JKI Open Journal Systems (Julius Kühn-Institut)

Koch, Eckhard

Herz, Annette

Kleespies, Regina G.

Schmitt, Annegret

Stephan, Dietrich

Jehle, Johannes A.

German

Statusbericht Biologischer Pflanzenschutz 2018

Smit, Inga

Haase, Norbert U.

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
24    
01-04 Application of NIR technology to predict minor components in raw and 
processed potatoes 
Inga Smit, Norbert U. Haase 
Max Rubner-Institut, Department of Safety and Quality of Cereals, Detmold, Germany 
E-mail: inga.smit@mri.bund.de 
 
Being a staple food potatoes are grown in many countries with a world-wide production of 
380 Mio tonnes in 2014 [1]. In Germany the per capita consumption of potatoes is about 
56.8 kg in the financial year 2015/2016 with a share of 60% of processed potatoes [2] such as 
fried products (e.g. French fries). Industrial processing of French fries includes several steps 
like quality control of raw material, blanching, par-frying and freezing [3]. End-frying as the 
last preparation step is mainly done in canteens or at home. In fried products the heat-
induced contaminant acrylamide can be formed via the Maillard reaction depending on the 
amount of the precursors reducing sugars (glucose, fructose) and asparagine [4]. 
Different NIRS applications have been tested for potatoes during the last decades. Good 
predictions of the dry matter and starch content have been established by measuring the 
raw grounded tuber [5]. Potato cultivars used for processing of French fries usually contain a 
high amount of dry matter that mainly consists of starch. Due to their low concentration, 
reducing sugars in the raw tuber (3-24 mmol/kg) and likewise, the acrylamide in the deep fat 
fried product are minor components [4]. NIRS-based predictions of reducing sugars in the 
raw material would be an advantage in the quality control of industrial French fries 
processing [5]. However, acceptable predictions for such minor components are hardly 
reachable [5,6]. Nonetheless, in potato breeding process less exact predictions could be a 
useful complementation in the phenotyping of new breeding lines.  
Within a current project (DEPOLA, starting 2017) we try to develop a NIRS model to be used 
as a valid screening tool in identifying potato genotypes with a low acrylamide potential. To 
perform the trial, a set of 185 genotypes from German and Turkish breeding programs is 
grown in both countries of contrasting climatic conditions. The total sample number will 
reach at the projects end 1600 including field replications, several locations (three per 
country) and different storage treatments. Yet, a subset of 96 samples is analyzed. The 
quality parameters that were used for model development are dry matter, starch, glucose, 
fructose, sucrose, colour (L*a*b* values) and acrylamide. NIR measurement was repeated 
twice for each sample and a wavelength range of about 400-2500 nm was monitored with a 
FOSS XDS NIR spectrophotometer. 
Most quality parameters show a high variation within the data set, especially for acrylamide 
but also for the colour (a* value) and the glucose content, which is a basic requirement. 
Taking into account the size of the sample set a cross validation was performed. Besides, 
using non-treated spectra that seem to be well suited for the dry matter content (R² of 
calibration and prediction of 0.97 and 0.96, respectively), the first and second derivatives 
were used to model the prediction of the minor components. For glucose the R² of 
calibration and prediction were 0.85 and 0.59 when using the first derivative. By using the 
second derivative for acrylamide the R² of calibration and prediction were 0.91 and 0.41. The 
mathematical pre-treatments were able to improve the model indices. Even though the data 
set was small, it indicates capabilities of NIR technique as a screening tool for breeding 
purposes. Satisfactory information should be taken from a larger data set that we will gain by 
the end of the project in 2020. 
2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
25 
References  
[1] FAOSTAT, 2018.  
[2] DESTATIS, 2018.  
[3] MEDEIROS VINCI, R., et al., 2012: Food Chemistry, 133, 1138 – 1154.  
[4] HAASE, N. U., 2018: Kartoffelbau, 5, 44-49.  
[5] HAASE, N. U., 2011: Journal of Near Infrared Spectroscopy, 19, 37-45.  
[6] SCANLON, M. G., et al., 1999: Journal of the Science of Food and Agriculture, 79, 763–771. 


English

Application of NIR technology to predict minor components in raw and processed potatoes

Vermaak, Ilze

Tankeu, Sidonie Yankam

Djokam, Majolie

Sandasi, Maxleene

Chen, Weiyang

Viljoen, Alvaro

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
30 
Session 2 - Hyperspectral Imaging (Co-chairs: Devaux/Vermaak) 
02-01: Hyperspectral imaging in combination with chemometric data analysis – a 
powerful duo in the quality control of herbal medicines 
Ilze Vermaak1,2, Sidonie Yankam Tankeu1, Majolie Djokam1, Maxleene Sandasi1, Weiyang 
Chen1, Alvaro Viljoen1,2 
1Department of Pharmaceutical Sciences, Tshwane University of Technology, Pretoria, South Africa 
2 SAMRC Herbal Drugs Research Unit, Tshwane University of Technology, Pretoria, South Africa 
E-mail: vermaaki@tut.ac.za 
The quality control of herbal material is notoriously challenging due to the complex mixture 
of compounds present in plants. In addition, the variability in phytochemical profiles and 
toxicity issues associated with herbal products necessitates the development of reliable 
quality control methods. Analytical methods such as liquid chromatography coupled to mass 
spectrometry are time-consuming and requires considerable expertise. Hyperspectral 
imaging (HSI) integrates conventional spectroscopy and imaging to obtain spectral and 
spatial information from a sample. Once the method has been developed, the visual results 
are rapidly obtained and easy to interpret. In this study, the use of HSI in combination with 
chemometric data analysis in quality control will be illustrated using several examples: 
1) distinguishing between the whole dried fruit of Illicium verum (Chinese star anise) and
Illicium anisatum (Japanese star anise); 2) Stephania tetrandra (‘hang fang ji’) and its 
substitution or adulteration with Aristolochia fangchi (‘guang fang ji’); 3) determining the 
proportion of each constituent in a tea blend consisting of Aspalathus linearis (rooibos) and 
Agathoshma betulina (‘buchu’). Hyperspectral images were captured using a shortwave 
infrared (SWIR) pushbroom imaging system in the wavelength range 920–2514 nm. 
Multivariate software (Evince® and Matlab®) were used to analyse the data. Principal 
component analysis was applied to the images to investigate chemical differences between 
the species. Partial least squares discriminant analysis models were constructed by assigning 
the clusters to classes. The classification models were used to predict the identity of raw 
material replicates inserted into the model as well as the levels of adulteration in spiked raw 
materials. UHPLC-MS as an independent analytical technique was used to confirm chemical 
differences between the species. For the star anise example, a classification model was 
developed and used to accurately predict the identity of whole dried fruit of I. anisatum and 
I. verum. In the ‘fang ji’ example, the replicates for each plant species were predicted at a 
value > 99% for all the samples. Artificially adulterated samples were accurately predicted 
from as low as 10%. In the herbal tea blend example, the classification model was applied to 
determine the relative proportions of each blend constituent in intact tea bags. With the 
increasing need to regulate herbal products and ingredients, emerging technologies are 
providing alternative methods that allow the holistic analysis of the samples. Hyperspectral 
imaging in combination with chemometric data analysis is ideally suited as a tool for the 
quality control of herbal raw material as it is a visual, rapid, accurate and non-destructive 
method with high prediction ability. 


Hyperspectral imaging in combination with chemometric data analysis – a powerful duo in the quality control of herbal medicines

Krause, Julius

Hock, Jürgen

Gruna, Robin

Längle, Thomas

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
35 
02-05: Detection of anomalies in bulk materials using hyperspectral imaging 
Julius Krause1, Jürgen Hock2, Robin Gruna2, Thomas Längle2 
1Karlsruhe Institute of Technology, Vision and Fusion Laboratory, Karlsruhe, Germany 
2Fraunhofer Institute of Optronics, System Technologies and Image Exploitation IOSB, Karlsruhe, Germany 
E-mail: Julius.krause@kit.edu 
Optical spectroscopy in the electromagnetic spectrum from 780 nm to 2500 nm is an 
established laboratory method in science and quality control. Hyperspectral imaging camera 
systems with a sensitivity in this measurement range can be used in visual inspection and 
sorting systems [1]. 
However, in a measured spectrum, signals from different origins are superimposed. In 
addition, the spectrum in hyperspectral images changes depending on the viewing angle of 
the surface of a sample and its scattering properties [2]. Therefore, the absolute value of a 
spectral band can often not be used directly and data pre-processing methods are required 
for further analysis. 
The presented approach of a pre-processing and feature extraction method has the idea to 
decompose the spectrum into its absorption bands. Based on a physically motivated signal 
model, the parameters of the absorption bands are estimated [3]. 
Compared to classical methods of spectral signal processing, the description of the spectrum 
using the absorption bands offers some advantages, especially for calibration transfer 
between sensors with different characteristics. This approach also enables the development 
of better interpretable classifiers. In particular, single class classifiers can be created with a 
minimum of training data. A promising sorting application is the detection of anomalies in 
the N-H absorption bands, which can be caused by pyrrolizidine alkaloids in plant material. 
References 
[1] LAFONTAINE, M., BOCKAJ, Z., FREUND, M., VIETH, K. U., NEGARA, C., and T. LANGLE, 2015: Non-destructive 
determination of grape berry sugar concentration using visible/near infrared imaging and possible 
impact on wine quality. Tech. Mess.  
[2] BEYERER, J., FRESE, C., and F. PUENTE LÉON, 2012: Automatische Sichtprüfung : Grundlagen, Methoden 
und Praxis der Bildgewinnung und Bildauswertung. Springer Vieweg.  
[3] KRAUSE, J., 2018: Wavelet based feature extraction in near infrared spectra for compositional analysis 
of food. Proceedings of the 2017 Joint Workshop of Fraunhofer IOSB and Institute for 
Anthropomatics, Vision and Fusion Laboratory.  


Detection of anomalies in bulk materials using hyperspectral imaging

Nasar-Eddin, Gazela

Zheleva-Dimitrova, Dimitrina

Gevrenova, Reneta

Balabanova, Vessela

Simeonova, Rumiana

Danchev, Nikolay

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
113 
P-026: UHPLC-HRMS profiling of Clinopodium vulgare extract 
Gazela Nasar-Eddin1, Dimitrina Zheleva-Dimitrova2, Reneta Gevrenova2, Vessela Balabanova2, 
Rumiana Simeonova1, Nikolay Danchev1 
1Department of Pharmacology, Toxicology and Pharmacotherapy, Faculty of Pharmacy, Medical University 
of Sofia, Sofia, Bulgaria 
2Department of Pharmacognosy, Faculty of Pharmacy, Medical University of Sofia, Sofia, Bulgaria 
Introduction: Wild basil (Clinopodium vulgare L.) (Lamiaceae) is a perennial herbaceous plant 
widespread in Bulgaria. Aerial parts are used in Bulgarian folk medicine for treatment of 
diabetes, gastric ulcers and cancer. The herbal drug alleviates symptoms associated with 
mastitis, prostatitis, skin irritation and swelling. 
Materials and methods: Aqueous-methanol extract from Clinopodium vulgare was analyzed 
by ultra-high performance liquid chromatography (UHPLC) coupled to hybrid quadrupole-
Orbitrap high resolution mass spectrometry with heated electrospray ionization (HESI) after 
classical reverse phase chromatographic separation. The identification of selected 
compounds was made by HRMS and MS/MS data, and some of them were confirmed by 
reference standards.  
Results: More than twenty secondary metabolites were identified or tentatively elucidated in 
Clinopodium vulgare extract. Variety of phenolic (ferulic, coumaric), and mono-and di-
caffoylquinic acids were identified together with flavons O- and C- glycosides, flavonol and 
flavanon glycosides. Based on the MS and MS/MS spectra, comparison with reference 
standards and literature data, luteolin-7-glucoside, luteolin-O-neohesperidoside, luteolin-8C-
glucoside, apigenin-7-glucoside, naringenin-O-hexuronide, isosacuranetin-7-neohesperido-
side, together with neochlorogenic, 4-caffeoylquinic, 1,3- and 3,4-dicaffeoylquinic acids were 
reported in the species for the first time. Clinopodic acids A, В and С and their isobars were 
evidenced; rosmarinic acid was the major compound.  
Conclusions: Using these methods we received information that Clinopodium vulgare is a 
valuable source of bioactive compounds. The results are very helpful for further analysis. 


UHPLC-HRMS profiling of Clinopodium vulgare extract

Tabbert, Jenny M.

Riewe, David

von Studzinski, Christoph

Mewis, Inga

Arnold, Oliver

Schulz, Hartwig

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
116    
P-029: Basil cultivation without sunlight 
Jenny M. Tabbert1,2, David Riewe1, Christoph von Studzinksi3, Inga Mewis3, Oliver Arnold4, 
Hartwig Schulz1 
1Julius Kühn Institute, Federal Research Centre for Cultivated Plants, Berlin, Germany 
2Free University of Berlin, Institute of Pharmacy, Berlin, Germany 
3Humboldt University Berlin, Urban Plant Ecophysiology, Berlin, Germany 
4FutureLED GmbH, Berlin, Germany 
E-mail: jenny.koeppe@julius-kuehn.de 
 
To enable a high-quality as well as cost-efficient greenhouse production in temperate zones 
like Berlin and Brandenburg, Germany, all year round, an LED system was developed which 
optimally serves the plants needs in the photosynthetically active (400-700 nm) range. 
Additionally, ultraviolet A and B (280-400 nm) radiation can be added to the visible light 
spectrum. 
To evaluate the effectivity of these LED lights for the cultivation of certain aroma and 
medicinal plants, a randomized full-factorial experiment with two different light intensities 
(PPFD of 200 and 100 µmol/m2/s) and four independent replications with four basil cultivars 
(Ocimum basilicum L. var. cinnamomum `Cinnamon`, O. basilicum L. var. thyrsiflorum `Thai 
Magic`, O. basilicum L. var. odoratum `Anise` and O. basilicum L. var. purpureum `Dark Opal`) 
under the exclusion of natural sunlight was conducted. In a second experiment with 
identical study design, UV-A (315-400 nm) or UV-B (280-315 nm) light were added to the 
spectrum with the PPFD of 200 µmol/m2/s. 
Within the relatively short cultivation period of four weeks, `Cinnamon`, `Anise` and 
`Thai Magic` grown under the high light intensity reached a marketability, which is met 
under optimal commercial greenhouse cultivation conditions of the region, only within 
seven weeks. Lower radiation as well as the addition of UV radiation delays the development 
of all four basil cultivars by maximal nine days.  
Detailed results of the weekly assessment of plant height, plant development and leaf 
composition of volatile substances determined by GC-FID and GC-MS are provided to 
compare the efficiency of the novel cultivation system with respect to a cost-benefit 
calculation as compared to conventional systems.  
 
  


Basil cultivation without sunlight

Tais, Leslie

Böttcher, Christoph

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
117 
P-030: Metabolite profiling of winter wheat grains from Fusarium head blight infected 
plants 
Leslie Tais, Christoph Böttcher, Hartwig Schulz 
Julius Kühn-Institute (JKI), Institute for Ecological Chemistry, Plant Analysis and Stored Product Protection, 
Berlin, Germany  
E-mail: leslie.tais@julius-kuehn.de  
Fusarium head blight is one of the main fungal diseases of grain crops like wheat, barley or 
maize. The Fusarium species cause quality and yield reductions and it has been a great 
challenge for wheat producers to avoid consequent economic damage. Fungal pathogens 
not only result in a decrease in crop yield and quality, but also produce harmful mycotoxins 
which cause a health risk for humans and animals. Fusarium species accumulate a wide range 
of secondary metabolites contaminating cereal crops worldwide. 
To investigate wheat grains from plants infected with Fusarium head blight UHPLC/ESI-
QTOF-MS-based metabolite profiling studies were carried out. Wheat was grown in a field 
trial at Groß Lüsewitz (Germany) where Fusarium head blight occurred in 2017. Within the 
field trial eight different genotypes were grown without the use of any plant protection. To 
cover a wide range of metabolites with different polarity, two analytical methods were used 
to provide information about polar, semipolar and nonpolar compounds. In the 
chromatographic method specific UHPLC columns (C18 and C8), suited for metabolites of 
different polarity, were used. 
The mycotoxin concentrations of deoxynivalenol, nivalenol, diacetoxyscirpenol, zearalenon, 
fumonisin B1 and B2, T-2-toxin and HT-2-toxin were quantified for the eight different 
genotypes. Based on the metabolite profiles features correlating with the deoxynivalenol 
concentration where analysed and with the help of accurate mass tandem mass 
spectrometry annotated. Around 20 metabolites could be annotated including peptides with 
the amino alcohol leucinol, stress markers and hydroxy fatty acid ester.  


Metabolite profiling of winter wheat grains from Fusarium head blight infected plants

Schwake-Anduschus, Christine

Sciurba, Elisabeth

Begemann, Jens

Bonte, Anja

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
118    
P-031: Detection of ergot alkaloids in flour and pastries 
Christine Schwake-Anduschus, Elisabeth Sciurba, Jens Begemann, Anja Bonte 
Max Rubner-Institut, Detmold, Germany 
E-mail: anja.bonte@mri.bund.de 
 
Ergot alkaloids (EA) are secondary metabolites of filamentous fungi, primarily Claviceps 
purpurea. This species may infect plants of the grass family, including cereals like rye and 
wheat, and build sclerotia containing alkaloids. As EA have a vasoconstrictive effect, some 
substances are used in medical treatment, e. g. against sick headache or for stimulating 
uterine contractions. However, the consumption of highly contaminated foods with EA 
causes ergotism, an illness that led to death in the middle ages. Even nowadays a case of 
ergotism outbreak arose in Arsi and Ethiopia due to the consumption of infected cereals and 
further studies showed that EA still occur in rye-, wheat-, oats or even millet containing foods 
[1]. In 2012 the European Food Safety Authority (EFSA) established a tolerable daily intake 
(TDI) of 0.6 µg/kg body weight and an acute reference dose (ARfD) of 1 µg/kg body weight 
for the sum of 12 ergot alkaloids [2]. While the ARfD was not exceeded for any population 
group, high consumption scenarios revealed a dietary exposure above the TDI for toddlers 
[3]. Maximum limits of 0,5 g sclerotia/kg unprocessed grains were already set and thresholds 
for EA in grains, flours and processed cereals are scheduled [4,5]. More information about the 
relation factors between the EA concentrations in raw and processed materials are required 
to provide information for reasonable legislation [4]. In this study an uHPLC-Qtof-MS/MS 
method has been developed to identify at least 12 EA (Fig. 1) in flour and pastries. Further EA 
shall be detected to examine the conversion of EA from raw material to processed food.  
 
 
Figure 1: Ergot alkaloids (EA) detected with uHPLC-Qtof-MS/MS. 1. Ergometrin, 2. Ergometrinin, 
3. Ergosin, 4. Ergotamin, 5. Ergocornin, 6. Ergokryptin (α,β), 7, Ergocristin, 8. Ergosinin, 9. Ergotaminin, 
10. Ergocorninin, 11. Ergokryptinin (α,β), Ergocristinin. A: standard substances in solvent (c=10 ng/ml). 
B: naturally contaminated rye flour. Int.: Intensity 
 
2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
119    
References 
[1] MALYSHEVA, S. V., LARIONOVA, D. A., DIANA DI MAVUNGU, J., and S. DE Saeger, 2014: Pattern and 
distribution of ergot alkaloids in cereals and cereal products from European countries. World 
Mycotoxin Journal, 7, 217-230. 
[2] EFSA, 2012: Scientific opinion on ergot alkaloids in food and feed. EFSA Journal, 10, 2798. 
[3] EFSA, 2017: Human and animal dietary exposure to ergot alkaloids. EFSA Journal, 15, 4902. 
[4] KNIEL, B., MEIßNER, M., KOEHLER, P., and C. SCHWAKE-ANDUSCHUS, 2018: Studies on the applicability of 
HPLC-FLD and HPLC–MS/MS for the determination of ergot alkaloids in rye-containing breads. 
Journal of Consumer Protection and Food Safety, 13, 69-78. 
[5] EU, COMMISSION REGULATION (EU) 2015/1940 of 28 October 2015 amending Regulation (EC) No 
1881/2006 as regards maximum levels of ergot sclerotia in certain unprocessed cereals and the 
provisions on monitoring and reporting. Official Journal of the European Union, 2015, L283/3. 
 
  


Detection of ergot alkaloids in flour and pastries

Sonntag, Frederike

Bunzel, Diana

Pawelzik, Elke

Naumann, Marcel

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
122    
P-034: Antioxidants in tomatoes are influenced by potassium fertilization 
Frederike Sonntag1, Diana Bunzel2, Elke Pawelzik1, Inga Smit1, Marcel Naumann1 
1University of Goettingen, Department of Crop Sciences, Quality of Plant Products, Carl-Sprengel-Weg 1, 
37075 Göttingen, Germany 
2Max Rubner-Institut, Department of Safety and Quality of Fruit and Vegetables, Haid-und-Neu-Straße 9, 
76131 Karlsruhe, Germany 
E-mail: fsonntag@gwdg.de 
 
Tomato (Solanum lycopersicum L.) fruit contain several health beneficial antioxidants [1]. 
Their contents can be greatly influenced by abiotic factors such as light, temperature, or the 
nutritional status [2]. The macronutrient potassium (K) is essential for several physiological 
functions in plants, e. g. translocation of assimilates, activation of enzymes, maintenance of 
turgescence, and stomata regulation. 
The aim of the study was to investigate the impact of increasing K fertilization on the 
antioxidants ascorbic acid, phenolic compounds, carotenoids, and tocopherols in tomatoes. 
Three cocktail tomato cultivars (Primavera, Resi, and Yellow Submarine) raised in an outdoor 
pot experiment were treated with five rising K doses in the first study year 2014. In 2015, 
Primavera and Resi were selected for a subsequent experiment using the lowest and highest 
K doses. In this experiment, the lipophilic antioxidants were additionally measured in three 
different tomato ripening stages.  
Increasing levels of K fertilization distinctly affected the contents of antioxidants in cocktail 
tomatoes (Table 1). However, most of the effects were not consistent across all three cultivars 
and the two study years. In 2014, K fertilization level positively correlated (p≤0.05 or 0.01) 
with ascorbic acid and γ-tocopherol in Resi and with p-coumaric acid in Primavera, while 
significant negative correlations were observed for narigenin and ß-carotene in Primavera 
and for β-tocopherol and δ-tocopherol in Yellow Submarine. In contrast, significant positive 
correlations between K fertilization level and ascorbic acid, p-coumaric acid and caffeic acid 
were demonstrated for both, Primavera and Resi, in 2015. As opposed to 2014, the 
tocopherols in Resi and Primavera negatively correlated with increasing K fertilization. The 
only antioxidant that consistently showed positive correlations with increasing K doses 
across cultivars and study years was p-coumaric acid. 
In summary, the content of plant antioxidants in cocktail tomatoes cultivated outdoors can 
be positively or negatively affected by K fertilization. However, other abiotic factors, such as 
variation in light and temperature may impact or even inverse those effects [3,4]. 
 
2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
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Table 1: Pearson correlation between the concentration of fruit K and antioxidants. 
 Primavera Resi Yellow Submarine Primavera Resi 
 2014 2014 2014 2015 2015 
ascorbic acid 0.028 0.477* -0.081 0,978** 0,904** 
p-coumaric acid 0.666** 0.375 0.309 0,923** 0,979** 
caffeic acid -0.221 0.392 0.039 0,769* 0,829* 
ferulic acid -0.326 0.293 -0.226 0.326 0.471 
sinapinic acid 0.014 -0.067 -0.129 -0.039 -0.395 
quercetin 0.198 0.048 0.295 -0.606 0.259 
narigenin -0.489* -0.220 -0.291 -0.700 -0.174 
ß-carotene -0.686** 0.255 0.060 0.357 0,513* 
lycopene -0.307 -0.229  0.187 0.135 
α-tocopherol  0.198 -0.351  -0,596** 
β-tocopherol  0.030 -0.488*  -0.271 
γ-tocopherol 0.313 0.696** -0.411 -0,553** -0,601** 
δ-tocopherol 0.006 0.195 -0.479* -0,778**  
*The correlation was significant at the level of p≤0.05 (2-sided) and with two** at the level of p≤0.01 
(2-sided). The number of observations was ≥ 8 and if there is no value the concentration of the 
antioxidant was below the detection limit. The correlation for ß-carotene, lycopene, α-, β-, γ-, and δ-
tocopherol in 2015 was performed with all ripening stages. 
 
References 
[1] PERVEEN, R., SULERIA, H. A. R. and F. M ANJUM, et al., 2015: Critical Reviews in Food Science and 
Nutrition, 55, 919–929. 
[2] GAUTIER, H., DIAKOU-VERDIN, V., and C. BÉNARD, et al., 2008: Journal of Agricultural and Food Chemistry, 
56, 1241–1250. 
[3] EHRET, D.L., USHER, K., and T. HELMER, et al., 2013: Journal of Agricultural and Food Chemistry, 61, 
1138–1145. 
[4] BALLIU, A., and V. IBRO, 2000: II Balkan Symposium on Vegetables and Potatoes, 579, 385–388. 
  


Antioxidants in tomatoes are influenced by potassium fertilization

Millan, Gerardo Gomez

King, Alistair W.T.

Llorca, Jordi

Sixta, Herbert

2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
127    
P-037: A study of the decomposition products of furfural, xylose and isophorone using 
NMR 
Gerardo Gomez Millan1,2, Alistair W. T. King3, Jordi Llorca1, Herbert Sixta2 
1Department of Chemical Engineering, Institute of Energy Technologies and Barcelona Research Center in 
Multiscale Science and Engineering, Universitat Politècnica de Catalunya, Barcelona, Spain 
2Department of Bioproducts and Biosystems, School of Chemical Engineering, Aalto University, Espoo, 
Finland 
3Materials Chemistry Division, Chemistry Department, University of Helsinki, Helsinki, Finland 
E-mail: gerardo.gomezmillan@aalto.fi 
 
In recent years we have witness lots of activity to upgrade sugars contained in lignocellulosic 
biomass into ethanol and other value-added chemicals. An interesting catalytic route, 
namely the dehydration of sugars (pentoses and hexoses found in lignocellulose) to furans, is 
considered one of the most promising routes for the production of platform chemicals and 
fuels [1]. One attractive furanic compound, furfural (FUR), has been identified as a direct or 
indirect feedstock to more than 80 chemicals [2,3]. The current FUR production uses mineral 
acids at approximately 200 °C, providing around 50 mol% yield [4]. Low yields in this process 
are mainly due to FUR decomposition with other compounds via resinification and 
condensation producing insoluble polymers (humins) [5]. A practical way to inhibit the 
formation of humins is to extract the FUR instantaneously from the aqueous solution into an 
organic phase [6]. 
In this study, the production of FUR from xylose was carried out using a biphasic batch 
reaction system. Isophorone and cyclopentyl methyl ether (CPME) were used to extract FUR 
from the aqueous phase to enhance the overall FUR yield by limiting its degradation. Due to 
their water-immiscibility nature, these organic solvents do not require salt addition, which is 
a significant advantage over other water-miscible organic solvents. The effect of time, 
temperature and organic-to-aqueous ratio on xylose conversion and FUR yield were 
investigated. Experiments conducted at three temperatures (170, 190 and 210 °C) were 
studied in a stirred microwave-assisted batch reactor, which established the optimal 
conditions to obtain the highest FUR yield. The maximum FUR yields obtained from xylose 
were 78 mol% when using CPME and 48 mol% when using isophorone with an aqueous to 
organic phase ratio of 1:1.  
In the present work from isophorone and CPME, the latter demonstrates a higher selectivity 
towards FUR (and thus higher FUR yield) without decomposition. This suggests that FUR 
undergoes decomposition reactions, potentially including isophorone as a co-reactant. 
Alternatively, the rate of degradation of FUR may be increased by an increasing content of 
water at temperatures approaching 200 °C. These possibilities were investigated by NMR 
analysis of the degradation of FUR: isophorone molar ratios of 1:1 and 1:10 at 190  °C over 
30 min (Figure 1). Potential mechanisms for this degradation might be, for example, Diels-
Alder cycloaddition (isophorone as hindered dienophile), Aldol condensation (isophorone C6 
reacting as nucleophile at the FUR aldehyde), Baylis-Hillman reaction (isophorone C2 
reacting as nucleophile at the FUR aldehyde) and Michael addition (isophorone C3 as α-β 
unsaturated electrophile). Other reactivity may of course be possible [7,8,9].  
2nd International Plant Spectroscopy Conference (IPSC) 2019, Berlin, 24 - 28 March 
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Figure 1. 1H NMR spectra (DMSO-d6 at 27 oC) of 1:10 molar equivalents of FUR:isophorone heated at 
190 oC for 30 and 120 min. 
 
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A study of the decomposition products of furfural, xylose and isophorone using NMR

Julius Kühn-Institut

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