Documente Academic
Documente Profesional
Documente Cultură
VETERINAR CLUJ-NAPOCA
UNIVERSITATEA LIEGE
Facultatea de Zootehnie i Biotehnologii
Gembloux Agro BioTech
CONDUCTORI TIINIFICI:
Prof.dr.ing. Liviu Al. Mrghita
Prof.dr. Eric Haubruge
Cluj-Napoca
2013
CUPRINS
INTRODUCERE
I.
II
II.1.
II.2.
Scopul tezei ..
II.3.
III
MATERIAL I METODE..
III.1.
PROBE DE MIERE............................................................................................
III.2.
IV
REZULTATE I DISCUII..........
IV.1.
IV.1.1.
IV.1.2.
10
IV.1. 3
10
IV.1.4.
12
IV.1.5.
12
IV.1.6.
13
IV.1.7.
13
IV.1.8.
14
IV.1.9.
Determinarea vscozitaii..............................................................................
16
IV. 2.
DETERMINRI CROMATOGRAFICE........................................................
17
IV.2.1.
17
IV.2.2.
18
miere...........................................................................................................
IV.3.
DETERMINRI SPECTROSCOPICE..........................................................
21
IV.3.1.
21
IV.3.2.
23
IV.3.3.
29
IV.3.4.
31
CONCLUZII GENERALE..
32
BIBLIOGRAFIE............................................................................................
33
INTRODUCERE
de
analiz
utilizate,
metodele
fizico-chimice,
cromatografice
spectroscopice.
Principalele obiective ale tezei sunt :
-
n vederea determinrii
Mare, Slaj i Timioara. Zona 2 a cuprins probe din sud-vestul i sudul rii: Clrai,
Dolj, Giurgiu, Teleorman i Vlcea. Zona 3 a reprezentat-o partea de est a Romniei:
judeele Bacu, Botoani, Buzu, Galai, Suceava, Tulcea i Vaslui.
Romnia
Zona 1
2009
S1
S2
S3
S8
S9
S10
S12
S13
S24
S16
S17
S18
S20
S22
Zona 2
2010
2011
2009
2010
S23
S15
S28
S48
S51
S53
S58
S4
S6
S14
S19
S25
S27
S35
S36
S37
S38
Zona 3
2011
S50
S57
2009
2010
2011
S5
S7
S11
S21
S29
S30
S31
S32
S33
S34
S39
S40
S41
S42
S52
S55
S56
11
5.36%.
Neexistnd valori
extreme (outlieri), valoarea medie obinut pentru acest parametru a fost de 2.321.2.
13
14
Figura 11. Termogram specific mierii n care sunt prezentate grafic temperatura de
tranziie sticloas (Tg) i temperatura de topire (fuziune) (Tf)
Rezultatele obinute pentru probele de miere luate n studiu sunt prezentate n
tabelul 1.
Tabel 1.
Valorile determinate pentru temperatura de tranziie sticloas Tg i fuziune (topire) Tf
Proba
Tg (C)
Tf (C)
H (J/g)
S1
-44.61
46.69
18.64
14
S14
-42.71
52.72
21.20
15
S15
-42.20
40.35
0.39
23
S23
-40.9
42.90
8.75
25
S25
None
50.43
18.02
33
S34
None
51.15
13.99
44
S51
-36.17
60.97
0.73
49
S57
-39.83
61.54
4.53
50
S58
-37.03
64.12
0.78
15
Figura 12. Efectul temperaturii asupra curbelor vscozitii ale diferitelor probe de
miere
Dup ce mierile au fost tratate termic timp de o or i treizeci de minute la
55 C, s-a trecut la msurarea vscozitii (la temperaura de 20C). Valorile
vscozitii specifice mierii au fost cuprinse ntre 4.72 i 62.96 Pas.
o
17
50
Concentraie %
40
30
20
10
0
Fructoz
Glucoz
Sucroz
Turanoz
Maltoz
Isomaltoz
Erloz
18
S 1
2500000
Intensitate / Intensity
2000000
1500000
1000000
500000
10
20
30
40
50
60
Dimetil sulfid, acetona, 3-hidroxi-2-butanona, linalool oxidul, acidul acetic, 2furancarboxaldehida, benzaldehida, linalool L, hotrienol, 4-ketoisophorona,
epoxylinalool, benzenmetanol pentru zona 1
19
Benzenetanol
Benzaldehida
2-furancarboxaldehida
Acid acetic
Linalool oxid
Etanol
Aceton
30
25
Zona 1
20
Zona 2
15
Zona 3
10
5
0
Figura 16. Comparaie ntre valoriile medii obinute pentru compui volatili majori din
mierea colectat din cele trei zone
Urmtoarea etap a constat n clasificarea compuilor identificai n clase
chimice (Figura 17). S-a remarcat astfel o diferen semnificativ ntre diferitele zone
studiate, aa nct acizii carboxilici sunt prezeni n procent mare n probele din
Transilvania, 32.22% i Oltenia 30.36% . Procentajul de aldehide n Zona 1, Zona 2 i
Zona 3 este destul de important, respectiv 27.63%, 22.34% i 13.43%. Alcoolii
constituie o parte important a probelor de miere romneti, atingnd valori de 28.35
% pentru mierea din Zona 3, 23.87% pentru Zona 2, 19.13% pentru Zona1.
20
Eteri
Aromatici
100
Acid carboxilic
Azotai
80
Alcooli
60
Aldehide
Alifatici
40
Esteri
20
Cetone
Sulfuri
0
Z1
Z2
Z3
21
cele mai multe informaii spectrale i s-au identificat lungimile de und unde sunt
diferene de absorie ntre probe.
22
Scores on PC 8 (0.09%)
3
2
1
0
-1
-2
20
Scores on PC 2 (27.39%)
-20
-40
-20
20
40
Scores on PC 1 (68.39%)
23
VALIDARE
CALIBRARE
Selectarea a n probe
Valori NIR
Valori de referin
Selectarea a n probe
Valori NIR
Valori de referin
PREDICIE
Probe necunoscute
Valori NIR
Creeare model
matematic
Ecuaie de calibrare
Ecuaie de calibrare
Comparare parametrii
sta
Ecuaia de calibrare
Valori prezise
24
Uniti
Units
Media / Mean
Gam / Range
Deviaia standard
Standard deviation
mS/cm
0.12
0.07-0.18
0.02
17.01
14.80-21-30
1.38
meq/Kg
13.76
6.63-53.00
7.16
meq/Kg
1.07
0.15-9.80
1.35
Pas
%
%
%
%
%
%
%
27.47
43.43
30.46
1.00
2.08
3.01
0.39
1.79
4.73-62.96
33.80-48.16
22.32-43.71
0.00-5.51
0.38-2.77
0.68-4.16
0.11-0.90
0.00-3.19
14.51
2.68
3.98
1.05
0.53
0.69
0.18
0.65
Tabel 3.
Modelul de calibrare global pentru principalii indici de caliatate ai mierii: Date statistice referitoare la calibrare i validare
Parametru
Parameter
Zona
Zone
Regiuni
spectrale
Spectral range
(nm)
Valori extreme
Outliers
PLS
factor
Calibrare
Calibration
Validare ncruciat
Cross validation
RMSEC
R2
RMSECV
R2
Toate zonele
Tot spectrul
S37; S7
0.826
0.635
0.868
0.579
Toate zonele
Tot spectrul
S21
11
0.015
0.656
0.018
0.501
Toate zonele
Tot spectrul
S18
11
2.759
0.604
3.605
0.334
Toate zonele
Tot spectrul
11
0.355
0.483
0.443
0.221
Vscozitate / Viscosity
Fructoz / Fructose
Glucoz/ Glucose
Zaharoz / Sucrose
Turanoz / Turanose
Maltoz / Maltose
Izomaltoz / Isomaltose
Erloz / Erlose
Toate zonele
Tot spectrul
Tot spectrul
Tot spectrul
Tot spectrul
Tot spectrul
Tot spectrul
Tot spectrul
Tot spectrul
5.561
0.840
6.352
0.796
4
12
13
2
4
13
2
1.024
1.656
0.461
0.408
0.388
0.051
0.451
0.839
0.804
0.844
0.964
0.71
0.912
0.946
1.090
1.943
0.681
0.441
0.399
0.128
0.491
0.800
0.769
0.776
0.958
0.823
0.970
0.936
Toate zonele
Toate zonele
Toate zonele
Toate zonele
Toate zonele
Toate zonele
Toate zonele
Astfel se constat c cele mai bune rezultate s-au obinut pentru turanoz
(RMSECV=0.441 ; RMSEC=0.408 ; R2=0.96) i erloz (RMSECV=0.491 ;
RMSEC=0.451 ; R2=0.94).
Deviaia
standard
Standard
deviation
SEC
R2
SECV
R2
17.25
0.99
0.159
0.974
0.167
0.972
0.36
0.17
0.060
0.871
0.072
0.820
4.33
0.32
0.189
0.642
0.218
0.525
10.84
4.70
2.538
0.698
3.387
0.480
Fructoz / Fructose
37.78
2.25
1.461
0.577
1.582
0.504
Glucoz / Glucose
32.27
3.71
1.307
0.876
1.478
0.841
Maltoz / Maltose
3.83
0.97
0.582
0.641
0.628
0.582
Fructoz/Glucoz / Fructose/Glucose
1.17
0.13
0.046
0.880
0.056
0.824
Zaharoz / Sucrose
0.95
1.41
0.371
0.931
0.571
0.837
Raffinos / Raffinose
0.40
0.23
0.181
0.359
0.190
0.292
Erloz / Erlose
0.52
0.41
0.19
0.781
0.218
0.716
Melebioz / Melibiose
0.68
0.33
0.106
0.899
0.132
0.845
Palatinoz /Palatinose
0.11
0.06
0.034
0.661
0.037
0.590
Panoz / Panose
0.15
0.09
0.062
0.502
0.070
0.373
Turanoz / Turanose
1.32
0.34
0.284
0.305
0.291
0.277
Parametru / Parameter
50
Concentraia %
40
30
20
10
0
Fructoz
Glucoz
Maltoz
3,0
Concentraia %
2,5
2,0
1,5
1,0
0,5
0,0
Zaharoz
Raffinos
Erloz
Melibios
Palatinos
Panos
Turanoz
28
29
Tabel 5.
Caracteristici ale modelului PLS pentru diferii parametri ai mierii de salcm realizat pe domeniul spectral 3599-600 cm-1
Parametru
Parameter
Zona
Zone
Regiuni
spectrale
Spectral range
(nm)
Valori extreme
Outliers
25;34;21
PLS
factor
Calibrare
Calibration
Validare ncruciat
Cross validation
RMSEC
R2
RMSECV
R2
0.614
0.549
0.684
0.454
Toate zonele
Tot spectrul
Toate zonele
Tot spectrul
12
0.007
0.904
0.020
0.630
Toate zonele
Tot spectrul
15
1.878
0.930
4.017
0.687
Fructoz / Fructose
Toate zonele
Tot spectrul
12
0.637
0.940
1.529
0.880
Glucoz/ Glucose
Toate zonele
Tot spectrul
11
1.223
0.904
1.886
0.797
Zaharoz / Sucrose
Toate zonele
Tot spectrul
0.434
0.831
0.485
0.725
Turanoz / Turanose
Toate zonele
Tot spectrul
0.181
0.879
0.556
0.814
Maltoz / Maltose
Toate zonele
Tot spectrul
0.324
0.779
0.378
0.706
Izomaltoz / Isomaltose
Toate zonele
Tot spectrul
15;10;04;13;22
0.061
0.880
0.733
0.823
Erloz / Erlose
Toate zonele
Tot spectrul
15
0.264
0.816
0.307
0.762
13;22
15; 58
Pentru domeniul spectral 3599-600 cm-1 valorile obinute pentru RMSEC sunt
cuprinse ntre 0.007 i 1.878, valorile pentru RMSECV se integreaz n intervalul
0.549 i 0.940, iar valorile coeficientului R2 sunt cuprinse ntre
0.549 0.940
32
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34