NEWS 03.2010 GB - Shimadzu...Shimadzu’s EDX-720 X-ray fluo-rescence spectrometer, FP-meas-urements...

NEWS

3/2010

NEWS

Quality by Design:UHPLC hardware meetsDryLab®2010-Software

Hard currency?Hardness testingon different coins

A granular look atsugar: Use of novelanalysis methods

Plastic Planet:Heavy metals insoft drinks?

Do rusty knights arise from rusty cookingpots? – Is RoHS to blame for rust formation? »2

Meat matters – Determination of moisture and fat in pork meat »4

“Plastic Planet” – Determination of heavy metals in soft drinks stored in PET bottles »7

A granular look at sugar – Use of novel analysis methods »8

Hard currency? – Hardness testing on different coins »10

How physics discovered TOC – Determination of algae in photobioreactors »12

Bitter, fresh, hoppy ... – Determination of aroma compounds in beer »16

Sensitivity meets robustness and precision – Evaluation of a novel TNM analytical technique »18

Product Detection in Electro-chemical Cells »20

“Gentlemen, start your engines!” – Determination of Additive Elements in oils »22

White giant or white dwarf? – Particle size distribution measurements of TiO2 »14

Tailor-made FTIR accessories »19

The perfect all-rounders in UV-VIS spectroscopy »23

Quality by Design – UHPLC hardware meets DryLab®2010 software »24

A system that rocks – The GCMS-QP2010 Ultra European Conferences Tour »27

Consumables for GC »28

APPLICATION

TELEGRAM

SOFTWARE

WEBSITE

CONFERENCE

READ FOR YOU

New grounds in analysis.

The Shimadzu Web-App available at December 2010. Coming soon: Apple®-App

APPLICATION Shimadzu News 3/2010

2

Do “rusty knightcooking pots? Is

How can this be? Afterjust a few weeks, thenew ‘stainless steel’cookware set shows rust spots –on the bottom, the grip or the lid.Do they occur from flash rust,defective material or flawed man-ufacturing processes?

To protect stainless steel fromcorrosion, a chromium – moreprecisely hexavalent chromium –protective layer has been used inthe past. However, Cr (VI) is

highly toxic, mutagenic and car-cinogenic. Its use is thereforestrongly regulated in the 2001/95/EG RoHS (restriction of haz-ardous substances) directive. InGermany, the RoHS directive aswell as the EU directive WEEE(Waste Electrical and ElectronicEquipment) came into effect inGerman law in March 2005 withthe implementation of the Elec-trical and Electronic EquipmentAct (ElektroG). The transitionperiod for the manufacturers and

Flash rust or batter coating? Rusty knights* have nothing in common with rusty

cookware.

Shimadzu NEWS, Customer Magazine of Shimadzu Europa GmbH, Duisburg

Publisher:Shimadzu Europa GmbHAlbert-Hahn-Str. 6 -10 · D - 47269 DuisburgPhone: +49 - 203 - 76 87- 0 Telefax: +49 - 203 - 76 66 [email protected]

Editorial Team:Uta Steeger · Phone: +49 - 203 - 76 87- 410 Ralf Weber, Tobias Ohme

Design and Production:m/e brand communication GmbH GWADüsseldorf

Circulation:German: 7,200 · English: 18,510

©Copyright:Shimadzu Europa GmbH, Duisburg, GermanyNovember 2010

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APPLICATIONShimadzu News 3/2010

s”* arise from rustyRoHS to blame for rust formation?

industries involved ended in July2006. Today, all electronic prod-ucts must therefore be RoHScompliant.

However, this directive does notjust impact the electronics indus-try. For instance, a fastener man-ufacturer cannot know in themanufacturing process, what ascrew will subsequently be usedfor. This is why the use of Cr(VI) in the production of fasten-ers is increasingly being discon-tinued.

To protect steel from corrosion,dozens of non-metallic andmetallic coating as well as combi-nation coating processes can beused instead of Cr (VI). Some ofthese are, for example:• Lubricating or coating with an

easily removable film (oiling)• Paint coating with humidity-

resistant dyes• Coatings applied via tin or

zinc immersion baths (hot-dipgalvanization)

• Galvanically applied nickel, tin,zinc, copper or chromium coat-ings

• Black finishing (FeO and Fe2O3conversion coating), phosphat-ing.

Rust isn’t just equal rust

Let us take a closer look at rust.18/10 stainless steel, often used inthe manufacturing of cookware isa metal alloy consisting of 18 %chromium and 10 % nickel. Since

Chromium is present in its metal-lic form (oxidation state 0), it isnot considered to represent ahealth hazard.

18/10 stainless steel is in principlerustproof but not durably resist-ant against chloride and acids,which, in the form of kitchensalt, fruit acids or vinegar, comeinto contact with pots and pans.

The passive protective coating ofstainless steel is durable only aslong as the surface is metallicallybright. When metal particles stickto the steel surface, they cancause corrosion. It is thereforeadvisable to avoid touching thecookware surface with steel oriron particles (especially steelscouring pads).

Non-dissolved salt particlessticking to the bottom can alsoattack the cookware surface. Inthis case, an increased chlorideconcentration develops locally,causing black stains on the metalsurface. The chloride attack iseven stronger at elevated temper-atures. Only thorough cleaningwill help in this case.

Fastening material – a critical point

Figure 1 shows screws for fasten-ing the grip of a lid. The right-hand screw already shows signsof severe corrosion after just afew weeks of service. It is remark-able that the surrounding materialhas remained rust-free.

The left-hand screw is a replace-ment part from the cookwaremanufacturer. Rusting may havemany causes – extraneous rustcaused by the use of a steelscouring pad or damage to theprotective layer of the screw. Butit may also be due to use of alow-priced, non corrosion-resist-ant screw ...

X-ray fluorescence analysismeasures element composi-tion of a sample – qualita-tively and quantitatively

Methods such as X-ray fluores-cence analysis can be of value tocookware manufacturers. UsingShimadzu’s EDX-720 X-ray fluo-rescence spectrometer, FP-meas-urements (fundamental parame-ters) of both screws and therespective surrounding materialwere carried out.

Figure 1: Mounting screw for lid

Table 1: Results X-ray fluorescence analysis

The material of the corrodedscrew (right-hand) was found todiffer markedly from the othermaterials analyzed. Since bothscrews looked identical, thecookware manufacturer could notrecognize the dissimilar materialproperties. X-ray fluorescence isa straightforward, fast and non-destructive method enabling reli-able quality control of propri-etary products as well as those ofsuppliers.

*In some European areas French

Toast is known as “Rusty Knights”,

referring to their golden armor.

We will gladly send you further infor-

mation. Please note the appropriate

number on your reply card. Info 385

Fe [%] Cr [%] Ni [%] Mn [%]

Plate (right-hand)

Screw (right-hand)

Plate (left-hand)

Screw (left-hand)

72.2

74.7

72.2

71.9

18.5

25.2

18.6

17.6

7.6

– –

7.5

8.3

1.6

0.2

1.7

2.2


4

The determination of mois-ture in the quality controlof meat is important inassessing impurities such as extrawater or salts for preservation ofthe natural product. Too muchsalt is unhealthy and may have anegative impact on the humanblood pressure system. A highwater content is problematicwhen cooking or grilling and themeat is dry and tough afterwards.

Various analysis techniques canbe used in salt determination, e.g.free energy dispersive X-ray anal-ysis. UV-VIS instrumentationanalyses the quality of meat andmeat products from a differentperspective by determination ofhydroxyproline (connective tis-sue). The FT-NIR measurementtechnique can determine severalcharacteristics from meat (such asfat and moisture) in one measure-ment without time-consumingsample preparation.

Meat mattersDetermination of moisture and fat in pork meat with measurement technique

Figure 1: FT-NIR spectra from pork meat (black line) and dried meat (red line).

The transparent boxes in blue mark the change of signals due to moisture, the blue

vertical lines mark the approx. position of the main sample signal, predominantly

-OH from water

Table 1: Meat products and typical values for fat, moisture and protein (g/100g)

as found in literature (Source: 1. FNB+FSB, Heinzig, 2002, 2. Wikipedia- Liste der

Inhaltsstoffe von Fleisch, 2010 )

Quality control

Conventional analysis in thequality control of meat needsseveral process steps and is time-consuming. This application willshow an easy and simple non-destructive method for the deter-mination of total fat and moisturein meat products with FT-NIRanalysis.

The classical applications of qual-ity control target at farm prod-ucts such as grain, milk and oily

fruits. With animal food, themoisture (OH-Bonding) is ana-lyzed as well as protein- (eggwhite, NH-Bonding), raw fibers-(fibers, CH-Bonding and other),carboxylic groups in polymers(COOH) and fat content (CH-Bonding).

A typical NIR spectrum is shownin figure 1. The NIR spectrumcontains information on combi-nation bands and overtones ofvibrations in the infrared-lightregion. In comparison to the

-0.20-0.15-0.10-0.050.000.050.100.150.200.250.30

0.40

0.50

0.60

0.70

0.80

0.90

1.00

1.10

0.35

0.45

0.55

0.65

0.75

0.85

0.95

1.05

1.151.201.25

9500 9200 8900 8600 8300 8000 7700 7400 7100 6800 6500 6200 5900 5600 5300 5000 4700 4400 4000

1/cm

Abs

.

Item Fat Moisture(water) Protein

Boiled sausage

Liver sausage

Raw bacon (ham)

Pork meat

Bacon

Cooked bacon (ham)

60.0

55.2

69.5

60.7

54.4

73.8

12.0

16.7

18.3

28.7

16.0

18.4

25.0

22.8

4.4

9.6

28.9

3.9

5


FT-NIR

Figure 2: PLS reconstruction of the measured spectrum and the difference spectrum

from measured minus calculated spectrum

Figure 3: The spread of measurement points in the range from 4 to 50 % fat in meat

and meat products. Scale is actual vs. predicted value of fat in percentage values.

Table 2: Calibration results for the fat and moisture determination in meat products

highly resolved signal structuresof the mid-infrared spectrum theNIR spectrum shows broad,smooth signal structures, makingthe whole spectrum sensitive forquantitative analysis.

Fat in pork meat

In order to establish a calibrationmodel, 104 pork-based meatproducts were analyzed. Thesources of the meat were bothsupermarkets and butchers. Theitems included low-fat pork (filetwith 5.9 % fat), a pork tongue

sausage with 20 % fat, cookedsausage with approx. 30 %, andbacon with 45 % of fat.

Reference Methods

The reference values of fat weredetermined according toCHE004W (NEN-ISO 1443/NEN-ISO 1444, Meat and meatproducts – Determination of totalfat content / Meat and meat prod-ucts – Determination of free fatcontent). The fat is extractedfrom the samples after acid hy-drolysis. The extraction was car-

ried out with petroleum etherafter which the ether was evapo-rated and the remainder wasdried and weighed (Soxhletextraction).

Sample preparation for FT-NIR measurement

The samples were homogenizedwith a mixer. A portion of themeat was transferred into a dis-posal Petri dish. Tests showedthat error due to the polymericmaterial is in an acceptable range,and even better than when usinga glass Petri dish. The StandardError of Prediction (SEP) of thecalculation was 0.157 % for mois-ture and 0.166 % for fat. Packingthe sample to the bottom of thePetri dish was beneficial. Thiscorrelated to the rule for diffusereflectance for powders, where amaterial thickness of �

0.000.050.100.150.200.250.300.350.400.450.500.550.600.650.700.750.800.850.900.951.001.151.201.25

10000 90009500 80008500 70007500 60006500 50005500 40004500

1/cm

Abs

.

Component Fat Moisture

Number of factors

Correlation coeff.

MSEP*

SEP***Mean Squared Error of Prediction, **Standard Error of Prediction

6.00000

0.98817

0.02326

0.15251

6.00000

0.97759

0.04383

0.20936

0

5

10

15

20

25

30

35

40

45

50

0 5 10 15 20 25 30 35 40 45 50

Calibration of 92 meat and meat products – fat content

Actual [%]

Pred

icte

d [%

]

forms of meat and meat productswere analyzed – from filet tosmoked sausage and bacon. Forthe calibration model a PartialLeast Square method (PLS) wasinvestigated.

Calibration result

Report of PLS CalibrationCalibration table:Algorithm: PLS INumber of components: 1Number of references: 92Range: 4,000 - 10,000Centered data: Yes

Reconstruction

A good calibration based on PLSmodelling is indicated by theMean Squared Error of Predic-tion (MSEP), Standard Error ofPrediction (SEP) and the recon-struction of the spectra with thehelp of the factors analyzed. Infigure 2 the result of the recon-


6

minimum 3 mm is necessary, withhomogeneous particles and pack-ing of the sample.

Instrument and accessory

• IRPrestige-21 with NIR Kit• IntegratIR – Integrating sphere

for diffuse reflectance measure-ments with rough golden sur-face; the accessory was equip-ped with a rotating Petri dishholder for signal averaging overa wide surface of the meat sam-ple.

Discussion of NIR spectra

Figure 1 shows two spectra withdifferent moisture content. Thetop one is the natural meat andthe lower one is a meat powder.The diffuse reflectance FT-NIRspectra highlight the differences.The major changes are visible at:8694, 6890, 6091, 5950 and 4616 cm-1.

The first overtone from the OH-bonding is by definition around6900 cm-1 (approx. 1450 nm) forfree water. Water (in this casemoisture) can be free or bonded-style of water and other sub-stances, which will disappearunder drying conditions.

The meat sample shown wasdefined as having a water contentof 72.3 %, 19.4 % protein and 5.1 % fat (black in figure 1). Thedried sample contained 39.4 %fat (red in figure 1).

For the analysis, many validationchecks were carried out to estab-lish a robust calibration.1. The reproducibility, repeatabil-

ity and accuracy of thea. polymer-based Petri dish b. packing of meat samplec. mixed meat samples.

2. The reference methods for thedetermination of the fat, pro-tein and moisture contentswere analyzed following thespecified norms.

Based on this knowledge a cali-bration was established. Different

Figure 4: IRPrestige-21 with the NIR Kit and Pike IntegratIR –

diffuse reflection accessory

Table 3: Quality check of the FT-NIR calibration model using a certified meat sample

struction is shown. On top, themeasured spectrum is overlaidwith the recalculated spectrum.The difference between the spec-tra is visible at the bottom.

Reconstruction of the spectrumwith the help of the factorsshowed a good fit. The differencewas almost zero (violet in graphat bottom). Some noise wasapparent only in the water ranges.

A certified pork material wasused to prove the quality of thecalibration.

The reference value did not definethe reference method. Literaturementions that the Soxhlet methodis used for the determination offat, but it shows standard errorsranging from 0.41 to 1.14 %. Thisis a wide error range for onemethod and will influence thequality of the FT-NIR calibra-tion.

The calibration shown here isbased on 92 samples with fat con-tents in a range from 4 to 50 %fat in pork meat and meat prod-ucts.

Benefits

In comparison to wet chemicaltreatments of the meat, the analy-sis is simple and quick. The shortmeasurement time reduces costs,while the material is economicwith chemicals. The method saves95 % of the standard costs involved with conventional FT-NIR analysis.

The analysis results are good fora technique using diffuse reflec-tance method without tempera-ture control and a disposal sam-ple Petri dish. Compared with theSoxhlet method which is funda-mental for fat calibration theFTIR method is more sensitivebecause the SEP value of the fatcalibration is in a range of 0.15 %and for moisture 0.21 %. Com-paring the error from the disposalPetri dish which was calculated at approx. 0.166 % for fat and0.156 % for moisture, and theerror of the Soxhlet method, theNIR technique offers an alterna-tive method to the classical wetchemical treatments. The calibra-tion result is as good as the refer-ence method. Where the referencemethod is improved, the calibra-tion result will be even better.The same applies to the sample ofstandards, which can be evenmore than the approx. 100 usedin this application.




Item Sample Fat (%) Moisture (%)

Measurement NIR

Reference

Difference

Certified material

Pork

14.0299

14.30

0.2701

68.4339

68.8

0.3661

7


Figure 1: AA-7000G with GFA-7000 and ASC-7000

Table 1: Instrumental parameters for the determination of antimony

Today, food packaging consists of boxes, bottles, packets, cartonsand cans of various materials. Packaging provides a physical bar-rier between a product and the external environment, therebyensuring hygiene and reducing the risk of product contamination. Furthermore, today’s food packaging is marketing-oriented, and foodproducts are packaged mainly according to shelf-space and householdsizes rather than environmental consequences.

Almost 100 million tons of plastic materials are used every year through-out the world. Plastic production consumes 8 % of the world’s oil pro-duction. Each year, an estimated 500 billion to 1 trillion plastic bags areused worldwide, or over one million bags per minute. Each year, bil-lions of plastic bags end up as litter. Plastic bags and plastic rubbish inthe ocean kill as many as 1,000,000 sea creatures every year. Accordingto the film “Plastic Planet”, there are six times more plastics in theoceans than plankton.

Already in the early 1980s, the European Community introduced meas-ures regulating the management of packaging waste. In 2004, the Direc-tive was reviewed to provide criteria clarifying the definition of theterm ‘packaging’ and to increase the targets for recovery and recyclingof packaging waste. In the following year, the Directive was again revis-ed to allow new Member States to have transitional periods for meetingthe recovery and recycling goals with a recycling rate of 80 %. Further-more, the accumulated concentration of heavy metals such as lead, cad-mium, mercury and hexavalent chromium has been limited to 100 mg/kg.

Element Sb

Wavelength [nm]

Slit width [nm]

Atomization mode

Lamp current D2 BGC*[mA]

Atomization temperature [°C]

Matrix modifier

217.6

0.7

Graphite furnace

13

2,500

Pd/Mg matrix modifier

Antimony in PET bottles

Recently, it was found that bottled waters in PET containers are con-taminated with antimony (Sb), a potentially toxic heavy metal. Anti-mony trioxide is used as a catalyst in the manufacture of PET (poly-ethylene terephthalate) bottles, and PET typically contains severalhundred mg/kg of Sb. Leaching experiments have been performedwith a variety of liquids such as mineral waters and soft drinks in different PET bottles. The samples have been analyzed using the AA-7000G atomic absorption spectrophotometer with the GFA-7000high sensitivity graphite furnace and the ASC-7000 sample preparationstation as shown in figure 1.

All experiments were prepared with aqueous solutions containingantimony concentrations in combination with different matrices. Theexperimental parameters are listed in table 1.

PET bottles in a parked car

Experimental work has shown that malic acid (5 g/L), a mix of organicacids (malic acid, tartaric acid, and citric acid, each 5 g/L) and phos-phoric acid (0.1 mol/L) are able to dissolve antimony out of PET bot-tles and to stabilize it in the solution in much higher concentrationsthan water does. Most cola soft drinks contain concentrations of 5 to 9 mmol/L phosphoric acid. This acid concentration in cola soft drinksgenerates higher antimony concentrations, particularly at higher tem-peratures. In a real-life experiment, such as a cola bottle in a parkedcar in the summer at temperatures of up to 70 °C, antimony concen-trations of more than 6 μg/L have been measured. This concentrationexceeds the European limit of 5 μg/L antimony in drinking water.

We will gladly send you further information. Please note the appropriate



8

A granular look

Our experience with sugarstarts in early childhood– since breast milk con-tains lactose. Human sensoryperception alone is, however, notenough to properly assess theuseful but also potentially harm-ful effects of an age-old sweeten-er (saccharose). Nutrition re-searchers and physicians have, forthis reason, been focusing atten-tion for some time on sugar com-pounds, particularly glucose.

Significant progress in metabolicresearch on sugar could, however,only be achieved through theavailability of novel analyticalmethods. With its GC-MS (gaschromatography-mass spectrom-etry) systems Shimadzu opensnew ways to measure glucosemetabolism in humans and ani-mals with high precision, basedon analytical expertise developedover decades.

Much is already known aboutglucose, one of the componentsof household sugar. Daily glucoserequirement of adults is approxi-mately 180 g, of which the brainis the largest 'consumer', requir-ing 80 % of this amount for itsenergy supply. For this reason,glucose must be newly synthe-sized during short-term periodsof starvation. This process iscalled gluconeogenesis. It takesplace in the liver and in the renalcortex as well as in the intestine.Substrates are pyruvate, lactate,glycerol, alanine and, in rumi-

so-called isotopes, which are suit-able for use as labels. For hydro-gen there is the stable, non-radioactive protium isotope withmass 1 (symbol 1H) and deuteri-um with mass 2 (symbol 2H, orD in short). For carbon, there aretwo stable isotopes: 12C and 13C.

The natural abundance of theseheavy stable isotopes in glucose isvery low. Out of 1000 glucosemolecules, only one containsdeuterium bound to one of thesix carbon atoms. By drinking asmall amount of heavy water(D2O), the deuterium content inglucose molecules increases rela-tive to the natural level, thus pro-ducing ‘labeled’ (‘enriched’) glu-cose that differs from ‘normal’glucose. The so-called D2O

increased or decreased glucoselevel remain unclear. The synthe-sis rate of glucose and its con-sumption for the production ofenergy or conversion to othermetabolites is unknown. Theseprocesses can be elucidated usingspecial labeling techniques thatincorporate chemical probes, so-called ‘tracers’.

To monitor the dynamics of glu-cose metabolism (i.e. its synthesisand breakdown), it is useful toincorporate a labeled glucosetracer into the body’s metabo-lism. But how can such a glucosetracer be produced? For the ele-ments hydrogen, carbon and oxy-gen contained in glucose (molecu-lar formula: C6H12O6), natureoffers different heavy elements,

nants, propionate. Excess glucoseis stored in the body as glycogenand can be converted back to glu-cose when needed, for instanceduring physical activity.

Glucose concentration of blood(normally 90 - 110 mg/mL inhuman adults) mirrors the ‘static’component of glucose meta-bolism. However, the causes of

Use of novel analysis methods

Figure 1: Schematic representation of glucose metabolism

Figure 2: Fragmentation of glucose aldonitrile pentaacetate

GNGrel (% of GP) =E(C2)

[E(C5) + E(C6)]/3100

�

GNGabs (g Glucose / d) = GNGrel GP

�

9


at sugar

Figure 3: EI- and PCI-GC-MS spectra of the aldonitrile pentaacetate derivative (AAc) of glucose

(‘heavy water’) method outlinedbelow shows how gluconeogene-sis (in g glucose/day) can bedetermined after deuteriumenrichment of glucose.

The D2O (‘heavy water’)method

The D2O method is based on thefact that, after oral intake of D2O(0.6 g per kg body weight) with adeuterium content of > 50 %, arapid distribution in the bodywater pool (equivalent to approx-imately 60 % of the body weight)initially takes place. As a result ofenzymatic reactions, deuteriumatoms present in water moleculesare subsequently incorporated inglucose molecules. The differencebetween the deuterium content atcarbon atom C2 and the other C-atoms provides information onspecific metabolic pathways. Thedeuterium content in the differ-ent molecular positions can bemeasured via the aldonitrile pen-taacetate derivative of blood glu-cose using GC-MS.

The D-enrichment at C2, E(C2),is proportional to the total glu-cose produced in the body (GP),i.e. the sum of newly synthesizedglucose and ‘old’ glucose generat-ed from glycogen breakdown.

The D-enrichment at carbon C5,E(C5), is an indicator of newlysynthesized glucose. Due toenzymatic exchange reactions, D-enrichment at the other carbonatoms (with exception of C2) issimilarly high. Consequently, therelative gluconeogenesis GNGrel(in % of the glucose productionGP) and the absolute GNGabscan be calculated as follows:

Glucose production (GP) isdetermined in a separate study,for instance using deuterated glu-cose which possesses two D-atoms at carbon C6. The factorthree in equation (1) results froma total of 3 H-atoms or three D-atoms being bound to glucosecarbon atoms C5 and C6 (see fig-ure 2).

The D-enrichment E(C5)+E(C6)and E(C2) can be determinedwith relatively little analyticaleffort from the mass fragmentsm/z 145 (C5-C6), 187 (C3-C6)and 328 (C1-C6) of the deriva-

tized glucose using GC-MS(Junghans et al., 2010). The peakintensities of the mass fragmentswith their so-called isotopomersM+1, M+2 and M+3 (incorpora-tion of 1, 2 or 3 deuterium atomsper glucose molecule) requiredfor the calculation, can be ob-tained from the EI and PCI spec-trum of aldonitrile pentaacetatederivative of glucose (Figure 3).Interference of the m/z 145 frag-ment with another fragment isavoided by using a different glu-cose derivative.

D2O method harmless tohealth and environment

Does the deuterium isotope inthe D2O method constitute ahealth hazard to humans and ani-mals? The answer is no! For tworeasons:1. Chemical properties of glucose

and its metabolism as well asglucose-related metabolism arenot changed by deuteriumlabeling, as only approximately1 % of the glucose moleculesare labeled.

2. Isotopes of heavy and lighthydrogen (D and 1H) are sta-ble and, therefore, non-radio-active. They are completelyharmless, even for small chil-dren and pregnant women.

0

10

20

30

40

50

60

70

80

90

100

%

100 150 200 250 300 350 400

m/z

AAc (EI)

Rela

tive

isot

ope

abun

danc

e

0

10

20

30

40

50

60

70

80

90

100

%

100 150 200 250 300 350 400

m/z

AAc (PCI)

Rela

tive

isot

ope

abun

danc

e

The stable isotope labeling tech-nique discussed above, in combi-nation with sensitive and accurateGC-MS analysis methods, pro-vides significant advantages overthe radioactive labeling tech-niques used in the past. In-vivogluconeogenesis can be deter-mined without putting the studysubject (human or animal) or theenvironment at risk. The samplematerial, with respect to labeling,is indefinitely stable, since noradioactive decay takes place.

Junghans P, Görs S, Lang IS, Steinhoff J,

Hammon HM, Metges CC. (2010)

A simplified mass isotopomer approach

to estimate gluconeogenesis rate in vivo

using deuterium oxide. Rapid Commun

Mass Spectrom. 24 :1287-95.


10

Hardness tester HMV

Figure 1: Vickers small-load test on a 2-Euro coin

When it comes to moneymatters, a healthy sus-picion is advisable.When in doubt, even our ances-tors used their teeth to testwhether a gold coin was real orfake, as all too often a crude leador metal core lay hidden beneatha thin gold top layer.

Fortunately for the well-being ofour teeth, the exchange of goodstoday takes place without the useof cash, or with bank notes. Nevertheless, coins are still beingused as small change or for theoperation of vending machines.This is why, today, considerableamounts of coins still changehands. In the process, coins aresubjected to strong forces of wearand tear, either through abrasionin wallets or trouser pockets – orthrough ‘acid attacks’ by humanhands. And, in recent years, sincethe various currency conversions,many of us feel these coins liter-ally ‘melting away’ in our pock-ets.

Hardness tests for coins

But what is actually the currentstatus of coin hardness? In the

following tests the hardness oftoday’s domestic and foreigncoins was measured and was alsocompared with a selection of for-mer currencies.

An established method for hard-ness determination of coins isoffered by the Vickers micro-hardness test (small-load testing)according to ISO 6507-1. In this

method, a diamond in the formof a square-based pyramid withan aperture angle of 136° – com-monly referred to as an indenter– is pressed into the specimenunder defined force and duration.The indentation surface is calcu-lated from the length of the diag-onals of the remaining indenta-tion, determined via a micro-scope. The ratio of the testingforce (in units of Newton) to theindentation surface (d in millime-ters), multiplied with the correc-tion factor 0.1891, results in theVickers hardness (HV).

whereby

HV =d2

0,101*2*F*sin136°

2

d =2

d1 + d2

11


Table 1: Around the world – hardness testing on currencies

Table 2: D-Mark or Euro – which currency is harder?

The tests were carried out usingShimadzu’s proven HMV-2Tmicro-hardness tester. In additionto the fully automatic load-change mechanism, this instru-ment also features an automatedrevolving turret, which enables ashock-free exchange betweenobjective lens and indenter.

Since the indentation durationcan play a significant role in themeasurement of soft materials, allShimadzu hardness testers featurea time-controlled indentation –freely selectable between 5 and999 seconds. As recommended inthe Standard, the indentationduration in the following exam-ples was 15 seconds.

Russia has the ‘hardest’ currency

Although Shimadzu’s HMV-2Tseries instruments automaticallycalculate the HV-value and dis-play this on the large touch-screen, the HMV-2T used herewas equipped additionally withoptional automatic image recog-nition and data software. Themeasured values were transferreddirectly to the PC and the inden-tation images could be conve-niently viewed on a monitor. This extensive automated processguarantees exceptionally uniformand comparable measurements.All coins were subjected to fourmeasurements. The measuredresults shown represent the cal-culated mean values.

Interestingly, with the exceptionof the American and the Britishcurrencies, there is no correlationbetween the value of the coin andits degree of hardness. There arealso no significant differencesbetween the individual curren-

International coins: Currency Land HV2

1 Cent5 Cent10 Cent (Dime)25 Cent (Quarter)1 Penny2 Pence5 Pence10 Pence20 Pence1 Pound1 Yen (tested via HV1)5 Yen10 Yen50 Yen100 Yen500 Yen1 Krone5 Kronen10 Kronen1 Kopeke10 Kopeken50 Kopeken1 Rubel2 Rubel5 Rubel

USAUSAUSAUSAUKUKUKUKUKUKJapanJapanJapanJapanJapanJapanNorwayNorwayNorwayRussiaRussiaRussiaRussiaRussiaRussia

111.42138.45140.55146.55

94.46120.21137.20158.61154.37193.20

40.41157.12121.63148.30150.78169.60135.34128.16131.20158.60148.45128.38156.71171.79164.28

1 Pfennig

2 Pfennige

5 Pfennige

10 Pfennige

50 Pfennige

2 D-Mark

HV2 Today’s currency

1 Eurocent

2 Eurocent

5 Eurocent

10 Eurocent

50 Eurocent

2 Euro (inner piece)

2 Euro (outer ring)

104.94

104.76

146.02

138.75

148.93

142.86

155.34

HV2

102.92

106.31

138.00

138.10

145.66

143.52

Previous currency

cies, with the exception of the 1-Yen coin – this coin is made ofpure aluminum. The linguisticdescription of an especially ‘hard’currency therefore does not holdtrue.

But how does this apply to theEuro and the Eurocent?

As can be seen from table 2, theEuro lies in the midrange in theinternational comparison. But thedirect comparison between theD-Mark and the Euro also turnsout to be very similar. This is notsurprising, as essentially similaralloys were chosen for both cur-rencies.

By the way, Russia has the ‘hardest’ currency – with 154.16on average. Who would havethought this?


12

How physics discovered TOCBiomass determination of algae in photobioreactors using TOC

Physicists’ working withProfessor Hilmar Frankeat the department of‘Applied Physics’ (UniversityDuisburg Essen, Germany)excitement about TOC is obviousonly at a second glance. Theresearch group concentrated pri-marily on integrated optics andthe optics of polymers. Initiallyvia biofilm sensor technology andlater when they were working onthe development of an innovativelighting concept for photo-biore-actors, they turned to algae. Thislighting system stands out sincethe lighting of the reactor actual-ly occurs from within. Specially

designed optical waveguides areused which outcouple the previ-ously incoupled sunlight (or arti-ficial light) to specific areas in thereactor (see figure 1).

Originally, research was centeredon the development of a scalablephotobioreactor (PBR) for cou-pling to a power plant, wherebythe CO2 produced could be usedfor growing algae and, in turn,for the reduction of CO2 emis-sion of the power plant. Theintended use of the developedPBR is, however, much greater.Algae can be efficiently growninside a PBR, for instance for the

production of biodiesel, for foodsas well as for the cosmeticsindustry.

Interdisciplinary support

Since algae need a little more thanjust light, CO2 and water, Prof.Franke brought in the support ofgraduate students from the‘Water Science’ Master’s Program.This led to the establishment ofan interdisciplinary workinggroup centering on the develop-ment of photobioreactors in closecooperation with industry. Com-pared to other similar projects,the focus is on research, and

many new potentially innovativeapproaches are being pursued.

To measure the efficiency of thelighting system developed, thegrowth of the algae first neededto be monitored. A photometer isused to measure scattering andthe absorption of chlorophyllwhile providing information onalgal growth. On closer inspec-tion, this common method ap-peared to be too inaccurate andsusceptible to fluctuation. Thesame was true for the widely usedand very complex determinationof protein mass. Based on thesefacts, the group started to search

Prof. Hilmar Franke and Sascha Hendes at the TOC-VCPH

13


Figure 1: Assembly and possible uses for photobioreactors in power plants or as home

heating installations for the reduction of CO2 emissions

Figure 2: TOC calibration against the dry mass

Figure 3: Growth curves of microalgae in different nutrient media, measured using

Shimadzu’s TOC-VCPH

0

50

100

150

200

250

300

350

0 20 40 60 80 100 120 140

y = 2.0174x + 0.2465

R2 = 0.9997

TOC (mg C/L)

Calibration of the drywight against TOC

Dry

wig

ht (m

g/L)

0

300

600

0 20 40

Day (d)

Growth of algae under different nutrition messured with TOC

TOC

(mg/

L)

for a parameter for algae that wasrelatively constant, that could bedetermined with little effort andlow cost, and that would also besuitable for industrial monitor-ing.

Student Sacha Hendes (photo-graph below, measuring algaetogether with Hilmar Franke)had the idea to determine algalbiomass using TOC. This ideaalso appealed to the Shimadzuexperts, as it represented an inter-esting and unusual use of a TOCinstrument.

After several promising testmeasurements in Shimadzu’s lab-oratories, the TOC-VCPH wasselected for the development of ameasurement method for thedetermination of algal biomass.

Measuring method

The 4 to 10 μm sized Chlorellavulgaris microalgae could bemeasured directly after samplingfrom the reactor without theneed for further sample pretreat-ment. The difference method(TOC = TC - IC) was applied for biomass determination. It issuitable for all other single-celledalgae which exhibit a stable carbon content under variousgrowth conditions.

TC and TIC are determined, andthe TOC is calculated from these

values. Via calibration using theobtained dry mass of the algae,the mass percentage of the drybiomass can subsequently bededuced from the TOC value (seefigure 2).

The algae sample is first meas-ured and the TOC content isdetermined. The sample is subse-quently filtered through a 0.2 μmsyringe filter and the TOC con-tent is remeasured. This is donein order to distinguish how muchof the TOC originates from thealgae and how much can possiblybe attributed to extracellular sub-stances produced by the algae orreleased into the nutrient solutionafter they die off.

Results

The TOC determined in this waypoints to the carbon content ofthe measured algae. To draw con-clusions on the dry mass ob-tained, the carbon content of thealgae must be determined on apercentage basis. Several directand indirect methods are avail-able. The most straightforwardand highly reliable method is tocombust the washed and driedalgae using the TOC combustionmethod for particulate matter. Inthe second method, the algae arefiltered, dried and their mass issubsequently measured. In com-bination with TOC and photo-metric measurements, it is possi-

ble to determine a correlationbetween the TOC value and thealgal dry mass which providesinformation on the carbon con-tent of the algae. (In this way, thedry mass of the algae solutioninvestigated can be determinedvery accurately from the carbonmass fraction and the TOC val-ue.)

In order to demonstrate theapplicability for specification ofalgal growth, graduate studentDominik Gerhard investigatedalgal growth in various nutrientmedia using TOC in his thesisresearch (see figure 3). As a spe-cial cleaning measure for theTOC system when used duringcontinuous monitoring of algae,the syringe and the sample loopsmust be thoroughly cleaned usinga diluted hydrochloric acid solu-tion to prevent fouling by algae.

This is particularly important at the start of the weekend, asotherwise algal fouling can leadto higher measuring results.

Conclusion

The determination of algal bio-mass using TOC is a new methodthat has proven to be highly suit-able in a laboratory environmentfor the measurement of biomassyield in photobioreactors and forthe monitoring of algal growth.In combination with other sen-sors, additional information onthe condition of the algae can be obtained. In addition, thismethod can be easily modifiedand applied for the investigationof (micro)algal pollution in lakewater.

READ FOR YOU Shimadzu News 3/2010

14

White giant or white dwParticle size distribution measurements of TiO2 using

What do white tattooink, milk, toothpasteand lines on tenniscourts have in common?

In all cases, TiO2 (titanium diox-ide) is used as white pigment. In everyday use, it can be foundnearly everywhere – in paints,coatings, plastics, papers, inks,medicines as well as in tooth-paste. It is the widest used whitepigment due to its brightness andvery high refractive index of 2.7.

However, TiO2 is not only usedas a white pigment. It is also a

photocatalyst under ultraviolet(UV) light – and under visiblelight if it is doped with nitrogenions or with metal oxides. Thephotocatalyst TiO2 capturesultraviolet light and forms acti-vated oxygen from water or oxy-gen in the air. The activated oxy-gen is strong enough to oxidizeand decompose organic materialsand smelling gas. Photocatalyst

coating technology therefore addsadvanced functions to buildingmaterials, for instance sterilizing,deodorizing and anti-fouling.

TiO2 is produced in varying par-ticle sizes, is oil and water dis-persable, and as varying coatingsdepending on the applicationfield and industry.

Measuring small particles –Laser Diffraction

One method commonly used tomeasure particle size is laserdiffraction. When light hits a par-ticle, the resulting shadow imageis not sharply defined due to thewave-like nature of light. Itrather shows a light intensity pat-tern depending on the wavelengthand the particle size. The rela-tionship between measured lightintensity pattern and particle sizecan be derived from the so-calledMie theory.

Most laser diffraction particlesize analyzers on the market areequipped with several lightsources and/or detectors. Usingsuch instruments is problematicsince detectors or the light sourcehave to be switched if the entiremeasurement range is to be cov-ered. Switching needs time, recal-ibration is needed and the qualityof measurement data is poor inthe overlapping areas of thedetectors.

Figure 1 shows an example of aparticle size distribution usingthe Shimadzu SALD-7101 Parti-cle Size Analyzer. This setup fea-tures a perfect seamless and widemeasuring range. There are nopoints of discontinuity over theentire measuring range becausejust a single light source, a singleoptical system and a single mea-surement theory are needed. Thismethod is perfectly suited for

larger particles starting from 10 nm up to a range of a few mil-limeters.

Measuring tiny particles –Induced Grating Method

Dynamic light scattering (DLS) is the conventional method formeasuring particles in the rangeof a few nanometers. Howeverlight scattered by particles de-creases sharply for particle sizesof less than 100 nm. The IGmethod, developed by Shimadzu,uses diffracted light instead ofscattered light, and is free fromthese physical restrictions. Furthermore, it does not requireinput of the refractive index as ameasurement condition.

The IG method uses specific elec-trodes dipped into the samplesolution. A laser passes throughthe electrodes. If an electricalfield is applied to the electrodes,particles are “trapped” betweenthe free spaces of the electrodesresulting in a diffraction pattern.With dielectrophoresis switchedoff, the particles diffuse back intosolution and the detected dif-fracted light intensity decays,based on the difference in diffu-sion velocities of large (slow) andsmall (fast) particles.

This method enables stable mea-surements with excellent repro-ducibilities, particularly in thesingle nano range. It is virtuallyresistant to contamination andeven to the presence of small for-eign particles. Special require-ments of ambient air quality aswell as sample filtration aretherefore unnecessary. Measure-ments can also be carried outwithout any problems in manydifferent solvents.

Figure 2 shows an example of aparticle size distribution mea-

15

READ FOR YOUShimadzu News 3/2010

arf ?Shimadzu’s Particle Size Analyzers

100.000

90.000

80.000

70.000

60.000

50.000

40.000

30.000

20.000

10.000

0.000

25.000

20.000

15.000

10.000

5.000

0.000

Particle diameter [μm]

Cum

. % [%

]

Diff

. % [%

]

100.000

90.000

80.000

70.000

60.000

50.000

40.000

30.000

20.000

10.000

0.000

35.000

30.000

25.000

10.000

5.000

0.000

Particle diameter [nm]

Cum

. % [%

]

Diff

. % [%

]

sured with the IG-1000. The crit-ical range of measurements lessthan 10 nm is thereby extended.

Is TiO2 a white giant orwhite dwarf?

Both. TiO2 has a “giant” applica-tion field and is used as a whitepigment or as a photocatalyst.Depending on the applicationfield, the size range of the parti-cles differs. Sometimes the parti-cle diameter is in the range ofnanometers, and sometimes in the

range of micrometers. Sophisti-cated and advanced tools like thenew Shimadzu IG-1000 and theSALD series help in determiningparticle size distributions as accu-rately as possible.

Read for you in G.I.T. Laboratory

Journal 9-10/2010




Figure and Table 1: Particle Size Distribution of TiO2 / Average of ten consecutive

measurements including standard deviation / Setup Used: Shimadzu SALD 7101 with

batch cell / Measurement range: 10 nm - 300 μm

Figure and Table 2: Particle Size Distribution of TiO2 / Average of three consecutive

measurements including standard deviation / Setup used: Shimadzu IG-1000 /

Measurement range: 0.5 nm - 200 nm / Measurement principle: Induced grating

1.000 11.00010.000 1.000 100.00010.000

Measurement results IG-1000Median D [nm] Modal D [nm]

Mean Value

Std Dev

Maximum

Minimum

5.96

0.50

6.31

5.25

*Average of three measurements

6.08

0.17

6.25

5.85

Measurement results SALD 7101Median D [μm] Modal D [μm]

Mean Value

Std Dev

Maximum

Minimum

3.650

0.289

4.467

3.548

*Average of ten measurements

4.398

0.066

4.585

4.372


16

Bitter, fresh, hoppy ...

From Ján Hrivňák a),

Daniela Šmogrovičová b),

Pavol Nádasky̌ b) ,

Jana Lakatošová a), b)

a) Plant Production Research

Center Piešt’any, Institute of

Viticulture and Enology,

Matúˇ̌skova 25, 831 01 Bratis-

lava, Slovak Republic

b) Faculty of Chemical and Food

Technology, Slovak University

of Technology, Radlinského 9,

812 37 Bratislava,

Slovak Republic

This rapid sampling tech-nique is suitable for theanalysis of beer aromacompounds. The headspace (10mL) is passed through a micro-column filled with 5 mg of TenaxTA and thermally desorbed in amodified GC inlet. Eight com-pounds (from acetaldehyde to 2-phenylethanol) in four beersamples were analyzed. The cor-relation coefficients (r2), repeat-ability (RSD) and limits of detec-tion (LOD) were 0.9973 - 0.9994,2.1 - 6.9 % and 0.00002 - 0.13mg/L, respectively. The method-ology can be useful for routinebeer sample analysis.

Introduction

Beer aroma compounds are veryimportant as they make a majorcontribution to the quality of thefinal product. A variety of flavorcompounds may arise dependingon the beer type and storage con-ditions. Reliable and sensitiveanalytical methodologies arerequired for the extraction andanalysis of a great number of beeraroma compounds, ranging fromvery volatile all the way to high-boiling compounds.

Several extraction/concentrationmethods have been employed forthe analysis of beer volatiles.Headspace solid-phase micro-extraction (HS-SPME) is a sim-

ple, fast, sensitive and solvent-free extraction technique thatenables the extraction and con-centration steps to be performedsimultaneously [2 - 5]. However,the HS-SPME method, using thesyringe with a fiber or solventextraction method, is not appro-priate for the analysis of veryvolatile beer aroma compoundsespecially acetaldehyde, in viewof its pungent odor.

Headspace solid-phase microcol-umn extraction (HS-SPMCE) is auseful analytical tool for the anal-ysis of both very volatile andhigh-boiling compounds. Amongvolatiles, HS-SPMCE has beensuccessfully used for the quanti-tative analysis of vinyl chloride inwater [6], chloroform in urine [7]and benzene in air [8]. The aim ofthis work was to demonstrate theperformance of HS-SPMCE forthe quantitative analysis of bothvery volatile and higher-boilingbeer aroma compounds withinone sample run using GC-FID.

Instrumentation and chromatographic conditions

For the analysis, a 100-mL ali-quot of the beer sample wasquickly transferred into a 500-mLvolumetric flask containing 20 gNaCl and the flask was vigorous-ly shaken by hand at room tem-

Headspace solid-phase microcolumn extraction deter

Table 1: Correlation coefficients (r2), limits of detection (LOD), limits of quantification

(LOQ) and repeatability (RSD) of investigated analytes

Compound r2 LOD (mg/L) LOQ (mg/L) SD % (n = 5)

Acetaldehyde

Acetone

Methyl acetate

Ethyl acetate

Ethyl hexanoate

Ethyl octanoate

Ethyl decanoate

2-Phenylethanol

0.9989

0.9983

0.9991

0.9993

0.9993

0.9994

0.9991

0.9973

0.039

0.011

0.003

0.001

0.0002

0.0004

0.001

0.13

0.24

0.070

0.022

0.0068

0.0015

0.0028

0.0066

0.79

4.9

5.7

4.1

2.9

3.2

2.1

3.7

6.9

17


perature (22 ± 1 °C). After 10 -15 min equilibration, 10 mL ofthe headspace was withdrawn.The headspace content of thesyringe was immediately pushedthrough the microcolumn (1 mmI.D., packed with 5.0 mg of 60 -80 mesh Tenax TA). The loadedmicrocolumn was transferred to amodified GC inlet. The trappedaroma compounds were desorbedat 10 kPa by heating the micro-column to 230 °C for 1 min.After desorption, the carrier gaspressure was increased to 60 kPaand the temperature program wasstarted. During the analysis run,the microcolumn remained in theGC inlet. Analyses were carriedout on a Shimadzu GC-14 withFID where the liner was replacedwith a liner for the microcolumn.

Column: VF-WAXms capillarycolumn of 30 m length, 0.25 I.D.,0.5 μm film thicknesses (Varian,Lake Forest, CA, USA) Temperature program: 30 ºC (4 min), 5 ºC/min to 200 ºC andhold 10 min. Injector temperature: 230 ºCand Carrier gas: helium

Results and discussion

Acetaldehyde, acetone, methylacetate (representatives of veryvolatile compounds) and ethylhexanoate, ethyl octanoate, ethyldecanoate and 2-phenylethanol(representatives of higher boilingbeer aroma compounds) werechosen to confirm the versatilityand suitability of the new HS-SPMCE method. For quantitativeanalysis, five-point calibrationcurves over the range of the fol-lowing concentrations weremeasured: from 1 mg/L to 10mg/L for acetaldehyde, 0.1 mg/Lto 1 mg/L for acetone, methylacetate, ethyl hexanoate, ethyl

octanoate, ethyl decanoate, 2 mg/L to 20 mg/L for ethylacetate, and 1 mg/L to 50 mg/Lfor 2-phenylethanol in the 4 %(V/V) of ethanol. The correlationcoefficients (r2) listed in table 1varied from 0.9983 to 0.9996.

The repeatability of the method(RSD) was in the range of 2.1 to6.9 % (table 1). The limits ofdetection (LOD) and quantifica-tion (LOQ) were calculated byAdstat Calibration Program(Trilobite, Czech Republic) andshow good sensitivities for thereal sample analyses.

As an example, the chromato-gram of beer sample 1 is shownin figure 1; there are 19 peaksfrom very volatile compoundsand 94 peaks from higher boilingcompounds. Results of the quan-titative analysis of four samples(mean value of two measure-ments) are listed in table 2. Theresults in table 2 indicate relative-ly small differences between thecompositions of the studied com-pounds in the analyzed samples.The proposed method can be use-ful for the analysis of real sam-ples. The modification of the gaschromatographic inlet for thermaldesorption in the microcolumn is cost-effective, and replaces theexpensive thermal desorptionunit.

Conclusions

HS-SPMCE is a simple, fast andsensitive method for the routineanalysis of aroma compounds inbeer samples. Owing to the goodreproducibility of the method, itcan be used to compare the vola-tile profiles of different types ofbeers, study the development of aparticular beer during aging, orcorrelate with sensory analysisresults.

mines aroma compounds in beer

Table 2: Four sample results (mg/L) of studied beer aroma compounds analysis

Figure 1: Chromatogram of a beer sample

Acknowledgements

This work was supported by the Sci-

entific Grant Agency of the Ministry

of Education of the Slovak Republic

and the Academy of Sciences, regis-

tration number 1/0786/08.

References

[1] B. Vanderhaegen, H. Neven,

S. Coghe, K. J. Verstrepen,

H. Verachtert, G. Derdelincks,

J. Agric. Food Chem. 51 (2003)

6782

[2] C.L. Artur, J. Pawliszyn, Anal.

Chem. 62 (1990) 2145

Compound Sample 1 Sample 2 Sample 3 Sample 4

Acetaldehyde

Acetone

Methyl acetate

Ethyl acetate

Ethyl hexanoate

Ethyl octanoate

Ethyl decanoate

2-Phenylethanol

5.14

0.12

0.13

10.1

0.11

0.31

0.079

10.3

4.26

0.093

0.94

9.41

0.10

0.34

0.13

11.4

6.11

0.15

0.14

12.1

0.16

0.33

0.087

13.3

3.86

0.093

0.11

13.3

0.12

0.33

0.37

11.8

0 10 20 30

Time [min]

Abu

ndan

ce


18

Sensitivity meets robust and precisionEvaluation of a novel TNM analytical technique for c sample testing

This article introduces thevalidation and applicationof Total Nitrogen Mea-surement (TNM) as a powerfulanalytical technique for cleaningvalidation purposes after manu-facturing of Trypticase-Soy-Beanbroth (TSB) Mediafill batches atthe fill-and-finish pilot plant forparenterals at PDMS Schaff-hausen.

TNM (Total Nitrogen Measure-ment) is an analytical techniqueused for the determination oftotal water-borne nitrogen (TN)by means of oxidative combus-tion chemiluminescence. Bothcombustion tube and oxidationcatalyst are shared with TOC(Total Organic Carbon) analysis.The well-known TOC applica-tions used for Cleaning Valida-tion purposes are therefore com-plemented by the determinationof Nitrogen in the related sam-ples. This offers an enhancementof the analytical informationobtained from the cleaning vali-dation samples, particularly with

proteins and amino acids sinceNitrogen is an essential part ofthese compounds.

Linearity, range (0.05 - 0.85 μgNitrogen/mL), LOQ, accuracy,precision, and sample stability ofthe TNM method was validated.These parameters were tested forboth Glycine (used as Nitrogenreference standard) and TSB

Mediafill solution. Recovery ofTSB Mediafill from fill-and-finishpilot plant surface materials suchas boro-silicate glass and elec-tropolished steel was also deter-mined. Due to the lot-to-lot vari-ability regarding the Nitrogencontent of the TSB Mediafill, arepresentative aliquot of therelated lot was analyzed in eachsequence in order to determinethe Nitrogen content. The rela-tive amount of Nitrogen was 9 %related to the organic fraction ofthe tested TSB Mediafill solu-tion. This value was confirmedby an elemental compositionanalysis.

TNM showed less interferencewith the rinse water or swabsamples than to TOC. Further,the sensitivity of TNM was high-er than that of TOC. The TNMmethodology can therefore beconsidered as a robust and reli-able analytical technique forcleaning verification purposes.

Acceptance criteria forCleaning Validation in termsof TSB Mediafill residues on the equipment surface

Since the acceptance criterion(MAC = Maximum AllowableCarry-Over) of cleaning valida-tion applications is essential tothe method sensitivity, the valida-tion parameters are based on thiscritical concentration. A limit of10 ppm TOC (respectively 10 μgcarbon/mL) was set. The totalNitrogen amount of TSB Media-fill is 9.2 %; the TOC amount is35.8 % (average of six determina-tions, three lots included). Bothpercentages are based on theorganic substances present inTSB. The results obtained froman elementary composition anal-ysis of one TSB batch showedcomparable results.

The 10 ppm TOC limit (relatedto TSB) therefore corresponds to2.6 ppm TN. Since the volume ofthe last rinse (or the extractionvolume of the swab) is related tothe surface, the acceptance limitof 10 ppm TOC and/or 2.6 ppmTN should be based on a definedsurface area.

According to an internal bestpractice, the ratio of last rinsevolume to surface is 1,000 mL per m2. 10 ppm TOC corre-

TOC with TNM-1

19

TELEGRAMShimadzu News 3/2010

creased robustness and also sensi-tivity of TNM compared withTC. Nevertheless, the TC valueobtained from the samples yieldsadditional information regardingthe cleanliness of the equipment,while exceptionally high TC lev-els indicate a contamination ofthe equipment by organic com-pounds.

The use of NPOC (Non-Purge-able Organic Carbon) evaluatedduring method development ledto invalid results for both TOCand TN. This might have beencaused by the addition of hydro-chloric acid, necessary to purgeinorganic carbon from samplesbut also leading to precipitationand/or adsorption losses of theTSB proteins. The TC/TN modewas therefore used for develop-ment and validation of themethod.

A limiting factor in increasedsensitivity of TNM is the samplevolume, at most 300 μL (softwarelimitation). Compared with sam-ple volumes using a high sensitiv-ity catalyst for regular TOC anal-ysis, the injection volume forTNM is lower by a factor ofapprox. 15. Nevertheless, themethod showed sufficient sensi-tivity for the intended purpose.

The cleaning procedure aftermanufacturing of TSB Mediafillbatches at the fill-and-finish pilotplant for parenterals at Schaff-hausen was validated successfullyusing the reliable and robustTNM technique.




ness

leaning validation

Figure 1: IRAffinity -1 plus MIRacle10

Figure 2: GladiATR10

sponds to 1 μg TOC/cm2. This isequivalent to 0.26 μg TN/cm2. In the case of swab samples usedfor steel surfaces, an extractionvolume of 40 mL has to be takeninto account. For rinse samples,400 cm2 glass surface is rinsedwith 40 mL purified water.

The final MAC related concen-tration depends on the recoveryrate of TSB Mediafill proteins,which was 50 % (worst case). As a result, 0.13 μg TN/cm2 wasconsidered to be the MAC.

Discussion and Conclusion

The use of TNM for the determi-nation of TSB Mediafill proteinsfor cleaning validation purposeswas shown to be a sensitive,accurate, precise and robustmethod. The determination ofNitrogen in swab and rinse clean-ing validation samples is specificto protein-related substances.Since the pilot plant specificcleaning procedure includes onlynon-nitrogen containing deter-gents, Nitrogen signals can berelated specifically to TSB pro-teins or their degradation prod-ucts. In addition, TC (Total Car-bon) is measured in parallel.

The validation of a sensitive TCmode was not possible due to thevarying amount of inorganic car-bon such as carbonate in thewater used for analysis. This ledto precision issues for the TCmode at low concentrations.Since WFI or MilliQ water,which was used for both sampleand standard preparation, isessentially free from Nitrogen, nointerferences with the solventoccurred. This results in in-

With immediate effect, three new FTIR accessories for Shimadzu’s IRAffinity1 are available for many applications. This FTIR spectrophoto-meter is used in the pharmaceutical industry as well as in research anddevelopment.

• The HATR10 is a conventional horizontal ATR accessory for multiple reflectance

• The MIRacle10 features ATR (Attenuated Total Reflectance) as singlereflectance. Figure 1 shows how the sample top plate and the instrumenthousing lie in one plane. The accessory is tailor-made. For the ‘out ofcompartment’ MIRacle10, a new crystal design has been applied whichreflects the beam from within the sample compartment upward onto thesample plate

• The second type of single reflectance unit is the GladiATR10, where thediamond serves as sampling plate and optical crystal

Figure 1 shows how the acces-sories are easily installed in thesample compartment. All acces-sories are equipped with accessoryrecognition for working with auto-mated parameter sets. Users bene-fit from time savings made possibleby fast access to parameters setsand simpler cleaning procedures of the sample compartment andmeasuring plates.

Tailor-made FTIRaccessories

Many different types of“on-line analysis”methods have beendeveloped and applied in diverseareas of chemistry in order toprobe reaction pathways andconversion rates. In the case ofelectrochemistry, cyclic voltam-metry is a widely used techniquein the study of reactions on elec-trodes based on cyclic sweepingof the electrode potential in a cer-tain potential range. Nowadays,voltammetry is often combinedwith in-situ or on-line analysistechniques such as microscopy,spectroscopy, and chromatogra-phy. However, combining vol-tammetry with chromatographictechniques such as gas chromato-graphy (GC), ion chromatogra-phy (IC) and high performanceliquid chromatography (HPLC)has been limited due to the longanalysis times in the column. Todate, the combination of voltam-metry and chromatography inorder to identify reaction prod-ucts has been applied only forprolonged electrolyses [1].


20

Product detection in ele

This limitation of a direct combi-nation of voltammetry and chro-matographic techniques, especial-ly HPLC, has driven us to a newapproach using a Shimadzu “frac-tion collector” equipped with anin-house designed micron-sizedsample collecting tip for rapidsample collection close to theelectrode surface during voltam-metry, with subsequent analysisof sample fractions in an HPLCsystem. This idea has been ap-plied to glycerol electro-oxida-tion on platinum electrode inalkaline media, and concentrationchanges of glycerol and its reac-tion products can be visualized in good correspondence withvoltammograms. This straightfor-ward but novel combination ofcyclic voltammetry with HPLChas great promise for the study ofcomplicated multi-product elec-trochemical reactions.

Method

During the voltammetry, reactionvolumes of 60 μL each were col-lected on a 96-well microtiterplate using a Shimadzu Fraction

Collector (FRC-10A with LC-20AT pump) with a sampling tippositioned close to the electrodesurface, and analyzed by high-performance liquid chromatogra-phy (Shimadzu prominenceHPLC) with an Aminex HPX 87-H (Bio-Rad) column and 5 mM sulfuric acid as eluent. Col-umn temperature was maintainedat 30 °C in the column oven(CTO-20A) and the separatedcompounds were detected with arefractive index detector (RID-10A).

Results

A typical result for glycerol oxi-dation on platinum in 0.1 MNaOH is shown in figure 2. Figure 2a shows the voltammetriccurves both in the absence (dashedline) and presence (solid line) ofon-line sample collection. Sam-ples collected on microtiter plateduring the voltammetry are ana-lyzed in the HPLC system andmany peaks are observed in thechromatograms (Figure 2b), andare converted to their correspond-ing concentrations (Figure 2c).

Combining cyclic voltammetry and HPLC by employin

0

0.0

E / V (vs. RHE)

j / m

A c

m-2

0.4 0.8 1.2 1.6

2

4

6 (a)

Figure 1: Schematic diagram of the on-line sample collection with fraction collector

(FRC) and subsequent analysis of sample fractions in an HPLC system. WE = Working

Electrode, RE = Reference Electrode, CE = Counter Electrode.

Figure 2a: Voltammogram of glycerol oxidation (0.1 M) on Pt electrode with (solid line)

and without (dashed line) sample collection in 0.1 M NaOH. Scan rate is 1 mV/s.

Figure 2c: Plots showing the concentrations of glycerol and its electro-oxidation

by-products as a function of potential: � glycerol, � glyceric acid, � glycolic acid,

� formic acid, � oxalic acid, tartronic acid. (Reprinted with permission from Ref. [1].

Copyright 2010. ACS)

21


In the case of glycerol oxidation,the scan rate of voltammetry andflow rate of sample collectionwere optimized at 1 mV/s and 60 μL/min respectively. Each datapoint in figure 2c therefore repre-sents the average concentrationover a 60 mV potential range.Figures 2b and 2c clearly showfive different soluble productsformed during the glycerol oxida-tion, as indicated in the figurecaption. More detailed informa-tion as well as a comparison withthe same reaction on a gold elec-trode is available in reference 1.

Conclusion and outlook

It was demonstrated the combi-nation of voltammetry with achromatographic technique usingfraction collector for online sam-ple collecting during voltammet-ry, with subsequent sample analy-sis in an HPLC system. When

applying this method to glyceroloxidation on a platinum electrodein alkaline media, various reac-tion products are detected andcorrespond well with the currentprofile simultaneously obtainedusing voltammetry. It is expectedthat this combination will enablenew insights into many othermulti-electron electrochemicalreactions producing soluble inter-mediates and products.

Smaller sample collection vol-umes will allow slower samplecollecting flow rates, leading tosmaller disturbances on thevoltammetry at higher scan rates.At present, the combination isstill limited by the “innate” char-acteristic of the sample collectingpump. Slow flow rate in the sam-ple collecting pump causes pulse-like sample collection from theelectrode surface. In addition, allsamples pass through the insideof the pump, and the volume in

the pump should match that ofthe collected samples. The insidevolume of the pump thereforeneeds to be as small as possible.

Acknowledgement

This research has been performed

within the framework of the Catch-

Bio program. The authors gratefully

acknowledge the support of the

Smart Mix Program of the Nether-

lands Ministry of Economic Affairs

and the Netherlands Ministry of

Education, Culture and Science.

From Youngkook Kwon,

Marc T. M. Koper

Leiden Institute of Chemistry,

Universiteit Leiden, P.O. box 9502,

2300 RA Leiden, The Netherlands

Reference

[1] Combining voltammetry with

HPLC: application to electro-

oxidation of glycerol, Anal.

Chem. 2010, 82, 5420-5424.

ctrochemical cellsg fraction collection

Figure 2b: Chromatogram from HPLC analysis at 30 °C with samples collected

during voltammetry.

-100

6.0min.

Glycerol

Oxalic acid

Glyceric acid FA

Tartronic acidGlycolic acid

(b)

E / V

(vs.

RH

E)

7.0 8.0 9.0 10.0 11.0 12.0 13.0 14.0

-500

50100150200250300350400450500

1.2

1.0

0.8

0.6

0.4

0.2

550600650700

uV

0.0

(c)

0.4 0.8 1.2 1.6

90

0.0

0.4

0.8

100

E / V (vs. RHE)

Conc

entr

atio

n of

gly

cero

l (m

M) Concentration of products (m

M)


22

“Gentlemen, start your e

The determination of addi-tive elements, wear metalsand contaminants in usedlubricating oils is a typical rou-tine method in inductively cou-pled plasma optical emissionspectrometry (ICP-OES). Thisanalytical method helps to deter-mine component wear. TheICPE-9000 (Figure 1) is a simul-taneous vacuum ICP-OES spec-trometer, allowing analysis of anyelement in the wavelength rangeof 167 nm to 860 nm. The instru-ment is equipped with a highlysophisticated Echelle optical sys-tem and CCD detector allowingmulti-element analysis includingthe determination of sodium andpotassium.

International standard methodssuch as ASTM 5185 describedetermination of elements such ascalcium, magnesium, phosphorus,sulfur and zinc based on oil solu-ble metals for calibration.

Where does oil contami-nation come from?

Wear metals such as copper andiron may indicate wear in anengine or any oil wetted com-partment. Boron, silicon or sodi-

um may indicate contaminationfrom dirt or antifreeze leading tofailure. Additive elements such ascalcium, phosphorus and zinc areanalyzed for depletion and subse-quent wear since these elementsplay a key role in lubricationcharacteristics. Routine monitor-ing of metals in lubricating oils isvery important since it not onlyreduces the expense of routinelydismantling components for visu-al inspection, but can also indi-cate unexpected wear prior tocomponent failure.

Flexible analytical tech-nique essential

High sample throughput as wellas easy handling of the systemconfiguration is essential for rou-tine oil analysis laboratories. Thewavelength flexibility of theICPE-9000 system allows usersto add new elements easily witheach change of oil program. Sinceall multi-element information isstored on a chip and available atall times, it is possible even afterthe analytical run to compare dif-ferent wavelengths in order tooptimize the method. The assis-

Determination of additive elements, wear metals and oils using ICP OES with oxygen plasma

Figure 1: ICPE-9000 simultaneous ICP-OES spectrometer with CCD detector

23

TELEGRAMShimadzu News 3/2010

ngines!”contaminants in lubricating

tant functions of ICPE solutionsoftware support the user duringwavelength selection and set theoptimum lines automatically.Spectral interferences are com-pensated by inter-element correc-tion standards as the softwareimplements a total of more than110,000 spectral lines. Anotherbenefit of the ICPE-9000 systemfor oil analysis is the verticaltorch position, which allows longanalytical sequences without pre-cipitation or clogging.

Optional oxygen kit

The system setup for oil determi-nations includes an optional oxy-gen kit consisting of an opti-mized organic solvent torch (Fig-ure 2) which allows the inlet ofan argon/oxygen gas mixture.For sample aspiration the ambi-ent temperature Scott type cham-ber with a coaxial nebulizer hasbeen used. The instrument isequipped with a dual view obser-vation mode which allows thedetermination of all elements inaxial as well as radial view in oneanalytical run. The instrumentalparameters for the determinationof oil samples are listed in table 1.

All standard and sample solutionswere prepared in the same wayusing xylene as a solvent andblank standard oil to adjust theviscosities.

Figure 2: 4-tube organic solvent torch

Table 1: System parameters for oil

analysis

ICPE-9000 with oxygen kit

Generator power

Plasma gas

Carrierer gas

Ar/O2 mix gas

Exposure time

Observation

direction

1.2 kW

10 L/min

0.7 L/min

0.01 L/min

15 sec

Axial and radial

Summary

The ICPE-9000 in the organicmode using the optional oxygenkit is an effective tool for theanalysis of wear and additivemetals in oils. The experimentaldata corresponds well with thecertified data of the referencesample. In addition to the majorelements in radial view, ICPE-9000 can also determine trace ele-ment concentrations in the oils atthe same time in axial view. Themethod is robust and can be fullyautomated in combination withthe ASC-6100 autosampler.

Oil keeps the motor running.Understanding the sources ofwear material in oil helps toincrease the quality of lubricantswhich extend the lifetime cycle of an engine. This is importantand reassuring, e.g. at Indy 500,when the drivers get the order: “Gentlemen, start your engines!”

Shimadzu, a worldwide market leader in spec-troscopy, offers customized solutions ranging fromUV-VIS to NIR technologies. The long tradition ofhighly sophisticated scanning spectrophotometerssuch as UV-160, UV-1600, UV-1650 and UV-1700 hasbeen rounded up with the UV-1800 which achievesa resolution of 1 nm, the highest in its class.

The instrument meets the requirements of Euro-pean and Japanese Pharmacopoeia. The high per-formance optical system of the UV-1800 consists ofa Czerny-Turner monochromator in a compactdesign.

Offering an array of user-friendly features, the UV-1800 can be used either as a stand-alone or as a PC-controlled instrument. It is the perfect toolfor solving applications in the pharmaceutical,environmental and biotechnology market as well asfor teaching purposes and at universities.

More than 15,000 Shimadzu users all over Europerely on the performance of this workhorse in spec-troscopy. Users replacing their older UV equipmentalso benefit from Shimadzu’s current European promotions program, such as the starter packageor the extended lifetime package.

The perfect all-rounder leads the way in findingsolutions.

The perfect all-rounders inUV-VIS spectroscopy




SOFTWARE Shimadzu News 3/2010

24

Quality by Design

QbD automated HPLCMethod Developmentusing DryLab®2010 en-ables the transfer of

HPLC methods into most-mod-ern Shimadzu UHPLC-technol-ogy. By remaining in the designspace, there is a much higher flex-ibility in adjusting working con-ditions according to individualneeds.

Shimadzu and the Molnar Insti-tute in Berlin cooperated in ap-plying well-known DryLab2010software and the new generationof Shimadzu UHPLC instru-ments.

With Drylab2010 it is now possi-ble to simultaneously optimizeseveral measured experimentalparameters (tG, T, pH or ternarycomposition of eluent B) with sixother derived factors (columnlength, -ID, dp, Flowrate, dwellvolume, extra column volume) tofurther define the Design Spaceof a separation. DryLab2010 usestwo-dimensional tG-T resolutionmaps [2]. By applying three ofthem, three-dimensional resolu-tion spaces can be created inwhich the combined influence of

three parameters can be assessedand optimized.

Molnár-Institute for applied chromatography

Founded in 1981, the Institutebrings 29 years of experience inhigh performance liquid chro-matography (HPLC). Dr. ImreMolnár, former coworker of Prof.Csaba Horváth from Yale and ofLloyd Snyder and John Dolan ofLCResources USA, is a well

UHPLC hardware meets DryLab®2010 software

known expert in HPLC methoddevelopment.

The Molnár-Institute plays asmall but essential role in theimprovement of worldwidehealthcare, ensuring safe productsin pharmaceutical, life science and food industries, while sup-porting research and developmentat universities. The Molnár-Insti-tute continuously serves compa-nies all over the world in success-fully designing and shaping

Figure 1: Shimadzu Nexera with LCMS 2020

Figure 2: Interface of Shimadzu’s LabSolution software

25

SOFTWAREShimadzu News 3/2010

HPLC method conditions. Byoffering software solutions,courses and development servic-es, the Molnár-Institute definesits mission in applying modernsoftware tools such as Dry-Lab2010 to increase efficiency inHPLC laboratories and to help tofind the best separation as soonas possible.

FDA, ICH and other regulatoryauthorities are now promotingand requesting the application ofQbD principles in order to easeexchange of complex informationon chromatographic selectivityand critical resolution values, soas to support better method con-trol including method transfer.Furthermore, the ICH Q8 hasmade a clear movement towardsmore flexibility in supportingdevelopment of new products.

Quality by Design

The Quality by Design (QbD)concept was outlined by qualityexpert Joseph Juran (1904 - 2008),stating that quality can be plan-ned, and that most quality prob-lems relate to the way it wasplanned originally.

The ideal state for pharmaceuticalmanufacturing in the 21st centurymeans • understanding the product and

its production processes• understanding the method-

ologies (HPLC, etc.) whichgenerate data to support theproduct quality.

DryLab applies QbD principlesince 20 years with a systematicevaluation of parameters influ-encing method performance(selectivity, resolution). DryLabsimplifies and speeds up the pro-cess of developing excellent chro-matographic separations by en-abling users to model changes inseparation conditions using theirpersonal computer. The time-consuming laboratory runs thatare typically required to achieve asatisfactory separation or devel-opment of a complete method arereplaced with instantly generatedchromatograms corresponding to

conditions that can be individual-ly selected.

DryLab is useful in almost allchromatography applications inthe lab. The software helps to• quickly find a good set of

separation conditions• develop complete method in

minimal time• evaluate method robustness• shorten run times• transfer methods to better and

more modern instruments suchas Shimadzu Nexera

• easily carry out validation of methods

• find the best separation conditions for any componentin a mixture

• fine tune or troubleshoot existing methods

• make the method fit to its purpose

• adjust methods for ageingcolumns.

Design of Experiments

Preliminary evaluation deter-mined that the most influentialexperimental variables on critical

resolution (separation betweencritical peak pair) were• Gradient time (tG) (strongest

influence) (2 runs, factor 3 dif-ference)

• Temperature (T) (moderateinfluence) (2 runs, 30 °C differ-ence)

• Ternary eluent composition (% tC), (fairly strong influencefor most compounds)

• Eluent B: 100 % MeOH,(50 : 50) (MeOH : AN), 100 %AN

• pH (strong influence for polarcompounds, s.a. acids, bases,zwitterions) (f.e. pH: 2.2, 2.8,3.4).

The most popular model is thetG-T-model which works wellwith UHPLC and representsmore than 10,000 virtual chro-matograms [2]. The experimentscan be run automatically andunattended overnight using theShimadzu LabSolution software.

The Cube

Based on the principles of theSolvophobic Theory [1] DryLab

2010 calculates continuouschanges in the selectivity ofReversed Phase (RP) separations.Retention forces are based pri-marily on highly organized waterstructure and on the tendency ofwater to reduce the cavity inter-faces between the C18-silica sur-face and nonpolar molecules.Lipophobicity of water can bereduced by dilution with strongeluents MeOH or AN. This ishow the Molnar-Institute carriesout RP-gradient elution. �

Figure 3: Experimental design for a three-dimensional HPLC method optimization

Figure 4: Design Space Visualization with DryLab®2010

SOFTWARE Shimadzu News 3/2010

26

The Cube is calculated fromtwelve experiments using tG-Tmodels at • different ternary compositions

of the weak retarding eluent B(MeOH, AN or 50 : 50-mix) or

• three different pH-values

and it represents over 106 mod-eled chromatograms while evalu-

models, at three different valuesof a third parameter.

Each point in these 3D resolutionspaces corresponds to a highlyaccurate chromatogram [3].

The best chromatogram is avail-able in one second. Red color inthe resolution map means that the

ating multiple parameters simul-taneously. With just one mouse-click the best separation out ofca. 106 runs can be found in theCube. The Cube also helps topartially or fully replace expen-sive acetonitrile with methanol.The input data necessary forthese 3D models is depicted inthe figure below: three tG-T

Figure 5: DryLab 3D model

Figure 6: Gradient Editor

critical peak pair is better separat-ed than baseline resolution (Rs,crit > 1.5). The critical (least wellseparated) peak pair is shownwith different colors than theother peaks.

At the optimum setting of the tG,T and pH or ternary compositioncan further optimize separationusing different gradient stepswhile controlling the influence ofthe flowrate, column dimensionsand dwell volume on the separa-tion selectivity.

In the gradient editor points canbe added and moved with themouse. Selectivity changes withup to 10 gradient points can beobserved immediately togetherwith separation changes. Further-more, the changes can be studiedwhile modifying flowrate or col-umn dimensions and altering theresolution.

Precision of predictions

The predicted runs deviate fromthe corresponding experimentswith an average less than 0.2 % of the peaks’ retention times.This reduces trial & error runstremendously and increases workefficiency.

References

[1] Solvophobic Interaction with

Nonpolar Stationary Phases in

Liquid Chromatography, Cs.

Horváth, W. Melander, I.

Molnár J. Chromatogr. 125

(1976) 129-156.

[2] Rapid high performance liquid

chromatography method devel-

opment with high prediction

accuracy using 5 cm long nar-

row bore columns packed with

sub-2μm particles and Design

Space computer modeling,

Sz. Fekete, J. Fekete, I. Molnár,

K. Ganzler, J. Chromatogr. A,

1216 (2009) 7816-7823.

[3] Aspects of the “Design Space”

in high pressure liquid chro-

matography method develop-

ment

I. Molnár, H.J. Rieger, K. E.

Monks J. Chromatogr. A, 1217

(2010) 3193-3200.

27

CONFERENCEShimadzu News 3/2010

A system that rocksThe GCMS-QP2010 Ultra European Conferences Tour 2010

The new GCMS-QP2010Ultra had its worldwidepremiere on the Riva conference in May 2010. Thisevent, officially called the “34th

International Symposium on Capillary Chromatography”, isthe most prestigious internationalconference for gas chromatogra-phy. More than 700 participantsfrom all over the world wereattending this year.

Every second year the conferenceseries takes place in Riva del Gar-da, Italy, hence the name “RIVAconference”, every other year out-side Europe, mostly in US. TheRIVA conference 2010 was heldjointly with the 7th GCxGC Sym-posium. GCxGC (also calledcomprehensive 2D-GC) is a rap-idly growing GC technique forthe analysis of very complex sam-ples especially those of naturalorigin, i.e. food, petrochemical,environmental or clinical samples,and is generally viewed as themost important new developmentin gas chromatography in recentyears.

Lectures and presen-tations on the pacesettingGCMS-QP2010 Ultra

The new GCMS-QP2010 Ultraattracted a lot of attention. Itsextraordinary high scan speedmakes the system the onlyquadrupole MS on the marketsuitable for GCxGC analysisusing a normal mass range. Thepatented ASSP technology

(Advanced Scanning Speed Proto-col) maintains system sensitivity,even at ultra-fast scanning (20,000amu/sec) without any peak skew-ing being observed.

Results obtained using Shimadzu’snew GCMS-QP2010 Ultra werealso presented in the conferenceby Prof. Mondello and his co-worker Dr. Giorgia Purcaro in the lecture “New Frontier inUltra Fast GC/MS. Rapid Qua-drupole Technology (20,000 amu/sec) for Qualitative and Quantita-tive Analysis.” At the end of theconference, Giorgia Purcaro wasawarded with the important Leslie

Figure 1: 48th Annual Meeting of the International Association of Forensic Toxicologists

(Bonn, Germany)

Figure 2: 28th International Symposium on Chromatography (Valencia, Spain)

S. Ettre Award for her outstand-ing results and presentation cover-ing “Extending the Realm ofQualification and Quantificationin Comprehensive Two-Dimen-sional Gas Chromatography toQuadrupole Mass Spectrometry.”

Overall, Shimadzu was presentwith five lectures in the confer-

ence program (four by Prof. LuigiMondello, Prof. Paola Dugo andco-workers), one lecture by Mrs.Susanne Böhme (Shimadzu Euro-pa GmbH) and eleven poster pre-sentations (nine from the Univer-sity of Messina, one from the University of Wuppertal and onefrom Shimadzu Corporation).

The GCMS-QP2010 Ultra wasalso the main topic in the Shi-madzu company seminar whereDr. Margit Geissler (ShimadzuEuropa GmbH) and Dr. GiorgiaPurcaro from the University ofMessina presented the features ofthe new instrument and recentresults for fast GCMS and com-prehensive 2D-GC with quadru-pole MS detection measurements.

International press conference

In a separate event, the newlylaunched GCMS-QP2010 Ultrawas introduced to a group of

international editors from leadingpublications. At the booth, theycould get all relevant in-depthinformation as well as details ofthe system’s outstanding perfor-mance.

The following press conferencecovered international market top-ics presented by Shimadzu’s Euro-

pean and North-American prod-uct managers. Shuichi Kawana,Developing Engineer from theR+D department at ShimadzuCorporation, highlighted theextraordinary features of the newinstrument. Following these pre-sentations, Prof. Mondello ex-plained the benefits of the newinstrument from the perspectiveof a high-end user.

Comprehensive 2D-GC in routine applications and food analysis

In August 2010, a new applicationdemonstrating the use of compre-hensive 2D-GC for drug screen-ing in a routine clinical laboratoryusing the new GCMS-QP2010Ultra gained a lot of attentionduring the TIAFT conference(“48th Annual Meeting of theInternational Association ofForensic Toxicologists”) and JointMeeting with the Society of Toxi-cological and Forensic �

Follow us on: www. .com/ShimadzuEurope

CONFERENCE

WEBSITE

Shimadzu News 3/2010

28

A new service in the GC section of the Shimadzu website provides usersinformation about the different consumables used in a gas chromatographicsystem, e.g. ferrules, liners, vials etc.

Details are listed for each part, as shown in the example below for the microsyringes for the AOC-20i/s autoinjector/autosampler (table 1 and table 2).

Ordering the right part for gas chromatographic systems now becomesmuch easier.

Consumables for GCNew website service www.shimadzu.eu/products/chromato/consumables/

P/N 221-34621SG Article Structure Description

Syringe

Sample

Needle

Needle length

Needle outer diameter

Point style needle tip

Additional remarks

Packing

0.5 μL microsyringe

Liquid injection

Removable needle

42 mm

23 gauge (0.63mm)

Conical (point style AS)

1 pcs

Table 2: Detailed article description

Table 1: Microsyringes for AOC-20i/s autoinjector/autosampler

Chemistry (G

NEWS 03.2010 GB - Shimadzu...Shimadzu’s EDX-720 X-ray fluo-rescence spectrometer, FP-meas-urements...

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