EP3902403A1 - A method of detecting harmful substances - Google Patents
A method of detecting harmful substancesInfo
- Publication number
- EP3902403A1 EP3902403A1 EP19836853.2A EP19836853A EP3902403A1 EP 3902403 A1 EP3902403 A1 EP 3902403A1 EP 19836853 A EP19836853 A EP 19836853A EP 3902403 A1 EP3902403 A1 EP 3902403A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- sample
- glycidol
- mcpd
- ester
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 69
- 239000000126 substance Substances 0.000 title description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 97
- 150000002148 esters Chemical class 0.000 claims abstract description 84
- -1 glycidol ester Chemical class 0.000 claims abstract description 50
- NOUDDDRYIOHXHS-UHFFFAOYSA-N 3-chloropropane-1,1-diol Chemical compound OC(O)CCCl NOUDDDRYIOHXHS-UHFFFAOYSA-N 0.000 claims abstract description 35
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 48
- 239000003960 organic solvent Substances 0.000 claims description 46
- 239000010410 layer Substances 0.000 claims description 40
- 239000002253 acid Substances 0.000 claims description 38
- 239000006172 buffering agent Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 31
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 26
- 125000004432 carbon atom Chemical group C* 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000011161 development Methods 0.000 claims description 25
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000003125 aqueous solvent Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 150000003138 primary alcohols Chemical class 0.000 claims description 21
- 230000003287 optical effect Effects 0.000 claims description 19
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 18
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 16
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 16
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 150000004703 alkoxides Chemical class 0.000 claims description 14
- 239000012044 organic layer Substances 0.000 claims description 14
- 239000001509 sodium citrate Substances 0.000 claims description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical group O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000872 buffer Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 238000011088 calibration curve Methods 0.000 claims description 11
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 10
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical group CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 229960005235 piperonyl butoxide Drugs 0.000 claims description 8
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 8
- MNHKUCBXXMFQDM-UHFFFAOYSA-N 4-[(4-nitrophenyl)methyl]pyridine Chemical compound C1=CC([N+](=O)[O-])=CC=C1CC1=CC=NC=C1 MNHKUCBXXMFQDM-UHFFFAOYSA-N 0.000 claims description 7
- 229940044613 1-propanol Drugs 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 239000008157 edible vegetable oil Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims description 3
- 125000001475 halogen functional group Chemical group 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 239000003153 chemical reaction reagent Substances 0.000 description 26
- 238000001514 detection method Methods 0.000 description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 9
- 239000000356 contaminant Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019482 Palm oil Nutrition 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000003925 fat Substances 0.000 description 4
- 235000019197 fats Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000002540 palm oil Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000011002 quantification Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- 150000002924 oxiranes Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 2
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 2
- 235000019774 Rice Bran oil Nutrition 0.000 description 2
- 235000019486 Sunflower oil Nutrition 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 125000003158 alcohol group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- 230000000711 cancerogenic effect Effects 0.000 description 2
- 239000000828 canola oil Substances 0.000 description 2
- 235000019519 canola oil Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 125000003262 carboxylic acid ester group Chemical group [H]C([H])([*:2])OC(=O)C([H])([H])[*:1] 0.000 description 2
- 231100000315 carcinogenic Toxicity 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 235000019219 chocolate Nutrition 0.000 description 2
- 239000006071 cream Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- 235000013310 margarine Nutrition 0.000 description 2
- 239000003264 margarine Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000008165 rice bran oil Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 235000011149 sulphuric acid Nutrition 0.000 description 2
- 239000002600 sunflower oil Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- RZWHKKIXMPLQEM-UHFFFAOYSA-N 1-chloropropan-1-ol Chemical class CCC(O)Cl RZWHKKIXMPLQEM-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000012041 food component Nutrition 0.000 description 1
- 239000005417 food ingredient Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 230000003902 lesion Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 231100000417 nephrotoxicity Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000002381 testicular Effects 0.000 description 1
- 231100000281 testicular toxicity Toxicity 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C3/00—Fats, oils, or fatty acids by chemical modification of fats, oils, or fatty acids obtained therefrom
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
- A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
- A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
Definitions
- This invention relates to the detection of harmful substances in edible foodstuffs, such as edible oils.
- Chloropropanols like 3-monochloropropane diol (3-mcpd), and their derivatives are foodborne contaminants that can be formed during the processing of various fatty acid rich foodstuffs.
- 3- mcpd are formed in the presence of glycerol, chloride ions and heat, and their metabolites have been linked to mechanisms that promote testicular and renal toxicity.
- the fatty acid esters of 3-mcpd are also commonly found in various food types and food ingredients, in particular refined edible oils.
- glycidols or glycido fatty acid esters may also be detected in significant concentrations in refined edible oils.
- GEs have been identified as a new class of food-processing contaminant and they contain a terminal epoxide group, with various fatty acid compositions. Furthermore, GEs have also been linked to the formation of carcinogenic lesions.
- 3-mcpd and glycidol have been categorised as “possible human carcinogens” (Group 2B) and “probably carcinogenic to humans” (Group 2A), respectively, by the International Agency for Research on Cancer (IARC).
- IARC International Agency for Research on Cancer
- regulatory bodies and current industry roadmaps have aimed to reduce the levels of 3-mcpd and GEs to less than 2 ppm and 1 ppm, respectively, by September 2019.
- GC/MS gas chromatography/mass spectrometer
- a method of quantitatively determining the combined amount of 3-monochloropropane diol (3-mcpd), 3-mcpd ester(s), glycidol and glycidol ester(s) suspected to be present in an original sample comprising:
- the amount of glycidol ester and/or glycidol in an original sample may be determined by subtracting the amount of 3-monochloropropane diol and/or 3-mcpd ester(s) determined in step (b) from the combined amount determined in step (a).
- the suitable compound comprising a pyridine ring may be independently selected from:
- Ft 1 represents N0 , CN, S0 3 R 4 , C0 2 R 5 , CONR 6 R 7 ;
- R 2 and R 3 independently represent halo, C 1-4 alkyl or OR 8 ;
- R 4 to R 7 independently represent C M O alkyl
- R 8 represents C 1-4 alkyl
- X represents H C1-4 alkyl, -COOH, or COOR 9a ;
- Y represents H, C1-4 alkyl, OR 9b , or NR 10 R 11 , SO3R 12 , CN, N0 2 , C0 2 R 13 , CONR 14 R 15 ;
- Z represents H, COR 16 , or -(CH 2 ) n Ar;
- W represents H, CH 2 OR 17 ;
- V represents H, C1-4 alkyl, -COOH, or COOR 18 ;
- R 9a and R 9b to R 18 represents H or C 1-4 alkyl;
- Ar represents an aromatic ring system;
- n is from 1 to 10;
- a and BB represent H, Ci- 4 alkyl, OR 19 , or NR 20 R 21 , S0 3 R 22 , CN, N0 , C0 2 R 23 , CONR 24 R 25 ; and
- R 19 to R 25 represents H or Ci- 4 alkyl, provided that when A is H then BB is not H and when BB is H then A is not H.
- the suitable compound comprising a pyridine ring may be selected from:
- the combined sample may be obtained by:
- the aqueous solvent mixture of step (ai) may comprise water and a buffering agent, where the pH of the aqueous solvent mixture is from 4 to 7, optionally wherein the buffering agent is sodium citrate buffer.
- the colour development agent in step (bi) may be an aqueous inorganic base, optionally wherein:
- the colour development agent may be aqueous potassium carbonate
- the concentration of the colour development agent may be from 500 nM to 1 M; and/or
- the aqueous inorganic base may be added in an amount sufficient to provide the colour- developed sample with a pH value of at least 1 1.
- the organic solvent added to the coloured sample in step (ci) may be selected from one or more of acetophenone, diethyl ether, toluene, ethyl acetate, optionally wherein the organic solvent is ethyl acetate.
- the 3-monochloropropane diol sample may be obtained by:
- the aqueous solvent mixture of step (aii) may comprise water and a buffering agent, where the pH of the aqueous solvent mixture is from 4 to 7, optionally wherein the buffering agent is sodium citrate buffer.
- the colour development agent in step (bii) the colour development agent may an aqueous inorganic base, optionally wherein: (iia) the colour development agent is aqueous potassium carbonate; and/or (iib) the concentration of the colour development agent is from 500 nM to 1 M.
- the organic solvent added to the coloured sample in step (cii) may be selected from one or more of acetophenone, diethyl ether, toluene, ethyl acetate, optionally wherein the organic solvent is ethyl acetate.
- the first sample may be obtained by:
- the organic solvent added to the original sample of step (aiii) may be iso-octane and/or chloroform.
- the base may be a hydroxide (e.g. sodium or potassium) and/or the primary alcohol having from 3 to 5 carbon atoms is 1 -butanol optionally wherein the concentration of the potassium hydroxide in the primary alcohol having from 3 to 5 carbon atoms is from 1 to 5 wt/vol%; or
- a hydroxide e.g. sodium or potassium
- the primary alcohol having from 3 to 5 carbon atoms is 1 -butanol optionally wherein the concentration of the potassium hydroxide in the primary alcohol having from 3 to 5 carbon atoms is from 1 to 5 wt/vol%; or
- the alkoxide may be a metal 1 -butoxide (e.g. sodium or potassium 1 -butoxide).
- a metal 1 -butoxide e.g. sodium or potassium 1 -butoxide
- the acid dissolved in water in step (ciii) is not hydrochloric acid, optionally wherein:
- the acid is acetic acid or H 2 SO 4 ;
- the concentration of the acid in water is from 1 to 3 vol%.
- the buffering agent in step (eiii) may be sodium citrate buffer and the buffering agent provides the first sample with a pH of from 4 to 7.
- the second sample may be obtained by:
- the organic solvent added to the original sample in step (aa) may be iso-octane and/or chloroform.
- the base in step (cc) may be a hydroxide (e.g. potassium or sodium hydroxide) and/or the primary alcohol having from 3 to 5 carbon atoms is 1 -butanol, optionally wherein the concentration of the potassium hydroxide in the primary alcohol having from 3 to 5 carbon atoms is from 1 to 5 wt/vol%.
- the acid dissolved in water in step (dd) is not hydrochloric acid, optionally wherein:
- the acid is acetic acid or H 2 SO 4 ;
- the concentration of the acid in water is from 1 to 3 vol%.
- the buffering agent in step (ff) may be sodium citrate buffer and the buffering agent provides the first sample with a pH of from 4 to 7.
- the acid and primary alcohol having from 3 to 5 carbon atoms used in step (aa) are H 2 SO 4 and 1 -propanol, respectively.
- the optical property measured may be selected from absorbance, transmittance or reflectance, optionally wherein the optical property measured is absorbance.
- the original sample may be an edible oil, an edible fat or a combination thereof.
- Fig. 1 Depicts the calibration curves prepared using standard samples containing: (a) a mixture of 3-mcpd, glycidol and their esters; and (b) 3-mcpd and its ester.
- Fig. 2 Depicts the sample preparation and detection of a combined amount of 3-mcpd, 3-mcpd ester, glycidol and/or glycidol esters.
- Fig. 3 Depicts the transesterification of 3-mcpd esters and glycidol esters to 3-mcpd and glycidol respectively.
- Fig. 4 Depicts the reaction of 3-mcpd and glycidol with 4-(4-nitrobenzyl)pyridine (NBP).
- Fig. 5 Depicts the sample preparation and detection of 3-mcpd and/or 3-mcpd ester.
- Fig. 6 Depicts the reaction of glycidol and glycidol esters with acid/alcohol.
- the composition contains any 3- monochloropropane diol and glycidol (and derivatives thereof).
- a method of quantitatively determining the combined amount of 3-monochloropropane diol (3- mcpd), 3-mcpd ester(s), glycidol and glycidol ester(s) suspected to be present in an original sample comprising:
- the word“comprising” may be interpreted as requiring the features mentioned, but not limiting the presence of other features.
- the word“comprising” may also relate to the situation where only the components/features listed are intended to be present (e.g. the word“comprising” may be replaced by the phrases“consists of” or“consists essentially of”). It is explicitly contemplated that both the broader and narrower interpretations can be applied to all aspects and embodiments of the present invention.
- the word“comprising” and synonyms thereof may be replaced by the phrase“consisting of” or the phrase“consists essentially of” or synonyms thereof and vice versa.
- the method described above functions by way of an SN2 reaction between the chlorine atom of the 3-mcpd and/or glycidol (and their derivatives) to form a new compound that has sufficient conjugation to provide a suitable optical property for analysis. Further details of how the optical property may be captured and analysed is provided in the experimental section below, where absorbance is the measured optical property. However, it will be appreciated that other optical properties, such as transmittance or reflectance may be used instead using standard techniques or by analogy to the methodology described in the examples for absorbance.
- the term“derivatives of 3-mcpd” refers to esters of 3-mcpd.
- the term“3-mcpd ester” refers to a compound where one or both of the alcohol groups on 3-monochloropropane diol have reacted with a carboxylic acid (e.g. RCO 2 H) or an ester thereof (e.g. RCO 2 R’) to form an ester group.
- a carboxylic acid e.g. RCO 2 H
- an ester thereof e.g. RCO 2 R’
- R may have any suitable value and may be a C 1-50 alkyl group, a phenyl group or a heterocyclic group, which groups may be substituted or unsubstituted.
- the R’ group may be any suitable group, such as a C 1-5 alkyl group.
- the term“derivatives of glycidol” refers to esters of glycidol.
- the term“glycidol ester” refers to a compound where the alcohol group on the glycidol has reacted with a carboxylic acid (e.g. RCO2H) or an ester thereof (e.g. RCO2R’) to form an ester group.
- a carboxylic acid e.g. RCO2H
- RCO2R an ester thereof
- the combined sample used in step (a) may be obtained by: (ai) reacting a suitable compound comprising a pyridine ring in the presence of an aqueous solvent mixture with a first sample obtained from an original sample suspected to contain one or more of 3-mcpd, 3-mcpd ester(s), glycidol, and glycidol ester(s) to provide a reaction sample;
- the aqueous solvent mixture may comprise water and a buffering agent, where the pH of the aqueous solvent mixture is from 4 to 7.
- a buffering agent Any suitable buffering agent may be used.
- the buffering agent may be sodium citrate buffer.
- the colour development agent may be any suitable aqueous inorganic base.
- a suitable aqueous inorganic bases include, but are not limited to, aqueous potassium carbonate.
- the concentration of the colour development agent in the aqueous solution may have any suitable concentration, for example the concentration may be from 500 nM to 1 M.
- the colour development agent is added to the aqueous solution of step (ai) in an amount sufficient to provide the desired effect, this amount may be determined by the skilled person in accordance with routine trial and error or based upon their knowledge and expertise in this field.
- the aqueous inorganic base may be added in an amount sufficient to provide the colour-developed sample with a pH value of at least 1 1 .
- the organic solvent added to the coloured sample may be selected from one or more of acetophenone, diethyl ether, toluene, ethyl acetate, optionally wherein the organic solvent is ethyl acetate.
- the solvents may be selected individually or selected to work in concert with one another. For example, when diethyl ether and/or ethyl acetate are used as the organic solvent an immiscible organic layer may form and be separated from the aqueous layer.
- the first sample may be obtained by:
- step (eiii) adding a buffering agent to the aqueous layer to form the first sample.
- any suitable organic solvent may be used.
- suitable organic solvents include, but are not limited to iso-octane, chloroform and combinations thereof.
- any suitable base may be used.
- suitable bases include, but are not limited to, a hydroxide base (e.g. sodium hydroxide or potassium hydroxide).
- suitable primary alcohols include, but are not limited to, 1 -butanol.
- the resulting product of this reaction is a metal alkoxide and it follows that a suitable metal alkoxide that may be used herein may be a metal 1 -butoxide (sodium or potassium 1 -butoxide).
- any suitable acid may be used, provided that the acid is not hydrochloric acid.
- Suitable acids include, but are not limited to, acetic acid or H 2 SO 4 .
- Any suitable concentration of the acid may be used, for example, the concentration of the acid in water may be from 1 to 3 vol% (i.e. the concentration of the acid dissolved in water is from 1 to 3 vol%, which solution is then added to the basic sample).
- the buffering agent may be any suitable buffering agent that provides a suitable pH value for the first sample.
- the buffering agent may be sodium citrate buffer and/or the buffering agent may provide the first sample with a pH of from 4 to 7.
- the process described above allows one to obtain an understanding of the total amount of 3-mcpd, glycidol and their derivatives in the sample to be analysed.
- the above method is not capable of providing a break-down into the amount of the contaminants derived from 3-mcpd and the amount derived from glycidol.
- the process may further comprise the step:
- the above method allows one to calculate the amount of 3-mcpd and its derivatives in the sample.
- the amount of glycidol ester and/or glycidol in an original sample may be determined by subtracting the amount of 3-monochloropropane diol and/or 3- mcpd ester(s) determined in step (b) from the combined amount determined in step (a). This allows one to determine the total amount of contaminant and the amounts of contaminant derived from 3-mcpd and glycidol.
- the 3-monochloropropane diol sample used in step (b) may be obtained by:
- the aqueous solvent mixture may comprise water and a buffering agent, where the pH of the aqueous solvent mixture is from 4 to 7, optionally wherein the buffering agent is sodium citrate buffer.
- the colour development agent may be an aqueous inorganic base.
- a suitable aqueous inorganic bases include, but are not limited to aqueous potassium carbonate.
- the colour development agent in the aqueous solution may have any suitable concentration, for example the concentration may be from 500 nM to 1 M.
- the colour development agent is added to the aqueous solution of step (ai) in an amount sufficient to provide the desired effect, this amount may be determined by the skilled person in accordance with routine trial and error or based upon their knowledge and expertise in this field.
- the aqueous inorganic base may be added in an amount sufficient to provide the colour-developed sample with a pH value of at least 1 1 .
- the organic solvent added to the coloured sample may be selected from one or more of acetophenone, diethyl ether, toluene, ethyl acetate, optionally wherein the organic solvent is ethyl acetate.
- the solvents may be selected individually or selected to work in concert with one another. For example, when diethyl ether and/or ethyl acetate are used as the organic solvent an immiscible organic layer may form and be separated from the aqueous layer.
- the second sample may be obtained by:
- any suitable organic solvent may be used.
- suitable organic solvents include, but are not limited to, iso-octane, chloroform and combinations thereof.
- any suitable acid and alcohol may be used.
- the acid may be H 2 SO 4 and the alcohol may be 1 -propanol.
- any suitable base be used.
- suitable bases include, but are not limited to, a hydroxide base (e.g. sodium hydroxide or potassium hydroxide).
- suitable primary alcohols include, but are not limited to, 1 -butanol.
- the resulting product of this reaction is a metal alkoxide and it follows that a suitable metal alkoxide that may be used herein may be a metal 1 -butoxide (sodium or potassium 1 - butoxide).
- any suitable acid may be used, provided that the acid is not hydrochloric acid.
- Suitable acids include, but are not limited to, acetic acid or H 2 SO 4 .
- Any suitable concentration of the acid may be used, for example, the concentration of the acid in water may be from 1 to 3 vol% (i.e. the concentration of the acid dissolved in water is from 1 to 3 vol%, which solution is then added to the basic sample).
- the buffering agent may be any suitable buffering agent that provides a suitable pH value for the first sample.
- the buffering agent may be sodium citrate buffer and/or the buffering agent may provide the first sample with a pH of from 4 to 7.
- the methods described above require the use of a suitable compound comprising a pyridine ring to provide the desired reaction products for analysis.
- the compound in question may be selected independently from:
- Ft 1 represents N0 , CN, S0 3 R 4 , C0 2 R 5 , CONR 6 R 7 ;
- R 2 and R 3 independently represent halo, C1-4 alkyl or OR 8 ;
- R 4 to R 7 independently represent C1-10 alkyl
- R 8 represents C1-4 alkyl
- X represents H C1-4 alkyl, -COOH, or COOR 9a ;
- Y represents H, Ci- 4 alkyl, OR 9b , or NR 10 R 11 , S0 3 R 12 , CN, N0 , C0 2 R 13 , CONR 14 R 15 ;
- Z represents H, COR 16 , or -(CH 2 ) n Ar;
- W represents H, CH 2 OR 17 ;
- V represents H, Ci- 4 alkyl, -COOH, or COOR 18 ;
- R 9a and R 9b to R 18 represents H or Ci- 4 alkyl
- Ar represents an aromatic ring system
- n is from 1 to 10;
- a and BB represent H, Ci- 4 alkyl, OR 19 , or NR 20 R 21 , S0 3 R 22 , CN, N0 2 , C0 2 R 23 , CONR 24 R 25 ; and
- R 19 to R 25 represents H or Ci- 4 alkyl, provided that when A is H then BB is not H and when BB is H then A is not H.
- the suitable compound comprising a pyridine ring may be selected from:
- aryl when used herein includes Ce-14 (such as C 6 -i 3 (e.g. C6-10)) aryl groups. Such groups may be monocyclic, bicyclic or tricyclic and have between 6 and 14 ring carbon atoms, in which at least one ring is aromatic. The point of attachment of aryl groups may be via any atom of the ring system. However, when aryl groups are bicyclic or tricyclic, they are linked to the rest of the molecule via an aromatic ring.
- Ce-io aryl groups include phenyl, naphthyl and the like, such as 1 ,2,3,4-tetrahydronaphthyl, indanyl, indenyl and fluorenyl.
- Embodiments of the invention that may be mentioned include those in which aryl is phenyl.
- the optical property measured may be selected from absorbance, transmittance or reflectance, optionally wherein the optical property measured is absorbance.
- the original sample may be any suitable sample suspected of containing 3-mcpd and/or glycidol and their derivatives.
- suitable original samples include, but are not limited to, an edible oil, an edible fat or a combination thereof.
- the apparatus needed to carry out the detection include:
- Isooctane (analytical grade, 399%), chloroform (analytical grade, 399%), H 2 SO 4 (399%), 1- propanol (analytical grade, 399%), KOH (85% and above), 1 -butanol (analytical grade, 399%), sodium citrate (399%), ethanol (395%), glycerol (399%), 4-(4-nitrobenzyl)pyridine (98% and above), K 2 CO 3 (399%), ethyl acetate (analytical grade, 399%), acetophenone (analytical grade, 399%), toluene (analytical grade, 399%), acetone (analytical grade, 399%) and ethylene glycol (399%) were obtained from commercial sources and used directly without further purification to prepare the following solvents or reagents: • Solvents to dissolve the samples: isooctane or chloroform
- Reagent 1 H2SO4 in 1 -propanol, at a working concentration of 1 -5 pl_ of H2SO4 in 1 - propanol (1 ml.)
- Reagent 2 KOH in 1 -butanol, at a working concentration of 1 -5% KOH in 1 -butanol (w/v)
- Reagent 3 H 2 SO 4 in deionised water, with a working concentration of 1 -3% of H 2 SO 4 in deionised water (v/v)
- Reagent 4 sodium citrate buffer, with a pH of 4-7
- Reagent A 4-(4-nitrobenzyl)pyridine (NBP) dissolved in a mixture of ethanokglycerol, at a working concentration of 2-10% NBP (w/v).
- the percentage of ethanol in the ethanokglycerol mixture can range from 10-100% (v/v).
- the ethanol can be replaced by other solvents such as acetone or other polar solvents, while glycerol can be replaced by ethylene glycol.
- Reagent B K 2 CO 3 dissolved in deionised water, at a working concentration of 500 nM - 1 M
- Reagent C ethyl acetate, acetophenone, diethyl ether, or toluene
- a calibration curve can be obtained via the following steps:
- the samples should contain a total concentration of 3-mcpd, glycidol and their esters of 0.2 to 8 ppm, with the various sample concentrations spread across the entire range (e.g. 0.2, 0.5, 1 , 3, 5, 8 ppm).
- the samples should contain 3-mcpd and its ester concentrations of 0.1 to 5 ppm, with the various sample concentrations spread across the entire range (e.g. 0.1 , 0.5, 1 , 2, 3, 5 ppm).
- Example 1 Detecting the combined amount of 3-monochloropropane diol (3-mcpd), 3- mcpd ester, glycidol and/or glycidol ester
- the sample preparation involves the conversion of 3-mcpd esters and glycidol esters into 3-mcpd (22) and glycidol (24) respectively, while the detection step involves the use of 4-(4-nitrobenzyl)-pyridine (NBP) and a base to give a colour change when reacted with 3-mcpd or glycidol.
- NBP 4-(4-nitrobenzyl)-pyridine
- This detection method has been carried out on foodstuff samples which include RBDPO (refined, bleached and deodorised palm oil), palm olein, interesterified palm oil, sunflower oil, canola oil, solid stearin, cream margarine for cakes, confectionary fats for chocolate products and rice bran oil.
- RBDPO refined, bleached and deodorised palm oil
- palm olein refined, bleached and deodorised palm oil
- interesterified palm oil sunflower oil
- canola oil canola oil
- solid stearin cream margarine for cakes
- confectionary fats for chocolate products and rice bran oil solid stearin
- 0.1 -5 g ( ⁇ 0.1 %) of each sample was weighed into a tube.
- samples of 3 g ⁇ 3 mg were weighed into each tube separately.
- 3 mL of solvent was then added to each sample and mixed until the samples dissolved completely. If the sample is a solid, it can first be melted completely by heating it in an oven/water bath (e.g. at 30-80 °C, depending on the melting point of the solid), before adding the solvent to the sample.
- the mixture can be heated in an oven at 30-80 °C (depending on the melting point of the sample and boiling point of the solvent - isooctane is used if a temperature higher than 60 °C is required), until the sample dissolves completely and the solution appears clear.
- Reagent 2 4 mL of Reagent 2 (20) was then added to each sample (10), mixed and left to stand for 5-15 min.
- the addition of Reagent 2 is to covert 3-mcpd esters (13) and/or glycidol esters (14) into 3-mcpd (22) and/or glycidol (24) respectively (as shown in the reaction scheme in Fig. 3).
- 3.5 mL of Reagent 3 (30) was added to each samples, mixed and vortexed to neutralise the alkaline conditions (Fig. 2).
- the samples were then centrifuged at ref of 2,000 or higher for at least 1 min to give two layers. The organic layer was discarded and the aqueous layer was transferred into a new tube.
- the combined concentration of 3-mcpd, 3-mcpd esters, glycidol and/or glycidol esters can be determined from a calibration curve generated using standard samples containing various concentration of 3-mcpd, glycidol and their esters (Fig. 1 a).
- the detection of the amount of 3-monochloropropane diol (3-mcpd) and/or 3-mcpd ester in the samples was carried out using the apparatus and reagents listed above. Similar to Example 1 , the detection process is divided into two parts: sample preparation (6) and detection (8), as shown in Fig. 5. This method is substantially the same as the method in Example 1 , but it includes an additional step at the sample preparation phase to remove epoxide functional groups in glycidols and glycidol esters that might be present in the samples. This effectively deactivates the glycidols and glycidol esters, so that they will not react with NBP in the detection step to give a colour change.
- This detection method has been carried out on foodstuff samples which include RBDPO (refined, bleached and deodorised palm oil), palm olein, interesterified palm oil, sunflower oil, canola oil, solid stearin, cream margarine for cakes, confectionary fats for chocolate products and rice bran oil.
- RBDPO refined, bleached and deodorised palm oil
- palm olein refined, bleached and deodorised palm oil
- interesterified palm oil sunflower oil
- canola oil canola oil
- solid stearin cream margarine for cakes
- confectionary fats for chocolate products and rice bran oil solid stearin
- 0.1 -5 g ( ⁇ 0.1 %) of each sample was weighed into a tube.
- samples of 3 g ⁇ 3 mg were weighed into each tube separately.
- 3 mL of solvent was then added to each sample and shaken until the samples dissolved completely. If the sample is a solid, it can first be melted completely by heating it in an oven/water bath (e.g. at 30-80 °C, depending on the melting point of the solid), before adding the solvent to the sample.
- the mixture can be heated in an oven at 30-80 °C (depending on the melting point of the sample and boiling point of the solvent - isooctane is used if a temperature higher than 60 °C is required), until the sample dissolves completely and the solution appears clear.
- Reagent 1 (1 mL of Reagent 1 (12) was added to each sample (5), mixed and incubated in a water bath at 40-70 °C for 20-30 min.
- the addition of Reagent 1 is an additional step (compared to Example 1 ) and is important for the removal of epoxide functional groups in glycidols (24) and glycidol esters (14) that might be present in the samples (shown in the reaction scheme in Fig. 6).
- Reagent 2 4 mL of Reagent 2 (20) was then added to each sample (10), mixed and incubated at room temperature for 10-15 min.
- the addition of Reagent 2 is to covert 3-mcpd esters and other esters into 3-mcpd and the respective alcohols (as shown in the reaction scheme in Fig. 2).
- the concentration of 3-mcpd and/or 3-mcpd esters can be determined from a calibration curve generated using standard samples containing various concentration of 3-mcpd and its esters (Fig. 1 b).
- a comparison of the concentrations of 3-mcpd and/or 3-mcpd esters (in the various samples) determined by the current method to the concentrations as determined by GC/MS shows that the current method is able to achieve an accuracy and sensitivity comparable to that of the conventional GC/MS method (Table 1 ).
- Table 1 Comparing the various concentrations of 3-mcpd and/or 3-mcpd esters determined by the current method to the concentrations as determined by GC/MS
- the amount of glycidol and/or glycidol ester in the samples can be determined by subtracting the concentration of 3-mcpd and/or 3-mcpd esters (in Example 2) from the combined concentration of 3-mcpd, 3-mcpd esters, glycidol and/or glycidol ester (in Example 1 ) as shown below:
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- Biophysics (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Pathology (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SG10201811775Q | 2018-12-28 | ||
PCT/SG2019/050642 WO2020139198A1 (en) | 2018-12-28 | 2019-12-26 | A method of detecting harmful substances |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3902403A1 true EP3902403A1 (en) | 2021-11-03 |
Family
ID=69167883
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19836853.2A Pending EP3902403A1 (en) | 2018-12-28 | 2019-12-26 | A method of detecting harmful substances |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3902403A1 (en) |
CN (1) | CN113438897A (en) |
WO (1) | WO2020139198A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114609271B (en) * | 2022-02-22 | 2024-05-28 | 北京化工大学 | Method for simultaneously detecting 3-chloropropanol ester and glycidyl ester in vegetable oil based on magnetic solid phase extraction |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102937580B (en) * | 2012-11-02 | 2015-09-02 | 天津科技大学 | The detection method of ethylene oxidic ester in edible oil and fat |
GB2538758A (en) * | 2015-05-27 | 2016-11-30 | Green Lizard Tech Ltd | Process for removing chloropropanols and/or glycidol |
CN106290216B (en) * | 2016-09-21 | 2018-12-18 | 天津科技大学 | The detection method of ethylene oxidic ester in a kind of grease |
-
2019
- 2019-12-26 EP EP19836853.2A patent/EP3902403A1/en active Pending
- 2019-12-26 CN CN201980091844.2A patent/CN113438897A/en active Pending
- 2019-12-26 WO PCT/SG2019/050642 patent/WO2020139198A1/en unknown
Also Published As
Publication number | Publication date |
---|---|
CN113438897A (en) | 2021-09-24 |
WO2020139198A1 (en) | 2020-07-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Szydłowska-Czerniak et al. | Comparison of two analytical methods for assessing antioxidant capacity of rapeseed and olive oils | |
Ermacora et al. | A novel method for simultaneous monitoring of 2‐MCPD, 3‐MCPD and glycidyl esters in oils and fats | |
Kato et al. | Determination of triacylglycerol oxidation mechanisms in canola oil using liquid chromatography–tandem mass spectrometry | |
Burdge et al. | A method for separation of phosphatidylcholine, triacylglycerol, non-esterified fatty acids and cholesterol esters from plasma by solid-phase extraction | |
Pestana et al. | Quality changes and tocopherols and γ‐orizanol concentrations in rice bran oil during the refining process | |
Anyasor et al. | Chemical analyses of groundnut (Arachis hypogaea) oil | |
US20080282601A1 (en) | Hardened Vegetable Oils and Derivatives Thereof | |
Liaotrakoon et al. | Dragon fruit (Hylocereus spp.) seed oils: their characterization and stability under storage conditions | |
Rodrigues et al. | Phase equilibrium for the system rice bran oil+ fattyacids+ ethanol+ water+ γ-oryzanol+ tocols | |
Szydłowska‐Czerniak et al. | Antioxidant capacity of rapeseed meal and rapeseed oils enriched with meal extract | |
Chalapud et al. | Characterization of waxes and residual oil recovered from sunflower oil winterization waste | |
Mulia et al. | Green extraction of palmitic acid from palm oil using betaine-based Natural Deep Eutectic Solvents | |
EP3902403A1 (en) | A method of detecting harmful substances | |
Carelli et al. | Improved method for the determination of wax esters in vegetable oils | |
Upadhyay et al. | Development of a method employing reversed‐phase thin‐layer chromatography for establishing milk fat purity with respect to adulteration with vegetable oils | |
JPH04503858A (en) | Method and device for measuring non-triglycerides in oil | |
Adhami et al. | A novel process for simultaneous degumming and deacidification of Soybean, Canola and Sunflower oils by tetrabutylphosphonium phosphate ionic liquid | |
US4349353A (en) | Frying oil evaluator method and composition | |
Sonego et al. | Occurrence and migration study of chemicals from baking paper and aluminium foil | |
Redeuil et al. | Recommendations for oil extraction and refining process to prevent the formation of monochloropropane-diol esters in sunflower oil | |
CN107478744B (en) | The quartile length method of edible oil | |
Cansell et al. | Phospholipid profiles of oleaginous pressed cakes using NMR and gas chromatography | |
Ma et al. | Malondialdehyde, 4‐hydroxy‐2‐hexenal, and 4‐hydroxy‐2‐nonenal in vegetable oils: Formation kinetics and application as oxidation indicators | |
Hasenhuettl | Analysis of food emulsifiers | |
JP7222929B2 (en) | Method for Suppressing Increase in Anisidine Value and Decrease in Tocopherols in Oil and Fat Composition for Frying |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20210723 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: EXAMINATION IS IN PROGRESS |
|
17Q | First examination report despatched |
Effective date: 20231011 |