IM; TL IM, Lipozyme TL IM.

hypotriglyceridemic and anti-obesity effects. Such healthbeneficial effects of DAG oils are known to have resulted from the predominant presence of 1,3-DAGs in the oils. That is, in the human body 1,3-DAGs are less efficiently utilized in the resynthesis of TAGs for chylomicron formation and secretion compared with typical TAGs. Commercial DAG oils are commonly prepared via direct esterification of glycerol with free FAs using immobilized sn-1,3-specific lipases. For the preparation of 1,3DAGs, recent studies have used glycerolysis of plant oils (Dhara and Singhal 2014) as well as direct esterification of glycerol with free FAs (Meng and others 2014; Sanchez and others 2014) using Lipozyme RM IM and Lipozyme TL IM. All these published studies on the enzymatic synthesis of MAGs and DAGs employed a batch-type reaction system.

Structurally Modified Phospholipids The enzymatic structural modification of phospholipids is usually performed to alter and improve the physicochemical or nutritional properties of phospholipids for different applications. In particular, several researchers have recently attempted to prepare phospholipids enriched in health-beneficial FAs in order to utilize the phospholipids as an efficient carrier of the FAs. The reason is because bioavailability of FAs is greater in phospholipid form than in TAG form (Lemaitre-Delaunay and others 1999). Table 8 lists examples of recent studies to enzymatically prepare n-3 FA-rich phosphatidylcholine (Li and others 2014; Zhao and others 2014) and MCFA-rich phosphatidylcholine (Ochoa and others 2013; Kim and Yoon 2014). The researchers employed phospholipasecatalyzed interesterification or acidolysis for the structural modification of phosphatidylcholine. In particular, they used Lecitase Ultra, which is a commercial free PLA1 from T. lanuginosus/Fusarium oxysporum, as the biocatalyst, after immobilizing it on several different kinds of support materials. C1722 Journal of Food Science r Vol. 80, Nr. 8, 2015

Lysophosphatidylcholine is a derivative of phosphatidylcholine in which one of the 2 acyl groups is removed. Lysophosphatidylcholine can be used as an emulsifier which has enhanced oil-in-water emulsifying properties and improved emulsion stability under hot and acidic conditions and in the presence of salts as compared with phosphatidylcholine. Lysophosphatidylcholine is industrially prepared via PLA2 -catalyzed partial hydrolysis of phosphatidylcholine. The table shows that recent studies have attempted to prepare lysophosphatidylcholine through the partial hydrolysis of phosphatidylcholine using a commercial nonimmobilized free PLA2 called Lecitase 10L (from porcine pancreas, Novozyme) (Cabezas and others 2011) or direct esterification of l-α-glycerylphosphorylcholine with free FAs using Novozym 435 (Hong and others 2011). The published studies on the enzymatic structural modification of phospholipids employed a batch-type reaction system.

Conclusions This review covers the recent research trends on the enzymatic synthesis of 8 different kinds of SLs (MLCTs, HMFSs, CBEs, trans-free plastic fats, low-calorie SLs, health-beneficial FA-rich SLs, MAGs/DAGs, and structurally modified phospholipids) using lipases and phospholipases as the biocatalysts. The review provides concise information on 108 research articles published between 2010 and 2014 of which the topic is the enzymatic preparation of these specialty SLs, in regard to the product type, reaction scheme and type, enzyme type, and reactor type. Recently, the industrial applications of lipases and phospholipases as biocatalysts have been steadily expanding because they possess valuable and efficient catalytic attributes beyond attainment by chemical catalysts. However, only a few of the enzymes are available as biocatalysts in the industrial-scale synthesis of SLs because of the difficulties in establishing cost-effective scaling-up and downstream

processing protocols. So far, except for a few examples of success, the enzymatic preparation of SLs is still far from satisfactory commercialization. Nevertheless, these difficulties should not attenuate the value of enzymes as the biocatalysts for SLs synthesis. More research activities should be devoted to the practical and feasible commercial enzymatic production of SLs and their successful food applications.

References Adhikari P, Peng H, Zhang YF. 2012a. Oxidative stabilities of enzymatically interesterified fats containing conjugated linoleic acid. J Am Oil Chem Soc 89:1961–70. Adhikari P, Shin JA, Lee JH, Hu JN, Zhu XM, Akoh CC, Lee KT. 2010a. Production of trans-free margarine stock by enzymatic interesterification of rice bran oil, palm stearin and coconut oil. J Sci Food Agric 90:703–11. Adhikari P, Shin JA, Lee JH, Kim HR, Kim IH, Hong ST, Lee KT. 2012b. Crystallization, physicochemical properties, and oxidative stability of the interesterified hard fat from rice bran oil, fully hydrogenated soybean oil, and coconut oil through lipase-catalyzed reaction. Food Bioprocess Technol 5:2474–87. Adhikari P, Zhu XM, Gautam A, Shin JA, Hu JN, Lee JH, Akoh CC, Lee KT. 2010b. Scaledup production of zero-trans margarine fat using pine nut oil and palm stearin. Food Chem 119:1332–8. Akoh CC, Kim BH. 2008. Structured lipids. In: Akoh CC, Min DB, editors. Food lipids— Chemistry, nutrition, and biotechnology. 3rd ed. Boca Raton: CRC Press. pp 841–64. Baeza-Jimenez R, Miranda K, Garcia HS, Otero C. 2013. Lipase-catalyzed glycerolysis of fish oil to obtain diacylglycerols. Grasas Aceites 64:237–42. Bai S, Aziz S, Khodadadi M, Mitri CB, St-Louis R, Kermasha S. 2013. Lipase-catalyzed synthesis of medium-long-medium type structured lipids using tricaprylin and trilinolenin as substrate models. J Am Oil Chem Soc 90:377–89. Bang HO, Dyerberg J, Stofferson E. 1978. Eicosapentaenoic acid and prevention of thrombosis and atherosclerosis? Lancet 2:117–9. Bebarta B, Jhansi M, Kotasthane P, Sunkireddy YR. 2013. Medium chain and behenic acid incorporated structured lipids from sal, mango and kokum fats by lipase acidolysis. Food Chem 136:889–94. Bilgic S, Yesilcubuk NS. 2012. Lipase-catalyzed acidolysis of olive oil with echium oil stearidonic acid: optimization by response surface methodology. J Am Oil Chem Soc 89:1971–80. Bispo P, Batista I, Bernardino RJ, Bandarra NM. 2014. Preparation of triacylglycerols rich in omega-3 fatty acids from sardine oil using a Rhizomucor miehei lipase: Focus in the EPA/DHA ratio. Appl Biochem Biotechnol 172:1866–81. Brys J, Wirkowska M, Gorska A, Ostrowska-Ligeza E, Brys A. 2014. Application of the calorimetric and spectroscopic methods in analytical evaluation of the human milk fat substitutes. J Therm Anal Calorim 118:841–8. Caballero E, Soto C, Olivares A, Altamirano C. 2014. Potential use of avocado oil on structured lipids MLM-type production catalysed by commercial immobilised lipases. PLoS One 9:e107749. Cabezas DM, Madoery R, Diehl BWK, Tomas MC. 2011. Application of enzymatic hydrolysis on sunflower lecithin using a pancreatic PLA2 . J Am Oil Chem Soc 88:443–6. Cao Y, Qi SJ, Zhang Y, Wang XN, Yang B, Wang YH. 2013. Synthesis of structured lipids by lipase-catalyzed interesterification of triacetin with camellia oil methyl esters and preliminary evaluation of their plasma lipid-lowering effect in mice. Molecules 18:3733–44. Carlson SE, Rhodes PG, Ferguson MG. 1986. Docosahexaenoic acid status of preterm infants at birth and following feeding with human milk or formula. Am J Clin Nutr 44:798–804. Casas-Godoy L, Marty A, Sandoval G, Ferreira-Dias S. 2013. Optimization of medium chain length fatty acid incorporation into olive oil catalyzed by immobilized Lip2 from Yarrowia lipolytica. Biochem Eng J 77:20–7. Cervera MAR, Venegas EV, Bueno RR, Garcia IR, Guil-Guerrero JL. 2013. Acyl migration evaluation in monoacylglycerols from Echium plantagineum seed oil and Marinol. J Biosci Bioeng 115:518–22. Chae MH, Park HK, Kwon KI, Kim JW, Hong SI, Kim Y, Kim BH, Kim IH. 2011. Lipasecatalyzed interesterification in packed bed reactor using 2 different temperatures. J Food Sci 76:C555–9. Chen BQ, Zhang H, Cheong LZ, Tan TW, Xu XB. 2012. Enzymatic production of ABA-type structured lipids containing omega-3 and medium-chain fatty acids: Effects of different acyl donors on the acyl migration rate. Food Bioprocess Technol 5:541–7. Chnadhapuram M, Sunkireddy YR. 2012. Preparation of palm olein enriched with medium chain fatty acids by lipase acidolysis. Food Chem 132:216–21. Choi JH, Kim BH, Hong SI, Kim Y, Kim IH. 2012. Synthesis of structured lipids containing pinolenic acid at the sn-2 position via lipase-catalyzed acidolysis. J Am Oil Chem Soc 89: 1449–54. Chopra R, Rastogi NK, Sambaiah K. 2011. Enrichment of rice bran oil with alpha-linolenic acid by enzymatic acidolysis: Optimization of parameters by response surface methodology. Food Bioprocess Technol 4:1153–63. Compton DL, Laszlo JA, Appell M, Vermillion KE, Evans KO. 2014. Synthesis, purification, and acyl migration kinetics of 2-monoricinoleoylglycerol. J Am Oil Chem Soc 91:271–9. Compton DL, Laszlo JA, Evans KO. 2013. Influence of solid supports on acyl migration in 2-monoacylglycerols: Purification of 2-MAG via flash chromatography. J Am Oil Chem Soc 90:1397–403. da Silva RC, Soares FASD, Fernandes TG, Castells ALD, da Silva KCG, Goncalves MIA, Ming CC, Goncalves LAG, Gioielli LA. 2011. Interesterification of lard and soybean oil blends catalyzed by immobilized lipase in a continuous packed bed reactor. J Am Oil Chem Soc 88:1925–33. deAraujo MEMB, Campos PRB, Noso TM, Alberici RM, Cunha IBD, Simas RC, Eberlin MN, Carvalho PD. 2011. Response surface modelling of the production of structured lipids from soybean oil using Rhizomucor miehei lipase. Food Chem 127:28–33. Dhara R, Singhal RS. 2014. Process optimization of enzyme catalyzed production of dietary diacylglycerol (DAG) using TLIM as biocatalyst. J Oleo Sci 63:169–76.

Elibal B, Suzen HF, Aksoy HA, Ustun G, Tuter M. 2011. Production of structured lipids containing conjugated linolenic acid: Optimisation by response surface methodology. Int J Food Sci Technol 46:1422–7. Farfan M, Villalon MJ, Ortiz ME, Nieto S, Bouchon P. 2013. The effect of interesterification on the bioavailability of fatty acids in structured lipids. Food Chem 139:571–7. Foresti ML, Ferreira ML. 2010. Lipase-catalyzed acidolysis of tripalmitin with capric acid in organic solvent medium: Analysis of the effect of experimental conditions through factorial design and analysis of multiple responses. Enzyme Microb Technol 46:419–29. Gokce J, Yesilcubuk NS, Ustun G. 2013. Enzymatic production of low-calorie structured lipid from Echium seed oil and lauric acid: Optimisation by response surface methodology. Int J Food Sci Technol 48:1383–9. Hamam F, Budge SM. 2010. Structured and specialty lipids in continuous packed column reactors: Comparison of production using one and two enzyme beds. J Am Oil Chem Soc 87:385–94. Hong SI, Kim Y, Kim CT, Kim IH. 2011. Enzymatic synthesis of lysophosphatidylcholine containing CLA from sn-glycero-3-phosphatidylcholine (GPC) under vacuum. Food Chem 129:1–6. Ifeduba EA, Akoh CC. 2014. Modification of stearidonic acid soybean oil by immobilized Rhizomucor miehei lipase to incorporate caprylic acid. J Am Oil Chem Soc 91:953–65. Ilyasoglu H, Gultekin-Ozguven M, Ozcelik B. 2011. Production of human milk fat substitute with medium-chain fatty acids by lipase-catalyzed acidolysis: Optimization by response surface methodology. LWT-Food Sci Technol 44:999–1004. Jandack RJ, Whiteside JA, Holcombe BN, Volpenhein RA, Taulbee JD. 1987. The rapid hydrolysis and efficient absorption of triglycerides with octanoic-acid in the 1 position and 3 position and long-chain fatty acid in the 2 position. Am J Clin Nutr 45:940–5. Jennings BH, Shewfelt RL, Akoh CC. 2010. Food applications of a rice bran oil structured lipid in fried sweet potato chips and an energy bar. J Food Quality 33:679–92. Jin J, Li D, Zhu XM, Adhikari P, Lee KT, Lee JH. 2011. Production of diacylglycerols from glycerol monooleate and ethyl oleate through free and immobilized lipase-catalyzed consecutive reactions. New Biotechnol 28:190–5. Kadivar S, DeClercq N, Vande Walle D, Dewettinck K. 2014. Optimisation of enzymatic synthesis of cocoa butter equivalent from high oleic sunflower oil. J Sci Food Agric 94: 1325–31. Kanjilal S, Kaki SS, Rao BVSK, Sugasini D, Rao YP, Prasad RBN, Lokesh BR. 2013. Hypocholesterolemic effects of low calorie structured lipids on rats and rabbits fed on normal and atherogenic diet. Food Chem 136:259–65. Kelley NS, Hubbard NE, Erickson KL. 2007. Conjugated linoleic acid isomers and cancer. J Nutr 137:2599–607. Kennedy A, Martinez K, Schmidt S, Mandrup S, LaPoint K, McIntosh M. 2010. Antiobesity mechanisms of action of conjugated linoleic acid. J Nutr Biochem 21:171–9. Khodadadi M, Aziz S, St-Louis R, Kermasha S. 2013. Lipase-catalyzed synthesis and characterization of flaxseed oil-based structured lipids. J Funct Foods 5:424–33. Khodadadi M, Kermasha S. 2014a. Modeling lipase-catalyzed interesterification of flaxseed oil and tricaprylin for the synthesis of structured lipids. J Mol Catal B Enzym 102:33–40. Khodadadi M, Kermasha S. 2014b. Optimization of lipase-catalyzed interesterification of flaxseed oil and tricaprylin using response surface methodology. J Am Oil Chem Soc 91: 395–403. Kim BH, Akoh CC. 2006. Characteristics of structured lipid prepared by lipase-catalyzed acidolysis of roasted sesame oil and caprylic acid in a bench-scale continuous packed bed reactor. J Agric Food Chem 54:5132–41. Kim BH, Lumor SE, Akoh CC. 2008. Trans-free margarines prepared with canola oil/palm stearin/palm kernel oil-based structured lipids. J Agric Food Chem 56:8195–205. Kim HR, Hou CT, Lee KT, Kim BH, Kim IH. 2010. Enzymatic synthesis of structured lipids using a novel cold-active lipase from Pichia lynferdii NRRL Y-7723. Food Chem 122:846–9. Kim JH, Yoon SH. 2014. Effects of organic solvents on transesterification of phospholipids using phospholipase A2 and lipase. Food Sci Biotechnol 23:1207–11. Kim S, Kim IH, Akoh CC, Kim BH. 2014. Enzymatic production of cocoa butter equivalents high in 1-palmitoyl-2-oleoyl-3-stearin in continuous packed bed reactors. J Am Oil Chem Soc 91:747–57. Kleiner L, Vazquez L, Akoh CC. 2012. Increasing stearidonic acid (SDA) in modified soybean oil by lipase-mediated acidolysis. J Am Oil Chem Soc 89:1267–75. Kocak D, Keskin H, Fadiloglu S, Kowalski B, Gogus F. 2011. Characterization of terebinth fruit oil and optimization of acidolysis reaction with caprylic and stearic acids. J Am Oil Chem Soc 88:1531–8. Lee JH, Son JM, Akoh CC, Kim MR, Lee KT. 2010. Optimized synthesis of 1,3-dioleoyl-2palmitoylglycerol-rich triacylglycerol via interesterification catalyzed by a lipase from Thermomyces lanuginosus. New Biotechnol 27:38–45. Lee K, Shin JA, Lee KT. 2012. Enzymatic synthesis of structured lipids containing conjugated linolenic acids extracted from pomegranate seed oil and their physicochemical characteristics. J Agric Sci 39:395–405. Lei Q, Lee WL, Li TH. 2013. Design and synthesis of 1,3-dicapryloyl-2-acetylglycerol as molecular probe for triacylglycerol metabolism study. Eur J Lipid Sci Technol 115:232–8. Lemaitre-Delaunay D, Pachiaudi C, Laville M, Pousin J, Armstrong M, Lagarde M. 1999. Blood compartmental metabolism of docosahexaenoic acid (DHA) in humans after ingestion of a single dose of [13 C]DHA in phosphatidylcholine. J Lipid Res 40:1867–74. Li D, Adhikari P, Shin JA, Lee JH, Kim YJ, Zhu XM, Hu JN, Jin J, Akoh CC, Lee KT. 2010. Lipase-catalyzed interesterification of high oleic sunflower oil and fully hydrogenated soybean oil comparison of batch and continuous reactor for production of zero trans shortening fats. LWT-Food Sci Technol 43:458–64. Li RY, Pande G, Sabir JSM, Baeshen NA, Akoh CC. 2014. Enrichment of refined olive oil with palmitic and docosahexaenoic acids to produce a human milk fat analogue. J Am Oil Chem Soc 91:1377–85. Li X, Chen JF, Yang B, Li DM, Wang YH, Wang WF. 2014. Production of structured phosphatidylcholine with high content of DHA/EPA by immobilized phospholipase A1 -catalyzed transesterification. Int J Mol Med Sci 15:15244–58. Meng Z, Lu S, Geng WX, Huang JH, Wang XG, Liu YF. 2014. Preliminary study on acyl incorporation and migration in the production of 1,3-diacylglycerol by immobilized Lipozyme RM IM-catalyzed esterification. Food Sci Technol Res 20:175–82. Mensink RP, Katan MB. 1990. Effect of dietary trans fatty acids on high-density and low-density lipoprotein cholesterol levels in healthy subjects. N Engl J Med 323:439–45.

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Research trends in the SLs synthesis . . .

Research trends in the SLs synthesis . . .

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Mitra K, Kim SA, Lee JH, Choi SW, Lee KT. 2010. Production and characterization of alphalinolenic acid enriched structured lipids from lipase-catalyzed interesterification. Food Sci Biotechnol 19:57–62. Mohamed IO. 2012. Lipase-catalyzed synthesis of cocoa butter equivalent from palm olein and saturated fatty acid distillate from palm oil physical refinery. Appl Biochem Biotechnol 168:1405–15. Mohamed IO. 2013. Lipase-catalyzed acidolysis of palm mid fraction oil with palmitic and stearic fatty acid mixture for production of cocoa butter equivalent. Appl Biochem Biotechnol 171:656–66. Mounika C, Reddy SY. 2012. Specialty fats enriched with behenic and medium chain fatty acids from palm stearin by lipase acidolysis. J Am Oil Chem Soc 89:1691–7. Mu H, Xu X, Hoy CE. 1998. Production of specific-structured triacylglycerols by lipasecatalyzed interesterification in a laboratory-scale continuous reactor. J Am Oil Chem Soc 75:1187–93. Nagachinta S, Akoh CC. 2012. Enrichment of palm olein with long chain polyunsaturated fatty acids by enzymatic acidolysis. LWT-Food Sci Technol 46:29–35. Nagao T, Watanabe Y, Maruyama K, Momokawa Y, Kishimoto N, Shimada Y. 2011. One-pot enzymatic synthesis of docosahexaenoic acid-rich triacylglycerols at the sn-1(3) position using by-product from selective hydrolysis of tuna oil. New Biotechnol 28:7–13. Nunes PA, Pires-Cabral P, Guillen M, Valero F, Ferreira-Dias S. 2012. Batch operational stability of immobilized heterologous Rhizopus oryzae lipase during acidolysis of virgin olive oil with medium-chain fatty acids. Biochem Eng J 67:265–8. Ochoa AA, Hernandez-Becerra JA, Cavazos-Gardun A, Garcia HS, Vernon-Carter EJ. 2013. Phosphatidylcholine enrichment with medium chain fatty acids by immobilized phospholipase A1 -catalyzed acidolysis. Biotechnol Prog 29:230–6. Otero C, Marquez P, Criado M, Hernandez-Martin E. 2013. Enzymatic interesterification between pine seed oil and a hydrogenated fat to prepare semi-solid fats rich in pinolenic acid and other polyunsaturated fatty acids. J Am Oil Chem Soc 90:81–90. Ozturk T, Ustun G, Aksoy HA. 2010. Production of medium-chain triacylglycerols from corn oil: Optimization by response surface methodology. Bioresour Technol 101:7456–61. Pacheco C, Crapiste GH, Carrin ME. 2010. Lipase-catalyzed acidolysis of sunflower oil: Kinetic behavior. J Food Eng 98:492–7. Pacheco C, Palla C, Crapiste GH, Carrin ME. 2013. Optimization of reaction conditions in the enzymatic interesterification of soybean oil and fully hydrogenated soybean oil to produce plastic fats. J Am Oil Chem Soc 90:391–400. Palla CA, Pacheco C, Carrin ME. 2012. Production of structured lipids by acidolysis with immobilized Rhizomucor miehei lipases: Selection of suitable reaction conditions. J Mol Catal B Enzym 76:106–15. Pande G, Akoh CC. 2012. Enzymatic synthesis of trans-free structured margarine fat analogues using stearidonic acid soybean and high stearate soybean oils. J Am Oil Chem Soc 89:1473–84. Pande G, Akoh CC. 2013. Enzymatic synthesis of trans-free structured margarine fat analogs with high stearate soybean oil and palm stearin and their characterization. LWT-Food Sci Technol 50:232–9. Pande G, Sabir JSM, Baeshen NA, Akoh CC. 2013a. Enzymatic synthesis of extra virgin olive oil based infant formula fat analogue s containing ARA and DHA: One-stage and two-stage syntheses. J Agric Food Chem 61:10590–8. Pande G, Sabir JSM, Baeshen NA, Akoh CC. 2013b. Synthesis of infant formula fat analogs enriched with DHA from extra virgin olive oil and tripalmitin. J Am Oil Chem Soc 90: 1311–8. Perignon M, Lecomte J, Pina M, Renault A, Simonneau-Deve C, Villeneuve P. 2013. Activity of immobilized Thermomyces lanuginosus and Candida antarctica B lipases in interesterification reactions: Effect of the aqueous microenvironment. J Am Oil Chem Soc 90:1151–6. Qin XL, Huang HH, Lan DM, Wang YH, Yang B. 2014a. Typoselectivity of crude Geobacillus sp T1 lipase fused with a cellulose-binding domain and its use in the synthesis of structured lipids. J Am Oil Chem Soc 91:55–62. Qin XL, Wang YM, Wang YH, Huang HH, Yang B. 2011. Preparation and characterization of 1,3-dioleoyl-2-palmitoylglycerol. J Agric Food Chem 59:5714–9. Qin XL, Zhong JF, Wang YH, Yang B, Lan DM, Wang FH. 2014b. 1,3-Dioleoyl-2palmitoylglycerol-rich human milk fat substitutes: Production, purification, characterization and modeling of the formulation. Eur J Lipid Sci Technol 116:282–90. Ray J, Nagy ZK, Smith KW, Bhaggan K, Stapley AGF. 2013. Kinetic study of the acidolysis of high oleic sunflower oil with stearic-palmitic acid mixtures catalysed by immobilised Rhizopus oryzae lipase. Biochem Eng J 73:17–28. Ruan X, Zhu XM, Xiong H, Wang SQ, Bai CQ, Zhao Q. 2014. Characterisation of zero-trans margarine fats produced from camellia seed oil, palm stearin and coconut oil using enzymatic interesterification strategy. Int J Food Sci Technol 49:91–7. Sanchez DA, Tonetto GM, Ferreira ML. 2014. Enzymatic synthesis of 1,3-dicaproyglycerol by esterification of glycerol with capric acid in an organic solvent system. J Mol Catal B Enzym 100:7–18. Savaghebi D, Safari M, Rezaei K, Ashtari P, Farmani J. 2012. Structured lipids produced through lipase-catalyzed acidolysis of canola oil. J Agric Sci Technol 14:1297–310. Segura N, da Silva RC, Soares FASD, Gioielli LA, Jachmanian I. 2011. Valorization of beef tallow by lipase-catalyzed interesterification with high oleic sunflower oil. J Am Oil Chem Soc 88:1945–54. Sengupta A, Ghosh M. 2011. Hypolipidemic effect of mustard oil enriched with medium chain fatty acid and polyunsaturated fatty acid. Nutr 27:1183–93. Shin JA, Akoh CC, Lee KT. 2010. Enzymatic interesterification of anhydrous butterfat with flaxseed oil and palm stearin to produce low-trans spreadable fat. Food Chem 120:1–9. Silroy S, Ghosh M. 2011. Enzymatic synthesis of capric acid-rich structured lipids (MUM type) using Candida antarctica lipase. J Oleo Sci 60:275–80. Silroy S, Sengupta A, Bhattacharyya DK, Ghosh M. 2014. Optimization of reaction parameters of acidolysis reaction between mustard oil and capric acid by using Thermomyces lanuginosus lipase. J Food Sci Technol 51:715–21. Simoes T, Valero F, Tecelao C, Ferreira-Dias S. 2014. Production of human milk fat substitutes catalyzed by a heterologous Rhizopus oryzae lipase and commercial lipases. J Am Oil Chem Soc 91:411–9.

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Soares FASD, Osorio NM, da Silva RC, Gioielli LA, Ferreira-Dias S. 2013. Batch and continuous lipase-catalyzed interesterification of blends containing olive oil for trans-free margarines. Eur J Lipid Sci Technol 115:413–28. Sorensen ADM, Xu XB, Zhang L, Kristensen JB, Jacobsen C. 2010. Human milk fat substitute from butterfat: Production by enzymatic interesterification and evaluation of oxidative stability. J Am Oil Chem Soc 87:185–94. Stewart IM, Kristott J. 2004. European union chocolate directive defines vegetable fats for chocolate. Lipid Technol 16:11–4. Takeuchi H. 2010. Application of biotechnology in the development of a healthy oil capable of suppressing fat accumulation in the body. In: Bagchi D, Lau FC, Ghosh DK, editors. Biotechnology in functional foods and nutraceuticals. Boca Raton: CRC Press. p 104–12. Tang L, Hu JN, Zhu XM, Luo LP, Lei L, Deng ZY, Lee KT. 2012. Enzymatic interesterification of palm stearin with Cinnamomum camphora seed oil to produce zero-trans medium-chain triacylglycerols-enriched plastic fat. J Food Sci 77:C454–60. Tecelao C, Silva J, Dubreucq E, Ribeiro MH, Ferreira-Dias S. 2010. Production of human milk fat substitutes enriched in omega-3 polyunsaturated fatty acids using immobilized commercial lipases and Candida parapsilosis lipase/acyltransferase. J Mol Catal B Enzym 65:122–7. Teichert SA, Akoh CC. 2012. Modifications of stearidonic acid soybean oil by enzymatic acidolysis for the production of human milk fat analogues. J Agric Food Chem 59:13300–10. Tomarelli RM, Meyer BJ, Weaber JR, Bernhart FW. 1968. Effect of positional distribution on the absorption of the fatty acids of human milk and infant formulas. J Nutr 95:583–90. Turan D, Yesilcubuk NS, Akoh CC. 2012. Production of human milk fat analogue containing docosahexaenoic and arachidonic acids. J Agric Food Chem 60:4402–7. Turan D, Yesilcubuk NS, Akoh CC. 2013. Enrichment of sn-2 position of hazelnut oil with palmitic acid: Optimization by response surface methodology. LWT-Food Sci Technol 50:766–72. Wang XS, Li M, Wang T, Jin QZ, Wang XG. 2014a. An improved method for the synthesis of 2-arachidonoylglycerol. Process Biochem 49:1415–21. Wang XS, Liang L, Yu ZZ, Rui LL, Jin QZ, Wang XG. 2014b. Scalable synthesis of highly pure 2-monoolein by enzymatic ethanolysis. Eur J Lipid Sci Technol 116:627–34. Wang XS, Wang XG, Jin QZ, Wang T. 2013. Improved synthesis of monopalmitin on a large scale by two enzymatic methods. J Am Oil Chem Soc 90:1455–63. Wang YY, Xia L, Xu XB, Xie L, Duan ZQ. 2012. Lipase-catalyzed acidolysis of canola oil with caprylic acid to produce medium-, long- and medium-chain-type structured lipids. Food Bioprod Process 90:707–12. Xu X. 2000. Production of structured lipids: process reaction and acyl migration. INFORM 11:1121–31. Yamada K, Ibuki M, McBrayer T. 2005. Cocoa butter, cocoa butter equivalents, and cocoa butter replacers. In: Lai OM, Akoh CC, editors. Healthful lipids. Champaign: AOCS Press. p 642–64. Yang B, Wang WF, Zeng FK, Li T, Wang YH, Li L. 2012. Production and oxidative stability of a soybean oil containing conjugated linoleic acid produced by lipase catalysis. J Food Biochem 35:1612–8. Yang D, Gan LJ, Shin JA, Kim S, Hong ST, Park SH, Lee JH, Lee KT. 2013. Antioxidative activities of Ginkgo biloba extract on oil/water emulsion system prepared from an enzymatically modified lipid containing alpha-linolenic acid. J Food Sci 78:C43–9. Yang HL, Mu Y, Chen HT, Su CY, Yang TK, Xiu ZL. 2014a. Sn-1,3-specific interesterification of soybean oil with medium-chain triacylglycerol catalyzed by Lipozyme TL IM. Chin J Chem Eng 22:1016–20. Yang KZ, Bi YL, Sun SD, Yang GL, Ma SM, Liu W. 2014b. Optimisation of Novozym-435catalysed esterification of fatty acid mixture for the preparation of medium- and long-chain triglycerides (MLCT) in solvent-free medium. Int J Food Sci Technol 49:1001–11. Yeoh CM, Phuah ET, Tang TK, Siew WL, Abdullah LC, Choong TSY. 2014. Molecular distillation and characterization of diacylglycerol-enriched palm olein. Eur J Lipid Sci Technol 12:1654–63. Yuksel A, Yesilcubuk NS. 2012. Enzymatic production of human milk fat analogues containing stearidonic acid and optimization of reactions by response surface methodology. LWT-Food Sci Technol 46:210–6. Zhang JH, Jiang YY, Lin Y, Sun YF, Zheng SP, Han SY. 2013. Structure-guided modification of Rhizomucor miehei lipase for production of structured lipids. PLoS One 8:e67892. Zhao SQ, Hu JN, Zhu XM, Bai CQ, Peng HL, Xiong H, Hu JW, Zhao Q. 2014. Characteristics and feasibility of trans-free plastic fats through Lipozyme TL IM-catalyzed interesterification of palm stearin and Akebia trifoliata variety Australis seed oil. J Agric Food Chem 62:3293–300. Zhao TT, No DS, Kim BH, Garcia HS, Kim Y, Kim IH. 2014. Immobilized phospholipase A1-catalyzed modification of phosphatidylcholine with n-3 polyunsaturated fatty acid. Food Chem 157:132–40. Zhu XM, Hu JN, Lee JH, Dan Y, Lee KT. 2014. Oxidation and antioxidative effects of rosemary extract and catechin on enzymatically modified lipids containing different total and positional fatty acid compositions. Food Sci Biotechnol 23:1389–96. Zou XG, Hu JN, Zhao ML, Zhu XM, Li HY, Liu XR, Liu R, Deng ZY. 2014a. Lipozyme RM IM-catalyzed acidolysis of Cinnamomum camphora seed oil with oleic acid to produce human milk fat substitutes enriched in medium-chain fatty acids. J Agric Food Chem 62: 10594–603. Zou XQ, Huang JH, Jin QZ, Guo Z, Cheong LZ, Xu XB, Wang XG. 2014b. Preparation of human milk fat substitutes from lard by lipase-catalyzed interesterification based on triacylglycerol profiles. J Am Oil Chem Soc 91:1987–98. Zou XQ, Huang JH, Jin QZ, Liu YF, Song ZH, Wang XG. 2011. Lipase-catalyzed preparation of human milk fat substitutes from palm stearin in a solvent-free system. J Agric Food Chem 59:6055–63. Zou XQ, Huang JH, Jin QZ, Liu YF, Song ZH, Wang XG. 2012. Lipase-catalyzed synthesis of human milk fat substitutes from palm stearin in a continuous packed bed reactor. J Am Oil Chem Soc 89:1463–72.

Recent Research Trends on the Enzymatic Synthesis of Structured Lipids.

Structured lipids (SLs) are lipids that have been chemically or enzymatically modified from their natural biosynthetic form. Because SLs are made to p...
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