Tgp chi Khoa hpc - Cong nghe Thuy sdn
VAN DE TRAO QO\
HYDROXYAPATITE FROM SOLID FISH WASTE: A REVIEW HYDROXYAPTITE Tlf PHE PHAM RAN CV A CA: VANDE TRAO Ddi
Nguyen Vdn Hoa', Tran Thi Hodng Quyen', Tran Quang Ngpc'
Ngay nhan bai: 18/7/2014; Ngay phan bien thong qua 18/10/2014. Ngay duyet dang: 01/12/2014ABSTRACT
The waste from fish processing after the fish have been filleted can account for as much as 70% of the total catch weight. About 30% of such waste consists of scale and bone. Tills waste contains numerous valuable organic and inorganic components such as collagen and hydroxyapatite (HA), which have commercial value for use in manufacniringfiinctional foods, cosmetics, and biomedical products. In particular. HA has been widely used as a biocompatible ceramic but mainly for contact with bone tissue, due lo its resemblance lo mineral bone In this study, we have reviewed the characterization and applications of HA extracted from fish scale and bone. Moreover several HA-based highly porous composite materials used for bone tissue engineering were also presented Finally, a summary of HA preparation, characterization and applications will be given, together with the perspectives on this field of research
Keywords Hydroxyapatite. fish bone, bone engineering, blocomposites TOM TAT
Phd phdm tir qud trinh che bien cd cd thi len tai 70% so v&i long khoi lupng cd ban dau. Trong do. khodng 30%
khdi lupng phe phdm nay Id da cd vd xuang cd. Chung co chua mpl sd lucmg ddng ki chdt vd ca vd hOu ca co gid tii nhu collagen vd hydroxyapatite (HA). Ddy Id nhirng chdt co gid tri thuang mai cao trong sdn xudt thitc phdm chdc nang, my phdm vd cdc sdn phdm y sinh. Ddc biet, HA dd dupe su dung rong rdi du&i dang gom sinh hpc. chu yeu a phdn tiep xuc V&I md xuang. nha vdo thdnh phdn cua no tuang ttr nktr thdnh phdn voca cua xuang nguai. Trong bdi viet ndy, chung tdi gldi thieu long quan cdc nghien cuu gdn ddy ve dieu che, ti'nh chdt vd khd ndng ung dung ciia HA. ddng thai du dodn trien vpng cua linh vuc nghien cuu ndy lai Vi4l Nam
Tit khda: Hydroxyapatite. xuang cd, ky thudt xuang, vdt li^u td hpp sinh hpc I. INTRODUCTION
In the fish filleting process, only about one-third of the whole fish is used [4.5,10]. Thus, the filleting industry generates as much as 70% solid wastes from original fish materials. This waste consists of trimmings, fins, viscera, head, bone, and stdn. Majority of fishenes byproducts are presently employed to produce fish oil.
fishmeal, fertilizer, pet food and fish silage [4. 5]. However, most of these recycled products possess low economic value. Recent studies have identified a number of bioactive compounds fi^om remaining fish muscle proteins, collagen and gelatin, fish oil, fish bone, intemat organs and shetlfish and cnjstacean shells [14,15,16].
Generally, a far better profitability is obtained by producing human consumabtes and the highest profitability is cun'ently expected from bioactive compounds. These bioactive compounds can be extracted and purified with technologies varying from simple to complex and such compounds may include preparation and isolation of bioactive peptides, oligosaccharides, fatty acids, enzymes, water-soluble minerals and biopolymers for biotechnologicat and pharmaceutical applications. Furthermore, some of these bioactive compounds have been identified to possess nutraceutical potentials that are beneficial to human health promotion [8]. Therefore, the development of new technologies in search of novel bioactive compounds from manne processing by-products wilt bring more value out of what is today considered a waste and it represents unique challenges and opportunities for the seafood industry.
' TS. Nguyin Van Hba, ^TS. Tran Thj Hodng Quyen, ^ S . Tr&n Quang Ngpc Khoa C6ng ngh§ lh^rc phim - TnJong Dai hgc Nha Trang
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Hydroxyapatite {HA, Ca,(,{P0^)g(0H)2) was demonstrated to be an attractive material for biomedical applications mainly in orthopedics and dentistry since it presents a chemicat composition ctose to that of the bone (65 - 70 vrt%) and teeth { - 99 wt%). HA has good biocompatibitity, bioactivity, high osteoconductive and non-inflammatory behavior, and non-immunogenicity properties [21]. tt can also easily be processed to matrices with interconnecting pores bone ingrowth. Therefore, many methods have been used to prepare HA such as ultrasonic irradiafion, emulsion liquid membrane, microwave-mediated metathesis, expeditious microwave irradiation, RF thermal plasma, chemicat precipitation, microemutsion and hydrolysis [20]. However, these synthesis processes might be either complicated or biotogicatly unsafe, therefore, recently natural HA bioceramics has been extracted by normal catcinafion of some biowastes such as fish bones, bovine bones, teeth and bones of pig, etc Moreover, extraction of HA from bio-waste is both economicatty and environmentally preferable.
In the study, we would lit<e to present an overview of HA preparation, charactenzation and the perspectives of HA applications.
II. PREPARATION METHODS AND CHARACTERIZATION OF HA FROM FISH SCALE AND BONE So far, a variety of methods for synthesizing HA have been devetoped. The methods involve vanous types of known chemicat synthesis routes, including hydrothermal [30], liquid membrane [13]. precipitation [26], radio frequency thermal plasma [29], ultrasonic precipitation [2]. reverse micro emulsion [11], sol-gel [9] and polymer-assisted methods [27]. On the one hand, most of the procedures for synthesizing HA are biologically hazardous and they have a complicated process. These synthetic procedures have also led to the formaton of non-stoichiometnc products [17]. On the other hand, synthetic HA with a Ca/P ratio near 1.67 is stable when sintered in dry or wet air below 1200''C, but HA often loses its OH groups gradually at higher temperature. It can be transformed to oxyapatite such as Ca,(,0(POJg or Ca(POJgO, and after that these oxyapattes are normally dissociates into the pnaducts a-Ca.^{PO^^, Ca^PPj and Ca^P^Og at 1450°C [31]. Moreover, it is difficult to prepare HA crystals from aqueous solutions due to the high chemical affinity of the materials to some ions, the complex nature of the calcium phosphate system, and the roles of kinetic parameters [17].
Recently HA has been prepared from various bio-waste, including corals [7, 19], cuttlefish shells [23], fish scales and bones, porcine teeth and bones, and bovine bones [1, 25], tn particutar, extraction of HA from these sources is an interesting process. Itisnotonty because ofsomesupenor characteristics of the extracted HA, but also due to the environmental benefits of waste recovery. Moreover, compared with HA produced by synthetic methods as described above, HA extracted from bio-waste is a biologically safe (i.e.. no chemicals are often required) and potentially lucrative process, especially given the growing global demand for HA bioceramics.
Nowadays, a variety of techniques for producing HA from bio-wastes with appreciable quantities have been developed, especially for fish bone and fish scale. Generally, preparation of HA using these biowastes usually involves a few hours annealing during which the organic materials in the bone get removed, leaving pure HA as the residue (figure 1) There are now five primary methods including calcination, enzymatic hydrolysis, plasma processing, subcritical water pnacessing, and hydrothermal hydrolysis, the most widely applied technique of which is the calcination of by-products at high temperature due to its ease of targe scale production and relatively low cost.
HApradKt
e 1, Preparation of HA via extraction of minerals from some biowastes.
Copyright Elsevier and reproduced with permission |24|
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As indicated in Table 1. a few studies have recently reported on the utilization of fish scales and bones to produce HA. For example, Ozawa and Suzuki [22] prepared HA with microstructurai particles through treatment.They reported that fish bone heated at temperatures <1300°C maintains a porous structure, with a sintered wall and a major crystalline phase of hydroxyapatite (figure 2). Recently, Huang et al. [12] fabricated nano-sized HA particles with Ca/P ratio of 1.76 from fish scale using enzymatic hydrolysis method (figure 3). A tilapia fish-scale was hydrolyzed using protease N for 2.5 h, and fiavourzyme for 0.5 h at an optimal pH and temperature, followed by stining in a boiling water bath for 10 mins and subsequent sintering at 800-C.
Figure 2. SEM micrograph of fish-bone ceramic healed at (a) 800° and (b) 1000°C for 1 h in air Copyright John Wiley and SODS nith permission 122|
Table 1. Recent progress in the synthesis of HAp from fish scale and bone Authors/Year
Huang et al.
2011
Mondaletat.
2010
Coelhoetat.
2006 Ozawa and Suzuki 2002 Kim et al.
1997
Brief description Hydrolysis of a tilapia fish-scale using protease N for 2.5 h, and fiavourzyme for 0.5 h at an optimal pH and temperature, followed by stirring in a boiling water bath for 10 mm and subsequent sintering at SOCC Treatment of Labeo rohifa fish-scale using HCI and then NaOH, followed by stirring in a boiling water bath for 20 mm and subsequent calcination at various temperatures (800-1400"C)
Thermal treatment of bones originated form Brazilian river fish at 900"C for 4 - 12 h, followed by milling at 300 rpm for 2 - 16 h using a high-energy milling
Theimat treatment of Japanese sea bream fish bone at 600-1300='C
Thermal treatment of Tuna bone at 850 °C for 2 h
Characteristics of powder
Agglomerated HA nanopartictes
HA powder of submicrometric size Irregular stoichiometnc HA nanopartictes of various sizes HA of macroporous structure HA of microporous structure
Ref.
[12]
[18]
[6]
[22]
[3, 28]
Figure 3, SEM images of the HA powder (a), sintered HA (b) and EDS analysis of HA powder.
Copyright Elsevier with permission |12i
More recently, Kim et al. [28] isolated successfully pure natural nano-HA from tuna bone by employing the alkaline hydrolysis and thermal calcination methods. The thermal calcination method produces good crystallinity with dimensions 0.3 -1.0 /^m at 250''C for 5h. whereas the alkaline hydrolysis method produces nanostructured HA crystats with 17-71 nm tength and 5 -10 nm width at 900°C for 5h.
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Figure 4. SEM of the nanostructured HA powder obtained from the bones of Brazilian r i \ e r fish after milling for (a) 2h, (b) 4h, (c) 8b, and (d) 16h. Copyright AIP Publishing LLC with permission 16]
The elemental composition or purity of obtained HA is an important key for further applications. Raw fish bone contains large amount of organics, and even after heat treatment up to OOCC, it has partially shown grayish or black color with cariaon residue (0.5%) [22]. However, powder can become completety white by heating at 900°C and reduced to powder using a high-energy bait mill, in order to obtain a natural nanostructured HA powder (Figure 4) [6], The CaP rafio was not be changed by high temperature, while the main natural impurities such as sodium, magnesium, and potassium were slightly tost by heafing at 1300°C [22]. The chemical analyses in the previous studies suggest good quality offish-bone-extracted HA as a mineral resource for further application [3, 6, 18,22,28].
III. APPLICATIONS OF HA PREPARED FROM FISH SCALE AND BONE
Today the properties of HA extracted from fish scale and bones have been taken into investigation with the purpose of applying HA in many fields, especially in orthopedics and denfistry. For example, Huang et al. [12]
evaluated the biocompatibitity of HA crystals fi"om fish scale by cytotoxicity and cell proliferation with human osteobtast-like ceil MG-63 [12]. Under the osteogenic-inductive cultural condition. HA promoted osteogenic differentiation and mineralization of MG63 cells. As indicated by the in vitro mineralization, MG-63 cells can differentiate into bone forming celts (Figure 5). However, Kim et al. [28] checked the cytotoxicity and cell proliferation of MG-63 human osteosarcoma celt on micro and nanosized HA prepared from Thunnus obesus bone at different concentrations and days. They found that MG-63 cells grew rapidly on the control plate, whereas limited and lesser cell growth was observed on treated HA particles. The cell proliferation rate on HA was slower than that under the control. Moreover, the experiments demonstrated that micro and nanopartictes had similar cytotoxicity on the MG-63 ceil tine.
Figure S. Von Kossa slains of MG63 cells coculturcd with (A) 20mg;iiii MA extracted from tisli SLJIO 20mg/ml HA from Sigma pardcles. Mineralized matrix formation i:i ilie most reliable indicator of 11
capacity of materials. Copyright Elsevier with permission [12|
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IV. CONCLUSIONS AND PERSPECTIVESBesides the synthetic HA. a variety of HA extracted from fish scales and bones was aiso developed for potential applications. The HA from fish scales and bones has the size ft-om micro to nano. Their composition is suitable for medical and biotechnological applications. However, when considered for use in daily iife, the health risk associated with HA-based materials needs to be evaluated through Uie investigation of the toxicity and biocompatibitity of these matenats. Since Vietnam is one of the largest fish food producers in the world fish scales and bone have tremendous unexploited potential for preparing HA.
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