This document discusses eliminating the need for matrix-matched calibration standards for pesticide residue analysis of QuEChERS extracts using an automated solid phase extraction cleanup procedure. It finds that an Instrument Top Sample Preparation (ITSP) robotic SPE cleanup using Z-Sep/C-18/CarbonX cartridges more effectively removes non-polar matrix like oils from complex samples compared to dispersive SPE. This improved matrix removal allows the use of solvent-only calibration standards and obtains acceptable recoveries for most pesticides tested, especially for analyses of spices, food ingredients, kiwifruit, and marigold oleoresin extracts.
Differentiation of Cultivars of Spanish Olive Oils Using Multiple LC/MS Analy...PerkinElmer, Inc.
The patterns of organic components in olive oils relate to the geographic origin, cultivar and processing methods for the olives. In this study a statistical analysis of the chemical components of authentic monovariatal virgin olive oils from Spain was used to determine markers for the cultivars. These markers could be used to confirm the provenance and origins of olive oil samples. Different LC/MS methods were used to measure the levels of a large number of polar and non-polar organic components in the oils. Results from the separate analyses were combined with data fusion. A statistical comparison with the combined results improved the discrimination of cultivar groups, when compared to a single LC/MS analytical method.
Differentiation of Cultivars of Spanish Olive Oils Using Multiple LC/MS Analy...PerkinElmer, Inc.
The patterns of organic components in olive oils relate to the geographic origin, cultivar and processing methods for the olives. In this study a statistical analysis of the chemical components of authentic monovariatal virgin olive oils from Spain was used to determine markers for the cultivars. These markers could be used to confirm the provenance and origins of olive oil samples. Different LC/MS methods were used to measure the levels of a large number of polar and non-polar organic components in the oils. Results from the separate analyses were combined with data fusion. A statistical comparison with the combined results improved the discrimination of cultivar groups, when compared to a single LC/MS analytical method.
Lead Generation for Small Business: Experts Weigh In
Managing your sales using a simple CRM is critical. The question is how do you even generate leads in the first place? Lead generation is the lifeblood of small businesses. If done right, generating great quality leads can be a major catalyst for growth and revenue. But with so many lead generation tactics and approaches available out there, small businesses want to know which are the most effective to use.
To help answer this question, we’ve reached out to a panel of small business sales and marketing experts and asked them all a single question: “What is the most effective lead generation technique(s) for small businesses“?
A SIMULATE MODEL FOR ANALYZING THE EFFECT OF ENGINE DESIGN PARAMETERS ON THE ...Barhm Mohamad
A mathematical and simulation model has been developed to simulate a spark ignition engine
operation cycle. The programme written from this simulation model and modified so can be used to
assist in the design of a spark ignition engine for alternative fuels as well as to study many design
parameters such as the effect of engine design parameter like stroke and diameter of the cylinder on
the performance and exhaust emissions of spark ignition engines
Workshop "How to pitch to a corporate VC" @ Start Summit 2013 in St. GallenPenny Schiffer
Penny Schiffer and Jonathan Grahm, Swisscom Ventures; Summary: Corporate Venture Capital is the practice where a large firm takes an equity stake in a small but innovative or specialist firm, to which it may also provide management and marketing expertise and other assets like customer access or IT infrastructure. The objective for the corporate is to gain a specific competitive advantage, benefits for a startup may include speed of execution and access to resources.
In this workshop we explained the concept of corporate venture capital, gave an overview over such activities in Switzerland and provided examples of how startups have used corporate venture capital to achieve their goals. We then worked on concrete examples – own startup ideas or case studies – to explore how to pitch to a corporate venture capitalist. We discussed pros and cons of such concepts and potential roadblocks. www.startsummit.ch
Development and method validation for determination of Deltamethrin residue i...IOSR Journals
Olive oil is the most important commodities produced in the Mediterranean region. Due to its significant economical importance, the usage of pesticides in its production is systematic, by using a wide range of plant protection products with a variety of modes of action. As a consequence, monitoring of their residue levels in these products is a necessity. In the present study a reversed-phase high performance liquid chromatography method, with a short sample preparation step, based on acetonitrile extraction is developed and validated in olive oil, with a large scope that includes Deltamethrin as pesticide. Good sensitivity and selectivity of the method were obtained with limits of quantification at 0.2 mg kg-1. Deltamethrin has recovery rate which is of about 80℅. We confirm also the efficiency of alumina, used as adsorbent in the clean up step, to remove triglycerides and to get a pure extract. The agronomic implementation of this protocol allows us to determine the influence of some parameters on the dose and the period of treatment affecting the detected quantities of Deltamethrin residues in the produced olive oil. Indeed, we prove that the treatment dose should be specific for each case considering the olive variety, the geography of the orchard, and the predicted harvest time to determine the convenient dose of treatment. In addition, the results show that the preventive treatment at the blooming phase, does not lead to the concentration of Deltamethrin residues in the oil as it happens at the lipogenesis phase.
Lead Generation for Small Business: Experts Weigh In
Managing your sales using a simple CRM is critical. The question is how do you even generate leads in the first place? Lead generation is the lifeblood of small businesses. If done right, generating great quality leads can be a major catalyst for growth and revenue. But with so many lead generation tactics and approaches available out there, small businesses want to know which are the most effective to use.
To help answer this question, we’ve reached out to a panel of small business sales and marketing experts and asked them all a single question: “What is the most effective lead generation technique(s) for small businesses“?
A SIMULATE MODEL FOR ANALYZING THE EFFECT OF ENGINE DESIGN PARAMETERS ON THE ...Barhm Mohamad
A mathematical and simulation model has been developed to simulate a spark ignition engine
operation cycle. The programme written from this simulation model and modified so can be used to
assist in the design of a spark ignition engine for alternative fuels as well as to study many design
parameters such as the effect of engine design parameter like stroke and diameter of the cylinder on
the performance and exhaust emissions of spark ignition engines
Workshop "How to pitch to a corporate VC" @ Start Summit 2013 in St. GallenPenny Schiffer
Penny Schiffer and Jonathan Grahm, Swisscom Ventures; Summary: Corporate Venture Capital is the practice where a large firm takes an equity stake in a small but innovative or specialist firm, to which it may also provide management and marketing expertise and other assets like customer access or IT infrastructure. The objective for the corporate is to gain a specific competitive advantage, benefits for a startup may include speed of execution and access to resources.
In this workshop we explained the concept of corporate venture capital, gave an overview over such activities in Switzerland and provided examples of how startups have used corporate venture capital to achieve their goals. We then worked on concrete examples – own startup ideas or case studies – to explore how to pitch to a corporate venture capitalist. We discussed pros and cons of such concepts and potential roadblocks. www.startsummit.ch
Development and method validation for determination of Deltamethrin residue i...IOSR Journals
Olive oil is the most important commodities produced in the Mediterranean region. Due to its significant economical importance, the usage of pesticides in its production is systematic, by using a wide range of plant protection products with a variety of modes of action. As a consequence, monitoring of their residue levels in these products is a necessity. In the present study a reversed-phase high performance liquid chromatography method, with a short sample preparation step, based on acetonitrile extraction is developed and validated in olive oil, with a large scope that includes Deltamethrin as pesticide. Good sensitivity and selectivity of the method were obtained with limits of quantification at 0.2 mg kg-1. Deltamethrin has recovery rate which is of about 80℅. We confirm also the efficiency of alumina, used as adsorbent in the clean up step, to remove triglycerides and to get a pure extract. The agronomic implementation of this protocol allows us to determine the influence of some parameters on the dose and the period of treatment affecting the detected quantities of Deltamethrin residues in the produced olive oil. Indeed, we prove that the treatment dose should be specific for each case considering the olive variety, the geography of the orchard, and the predicted harvest time to determine the convenient dose of treatment. In addition, the results show that the preventive treatment at the blooming phase, does not lead to the concentration of Deltamethrin residues in the oil as it happens at the lipogenesis phase.
Markers for Spanish Olive Oil Cultivars – Statistical Analysis of Polar Comp...PerkinElmer, Inc.
Polar components such as phenolic acids and lignans are present in olive oils. Secoiridoids; phenolics which include an elenolic acid moiety, are unique to the Olearaceae family. These compounds are known to have beneficial health effects due to their antioxidant properties and are associated with the organoleptic properties. Measuring the levels of these polar components in oils from different cultivars and geographic origins is of interest for nutritional and authenticity reasons. In this study a statistical analysis of the polar chemical components of olive oils was used to determine potential markers for olive cultivars. These markers could be used to confirm the provenance of unknown samples.
Metabolic engineering for oil quality improvementSenthil Natesan
The most important oilseed crops are Oil palm, Soybeans, Rapeseed and Sunflower,which together account for ≈ 79% of the total production of oils.Oils that are low in palmitic acid and rich in either oleic acid or stearic acid are novel oils. Selective breeding utilizing natural variants or induced mutations has been used to develop a range of improved oils. The vegetable oil is used for different applications as renewable sources of food used for frying, baking, processed foods,Fuel (Biodiesel),medicine and can be used as industrial raw material for preparation of soaps, detergents, paints, lubricants etc.
The recommended ratio of omega6/omega3 fatty acids in the human diet is approximately 2:1 to 6:1 (Simopoulos., 2000; Wijendran and Hayes., 2004) and the much higher ratio of omega 6 fatty acids in the typical Western diet (approximately 20:1) is thought to be a major contributor to cardiovascular disease (Simopoulos., 2000).
For metabolic engineering of oil quality improvement fatty acid composition and enzymes involved are very important so we can reduce expression of endogenous enzymes by adding new enzyme ,overexpressing existing enzyme and by using antisense RNA. It proved that genes for membrane-bound fatty acid-modifying enzymes not only from plants but also from bacterial,animal,yeast have been shown to function in transgenic plants.The enzymes such as Fatty acid synthase ,Thioesterases ,Elongases ,Desaturases ,Stearoyl-ACP desaturase ,Δ12-desaturase, , Δ15-Desaturase ,Acyltransferases and Hydroxylases are important in fatty acid manipulation.Suppression of the oleate D12-desaturase gene (which normally converts 18:1 to 18:2) in soybean, sunflower, cotton and canola has resulted in the production of oils with a high oleic acid content, which have greater oxidative stability and improved performance in high-temperature cooking applications. (Metzger and Bornscheuer., 2006).
Differentiation of Olive, Vegetable and Seed Oils by LC/MS Analysis of Triacy...PerkinElmer, Inc.
Extra virgin olive oil has been adulterated throughout history with less expensive oils such as soybean or hazelnut oil. Detecting adulteration is important for maintaining both the safety and consumer confidence of this product. This study reports on the measurement of the triacylglyceride composition of a large number of olive oils and other seed and vegetable oils using a simple LC/MS method, together with statistical analysis of the results to find indicators for different oil types.
Dissolution Method Validation with Reverse Phase Chromatographic Method for D...BRNSS Publication Hub
The present analytical work is a unique method development and validation for the determination of dissolution of Eltrombopag using reverse phase high-performance liquid chromatography (HPLC) with isocratic elution technique. HPLC method for quantification of drug in dissolution samples of Eltrombopag tablet is developed and validated. About 0.5% polysorbate 80 in phosphate buffer of pH −6.8 is used as dissolution medium and paddle (USP-II) as apparatus at 50 rpm. The sample was withdrawn after 45 min. The developed HPLC method was used for quantitative estimation of drug release in dissolution samples of Eltrombopag tablet. Here, the stationary phase used was Xbridge C18 (50 mm × 4.6 mm × 5 μm), mobile phase was 25% ammonium formate and 75% acetonitrile. pH of the buffer solution was maintained at 3.0, flow rate 1.0 ml/min. Eluted material underwent for monitoring at the detector wavelength of 230 nm. Retention time for Eltrombopag was found to be 2.16 min; and linearity range was 3.516 µg/mL–131.862 µg/mL. The new method was evaluated according to the ICH guideline and as far as validation results are concern correlation coefficient value that was 1.0000 for the compound, percentage recovery 99.4%, and repeatability results relative standard deviation 0.6 for Eltrombopag. The developed HPLC method was found to be a simple and rapid one for regular analysis in professional laboratory.
1. Eliminating the need for Matrix-matched Calibration Standards
for GC and LC Pesticide Residue Analyses of QuEChERS Extracts
using a Robotic Solid Phase Extraction Clean-up Procedure.
www.hill-laboratories.com
1. OVERVIEW 2. KIWIFRUIT
6. REFERENCES AND
ACKNOWLEDGEMENTS
5. DISCUSSION
3. SPICES BY LC-MS/MS 4. CONCENTRATED FOOD
INGREDIENTS BY LC-MS/MS
1.
2.
Figure 1: ITSP cartridges.
Bruce Morris*
, Richard
Schriner*
, Rick Youngblood#
and Kim Gamble#
.
*R.J. Hill Laboratories, Hamilton, New Zealand.
#
ITSP Solutions Inc., Hartwell, GA.
Standard EN QuEChERS method1
:
• Acetonitrile/water extraction with “salting-out” and citrate
buffering.
• Dispersive SPE (dSPE) clean-up with MgSO4
/ primary-secondary
amine (PSA) alone, or in combination with reversed phase (C-18)
silica and graphitized carbon black (GCB).
• Dilution in aqueous formate or acetate buffer, followed by
LC-MS/MS analysis.
• Addition of analyte protectants and GC-MS/MS analysis.
• Matrix-matched calibration standards generally used to
compensate for matrix effects, especially for complex spice/herb
or concentrated food ingredient samples.
ITSP (Instrument Top Sample Preparation):
• Robotic solid-phase extraction (SPE) clean-up, using miniaturized
cartridges on a CTC autosampler (Figure 1).
• Replaces dSPE step, giving improved clean-up and matrix removal.
• Stationary phases: LC-MS/MS - Z-Sep/C-18/CarbonX.
GC-MS/MS - MgSO4/PSA/C-18/CarbonX.
• Elution solvents: LC-MS/MS -1:1 MeCN/MeOH +100mM NH4
formate
(pH 5.8).
GC-MS/MS - acetonitrile/0.5% formic acid.
• Enables the use of solvent-only calibration standards.
EN 15662: Determination of Pesticide Residues Using GC-MS and/or LC-MS (/MS)
following Acetonitrile Extraction/Partitioning and Clean-up by Dispersive SPE -
QuEChERS method. In European Committee for Standardization, Technical Committee
CEN/TC 275; "Food analysis - Horizontal Methods"; Brussels, Belgium, 2008 ().
Increase Removal of Fat and Pigment from Avocado Extracts Prior to GC-MS Analysis of
Pesticide and Metabolite Residues. Katherine K. Stenerson and Jennifer Claus, Reporter
US Volume 31.2 - http://www.sigmaaldrich.com/technical-documents/articles/
analytical/food-beverage/avocado-extracts-zsep.html#sthash.ZMJzHRdC.dpuf.
Acknowledgement: We acknowledge the support of Supelco (Dr. Michael Ye) in
developing Z-Sep as a stationary phase for multi-pesticide residue clean-up.
• These are used as food colorings or flavorings, such as paprika
color and marigold oleoresin, and are often highly colored and oily
(Figure 2).
• Effective removal of non-polar matrix oils is needed, otherwise
significant suppression/loss of non-polar pesticides is observed,
as seen with PSA dSPE clean-up of Marigold oleoresin (Figure 7).
• Use of Z-Sep/C-18/Cx packed ITSP cartridges for clean-up of
Marigold oleoresin resulted in acceptable recoveries of non-polar
pesticides, due to superior matrix oil removal (Figure 8).
Figure 7: Pesticide recoveries versus LC-MS/MS retention time
(aqueous to organic gradient, C-18 column), for PSA dSPE.
Suppression or loss of non-polar pesticides is evident.
Figure 8: Pesticide recoveries versus LC-MS/MS retention time
(aqueous to organic gradient, C-18 column), for ITSP
(Z-Sep/C-18/Cx), showing little suppression or loss of
non-polar pesticides.
• Comparisons of Marigold oleoresin and paprika color extracts, cleaned up
by LC-ITSP (Z-Sep/C-18/Cx), and three different dSPE phase mixtures are
presented in Figures 9 and 10.
• The greater removal of matrix (predominantly oils), by ITSP resulted in
fewer pesticides falling outside the 70 – 130% recovery bracket.
• Especially evident is the lower counts in the “outside 50 – 150%” and “out-
side 30 – 170%” brackets for ITSP compared with all three dSPE methods.
These brackets can be classified as “recovery failures”.
• Acequinocyl is an example of a non-polar compound, exhibiting low (7%)
recovery with PSA dSPE, and acceptable (66%) recovery using ITSP
clean-up of Marigold oleoresin (Figures 7 and 8).
• Acidic compounds such as Imazamox can be lost on PSA by ion exchange
(Figure 7), or on Z-Sep by lone-pair intaction with vacant Zr orbitals. Use of
formate buffer allows 70% recovery from ITSP (Figure 8).
• Azoles (e.g. Uniconazole) are also retained on Z-Sep (29% recovery off
Z-Sep/C-18 dSPE), however are recovered off ITSP (87%) with formate
buffer elution.
• Extracts contain oils
- These interferences are removed by GC-ITSP
clean-up (Figure 3).
Figure 3: GC-MS full-scan chromatograms showing removal of
non-polar matrix by GC-ITSP.
Figure 4: Kiwifruit extract LC-MS/MS spike recoveries, calculated
against solvent standards, showing suppression/loss
with PSA dSPE, avoided using Z-Sep/C-18/Cx ITSP.
• Kiwifruit matrix is poorly removed by PSA dSPE giving suppression
of some analytes (Figure 4):
- Acrinathrin, empenthrin and flufenoxuron (non-polar,
effected by oils).
- Clethodim appears to be retained by PSA.
• ITSP (Z-Sep/C-18/Cx)clean-up showed lack of suppression or
losses (Figure 4), with improved oil removal, allowing use of
solvent-only standards.
• Spices commonly have high oil content and color (e.g. carotenoids),
or non-polar flavor compounds (e.g. curcumin in turmeric,
capsaicin in chili pepper), which may interfere with LC-MS/MS.
• Turmeric and chili pepper powder extracts were cleaned up by
LC-ITSP (Z-Sep/C-18/Cx), and compared with three different dSPE
phase-mixtures (Figures 5 and 6).
• ITSP clean-up performed best, resulted in fewer pesticides falling
outside 70 – 130% recovery than dSPE, and fewer “failures” (outside
30 – 170%), due to loss or suppression.
• One pesticide (trinexapac-ethyl) failed to be recovered from all
clean-ups.
TURMERIC
Figure 5: Comparison of LC-MS/MS pesticide recoveries from
Turmeric extract, cleaned up by ITSP or dSPE,
calculated against solvent-only calibration standards.
CHILI POWDER
Figure 6: Comparison of LC-MS/MS pesticide recoveries from
Chili powder extract,cleaned up by ITSP or dSPE,
calculated against solvent-only calibration standards.
Figure 9: Comparison of LC-MS/MS pesticide recoveries from
Marigold oleoresin extract,cleaned up by ITSP or dSPE,
calculated against solvent-only calibration standards.
MARIGOLD OLEORESIN
Figure 10: Comparison of LC-MS/MS pesticide recoveries from
Paprika color extract,cleaned up by ITSP or dSPE,
calculated against solvent-only calibration standards.
PAPRIKA COLOR
QuEChERS methods commonly use matrix-matched calibration
standards, to overcome suppression or enhancement of instrument
signals by sample matrix. Non-polar matrix (oils) can be
problematic for LC-MS/MS analyses of more difficult sample types,
such as spices/food ingredients. Z-Sep/C-18 dSPE has been shown
to be more effective than PSA/C-18 at removing oils.2
Data
presented here shows that Z-Sep/C-18, packed into an ITSP
cartridge, removes more non-polar matrix than PSA dSPE and also
gives improved pesticide recoveries compared with dSPE using
Z-Sep/C-18, or PSA/C-18. Effective matrix removal by ITSP allows
use of solvent-only LC-MS/MS calibration standards with
acceptable recoveries of most pesticides in the large suite trialled
(422 LC-MS/MS analyte peaks).
Figure 2: ITSP clean-up of QuEChERS extracts for LC-MS/MS,
using Z-Sep/C-18/ Carbon-X stationary phase.
Imazamox
Acequinocyl
Non-polar pesticides
Marigold Oleoresin PSA dSPE clean-up
LC-MS/MS analyte recovery vs. retention time
%
Pesticide
Recovery Bracket
Total
Count
Tumeric (422 Compounds/Isomer/Homologues)
Recovery Bracket
Chilli Pepper Powder (422 Compounds/Isomer/Homologues)
%recovery
Retention time (min)
Marigold Oleoresin ITSP clean-up
LC-MS/MS analyte recovery vs. retention time
%recovery
Retention time (min)
Imazamox
Acequinocyl
Total
Count
Recovery Bracket
Marigold Oleoresin (422 Compound/Isomer/Homologues)
Recoveries of Selected Analytes from Kiwifruit Extracts
Total
Count
Recovery Bracket
Paprika Colour (422 Compound/Isomer/Homologues)
Total
Count