VE 3-MCPD VA CONG NGHE SAN XUAT NC TNG SACH

TS. Tran Bch Lam HBK tp HCM

1. Ve 3-MCPD Mc o oc hai cua cac dan xuat chloropropanol Nhng nghien cu ve oc tnh cua 3-MCPD thc hien tren vi sinh vat, chuot bach va chuot cong cho thay: Khi tiem 3MCPD co nguyen t anh dau 14C tren chuot cong lieu 100mg/kg the trong thay 30% bai tiet dang CO2, 8,5% bai tiet nguyen trang qua nc tieu. Mot nghien cu khac tng t, dung phng phap anh dau 36Cl th nhan thay 23% bai tiet qua nc tieu dang beta-chlorolactate. Chng to co ao thai. Theo cong bo cua WHO FOOD ADDITIVES SERIES 48 da tren nhieu ket qua nghien cu th s chuyen hoa 3MCPD ong vat co vu chu yeu la tao thanh betachlorolactate, va axit oxalic, trong khi chuyen hoa vi khuan chu yeu tao glycidol la mot chat gay ot bien gen. Beta-chlorolactate co tac dung km ham mot so enzyme lam giam hoat tnh cua tinh trung, anh hng en tnh nang sinh san cua chuot. Tang nong o ure va creatin trong mau anh hng en chc nang than. Lieu gay chet ty le 50% (LD50) cua 3-chloro-1,2-propanediol qua ng mieng oi vi chuot cong la 150 mg/kg the trong (Ericsson & Baker, 1970). anh gianh lng 3-MCPD (FDA My nam 2000) ve kha nang gay ung th chuot a xac nh lieu dung 2,1 g/kg the trong mot ngay co xac suat gay ung th chuot cong la 1/106. C quan nay khong khang nh c 3-chloro-1,2-propanediol co phai la mot chat gay ung th ngi hay khong. Uy ban khoa hoc Thc pham EU (SCF) Joint WHO/FAO Expert Committee on Food Additives (JECFA) a khuyen cao ve ngng 3-MCPD toi a moi ngay (Tolerable Daily Intake) la 2 g/kg the trong. ieu kien hnh thanh oc to Nghien cu phan ng hnh thanh va phan huy 3-MCPD (DOLEZAL M. ; CALTA P. ; VELISEK J 2004) thay rang: k1 k2

Glycerol + Cl-

Chloropropanol

Phan huy

Phan ng nay tao ra cac san pham: monochloropropanol, dichloropropanol, monochloropropanediol, nhng nhieu nhat la 1,3- dichloro- 2- propanol (1,3- DCP) va 3- monochloropropanol (3- MCPD).

3- monochloropropanol (3- MCPD)

1,3- dichloro- 2- propanol (1,3- DCP)

Cng o phan ng tao 3-MCPD phu thuoc manh vao nhiet o. ieu kien toi u la 2300C th lng 3-MCPD tao thanh la 50 mg/kg glycerol tham gia phan ng. 1000C ham lng 3-MCPD sinh ra ch la 0,6mg/kg. Hang so toc o phan ng k1 tao 3-MCPD t glycerol nho hn hang so toc o phan ng k2 phan huy 3-MCPD. 2. Thc pham nao co cha 3 MCPD Ket qua khao sat 300 mau thc pham, 90 mau nc tng va nhieu phu lieu thc pham chau Au va Canada thay rang 89/300 san pham thc pham c khao sat co cha 3MCPD, gom cac san pham nng (banh m, banh qui man), san pham rang (ca phe) ham lng trung bnh 0,012ppm, cac phu lieu la dextrin vang san xuat bang phng phap axit, malt bia cung co chat nay. Trong so cac thc pham c khao sat th nc tng, dau hao la nhng san pham co ham lng 3MCPD cao nhat ma nguyen nhan la phng phap san xuat. 22% so mau tng EU phan tch co oc to chloropropanol, ham lng cao nhat tm thay la 93ppm. Ham lng trung bnh cua 90 mau nc tng xet nghiem Canada la 18ppm, trong o mau co ham lng cao nhat la 330ppm. Nc tng do lam gia v, c dung trong ba an hoac dung trong che bien, nen lng s dung nho, chiem khoang t 0,1 en 1% ham lng thc an. 3. Lam the nao e san xuat nc tng khong co chloropropanol Nc tng, x dau, tau v yeu la cac san pham thuy phan t protein thc vat con goi chung la HVP (hydrolyzed vegetable protein) . Viet Nam, nc tng la san pham thc pham truyen thong c s dung pho bien khap 3 mien Bac, Trung, Nam. Nguyen lieu: Nguyen lieu san xuat tng la cac nguon protein thc vat, co the t hat: - Lua m, 2

- Ngo hat (bap) - au nanh Hay t banh kho dau au nanh, au phung hoac gluten bot m, gluten bap Hien tai Viet Nam co cac nguon nguyen lieu nh sau ang c s dung: Ba kho au nanh trch ly cua Argentina Ba kho au phong trch ly cua An o Ba kho au nanh trch ly cua My (au nanh t My va Argentina la GMO) Banh kho dau au phong ep thu cong con 5-8% chat beo Banh kho dau au phong ep cong nghiep con 3-5% chat beo Ham lng protein tong trong cac nguyen lieu nay 42-50%. Ham lng chat beo t 0,1 en 8% Cong nghe: S thuy phan protein la c s cua cac phng phap cong nghe che bien nc tng n H2O n H2O n H2O Protein peton petide axit amin Xt xt xt Ban chat cua s thuy phan protein la s thuy phan lien ket peptide. Do lien ket peptide la mot lien ket manh, s thuy phan xay ra trong ieu kien co xuc tac. Tac nhan xuc tac hoa hoc la axit hoac kiem va tac nhan xuc tac hoa sinh hoc la nhom enzym thuy phan protein co ten chung la protease. Trong che bien, s thuy phan protein c ng dung e thu nhan cac san pham thuy phan hoan toan hoac thu nhan cac san pham thuy phan cha hoan toan. Cac san pham thuy phan cha hoan toan (Protein hydrolysates) hay b ang, Nhat la khi no c thuy phan bi cac protease cua vi khuan. V ang lien quan ti cac peptide cha cac axit amin k nc. San pham co v ang khi mc o thuy phan, ch at t 4 en 40%. V ang ch anh hng en tnh chat cam quan, khong anh hng en gia tr dinh dng. e san xuat nc tng co ti 3 phng phap cong nghe: cong nghe vi sinh, cong nghe hoa hoc va cong nghe enzym. Phng phap cong nghe axit nc ta cho ti nay nc tng cong nghiep c san xuat t banh dau chu yeu bang phng phap thuy phan hoa hoc s dung tac nhan xuc tac la HCl. Quy trnh cong nghe nh s o sau:

Banh dau XAY NHO

HCl

THUY PHAN E NGUOI TRUNG HOA E LANG LOC THO

Na2CO3

BA Dd NaCl

Phu gia

PHOI CHE LOC TINH THANH TRUNG

NAU

Loc

Ba

Nc tng
Dung HCl nong o 6-10 N, nhiet o 100 1800C, thi gian thuy phan 24 en 72 gi. Neu gia tang ap suat, se giam c thi gian. Do nhiet o cao va nong o axit ac, mot so axit amin b pha huy trong qua trnh thuy phan. Tryptophan b pha huy hoan toan, cac axit amin cha lu huynh b mat 10-30%. Cac axit amin cha nhom -OH b phan huy mot phan Trong thc te phng phap thuy phan bang axit a c ng dung trong ky nghe san xuat nc tng hoa giai con goi la x dau hay tau v yeu. Phng phap thuy phan bang axit co u iem la re va nhanh, hieu suat thuy phan cao t 85 en 90 %, thi gian

va quy trnh san xuat c rut ngan, san pham giau axit amin va de bao quan. Mui v nc tng rat ngot va thm. Nhc iem cua thuy phan bang axit la: Chi ph nang lng va thiet b cao do phai chu nhiet va chong axit an mon, viec s dung HCl ac oc hai va gay o nhiem moi trng, trong qua trnh thuy phan nhiet o cao vi xuc tac axit HCl ac, se lam phan huy hoan toan Trp va mot phan Thr, Ser, Met, Cys. Ngoai ra khi nong o HCl cao va nhiet o cao thng xay ra phan ng gia Cl2 hoac HCl vi glycerol co trong chat beo sinh oc to 3-MCPD. Theo quy nh cua Bo Y te Viet Nam ve an toan thc pham, nong o toi a cho phep trong san pham nc tng la 1mg/kg. cac nc EU gii han ham lng 3-MCPD trong nc tng la 0,02ppm. Chon cong nghe thay the Ve nguyen tac co the dung kiem e thuy phan nhng tai sao trong cong nghiep rat han che thuy phan protein bang kiem. S dung xuc tac kiem la NaOH, nong o 4-8 N, nhiet o 100 - 1100C, thi gian 24 en 36 gi. Thuy phan trong ieu kien nay th tryptophan c bao toan, nhng xay ra hien tng racemic hoa. San pham thuy phan la hon hp racemic D,L-aminoacid, lam giam gia tr dinh dng. Ngoai ra con xay ra s oxy hoa mot so axit amin khac. Kiem xuc tac cho phan ng tao lysinoalanine lam giam lysine trong thc pham V vay trong san xuat thc pham t khi dung kiem e thuy phan protein Phng phap cong nghe vi sinh Giong nh san xuat nc mam tan dung nguon enzym ngay trong ban than nguyen lieu, trong san xuat tng, ngi ta s dung nguon enzym protease do vi sinh vat sinh ra trong qua trnh len men. ac iem cua viec len men bi vi sinh vat la hieu suat thuy phan thap va thi gian thuy phan keo dai. V vay san pham proteolysat la hon hp gom ca protein, pepton, peptide va axit amin, ma ien hnh la tng Bac. Cac san pham nay thng kho bao quan, do trong san pham co nhieu enzym khac gay nen s bien oi chat lng v vay can co bien phap c che enzym hay thanh trung san pham khi a thuy phan at yeu cau. Cac enzym endoprotease cua vi khuan thuy phan ac hieu tai v tr lien ket cac axit amin k nc. V vay cac peptides tao thanh se co axit amin k nc au chuoi, lam tang kha nang b ang. Cung co the ket hp cong nghe vi sinh va axit e khac phuc nhc iem. Phng phap cong nghe vi sinh co quy trnh cong nghe nh sau:

BANH DAU NAU AP SUAT LAM NGUOI XAY NHUYEN Vi sinh vat CAY THUY PHAN 1 VSV , dd NaCl THUY PHAN 2 LOC 3 ngay 3 en 6 thang Ba

TIET TRUNG

Nc tng

e rut ngan thi gian va on nh chat lng san pham th nen s dung che pham enzym thay the len men bang vi sinh vat. Phng phap cong nghe enzym Quy trnh cng ngh sn xut nc tng bang phng phap enzym nh sau: Theo e ngh cua cong ty Novo quy trnh enzyme vi 5 enzym c phoi hp s dung gom protease, cellulase, amylase. Quy trnh nay co u iem la ieu kien thuy phan on hoa, hoan toan khong s dung hoa chat, khong lam bien oi thanh phan axit amin ban au, nhng hieu suat toi a ch at 70%. e khac phuc nhc iem cua ca hai phng phap tren va bo sung u iem cho nhau, ta ket hp thuy phan bang axit vi thuy phan bang enzym. 6

Cong nghe enzyme ket hp axit Co the thc hien thuy phan bang enzym trc roi sau o mi thuy phan bang axit hoac thuy phan bang axit roi sau o thuy phan bang enzym. Quy trnh c la chon nh sau:

BANH DAU
XAY NHO THANH TRUNG CHNH pH THUY PHAN 1 THUY PHAN 2 E NGUOI Na2CO3 TRUNG HOA LOC THO Phu gia PHOI CHE Ba Nau, loc NaCl

Enzym HCl

LOC TINH

Nc tng
7

Viec s dung enzym protease ket hp axit xuc tac qua trnh thuy phan co u iem la giam thieu s dung hoa chat oc hai, giam thieu o nhiem moi trng, rut ngan thi gian san xuat. Co the san xuat tren he thong thiet b san co.

So sanh cac phng phap

iem Phng phap cong ac nghe cong nghe Tac chat thuy Axit phan la Hoa hoc HCl ac Tnh chat u iem san pham Khong an toan Chi ph hoa do cha chat re 3- MCPD Thi gian ngan Nhc iem Tieu hao nang lng, an mon O nhiem moi trng

Kiem

1,3- DCP Tac chat thuy Tao phan la D-aminoacids NaOH ac Lysinoalanin

hao nang Chi ph hoa Tieu chat re lng, an mon thiet Thi gian ngan b Dien tch nha xng ln. Thi gian keo dai. S dung nhieu loai enzyme. Chi ph cao Hieu suat toi a 70% Chi ph enzym cao hn hoa chat

Vi sinh

Enzym

Enzym

Enzym ket hp axit

Tac nhan thuy An toan t tieu hao nang phan la vi sinh lng vat Giam 80% Tac chat thuy An toan phan la enzym Mui v co the nang lng ieu chnh pH trung tnh Thi gian ngan Tac chat thuy An toan Giam 70% phan chu yeu Mui v khong nang lng la enzym khac biet Thuy phan tren 85% protein

Ngoai 3 phng phap chnh neu tren con co nhng phng phap cong nghe tng t san xuat t nguyen lieu au nanh hat bang phng phap vi sinh, hay thay oi thanh phan nguyen lieu ba dau au nanh, ba dau au phung, ket hp gluten bot m... Moi phng phap san xuat se cho mot san pham co ten goi khac nhau va mui v cung khac nhau. Tuy vao th trng ma nha san xuat se chon loai san pham thch hp nhng can phai am bao tieu chuan ve sinh an toan thc pham. Quy trnh enzym ket hp a c chung toi chuyen giao cho cac doanh nghiep san xuat nc tng tai An Giang thong qua S Khoa hoc Cong nghe An Giang ngay 10/10/2005. at tieu chuan ve Chloropropanol (3-MCPD va 1,3-DCP).

Cac enzyme s dung la san pham enzyme cua Novo c JECFA (Joint FAO/WHO Expert Committee on Food Additives va FCC (Food Chemical Codex) cong nhan at tieu chuan dung cho thc pham va a c cong bo chat lng vi Bo Y te Viet nam. Tai lieu tham khao 1. C03017, C03018 and C03019: The origin and formation of 3-MCPD in foods and food ingredients, 2006 2. DOLEZAL M. ; CALTA P. ; VELISEK J., Formation and decomposition of 3chloropropane-1,2-diol in model systems , Czech journal of food sciences (Czech j. food sci.) ISSN 1212-1800 2004, vol. 22, NS, pp. 263-266 3. Products data sheet Novozymes 4. Schlatter, A.J. Baars, M. DiNovi, S. Lawrie, and R. Lorentzen, WHO food additives series: 48 Safety evaluation of certain food additives and contaminants , 3-chloro-1,2-propanediol