3D-Darstellung, NASA/JPL-Caltech

Two techniques, one system

Nexera-i MT – HPLC plus UHPLC

Vanillin – natural or synthetic?

Analyzed using IRMS and GCMS

Anniversary: 60 years of GC and IR

Shimadzu as pioneer of the first hour

Pharmaceutical

Plastics and Rubber

Clinical

Chemical, Petrochemical,Biofuel and Energy

MARKETS

Food, Beverages, Agriculture

Environment

Automotive

CONTENT

Vanillin – natural or synthetic? GCMS and IRMS acquire the isotopic fingerprint of vanillin 4

Safe, clean and free of harmful substances? Analytical methods for plastic packaging of foods 6

New – Application Handbook Liquid Chromatography 12

Coenzym Q10: analysis of a sensitive substance – Analysis ofunstable compounds using onlineSFE-SFC 16

APPLICATION

GC pioneers of the first hour 60 years of gas chromato-graphy 13

Technological driver and market leader Milestones in 60 years ofIR history 14

Long-time partners – Shimadzutesting equipment at VladivostokUniversity’s Engineering School 18

LATEST NEWS

Rivals in femtogram-level analysis –The new GCMS-TQ8050 rivals HRMS’s sensitivity 2

Two techniques, one system – Nexera-i MT – Method transfer made easy 10

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SHIMADZU NEWS 3/2016

Rivals in femtogram-levelanalysisThe new GCMS-TQ8050 rivals HRMS’ssensitivity

Figure 1: GCMS-TQ8050

S ince Shimadzu launched thetriple quadrupole gas chro-matograph mass spectro -

meters GCMS-TQ8030 andGCMS-TQ8040 in 2012 and 2014,the systems have become well-established in environmental andfood safety (multicomponentresidual pesticide analysis), foren-

sic toxicology and metabolomics(metabolites analysis).

As regulatory bodies are increas-ingly opening the market ofultra-trace analysis not only toHRMS (high-resolution MS) butalso to triple quadrupole systems,it is necessary to develop systems

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3SHIMADZU NEWS 3/2016

Table 1: Comparison table GCMS-TQ8050 vs. HRMS on a real sample. Quantitative value of DXNs contained in real sample (pg/g).

I.D. Compound name

GC-MS/MS GCHRMS GC-MS/MS GCHRMS GC-MS/MS GCHRMS GC-MS/MS GCHRMS

Egg fat Pig fat Salmon Oliveoil

1234567891011121314151617

NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND

NDNDNDNDNDNDNDNDNDNDNDNDNDNDNDNDND

NDNDNDNDNDND(1.1)NDNDNDNDNDNDNDNDNDND

NDNDNDNDNDNDND(0.3)ND(0.2)NDNDNDNDNDNDND

NDNDNDNDND(0.2)(0.5)(0.4)ND(0.3)NDNDNDNDNDNDND

2,3,7,8-TeCDD1,2,3,7,8-PeCDD

1,2,3,4,7,8-HxCDD1,2,3,6,7,8-HxCDD1,2,3,7,8,9-HxCDD

1,2,3,4,6,7,8-HpCDDOCDD

2,3,7,8-TeCDF1,2,3,7,8-PeCDF2,3,4,7,8-PeCDF

1,2,3,4,7,8-HxCDF1,2,3,6,7,8-HxCDF1,2,3,7,8,9-HxCDF2,3,4,6,7,8-HxCDF

1,2,3,4,6,7,8-HpCDF1,2,3,4,7,8,9-HpCDF

OCDF

NDNDNDNDND(0.6)(0.3)(0.2)ND(0.1)NDNDNDNDNDNDND

NDNDNDND(0.3)(0.5)3.6(0.3)(0.2)(0.2)NDNDNDNDNDNDND

NDNDNDNDNDND(1.0)NDNDNDNDNDNDNDNDNDND

that cover HRMS’s sensitivitywith robustness and ease of use.

Instrument detection limit on femtogram level

In this scope, Shimadzu has collaborated with referenced lab-oratories in the field of POPs(Persistent Organic Pollutants)analysis to develop adequatesolutions.

The new GCMS-TQ8050 is the brand-new system of the GC-MS/MS product range. Itachieves an instrument detectionlimit (IDL) approximately tentimes more precise than the pre-vious systems and is capable offemtogram level (parts per qua -dril lion) analysis.

New high-efficiency detector

The Shimadzu’s GC-MS/MSrange of instruments is alreadywell-known for its UFMS (Ultra-Fast Mass Spectrometry) features.Customers improve throughputas well as quality of data.

In order to leverage the UF-transmission off-axis ion opticalsystem to the utmost, a new highefficiency detector with height-ened amplification performancehas been adopted. A new shieldto further reduce noise pushesthe limit of detection and im -proves robustness of the systemfor daily analysis.

Combining off-axis ion optical,overdrive lens system and thenew detector features ensuresthat noise is minimized duringtrace analysis, where high ampli-fication levels are required.

In addition, the new detector hasa long service life, at least fivetimes more than previous sys-tems, enabling high sensitivityanalysis with longer stability.

Result

The new GCMS-TQ8050 perfect-ly fits for trace analysis applica-tions of extremely small quanti-ties of dioxin in food & feed andthe environment, POPs compo-nents, endocrine disruptingchemicals, impurities in pharma-ceuticals and banned drugs inhair samples.

Table 1 shows a real sample comparison between the GCMS-TQ8050 and a JEOLHRMS system.

Combined with the MIURAGO-HT series clean-up systemand BUCHI Speedextractor PSE(see dioxin S3 offer), it provides apowerful tool for dioxins analysis

in food & feed to meet the EUregulation 589/2014 since June2014.

LiteratureCommission Regulations (EC) No 152/2009

(Feed), (EU) No 589/2014 (Food)

Figure 2: Off-axis ion optics

Further information

on this article

• Flyer: Dioxin S3

Determination of the isotopicratios of hydrogen

For the above reason, more dif-ferentiating parameters should be

APPLICATION

4 SHIMADZU NEWS 3/2016

V anillin is the most popularflavor worldwide. It is tra-ditionally produced from

vanilla pods (Vanilla planifolia orother species) by maceration.However, natural vanilla produc-tion covers only 1 % of globaldemand. 99 % of vanillin flavor is produced synthetically (petro-chemical origin) or biotechnolog-ically (e.g. from ferulic acid,eugenol).

Between natural and syntheticvanillin is a cost factor of 100 :1.It’s no wonder that vanillin is oneof the most imitated additives infood products worldwide. Howcan consumers be protected fromfalse declaration and fraud?

Natural and synthetic vanillin ischemically identical, but an iso-topic signature is left by the rawmaterial and the productionprocess. Consequently, the “iso-topic fingerprint” can be used fordifferentiation.

GCMS and IRMS reveal compound-specific isotope signature

A common elemental analyzer,coupled to a high resolution sec-tor field mass spectrometer (Iso -tope Ratio Mass Spectrometer,IRMS) can be used for the deter-mination of the isotope signaturefrom pure material with high pre-cision and accuracy. However,the vanillin (target compound) ina vanilla extract from a complexmatrix ranges in concentrationfrom 2 - 300 µg mL-1.

The substances should thereforefirst be separated from eachother, after which isotopic ratiosof the target compounds as wellas of accompanying compoundswhen needed can be determined(Compound Specific IsotopeAnalysis, CSIA).

This can be accomplished by cou-pling of GCMS and IRMS. TheAustrian-based company ImprintAnalytics uses a ShimadzuGCMS (GCMS-QP2010 Ultra)for this coupling technique as aworldwide first.

The CSIA technique was firstused commercially for the deter-mination of the 13C/12C ratio invanillin (Hoffman und Salb, 1979[1]). However, the determinationof only 13C cannot differentiatebetween synthetic (petrochemi-cal) and biotechnological (e.g.ferulic acid, eugenol) origin ofvanillin. Furthermore, the 13Csignature can be manipulated byenriched raw material so as tocounterfeit a natural product.More differentiation characteris-tics should be included.

determined. Additional determi-nation of the isotopic ratios ofhydrogen has been proposed(Greule et al., 2010 [2]). How -ever, little data is available for

GCMS and IRMS acquire the isotopic fingerprint of vanillin

Vanillin – natural or synthetic?

Figure 1: Method for measuring the carbon isotopic ratio in vanillin (schematic drawing).

The sample is cold injected and the solvent is blown out from the PTV (vent).The Detector

Switching Device (DSD) from Shimadzu is located after the separation column, where the

matrix substances are separated. The gas flow is split after the DSD: the smaller part is trans-

ferred to the quadrupole mass spectrometer, where the substances are identified; the larger

part is flashed in the oxidation oven. The CO2 is transferred into the IRMS after removal of

water and the isotopic ratio is measured.

Natural vanilla. The name comes from the Spanish »vainilla«, small pod.

5SHIMADZU NEWS 3/2016

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this today. Imprint Analytics hasbuilt up a large database in thepast years which can be used todetermine the origin and authen-ticity of such samples.

Which methods does ImprintAnalytics use to verify whethervanillin is from natural, nature-identical or synthetic origin inextracts and end-products?

Materials and methods

Vanillin is extracted from an es -sence (or from the end-product).The solvent is 2-Methoxy-2-methylpropane (MTBE). 200 µLof the sample are used on theauto sampler (Shimadzu, AOC-5000).

Two separate analyses are per-formed to determine the isotopicsignatures of carbon and hydro-gen.

The samples are cold injectedwith a 10 µL syringe into theOptic-4 Multimode Inlet (GLSciences, Tokyo, Japan) at 35 °C.The solvent is removed for someseconds by blowing it out and the injector is then heated up to285 °C. The sample is transferredonto the column by splitlessinjection mode. Separation isdone using a ZB-5MSi column(60 m x 0.25 mm 1.4 µm,Phenomenex, Torrance, USA).The GC program is:

Temperature program: 35 °C, 1 min, Heating rate: 20 °C min-1 until300 °C, Pressure program: He carrier:300 kPa, flow control: linearvelocity, APC1 (pressure afterDetector Switching Device, DSD)100 kPa; Splitless time: 0.7 min.

The DSD from Shimadzu islocated after the separation col-umn. It enables total separationof the solvent and transportsother substances into the heart-cut purge. Vanillin and other substances with similar retentiontimes are transported by a T-piece into an inert silica glasscapillary with two directions: • separate substances which areidentified in the ShimadzuGCMS-QP2010 Ultra

• organic substances which areoxidized in the oven into H2Ound CO2 (Hekatech, Wegberg,Germany).

Water is removed with a NafionTM

membrane from the He flow(Hekatech, Wegberg, Germany)and CO2 gas is forwarded to theIRMS (Nu Instruments, Wrex -ham, UK) where the isotopicratio 13C/12C is determined (fig-ure 1).

The determination of hydrogenisotopes is similar, but more sam-ple material is required. Injectionvolume and blow-out time in theOptic-4 Multimode Inlet aretherefore increased. Vanillin iscarried into the pyrolysis oveninstead of an oxidation oven. In the pyrolysis oven, vanillin isreduced to H2 (and CO). H2 istransferred to the IRMS to deter-mine the isotopic ratio of 2H/1H.

Measured values are normalizedin two steps to ensure high meas-urement accuracy: each run witha reference gas, and each samplerow with a reference material (incase of hydrogen two referencematerials) with known isotopicratio. The normalization process

is verified by quality controlsamples. More replicate measure-ments are carried out for bothelements to ensure a high preci-sion.

Measured values are comparedwith a reference database (fig ure2). In this way, it is determinedwhether vanillin is from natural,nature-identical, or synthetic ori-gin. The composition of the iso-topes can also be used to proveauthenticity and the determina-tion of the geographical origin ofthe natural vanillin. The declara-tion of bourbon vanilla can beverified by this procedure, e.g.whether the vanilla really origi-nates from Madagascar.

Outlook

All vanillin sources can be deter-mined using the technology andmethod described. But new pos-sibilities to produce vanillin inthe future by other ways willoccur. For this reason, thismethod should be developed fur-ther. Oxygen isotopes should beconsidered in the future to ensurerobust results on the authenticityof vanillin. A third measurementis required, where the oxygen of

Further information

on this article

• Website: Imprint

Analytics

Figure 2: Isotopic signature of vanilla flavour. Possible isotopic signature ranges from natural,

biotechnological and synthetic vanillin are shown (data from Imprint Analytics).

vanillin reacts to CO in the plat-inum oven.

A large number of flavor sub-stances are falsified (e.g. benzal -dehyde from bitter almond, orcinnamaldehyde in cinnamon),just to mention some. ImprintAnalytics will develop moremethod applications for this field.

AuthorsDr. Balázs Horváth, Dr. David Psomiadis,

Dr. Bernd Bodiselitsch

Imprint Analytics GmbH,

Werner von Siemens Str. 1, 7343 Neutal,

Austria

Literature[1] Hoffman, P.G., Salb, M. (1979)

Isolation and stable isotope ratio analysis

of vanillin. J. Agric. Food Chem., 1979,

27 (2), pp 352-355

[2] Greule, M., Tumino, L.D., Kronewald, T.,

Hener, U., Schleucher, J., Mosandl, A., &

Keppler, F. (2010)

Improved rapid authentication of vanillin

using δ13C and δ2H values. European

Food Research and Technology,

231: 933-41

T he influence of cups, plasticbottles and film packagingon human health and the

environment is a challenge.Supermarket shelves are full ofproducts that are, in part, pack-aged in highly complex plastics.

These types of packaging materi-als are lightweight and also high-ly stable, and protect expensive aswell as easily perishable productsagainst environmental influences.At the same time, plastic packag-

seas – and in the stomachs of fishand seabirds.

Just to quantify, a brief look atGermany as one of the largestEuropean countries. In 2013,around 17.1 million tons of plas-tic packaging wastes were gener-ated. The increase to this highestlevel is attributable mainly tochanges in consumption patterns.Nearly 72 percent, i.e. 12 milliontons of the packaging wasteswent into recycling [1].

EU Ordinance on the Avoidance and Recovery of Packaging Wastes

As early as 1998, the EuropeanUnion adopted the Ordinance onthe Avoidance and Recovery ofPackaging Wastes (VerpackV) andamended it in the most recentversion of 2014 [2].

The objective of VerpackV is toavoid or reduce the environmen-tal impacts of packaging waste. In addition, the share of bever-ages filled in reusable drinkspackaging and environmental-

ing carries colorful printed adver-tising messages and fact-orientedproduct information.

But plastic packaging materialsare increasingly the subject ofcriticism, because undesirable andpotentially hazardous substancescan migrate from the packaginginto the foods when in directcontact. More plastic also meansmore waste. Plastics not only endup in recycling yellow bags andon landfills but also in rivers and

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6 SHIMADZU NEWS 3/2016

Safe, clean and free of harmfulsubstances?

friendly one-way drinks packag-ing should increase to at least 80 %.

According to a report of theEuropean Environmental Agency(EEA) in 2013, Europeans recy-cled more waste from 2001 to2010: the recycling share in -creased from 23 percent to 35percent – in absolute numbersthis was 63 million tons of house-hold waste which found a newdestination [3].

VerpackV and harmful substances

VerpackV also regulates the con-centration of harmful substancessuch as heavy metals that may bepresent in packaging materials.Accordingly, packaging or itscomponents may only enter cir-culation if the cumulative con-centration of lead, cadmium,mercury and chromium VI doesnot exceed 100 mg/kg.

In addition to the REACH Ordi -nance Annex XVII, there is a banon bringing certain cadmium-

Figure 1: EDX-7000P/8000P

Figure 2: ICPE-9820 ICP-OES spectrometer with ‘dual view’ optics

Analytical methods for plastic packaging of foods

Element

CdPbCrHgAs

Sample

Dry Method[mg/L]141105105

< 0.228

Wet Method[mg/L]140

< 0.211224.031

Microwave M.[mg/L]14010811225.630

Certified V.[mg/L]140.8107.6114.625.330.9

Dry Method[mg/L]21.013.116.2< 0.2

4

Wet Method[mg/L]21.4< 0.217.24.34

Microwave M.[mg/L]21.713.517.54.65

Certified V.[mg/L]21.713.817.74.53.93

*Detection Limit[mg/L]0.020.20.030.20.5

BCR680 BCR681

IMPRINT

Shimadzu NEWS, Customer Magazine of Shimadzu Europa GmbH, Duisburg

PublisherShimadzu Europa GmbHAlbert-Hahn-Str. 6 -10 · D-47269 DuisburgPhone: +49 - 203 - 76 87-0 Fax: +49 - 203 - 76 66 25shimadzu@shimadzu.euwww.shimadzu.eu

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Design and Productionm/e brand communication GmbH GWADüsseldorf

Circulation German: 5,720 · English: 4,510

CopyrightShimadzu Europa GmbH, Duisburg, Germany – November 2016.

Windows is a trademark of Microsoft Corporation. ©2016

Apple Inc. All rights reserved. Apple, the Apple logo, Mac OS and iOS are trademarks of Apple Inc.

7SHIMADZU NEWS 3/2016

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Table 1: Distribution of the elements Pb, Cd, Hg and Cr in polyethylene (reference material BCR 681), *Detection limit at sample preparation with delution of 0.2g /20mL

containing compounds into circu-lation if the cadmium contentexceeds 100 mg/kg (0.01 % bymass). These restrictions are mostimportant for plastic products asthey are produced and distrib-uted in high quantities.

In this case, a distinction is madebetween cadmium used for color-ing certain substances and mix-tures (e.g. cadmium sulfide orcadmium selenide) and cadmiumused as a stabilizing agent (e.g.cadmium stearate) for certainmixtures or products of vinylchloride polymers or copolymers.The addition of cadmium used asa dye is restricted in nearly alltypes of plastics, while theadmixture of cadmium as a stabi-lizer pertains to 13 vinyl chloride(co)polymer product groups (i.e.PVC), for example packagingmaterials.

Recycled plastics for food packaging?

Particularly, recycled plastics asmaterials for food packaging arein focus, for instance PET bot-tles. The plastics experts group at the Federal Institute for Con -sum er Health Protection andVeterinary Medicine has ex -plained this as follows:

The legal regulations for con-sumer goods are also applicableto recycled PET plastics. How -ever, due to possible improperuse and the generally non-homo-geneous input material, addition-al quality assurance measures arerequired. The input material forthe mechanical recycling processshould consist of at least 99 %original ‘food grade’ PET. Therecycling process applied must beable to remove migration-rele-vant substances from the polymermatrix that may be present due toprior use. The required cleaningefficiency is to be verified once in

terms of a ‘worst-case’ scenariousing model contaminants (surro-gates) and using a migration testor evaluation. An adequate quali-ty assurance analysis method isessential for monitoring of theproduction process [4].

Using spectroscopy, chromatog-raphy, mass spectrometry andmaterials testing technology,Shimadzu, as one of the world’sleading manufacturers of analyti-cal instrumentation, offers the

complete hardware and softwarerange for reliable determinationof hazardous substances andidentification of the materialsused.

Qualitative and quantitativedetermination of heavy metals

For rapid qualitative and quanti-tative determination of heavymetals in plastics (such as cadmi-um in the desired concentrationrange) used in food packaging,energy-dispersive X-ray fluores-cence spectroscopic analysis isthe method of choice. Shimadzu’sEDX series (EDX-7000P/8000P)enables the analysis of food pack-aging like plastic films, PET bot-tles, polystyrene yoghurt con-tainers and much more, in thelow-ppm range (figure 1). Thesample can be positioned directly

in the sample compartment with-out any complex sample prepara-tion.

The sample to be examined isirradiated from below with high-energy X-rays. When these hit anatom, an electron from one of thelowest energy levels of the K andL shells is excited energetically tosuch an extent that it is ejectedfrom its orbital position. Theresulting ‘hole’ is immediatelyoccupied by an electron falling

Figure 3: ICP-OES Spectrometer ICPE-9820

from a higher shell. This processreleases energy known as second-ary energy or X-ray fluorescenceenergy.

In the present example, this ele-ment-specific fluorescence radia-tion corresponds to the energydifference between the K or Lshell and the shell of the higherenergy levels from which the‘falling’ electron originates. Byknowing the energy ratios of theindividual elements, reliablequantitative analysis of an un -known sample is possible: thedetected X-ray fluorescence iselement-specific.

Simultaneous determination of heavy metals

Simultaneous determination ofheavy metals is carried out using

ICP-OES spectrometers such asthe ICPE-9820 (figure 3), whichare characterized by high sensi-tivity, a wide dynamic measuringrange and high sample through-put. The ICPE-9820 with CCD(charge coupled device) detectoris equipped with vacuum optics,setting new standards withrespect to performance, speedand operating costs.

After applying a suitable diges-tion method the plastic samplesare injected to the ICPE-9820. At argon plasma temperatures ofappr. 10,000 K the atoms and ionsare excited and subsequentlymoving back to ground state. At this step energy (light) isemitted in UV-VIS range. �

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8 SHIMADZU NEWS 3/2016

form needing a plasticizer tomake it more flexible. Soft PVCis used, for example, in the pro-duction of packaging films ap -plied as outer packaging of PETbeverage bottles. PVC films arealso still used at deli counters.

The radiation emitted is pro -cessed in the optical system andis measured by the CCD detec-tor. The emission spectrum(detected in the range of 167 to800 nm) contains information ofover 70 elements, which can beused for quantification. Thisquantitative determination of ele-ments is carried out using calibra-tion curves from multi-elementstandards. Figure 2 shows theoptical system of the ICPE-9820in ‘dual view’ for axial and radialplasma observation.

Various sample preparationmethods

Various methods are available forsample preparation. A widelyused method is microwave diges-tion, carried out in microwave-permeable pressure vessels in amicrowave oven. An example isthe treatment of samples using amixture of concentrated nitricacid with addition of a smallamount of hydrogen peroxide atelevated pressure-temperatureconditions. In addition, wet-ash-ing or dry-ashing, in which theorganic constituents of a solidsample are digested via combus-tion in a crucible, are also possi-ble.

The ICP-OES system configura-tion described here provides acurrent state of the art overviewof the determination of heavymetals in plastic packaging ac cor -ding to the European PackagingOrdinance. The actual concentra-tions of the individual substancesin the homogeneous samplematerial can vary considerablyand can be analyzed easily andrapidly using the ICPE-9820 fol-lowing sample preparation anddilution.

Identification of plastics, including main components and additives

FTIR spectroscopy using theIRAffinity-1S spectrophotometerin combination with ATR (atten-uated total reflectance) technolo-gy offers an ideal system configu-ration for the identification ofplastics. The determination ofpolymers takes place via dia-mond-ATR and enables unequiv-ocal determination of the main

components as well as the identi-fication of additives, for in stanceplasticizers, as a function of theconcentration.

PVC for instance is a very hardand brittle plastic in its initial

The use of the particularly harm-ful, endocrine disruptive plasti-cizer DEHP (a phthalate) has,however, been banned in packag-ing of fat-containing foods.Plasticizers used in food packag-ing materials pose a risk formigration of undesirable sub-stances into the food. The foodindustry therefore uses otherplastics such as polyethylene(PE), polypropylene (PP), poly-carbonate (PC) and polyethyleneterephthalate (PET).

The use of infrared spectroscopy

PE, PP, PC and PET were inves-tigated via infrared spectroscopyin about 30 food packagings(table 1) obtained from super-markets in the Netherlands andGermany. The packagings (trans-parent, colorless) were examinedfrom the inside and outside.Where the packaging consisted ofseveral components such as lids,bottle caps or film layers, forinstance as tamponage for liquids,these components were includedin the measurements. Consumerinformation on the label inform-ing of the polymer used was alsodetermined.

It is always astonishing that apolymer may be listed on theouter packaging label as PP orPET – and found in the measure-ments – while the inner packag-ing actually consists of a PE. Willthis not be a real challenge forthe recycling industry?

Sample measurement using theFTIR spectrometer takes placenon-destructively and withoutmuch time and effort. In particu-lar, comparison of the IR spec-trum of the actual measured sam-ple with comprehensive spectrallibraries allows the identificationof the material. In addition, it ispossible to obtain a clear indica-tion of whether it is a pure sub-stance, a product mixture or evena recyclate. In this investigation,only surfaces that could interactwith an infrared penetrationdepth of up to 2 µm were consid-ered.

Looking at the polymers identi-fied in Table 2, those listed on thelabel and the packaged food, it

4,500

0.0

cm-1

Abs.

0.2

0.4

0.6

0.8

1.0

1.2

4,000 3,500 3,000 2,500 2,000 1,750 1,500 1,250 1,000 750 500

4,500

0.000

cm-1

Abs.

0.025

0.050

0.075

0.100

0.125

0.150

0.175

0.200

0.225

0.250

0.275

0.300

4,000 3,500 3,000 2,500 2,000 1,750 1,500 1,250 1,000 750 500

Figure 4: Shown here is the packaging for apricots – a plastic box with lid and a label ‘Recy -

cling 5 for polypropylene’ under the box. The box is made of polypropylene (IR spectrum figure

4b), while the lid is made of PET (IR spectrum figure 4a).

4a

4b

9SHIMADZU NEWS 3/2016

APPLICATION

can be concluded that each poly-mer is used ubiquitously. Notrend could be found. In thesetypes of packaging, the visualappearance, the value and ulti-mately the price determines theso-called ‘make-up.’ Among thepolymers found, no PVC filmcould be identified.

Summary

The determination of plastic foodpackaging requires careful qualityassurance analysis using EDX,ICP-OES and FTIR spectrome-try. Investigation of transparentpackaging materials using FTIR-ATR technology, however, reveals

that the plastics indicated on therecycling symbol are not alwaysunequivocal. In some PET andPP samples, other plastics havebeen identified. Such mixturesplace high demands on the recy-cling industry. Further investiga-tions using complementary analy-sis methods on this topic shouldprovide more information andlead to a complete solution –including colorless and dyedmaterials up to black plastics.

Literature[1] Umweltbundesamt, Abfall- und Kreislauf -

wirtschaft – Verpackungsabfälle 2/2016

[2] Verordnung über die Vermeidung und

Verwertung von Verpackungsabfällen

(Verpackungsverordnung – VerpackV),

2014

[3] EEA Report, Managing municipal solid

waste, ISSN 1725 -9177, 2/2013

[4] Gesundheitliche Beurteilung von Kunst -

stoffen im Lebensmittelverkehr:

Stellungnahme der Kunststoffkommission

des Bundesinstituts für gesundheitlichen

Verbraucherschutz und Veterinärmedizin

zur Verwendung von Kunststofferzeug -

nissen für Mehrweganwendungen und von

Kunststoff-Recyclaten für die Herstellung

von Lebensmittelbedarfsgegenständen,

Bundesgesundheitsblatt, 1995, 38, 73

No:Type of foodN02:meatN03:meatN04: chicken meatN05: Egg cartonN06: chicken meatN07: StrawberriesN08: Salmon/egg saladN09: GrapesN10: SausagesN11: NutsN12:Wine cup,

disposableN13: Sliced cheeseN14: Small cakeN15:Mini wafflesN16: Flavored

waterN17: CookiesN18: Cup, disposableN19: Cup, disposableN21: inner SausageN22: Organic cling filmN23: Sweets, wine

gumsN24:ApplesN25: Sweets, wine

gums – sourN26: Organic breadN27: BreadN28:TomatoesN29 - ApricotsN30: Sweets,

liquoriceN31: Fruits,

self-serviceN32: Red currants

Container, external surfaceContainer, external surfaceContainer, external surfaceContainer

––Container, external surfaceContainer, external surfaceContainer, external surface

––Container, external surface

––

––––

Container, external surface––

Container, external surfaceCup, external surfaceCup, external surface

––––

Film

Container, blackFilm

––––––

Container, external surfaceFilm

––

Container, external surface

Sample Location of the label

1 PET1 PET1 PET1 PET––1 PET1 A-PET1 PET––1 PET––

––––1 PET––

05 PP05 PP06 PS––––Symbol

Symbol5 PP

––––––5 PP05 PP

––

PET

Recycling symbol Identification via FTIR

Container, cup, trayPE, PETPE, PETPE, PETPETPSPETPETPETPE, PETPETPS

PETPSPETPET

PPPPPSnonenonenone

PSPP

nonenonePETPPnone

none

PET

Lid, covernonenonenonenonenonePETPETPETnonePETnone

nonePETnonePE, PE plus

nonenonenonenonenonenone

nonePP, PP plus water?

nonenonePETPETnone

none

PET

Film, adhesive, tamponadePP, PEPP, PEPP, PEkeinPET plusPE, PE+ resinPET plus nonePE, PET, starchPETPP

PETPPPPkein

nonenonenoneCellulosePE, PETPP plus

PVC

PPPP

PP

PE

none

Table 2: Transparent, colorless packaging material and the infrared-identified main polymers found in the packaging

FTIR spectrometer IRAffinty-1S

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10 SHIMADZU NEWS 3/2016

Nexera-i MT – Method transfer made easy

Two techniques, one system – HPLCmeets UHPLC

I n recent years, there has beena strong focus on the use ofUHPLC instruments and

small particle columns to developfaster and better analytical meth-ods that improve efficiency andthroughput especially in R&Denvironments.

However, many of the analyticalmethods used in quality controllaboratories, including those listed in the pharmacopeia, areconventional HPLC methods.Transferring these HPLC meth-

ods to UHPLC and validating thenew methods is a time consumingand labor intensive task.

The Nexera-i MT incorporatestwo analytical flow lines with different system volumes into asingle compact integrated LC. By automatic switching betweenthese flow lines, Nexera-i MTseamlessly performs both HPLCand UHPLC analyses, preservingthe relative separation pattern bycompensating automatically fordifferences in system volume.

Figure 1: Nexera-i MT system

11SHIMADZU NEWS 3/2016

PRODUCTS

Consequently, Nexera-i MTachieves exceptional analyticalreproducibility when switchingfrom a system with large volumeto a system with smaller volume,or vice-versa.

The same technology also allowsNexera-i MT to match any exist-ing HPLC or UHPLC methodrun on competitive instrumentplatforms, eliminating the need toconsider and carefully matchplumbing to achieve identicalsystem volumes between instru-ments.

The instrument offers enhancedfunctionality to support thetransfer of existing HPLC meth-ods to faster UHPLC analyseswhile assuring high cross-com-patibility between the former andnew method conditions. It canalso be used for quick methoddevelopment in UHPLC modeand seamlessly convert intoHPLC methods for broaderapplicability by using a simpleconversion program.

Two independent flow lines

Nexera-i MT features two inde-pendent and dedicated flow lines,one for UHPLC and the otherfor HPLC analyses. Newly de -veloped Analytical ConditionsTransfer and Optimization(ACTO) technology minimizes

the effect of system volume differences between different systems on analytical results.

In addition to drastically improv-ing the efficiency and quality ofmethod development and transferefforts in quality control depart-ments, Nexera-i MT’s dual flowlines also maximize operationalefficiency by enabling a singleinstrument to run both HPLCand UHPLC analyses, asopposed to separate dedicatedinstruments for each method.

As an example application figure2 shows the analysis of five non-steroidal anti-inflammatory drugson a conventional HPLC systemfrom another vendor.

Method conditions:

Column: ACE Excel 3 SuperC18150 x 4.6 mm (ACT)

Mobile phase:A: 0.1 % formic acid in H2O B: 0.1 % formic acid in MeCN

Flow rate: 1 mL/min Temperature: 40 °C Detection at: 254 nm Sample: 0.6 mg Aspirin, 0.1 mgSulindac and 0.2 mg of Napro -xen, Flurbiprofen, Phenylbuta -zone in 1 mL Acetonitrile /Water (50 : 50 v/v)

Method transfer to a different system

If the HPLC system that wasused to develop and run thismethod needs replacement butthe same system is no longeravailable, the user will face theproblem of having to transfer themethod to another system, withdifferent performance parametersand system volume. This mayresult in a totally differentmethod that will render futureresults not comparable to previ-ous data. On the other hand,when purchasing an older instru-ment to match the method condi-tions, the chance can be missed toget the latest equipment thatcould still be used when a moreefficient, faster (UHPLC)method is required.

In this case, the Nexera-i MTsystem is the ideal solution. Thecustomer acquires state-of-the-artequipment offering all the latesttechnology, including pressureresistance up to 660 bar, auto-validation function and touchpanel control, and can accurately

5

0

Time [min]

mAU

200

400

600

800

1.000

10 15 20 25

Figure 2: Separation of five NSAID’s on a non-Shimadzu HPLC system

Time02025

% B207070

Gradient program

Followed by 11 min reequilibrationtime (20 % B) 36 min run time

reproduce HPLC analysis frompreviously used methods.

To illustrate these features, theanalysis shown in figure 2 wastransferred to the Nexera-i MTsystem. Method conditionsremained the same, while a smalldifference in system volumebetween the HPLC flow path and the other instrument wasaccounted for in the software(figure 3).

Using this feature and exactly thesame analysis conditions includ-ing column and sample, the chro-matogram could be reproducedalmost identically (figure 4a, b).

Method transfer tool increases efficiency with a mouse-click

Furthermore, by using themethod transfer tool in theLabSolutions Software themethod could be switched easilyto the UHPLC flow path and runtime was decreased by 19 min to an overall run time of 7 min(figure 4c, page 12).

And it doesn’t take an expertchromatographer to perform thiskind of increase in efficiency. The ACTO function included inLabSolutions is an easy-to-useinterface offering all necessarysteps at the click of a mouse. �

Figure 3: Gradient start adjustment in the LabSolutions software

PRODUCTS

12 SHIMADZU NEWS 3/2016

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Time [min]

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21Time [min]

0 1 2 3 4 5 6

Time [min]

Figure 4: Comparison of the separation of five NSAIDs on a non-Shimadzu HPLC system

a) the Nexera-i MT HPLC flow path (b) and in UHPLC mode (c)

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Download: Application

Handbook Liquid

Chromatography

The user only has to open thechosen HPLC method and clickthe method transfer button in the user interface (figure 5).Original and new method condi-tions including column dimen-sions and flow rate can be en -tered, and the software automati-cally calculates and incorporates

the new gradient profile andmethod parameters to a newUHPLC method, which runsthrough the UHPLC flow path of the system.

The combination of the Nexera-iMT system with LabSolutionsand the systems’ unified graphical

user interface and software allowintuitive operation independentof the user’s experience level. In addition, where another CDSis used, available software driversallow the Nexera-i MT’s specialfeatures to be used with mostother vendor software packages.

New – Application HandbookLiquid ChromatographyHPLC, UHPLC as well as

SFC systems are able toquantitatively analyze sub-

stances in mixtures containingmultiple ingredients by separatingand detecting target substanc es.

They are used to separate, quanti-fy, qualify or purify single com-ponents from a sample containingvarious analytes in differentmatrices.

Shimadzu offers a wide variety ofapplication-specific systems, suchas automated sample pretreat-

APPLICATION

Figure 5: Method transfer calculator

ment systems for amino acidanalysis or on-line sample trap-ping for the quantification ofresidual pesticides in food or soil.

SHIMADZU NEWS 3/2016 13

Tracera combines the GC-2010 Plus with a BID detector

GC pioneers of the first hour60 years of gas chromatography

W ith its 120 kg, the GC-1A could have beennamed a ‘Sumo wrestler’

among GCs. Everything, fromsample introduction, separation,detection up to chromatogramevaluation, was included within asingle structural framework.

The GC-1A was Japan’s first gaschromatograph; it was developedby Shimadzu in 1956, only fouryears after the British scientistA. J. Martin was awarded theNobel Prize for his groundbreak-ing research on gas chromatogra-phy, which he utilized togetherwith his colleague A.T. James.

With the GC-1A, Shimadzupushed forward the legacy of itsfounder family. Genzo ShimadzuJunior, the second-generationcompany leader, was one of the10 most important inventors ofJapan and was honored by theemperor at that time. In 2016,Shimadzu celebrates its 60th GCanniversary. Within the 141 yearsof Shimadzu’s company history,chromatography paved the wayand has set numerous milestonesthat today have be come technicalstandards and serve consumerprotection, environmental protec-tion and product safety.

Major analytical technology

Since its commercial introduc-tion, gas chromatography hasevolved into a major analyticaltechnology. Today, tens of thou-sands of GC systems are in use inall areas of industrial and phar-maceutical research and develop-ment, in basic research, environ-mental research, and in qualitycontrol. The separation of com-plex mixtures as well as the iden-

tification and quantification ofthe individual components is stillconsidered to be one of the mostimportant tasks in instrumentalanalysis.

“Contributing to society throughscience and technology” isShimadzu’s core philosophy. This also includes the continuousdevelopment of existing tech-nologies, exploring possibilitiesand pushing existing technicalboundaries. This has madeShimadzu a market leader and anestablished name in science andindustry.

GC milestones: hardware and software, central systems,detectors and accessories

Much of what has been technical-ly established in GC today hasoften been achieved throughhardware and software mile-stones. Between the first GC-1Aand the current ultra-modern,universal Tracera system with itsnovel BID (barrier ionization dis-charge) detector that can detectall substances except for heliumand neon, there have been numer-ous world premieres, advances inperformance and innovations thathave set technical and economictrends and standards.

• With the GC-3A series,Shimadzu introduced the firstmini GC, as a developmentresult of downsizing instru-ments.

• The GC-4A marks the stepfrom isothermal to tempera-ture-programmed chromatogra-phy, which allows the separa-tion of complex mixtures ofsubstances in significantly lesstime. The GC-4A, for the firsttime, implements the patenteddual-flow operation of twopacked columns.

• Automated chromatogram evaluation starts with the C-1Aintegrator.

• The GC-8A is the firstasbestos-free GC system. In combination with the AOC-8A autosampler, auto-mated measurement of samplesequences is possible.

• The GC-9A and -14B mark thetriumph of capillary versuspacked column chromatogra-phy. Now, it is possible toachieve separations of complexmixtures with improved resolu-tion and within a much shortertime.

• The GC-9A is the first gaschromatograph coupled to amass spectrometer. In additionto quantitative evaluation, themass spectrometer allows forthe identification of unknownsample components and leads to new scientific findings inenvironmental, pharmaceuticaland materials research. �

LATEST NEWS

1956196619811988199220002004200920102013

GC-1AGC-4AGC-8AGC-14BGC-17AGC-2010GC-2014GC-2010 PlusGC-2025Tracera

Year launched Model name

Table 1: History of Shimadzu gas chromato-

graphy systems

ometer in 1881. This workingprinciple is still used in modernIR spectrophotometers today.

First double beam self-recording infrared spectrophotometer

In the first half of the 20th centu-ry, Shimadzu grew significantlyunder the leadership of GenzoShimadzu Jr. He showed rare tal-ent as a remarkable inventor, andunder his guidance Shimadzu

von Fraunhofer made experimen-tal advances with dispersive spec-trometers that enabled spectros -copy to become a more preciseand quantitative scientific tech-nique.

Chemical IR spectroscopyemerged as a science in 1800through the work of Sir WilliamHerschel. Early IR instrumenta-tion was based on prisms or grat-ing monochromators. AlbertMichelson invented the interfer-

Milestones in 60 years of IR history

Technological driver andmarket leader

LATEST NEWS

14 SHIMADZU NEWS 3/2016

S ince the middle of the 20th century, spectroscopyhas been at the core of

Shimadzu’s analytical businessunit and a main driving force inthe company’s growth and repu-tation. Knowhow, technologicalskills and innovative power havebrought Shimadzu to a leadingposition in spectroscopy.

The promotion of the 60th IRanniversary kicked off in Septem -ber at the JASIS conference inTokyo, Japan.

The documented history of spec-troscopy already began in the17th century. Sir Isaac Newtonfirst applied the word spectrumto describe the rainbow of colorsthat combine to form white light.During the early 1800s, Joseph

diagnostics functions, make gaschromatography accessible toall users.

• The GC-2014 and GC-2025models for routine analyses are reliable and robust as wellas extremely cost-effective. The GC-2025 is the first systemmanufactured from RoHs-compatible components and isfully recyclable.

• The most recent development isthe Tracera with its novel BID

detector – the innovative tech-nology for the helium plasmageneration combines sensitivitywith so far unrivalled robust-ness and long-term stability,opening up entirely new possi-bilities in trace analysis.

Wide range of GC systems

Today, routine as well as high-end systems determineShimadzu’s product range – fromsmall and versatile through ultra-sensitive and highly productivesystems up to instruments thatbreak new technological grounds,for example the multiple heart-cut technology.

Numerous detectors complete thepicture, including new andadvanced technologies such as theBID helium ionization detector.

• With the GC-17A, gas pressuresand flows are now electronical-ly adjustable and can be modi-fied via flow and pressure pro-grams.

• The GC-2010 has set a long-term standard with respect todetection limits. Its outstandingreproducibility remains unde-feated until today.

• The LabSolutions softwarewith self-explanatory operationof the GC controls and novel

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System solutions, e.g. detector-switching or splitting, backflush-ing or auto samplers offer userscustomized as well as flexibleapplication possibilities.

Shimadzu’s 60 years of GC devel-opment stands for the company’sambition to continuously broad-en the horizon for GC analysiswith innovative and novel devel-opments.

15SHIMADZU NEWS 3/2016

progressed hand-in-hand withscience, building itself into aleader in technology. In this spir-it, the company developed itsfirst double beam self-recordinginfrared spectrophotometer: theAR-275. The instrument becamecommercially available in 1956and was robust enough even forexport overseas.

Several technical issues wereencountered in this developmentprocess: the manufacturing of alarge high quality artificial rocksalt crystal & the sensitivity andresponsiveness of the thermocou-ple used as a detector. One of thelessons learned at this early stagewas to develop and use an ownthermocouple, as the originallyapplied component importedfrom overseas had a compro-mised vacuum.

In 1959 the IR-27 platform waslaunched. This second generationof double beam self-recordingspectrophotometers was consid-erably smaller than the stand-alone AR-275 and was designedas a table top instrument. Thefinal model of this range was theIR-27G, launched in 1965.Weighing 130 kg, it was a heavyand bulky instrument requiring avery solid table.

A brief overview of techno-logical milestones

The AR-275 marked the start ofan outstanding line of infraredproducts spanning six decades ofinnovation. Some of the mostimportant Shimadzu milestonesof the past 60 years include:

• 1965: IR-27G First dispersivetable top instrument

• 1981: IR-435 First instrumentwith data processor. On theverge of the computer era, theIR-435 paved the way fromanalog to digital

• 1984: FTIR-4000 First FourierTransform Infrared Spectro -photometer, made possible bythe rapidly developing comput-er technology. FTIR loweredthe threshold for use of the IRspectrophotometer, and meas-urements could be done in sec-onds. New applications became

19561959196419651970197419771978198119841986198719881990199119921993

1994

199720002002

20082013

AR-275IR-27IR-27CIR-27GIR-400, IR-450IR-430IR-410IR-408, IR-420, IR-440IR-435IR-4000IR-460, FTIR-4100FTIR-4100, FTIR-4300IR-470IR-8100, FTIR-8100MFTIR-8500IRG-8000FTIR-8200, FTIR-8200DFTIR-8600FTIR-8100A, FTIR-8200AFTIR-8200PC,FTIR-8600PC, µIR-8000FTIR-8300, FTIR-8700FTIR-8400, FTIR-8900FTIR-8400S,IRPrestige-21IRAffinity-1IRTracer-100, IRAffinity-1S

Year launched Model name

Table 1: History of infrared spectrophoto -

meters from Shimadzu

possible, including foreign sub-stance analysis, verificationtesting, functional group identi-fication and quantitative analy-sis.

• 1990: FTIR-8100 First FTIRwith dynamic alignment stan-

dard. The following generationsfeatured the new Shimadzu“IRSolutions” software runningon PCs

• 2002: IRPrestige-21 First FTIRwith mid-near-far infraredmeasurement range and theflexibility to add the far infra -red measurement range (MCTdetector) and the near infraredmeasurement range (InGaAsdetector)

• 2008: IRAffinity-1 New bench-mark for entry level instru-ments with best in class per-formance

• 2013: IRTracer-100 First FTIRwith rapid scan function andLabSolution SW platform

Towards the future

Finally, in this IR celebrationyear, Shimadzu has launched theAIM-9000 FTIR microscope andfailure analysis system as succes-sor to the AIM-8800.

The AIM-9000 is intended as anFTIR microscope for all users.All important steps for microsample analysis, observation,measurement and analysis arehighly automated, making thissystem also suitable for less expe-rienced operators. Combinedwith the IRTracer-100, the AIM-9000 offers a staggering

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60-years-ir

AIM-9000 – Automatic Failure Analysis System featuring a unique concept in the field of micro sample analysis

LATEST NEWS

S/N ratio of 30.000/1 and has awide range of accessories formany different application types.

Shimadzu’s history in IR spansmany technological eras. Today,the Shimadzu spectroscopy port-folio includes software and hard-ware solutions such as UV-VISspectrophotometers, FTIR spec-trophotometers & microscopesystems, fluorescence spectro -photometers, energy dispersiveX-ray fluorescence spectrome-ters, Atomic Absorption Systems(AAS) and ICP-OES systems aswell as ICP-MS instruments.

A complete overview of modelnames and release dates of infra -red spectrometers sold byShimadzu is shown in table 1. In the past six decades the totalnumber of Shimadzu infraredspectrophotometers sold through -out the world has reached morethan 20.000 units, underliningShimadzu’s position as a leader inspectroscopy.

APPLICATION

16 SHIMADZU NEWS 3/2016

F ree radicals are short-livedmolecular fragments of oxy-gen and are suspected of

being responsible for aging pro -cesses but also for damage to cellsor enzymes. Cells, however, havetheir own defense mechanisms tocounter free radicals. Such anti -oxidants, like ascorbic acid orcoenzyme Q10, react with freeradicals and are provided bydietary intake.

UV-radiation, pollutants in theair or chemicals lead to the for-mation of highly reactive oxygenspecies, so-called free radicals inthe human body.

If they accumulate, they cancause cell damage and other signsof aging, for instance the forma-tion of wrinkles. Free radicals areeven associated with a number of

CO2 (at or above its critical tem-perature and critical pressure) isthe most commonly used super-critical fluid for chromatographicpurposes. In addition to its suit-able physico-chemical propertiesand availability, it is highly inert,non-toxic and inexpensive.

So far however, techniques likeSFC (supercritical fluid chro-matography) and SFE (supercriti-cal fluid extraction) could only beused as individual steps in ananalysis. The newest generationof instruments now combines theentire analysis, integrating samplepretreatment, chromatographicseparation and detection into asingle system. With the onlinecoupling of SFE and SFC, manualextraction and transfer steps arenow replaced by a fully automat-ed process. This does not only re -duce time and personnel expendi-ture but also eliminates manualerrors that can occur, e.g. duringdecanting or pipetting.

An additional advantage of theclosed online SFE-SFC system isthe gentle sample handling. Afterbeing placed in the instrument,the samples can be analyzed vir-tually without decomposition, asthe entire analytical process takesplace without exposure to lightor air and free from humidity.Therefore, the system is ideal forthe analysis of sensitive samples,for instance light-sensitive, easilyoxidized or readily hydrolyzedsubstances.

Online SFE-SFC analysis ofreduced coenzyme Q10

Online SFE-SFC analysis is alsoa gentle alternative to conven-tional solvent extraction for thesensitive coenzyme Q10 (figure 1).

diseases – including cardiovascu-lar disease and cancer.

In addition to the body’s ownantioxidants mentioned above,substances provided by dietaryintake can exhibit similar effects.The best-known examples arevitamins or their precursors. This also includes coenzyme Q10and its reduced form, which isstructurally related to vitamin Eand K.

Additionally to its antioxidantproperties, coenzyme Q10 is alsoinvolved in important biochemi-cal processes such as cellular res-piration due to its easy oxidiz-ability. So, how can such a sensi-tive and easily converted sub-stance be carefully analyzed?

Supercritical fluids for gentle extraction

For substances that are sensitiveto oxidation, analysis usingsupercritical carbon dioxide(CO2) offers a gentle alternativeto conventional solvent extrac-tion. Supercritical fluids combinethe properties of gases and liq-uids: they are low in viscosityand exhibit high diffusivities sim-ilar to gases, but they are alsoreadily soluble like liquids.

Coenzym Q10 – analysisof a sensitive substanceAnalysis of unstable compounds using online SFE-SFC

Figure 2: Flow diagram of the automated online SFE-SFC analysis

Reduced coenzyme Q10(Ubiquinol Q10)

Coenzym Q10(Ubiquinon Q10)

Reduction

Oxidation

Figure 1: Oxidized and reduced forms of coenzyme Q10

the oxidized form for compari-son, are shown in figures 3 and 4.

It can clearly be seen that follow-ing solvent extraction almost allof the coenzyme Q10 is present inits oxidized form, whereas in theonline SFE-SFC analysis only avery small proportion of the ana-lyte oxidized and is largely stillpresent in its original reducedform.

Online SFE-SFC is thereforevery well suited for the analysisof sensitive compounds such assubstances that are sensitive tooxidation. Additionally, theNexera UC avoids errors due toits high degree of automation andsimplifies sample handling.

17SHIMADZU NEWS 3/2016

APPLICATION

To obtain a direct comparison ofthe two techniques, the propor-tion of reduced and oxidizedcoenzyme Q10 in a dietary sup-plement was determined usingboth techniques.

The analyses were carried outusing Shimadzu’s Nexera UC(Kyoto, Japan), a modular all-round SFE-SFC system for high-performance, high-speed applica-tions. For solvent extraction, thecontent of a capsule of thedietary supplement was suspend-ed in ethanol and the coenzymeQ10 was extracted in an ultrason-ic bath. After filtration, the sam-ple was analyzed using SFCunder the conditions listed intable 1.

For the online SFE-SFE analysis,about 5 µL of the content of thecapsule was dripped onto a filterpaper and placed directly into anextraction vessel. The automatedanalysis is subsequently carriedout under the conditions listed intable 2. The static extraction stepis followed by dynamic extrac-tion in order to transfer the sam-ple to the column, where theactual chromatographic separa-tion takes place. A flow diagramof the process is shown in figure 2.

Summary

Both chromatograms, each in -clud ing a standard solution of

Table 1: Analytical conditions for solvent extraction-SFC

Table 2: Analytical conditions for online SFE-SFC analysis

0.0

-0.5

0.5

1.0

1.5

2.5

2.0

0.0 2.5 5.0 10.07.5 min.

0.0

0.5

1.0

1.5

0.0 2.5 5.0 min.

1. Coenzyme Q102. Reduced coenzyme Q10

Coenzyme Q10 standard solution

1

2

Dietary supplement

Peaks

uV (x 100,000)

1. Coenzyme Q102. Reduced coenzyme Q10

Coenzyme Q10 standard solution

1

2

Dietary supplement

Peaks

uV (x 1,000,000)

Figure 3: SFC chromatogram of coenzyme Q10 following solvent extraction Figure 4: SFC chromatogram of coenzyme Q10 following online SFE

ColumnColumn temperatureMobile phase

Flow rateTime programBack pressureDetectorInjection volume

Shimpack UC-RP (150 mm L. x 4.6 mm I.D., 3 µm)40 °CA: CO2B: MeOH3 mL/min5 % B (0 min) → 50 % B (5 - 8 min)10 MPaUV/VIS @ 220 nm1 µL

System Nexera UC SFC-UV system

SFEExtraction volumeStatic extraction

Dynamic extraction

SFCColumnColumn temperatureMobile phase

Flow rateTime programBack pressureDetector

0.2 mLTime: 0 - 2 minConc. B: 5 %Back pressure: 10 MPaFlow rate: 3 mL/minTime: 2 - 4 minConc. B: 5 %Back pressure: 10 MPaFlow rate: 3 mL/min

Shimpack UC-RP (150 mm L. x 4.6 mm I.D., 3 µm)40 °CA: CO2B: MeOH3 mL/min5 % B (0 min) → 50 % B (9 - 13 min)10 MPaUV/VIS @ 220 nm

System Nexera UC SFC-UV system

LATEST NEWS

18 SHIMADZU NEWS 3/2016

View from the Zolotoy Bridge in Vladivostok. The cable-stayed bridge was opened in July 2012 on the occasion of the asia-pacific economic summit (APEC).

Long-time partnersShimadzu testing equipment atVladivostok university’s EngineeringSchool

Figure 1: Rubber tensile test with AG-X

T wo years ago, the FarEastern Federal University(Vladivostok, Russia)

opened the unique Center ofMechanical Tests and MaterialStructural Analysis on the basisof Welding Department.

Shimadzu’s entire testing equip-ment product range is present:systems for static and dynamictests of metals and composites,

polymers, elastomers and plastics,construction materials, ceramicproducts, food, products frompulp and paper, textile and phar-maceutical industries. Today,bachelors, masters, PhD studentsor scientific researchers can con-duct investigations in this newhighly sophisticated laboratory.

The Center of Mechanical Testsand Material Structural Analysis

19SHIMADZU NEWS 3/2016

LATEST NEWS

was established as part of the university’s Engineering School.It consists of three departments:the Mechanical Tests Laboratory,Material Structural Analysis

Center activity: “We take part inmany interesting projects togeth-er with the largest Far Easternenterprises. For example, duringthe building of bridges across the

Laboratory and Sample Prepara -tion Laboratory. The Centerbecame a basis for scientificresearch as well as for specialinvestigations required by differ-ent factories, plants etc. Highlyqualified specialists from the uni-versity work in close cooperationwith the representatives of manyindustries.

Dozens of projects currentlyrunning

Currently, specialists from theCenter of Mechanical Tests andMaterial Structural Analysis takepart in more than 30 differentprojects. The field of research isquite wide with analysis of metalsand composites as well as otherconstruction materials, testing ofpolymers and ceramics, and spe-cial investigations for food, tex-tile and pharmaceutical indus-tries.

The head of the Center is Dr.Ekaterina Gridasova, AssociateProfessor of the Welding Depart -ment. She described to ShimadzuNews the main directions of the

repairing these parts very quickly.This is a pioneer project forRussia. The Center of MechanicalTests and Material StructuralAnalysis is working on this proj-ect together with Far EasternBranch of Russian Academy ofScience and JSC “ShipyardDalzavod.” The result is expectedto be interesting for both navyand civilian ship-building indus-tries.

The laboratory doesn’t onlywork with metals and alloys.Some time ago, a test run of silentblock materials was conducted.These components are used forstabilizer bars in automotiveapplications. This work was donefor “Repair Technology Center“,the manufacturer of automobileindustry spare parts.

The international “Arctic” project investigatingice cores

An important sphere of the Cen -ter’s activity is the support ofUniversity scientific researches.Different investigations are being

for rebuilding of ship dieselengine shaft parts using laser dep-osition. This technology avoidsthe need to replace worn-outparts of ship machinery, while

carried out for many scientificprojects. In addition, manyBaccalaureate, Masters and PhDtheses were written based onwork carried out in the Center.

A good example of such researchis the investigation of ice me -chan ical properties. These studiesare a part of a large project called“Arctic.” In the second year,many scientists from Russia,China, India, South Korea andNorway are taking part in theInternational Winter School “IceMechanics.” They investigate icecovers of Russky Island waterareas at the places of sampling aswell as in the laboratory. Forcompression tests of ice coresShimadzu’s AG-100kNX univer-sal test machine has been applied.

Cooperation betweenVladivostok, Osaka andDortmund universities

An important event for the Cen -ter was the award of internationalstatus. In the beginning of 2015,Far Eastern Federal Uni versity(Russia), Material Test Engineer -ing of Dortmund Technical Uni -versity (Germany) and WeldingResearch Institute of Osaka Uni -versity (Japan) signed a tripartiteMemorandum. The relationshipbetween these large �

Figure 2: Introduction to USF-2000

Figure 4: Dr. Ekaterina Gridasova,

head of the Center

Eastern Bosphorus Strait and theGolden Horn Bay (Zolotoy Rog),both in Vladivostok, Russia,many tests of high-strength bolts,fittings, cable-stayed connectionsetc. were made using Shimadzuinstruments such as the UH-1000kNI hydraulic universalmachine.

New laser deposition technology

Another important project is thedevelopment of a new technology

Figure 3: Signing of tripartite Memorandum of Collaboration

LATEST NEWS

20

Car Symposium

Bochum, GermanyFebruary 1 - 2, 2017www.car-symposium.de

EWCPS

St. Anton, AustriaFebruary 19 - 24, 2017www.ewcps2017.at

Anakon

Tübingen, GermanyApril 3 - 6, 2017www.gdch.de/anakon2017

SETAC

Brussels, BelgiumMay 7 - 11, 2017https://brussels.setac.org

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universities from three differentcountries is interesting not onlybecause of common scientificresearch op portunities, but alsobecause it provides new, inter-esting educational programs forstudents.

Today, in the framework of thelaboratory, the project of fric-tion welding of ship metal plateshas been realized. Far EasternFederal University receives car-bon steel samples from OsakaUniversity and conducts statictests of these samples, while col-leagues from Dortmund Uni ver -sity carry out dynamic tests.

Long-time partnership

The Center of Mechanical Testsand Material Structural Analysisand Shimadzu have been goodpartners for a long time.Shimadzu’s staff gives its clientsfull-scale assistance and support.

Shimadzu organized severaljoint workshops and seminarson the basis of Mechanical Testsand Material Structural AnalysisCenter. Visitors from differentlaboratories and plants could seehow Shimadzu instrumentswork, while getting much newinformation about applicationsof the equipment in food, phar-maceutical, polymers and elec-tronic industries. Such eventsincrease Shimadzu’s customernetwork and enable Shimadzucustomers to exchange theirexperiences.

2017 Fatigue TestsInternational Symposium

Of course, this relationship willgrow continuously. For nextyear, Far Eastern Federal Uni -versity is planning to organize aFatigue Tests InternationalSymposium. Shimadzu will sup-port this event.

The relationship between FarEastern Federal University andShimadzu is a good example ofthe fruitful teamwork of aworld-leading manufacturer ofanalytical instrumentation andone of the leading Federal uni-versities of Russia.

AuthorDr. Ekaterina Gridasova,

Far East State Technical University

Figure 5: The staff of the Center