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C146-E206

Shimadzus Solutions Provided by Mass Spectrometer

Mass Spectrometer General Product Catalog

Providing Excellence in Data Quality and Faster Speed, Shimadzu's Unique Technologies Achieve a New Global Standard in Mass Spectrometry

Shimadzu Corporation, a leader in the development of advanced technologies, introduces three new triple quadrupole mass spectrometers: LCMS-8040, LCMS-8080 and GCMS-TQ8030. The LCMS-8040 and LCMS-8080 expand the analytical range of Shimadzu's LC-MS/MS lineup while the GCMS-TQ8030 achieves the next progression in Shimadzu s GC-MS history of innovation. These are new addition to Ultra Fast Mass Spectrometry (UFMS) series, with further enhanced Shimadzu s proprietary high-speed Ultra Fast Technologies. The UFMS series not only provides higher sensitivity performance but also greater excellence in data quality, enabling dramatic improvements in analytical throughput and expanding the potential range of applications. Utilizing the same user-friendly interface as HPLC/UHPLC and GC/GCMS modules, LabSolutions workstation software provides intuitive functionality for more efficient data processing and an easier, more productive analytical workflow.

Shimadzu's UFMS Series

NEW NEW

NEW

LCMS-8080

LCMS-8040

GCMS-TQ8030

LCMS-8030

LCMS-2020

LCMS-IT-TOF

GCMS-QP2010 Ultra GCMS-QP2010 SE

High throughput Liquid Chromatograph Mass Spectrometer

LCMS-8080
LCMS-8080 triple quadrupole LC/MS/MS system that provides both best-in-class sensitivity and excellent quantitation performance. This excellent sensitivity is attained regardless of the situation, whether in drug development and manufacturing, clinical research, foodstuff and environmental analysis, or drug screening and excellent control and analysis software realizes a stress-free analysis environment.
80 Verapamil 0.5 pg/mL m/z 455.50 > 165.10 S/N 16

Lidocaine m/z 235.10 > 86.20 Carbamazepine m/z 237.10 > 194.00 300 Cilostazol m/z 370.10 > 288.00 5 pg/L

60 Intensity Intensity

200

40

20

100

0 0.00

0.25

0.50

min

1.00

1.25

1.50

min

MRM chromatogram of verapamil (0.5pg/mL) and lodocaine, carbamazepine and cllostazol (5pg/mL)

High throughput Liquid Chromatograph Mass Spectrometer

LCMS-8040
The LCMS-8040 is ultra fast and high sensitive triple quadrupole LC/MS/MS system, which is added on higher sensitivity performance to ultra fast performance of LCMS-8030. Improvement of sensitivity for ultra fast MRM and scan mode expands the potential range of LC/MS/MS applications.
10 ppb : Cloquintocet-mexyl 9.5X
100,000 1.50 1.25 1.00 0.75 0.75 0.50 0.50 0.25 0.00 18.0 19.0 min 0.25 0.50 1.00 ESI+ 336.20 > 238.00

10 ppb : Pyrazosulfuron-ethyl 7.4X


100 1.25 1.00 ESI+ 415.20 > 182.10 ESI 1.50

10 ppb : Linuron 5.2X


1,000 246.90 > 160.00

8040

8040

8040

8030
0.00 5.5 6.0

8030
0.00 6.5 7.0 min 14.0 14.5

8030

15.0

min

Comparison of simultaneous analysis results of three pesticide compounds by LCMS-8030 and LCMS-8040

Gas Chromatograph Mass Spectrometer

GCMS - TQ8030
Ultra Fast GC/MS/MS, GCMS-TQ8030, provides ease-of-use of GCMS and analysis accuracy of triple quadrupole mass spectrometer. Ultra fast scan/MRM simultaneous measurement, which is cultured by LCMS-8030, supports multi component simultaneous analysis for small amounts of molecules.

Black: Total ion chromatogram (m/z: 45 to 600) Blue: 275 > 241 Red: 275 > 111 Scan/MRM Analysis of Metabolites in Rat Urine

Mass Spectrometer Lineup


High throughput Liquid Chromatograph Mass Spectrometer

LCMS-8030
The LCMS-8030 is a next-generation ultra fast LC/MS/MS system applying to wide range of liquid chromatograph separation from HPLC to UHPLC systems. Ultrafast positive-negative ion switching and ultrafast scan speeds maximize analysis throughput.
x105

1.5

Intensity

1.0

0.5

0 0.25 0.5 0.75 1.00 1.25 1.5 1.75 min

Simultaneous MRM Positive-Negative chromatogram of 226 Pesticide Components (10 ng/mL)

High throughput Liquid Chromatograph Mass Spectrometer

LCMS-2020
The LCMS-2020 is a ultra fast liquid chromatograph mass spectrometer designed for ease of use as an HPLC detector. It is a suitable quadrupole mass spectrometer, which provides high cost performance, for the routine analysis work in your laboratory.
2500000 2250000 2000000 1750000 1500000 1250000 1000000 750000 500000 250000 0 TIC 212.00 256.00 300.00 344.00 388.00 432.00 476.00 520.00 564.00 608.00 652.00 696.00 740.00 784.00 828.00

0.0

0.5

1.0

1.5

2.0

2.5

min

Mass Chromatogram of Polyethylene Glycol 400

High throughput Liquid Chromatograph Mass Spectrometer

LCMS - IT - TOF
LCMS-IT-TOF systems are hybrid high performance liquid chromatograph mass spectrometer systems that include an integrated ion trap (IT) mass spectrometer and time-of-flight (TOF) mass spectrometer. Therefore, they provide both the MSn capability of IT, plus the high-resolution and high-accuracy mass analysis capability of TOF.
Sildenafil C22H30N5O4S Theoretical value: 475.2122

Mass Spectra of Sildenafil

Gas Chromatograph Mass Spectrometer

GCMS-QP2010
The GCMS-QP2010 Ultra features a newly designed data processing platform that achieves maximum scan speeds, 20,000 /sec, which is twice as fast as previous models. It also features an advanced scanning speed protocol (ASSPTM), which is patented technology that minimizes decrease of sensitivity higher scan speed than 10,000 /sec. ASSPTM realizes higher sensitivity at high scan speed.
Black: 1,111 /sec Red: 5,000 /sec Blue: 10,000 /sec

Previous method Propyzamide

Diazinon

Patented method (ASSP)

EI mass spectrum of prednisolone

Matrix Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer

Series
The AXIMA series includes four MALDI-TOF MS models, ranging from a linearonly model to a system equipped with an ion trap. A key feature of MALDI-TOF MS systems is their ability to acquire mass spectra directly from solid samples, such as tissue specimens and microorganisms.

Mass Spectrum of Bacillus Subtilis

Application Guide
Mass spectrometers are extremely good at obtaining molecular information, such as molecular weight and structural information. Consequently, they are mainly used for quantitative analysis and structural analysis, but the range of applications is expanding. Since current all mass spectrometers have many specific characteristics, it is difficult to decide which type of mass spectrometer is optimal for a particular application based on any simple criteria. This means the system must be selected based on user objectives, such as whether high sensitivity is required, high resolution is required, or a compact general-purpose system is required. Representative applications for each type of mass spectrometer are indicated below. Use this chart to help choose the best mass spectrometer for your analytical sample.

In s trument N a m e

LCMS-8080 LCMS-8040 LCMS-8030

LCMS-2020

LCMS-IT-TOF

GCMSTQ8030

GCMS-QP2010 Ultra

AXIMA Resonance AXIMA Performance

AXIMA Confidence AXIMA Assurance

EI , CI, NCI ESI N a noE S I Io nization M etho d AP CI AP P I DUIS M AL DI Qua dr upole Mass Spectrometer Ion Tr a p T OF MS MS MS / M S
(PSD only)

(Resonance only)

MSn Qualification and quantitation Qualification and quantitation Qualification and structural analysis Qualification and quantitation Qualification and quantitation

(Resonance only)

M ain Ap plica t ions

Qualification and structural analysis

Qualification

LCMS-8080 LCMS-8040 LCMS-8030 Environmental Atmosphere


Benzene, trichloroethylene, tetrachloroethylene, dichloromethane, etc.

LCMS-2020

LCMS-IT-TOF

GCMS-TQ8030 GCMS-QP2010 AXIMA Series Ultra

Soil

Trichloroethylene, tetrachloroethylene, dichloromethane, etc.

Water

Pesticides, PFOS/PFOA, algae bloom toxin, shellfish toxin, etc.

Fo od s

Ingredient analysis

Amino acids, sugars, catechins, vitamins, etc.

Additives Residual Pesticide

Colorings, antibacterial agents, etc. Insecticides, disinfectants, herbicides, etc.

Toxins Lifescience/ Pharmaceuticals Genomics Proteomics Metabolomics

Mycotoxins, etc. DNA, RNA Proteins, peptides Organic acids, amino acids, lipids, etc.

Synthetic compound

Low-molecular-weight compounds, antibiotics, antibacterial agents, natural medicines, steroids, etc. Pharmaceutical impurities, etc. Candidate compounds, etc. Metabolites, etc. Candidate compounds, etc. Residual solvents, etc. Surfactants, antioxidants, fullerenes, etc. Polymers, rubber, plastics, etc. Plasticizers, etc. Organic impurities, etc. Pharmaceuticals for treatment, etc. Hormones, etc. Acutely toxic substances, etc. Organic low-molecular-weight molecules, peptides, etc. Steroids, etc. Abused substances, etc.

impurities HTS Pharmacokinetics toxicity test Drug product Chemistry low-molecular-weight organic molecules Polymer composition analysis Additives Impurities Clinical Research Monitoring pharmaceuticals Endocrinology research Toxicology Biomarker discovery Fo re ns ics Doping testing Identification of target substances

* Primary structural analysis, excluding calculations of average molecular weight, degree of polymerization, and degree of dispersion

Mass spectrometers must first ionize sample molecules.


Many type of ionization have been developed. Electron ionization (EI) ionizes samples using accelerated thermal electrons, 70 eV. EI is generally used for samples, whose molecular weight is less than 1000. It is typically used in combination with a gas chromatograph to analyze highly volatile molecules or gases. Electrospray ionization (ESI) ionizes samples in solution by spraying them. It is mainly used in combination with liquid chromatographs. Matrix Assisted Laser Desorption/Ionization (MALDI) desorbs sample molecules by laser energy and ionizes those by transferring charge from matrix ions. MALDI can apply wide range of samples by changing matrix reagents, hence, this ionization method apply to synthetic polymer and complicated samples.

High Polarity

LCMS

Middle Polarity

GCMS S
Low Polarity 100 1000 5000 10000 Molecular Weight

MALDI
100000

ESI (El ec tr o s p r a y I o n i z a t i on )
A sample solution is introduced to capillary applying high electric voltage and sprayed at the edge of capillary. Droplets of sample solutions are charged and sample molecules are ionized in liquid phase. ESI is best suited to ionizing medium-to-high polarity substances, peptides, proteins, and oligonucleotides.

ESI

From column ESI probe

(1) Capillary
(2) (1)

(2) Nebulizer gas (3) Dry gas (4) DL (desolvation line)

(3)

(4)

DUI S (ESI + A P C I )
The DUIS-2020 is a dual ion source that ionizes samples using both ESI and APCI (atmospheric pressure chemical ionization) modes. This is best suited to ionizing low-to-medium polarity substances.

DUIS

From column ESI probe

(1) Nebulizer gas


(1)

(2) Corona needle (3) Dry gas (4) DL (desolvation line)

(2) (3)

(4)

M AL DI (M at r i x A s s i s t e d L a s e r Des or pt i o n / I o n i z a t i o n )
After applying the sample and matrices solution on a sample target and dry up, laser irradiates to sample spot. The sample and matrix molecules are desorbed and ionized, rapidly. MALDI enables to ionize high molecular weight compounds, such as proteins and polymers without dissociation.

: Sample molecules : Matrix : Positive ions : Negative Ions


Laser Vacuum

Sample Sample target Sample target

Generated ions are separated and detected based on differences in their mass-to-charge ratio ( m/z value).

Quadr upo l e M o d e l s
Quadrupole mass spectrometers use a set of four parallel electrode rods to form an electric field. This electric field is used to separate ions passing through the space formed by four rods based on their m/z value. Triple quadrupole mass spectrometers use three sets of quadrupoles configured in series to quantitatively analyze target molecules in highly contaminated samples, such as pesticides in foods, with extremely high sensitivity levels.

Ion Source

Quadrupole

Detector

T i m e-of -F l i g h t ( T O F ) Mo d e ls
The velocity of ions, which is accelerated by a fixed electric voltage, is depending on their m/z value. The velocity of lower m/z ion becomes faster. Time-of-flight mass spectrometer calculates m/z value from the ion velocity, i.e., time of flight of each ion, which takes to travel a fixed distance.

Ion source

Detector

H ybr i d M o d e l s
Hybrid mass spectrometers are a combination of an ion trap mass spectrometer and a time-of-flight mass spectrometer. An ion trap consists of two end cap and one single ring electrodes. An electric field formed by single ring electrode can trap ions in the space. A key feature of ion trap is high sensitive analysis and MSn analysis. Time-of-flight mass spectrometer can determine m/z values with high accuracy.

Detector Ion Trap Dual Stage Reflectron

Software LCMS-8030/8040

LabSolutions LCMS
LabSolutions LCMS software offers high functionality, yet is easy to operate.

M et hod Op t i m i z a t i o n
In MRM analysis, setting the MRM parameters, such as the m/z values for precursor ions (Q1) and product ions (Q3) and collision energy (CE) voltage, is extremely important. LabSolutions LCMS sets these parameters automatically. This optimization process enables analyzing target compounds with high sensitivity. The method optimization window is shown to the right. In addition to optimizing MRM parameters, the function enables product ion searches as well. Default settings can generally be used for electric voltage optimization and automatic product m/z selection settings, but it is also possible to change detailed settings, such as the number of selected product ions and the CE step size.

Parameters optimized for high-sensitivity detection of target components

Easily check optimization results on the window

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LC/ M S/ M S M e t h o d P a c k a ge
Shimadzu offers method packages that include method files with pre-registered MRM parameters optimized for quantitative and reference ions, LC separation parameters, retention times for each compound, peak identification parameters, and report templates for outputting quantitation results. If retention times are adjusted when the system is installed, based on the HPLC configuration delivered, the routine analysis work can be started as soon as the specified columns, mobile phases, and standard samples are supplied. Used in combination with the quantitation browser, method packages provide an ideal environment for confirming the separation and shape of chromatogram peaks for multiple components in simultaneous multi-component analysis. Since chromatogram and calibration curve displays are linked to component names, clicking on a component name automatically changes the displayed information accordingly, which allows correcting peak processing parameters and correcting calibration curves directly.

Software - LCMS -

Residual Pesticide LC/MS/MS Method Package

Veterinary Drug LC/MS/MS Method Package

Software - GCMS -

Water Quality Analysis LC/MS/MS Method Package

Drugs of Abuse LC/MS/MS Method Package

Software - AXIMA -

Quan Sol u t i o n
Quan Solution is Open access software for LC/MS/MS. By following the instruction on the screen, quantitative analysis of certain compound by certain methods can be performed simply from the start of data sampling to reports on quantitative results. Combining the Nexera MP system provide the ideal way to share a single LC/MS/MS system between multiple analysts just by registering the user names and e-mail address. Furthermore, if various UHPLC separation conditions are incorporates, a variety of types of rapid quantitative analyses can be performed with a single system. As same as Open solution, a series of analysis can starts by setting following three steps, Log in (step 1), sample registration and vial setting (step 2) and click start button (step 3). Administrator can change the analysis sequence. It is easy to apportion system usage so that large quantity analyses are performed when the system is free overnight, and small quantity analyses are performed during the daytime. Labor time and effort can be reduced by combining 4 LC/MS/MS package, preset analysis conditions and compound data. Sample registration by setting the standard samples, unknown samples, and QC samples at the specified positions.

System Application
11

Software LCMS-2020

LabSolutions LCMS LabSolut


LabSolutions LCMS is workstation software used for LCMS system control and data processing. LabSolutions LCMS is operated in the same manner as LCsolution, GCsolution, and GCMSsolution, which means even an inexperienced operator can do everything from making instrument tuning to setting analytical conditions, viewing or analyzing data, and preparing reports easily. The mass spectrometer can be operated in the same manner as absorption or fluorescence detectors.

Dat a Br ow s e r
The data browser allows detecting peaks, analyzing multiple sets of data, and comparing chromatograms and spectra, all on a single screen. The extensive and intuitive user interface supports the postrun analysis of the huge amount of data generated. It also allows displaying MS, PDA, and LC chromatograms tiled sideby-side or overlaid. The highly flexible report formatting function allows creating focused reports tailored to analytical operations, such as chromatograms, calibration curves, quantitative results, and summary reports.

Q uant i t ati o n B r o w s e r
The quantitation browser has four views; a [Quantitative Results View] for displaying the quantitative calculation results for each set of data, a [Method View] for displaying parameters in method files, a [Chromatogram View] for displaying chromatograms and sample information, and a [Calibration Curve/Spectrum View] for displaying the calibration curves and spectra for compounds. By editing a single method file, the data processing parameters in that method can be used to perform quantitative calculations on multiple sets of data. Quantitative calculation results for up to 1,024 data files acquired using the same method file can be collectively checked.

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Open Sol u t i o n
Open Solution is open access software for LCMS-2020 systems. It allows using Internet Explorer to confirm analytical results or output reports from any computer on the network. Open Solution provides a simple user interface that does not require detailed knowledge about analytical operations. Start analyses in only three steps. Simply log into Open Solution (Step 1), specify the minimum required settings, such as registering samples and specifying the analytical method, and place the vial in the specified position (Step 2). Then click the start button (Step 3). Data can be viewed and analytical instrument status monitored from a separate office. When an analysis is finished, an email is automatically sent to pre-registered email addresses. This email includes a web address for viewing the data, where analytical results can be easily confirmed and printed.

Software - LCMS Software - GCMS Software - AXIMA -

Laboratory

Open Solution (Web server) Internet Explorer LCMSsolution

Internet Explorer

System

Office
Internet Explorer Internet Explorer Internet Explorer

Application
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Software LCMS-IT-TOF

LCMSsolution L
L LCMSsolution is workstation software used for LCMS-IT-TOF system c control and data processing. B Because it is designed on the basis of sample concept of the works stations for other chromatograph products, it can be operated in the s same manner as LC, GC and GCMS. Furthermore, it ensures users c can use its functionality efficiently, such as auto-tuning the entire s system and automatic MS/MS functionality, even on more complicated hybrid MS/MS systems.

Dat a Ac qu i s i t i o n
LCMSsolution not only allows tuning instrument parameters, but it also enables easily setting mode-specific analytical conditions for a wide variety of measurement modes. An assistant bar ensures that even inexperienced users can navigate settings and operations to perform analyses easily. Parameters for the Mass Spectrometer can be specified in manual, auto, or direct event event. Parameters for the liquid chromatograph can be specified in a simple or detailed mode. These allow using a wide range of analytical conditions.

Dat a Pr oc e s s i n g
Data processing function analyzes the high-throughput and high-accuracy data obtained from the LCMS-IT-TOF system with minimal stress to the operation and quickly provides the necessary information. The data browser feature allows loading and viewing up to 64 sets of data at the same time. Files can be managed using intuitive operations. The quantitation browser enables simultaneously processing quantitation results from multiple sets of data acquired using the same method. A wide selection of identification and quantitative processing functions help to shorten the time for data analysis operations.

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For m ul a P r e d i c t o r
Formula Predictor is software used to predict the chemical composition formula of target peak. It uses a proprietary method to efficiently narrow down the number of candidates.

Me tID S o lu tio n
This software compares data from samples before and after they are metabolized to search for expected and unknown metabolites.

Software - LCMS Software - GCMS -

P r ot ei n A n a l y s i s S o f t w a r e
This software automates operations ranging from sample analysis to protein identification.

Op e n S o lu tio n C o mp o n e n tID
This is open-access software for LCMS-IT-TOF systems. Because this software can be operated without any special detailed knowledge, it eliminates the need for a specialized operator and provides an environment where anyone can perform analyses easily.

Software - AXIMA System

P r of i l i ng S o l u t i o n V e r . 1 . 1
This data viewer enables processing multiple files at the same time. It can be used to correct retention times and normalize mass accuracy and signal intensity. It also allows exporting data for use in commercial multivariate analysis software.

Application
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Software GCMS

GCMSsolution
GCMSsolution is workstation software for the GCMS-QP2010 series and GCMS-TQ8030. It uses One-Window technology to display information in a layout optimized to accurately and quickly acquire data and perform qualitative and quantitative analyses.

GCM S Ana l y s i s P r o g r a m
This is used to specify GCMS system configuration, MS tuning parameters, analytical conditions, and batch processing parameters for continuous analyses. It also displays a window for monitoring the system status, allowing continuously monitoring the status of both the GC and MS units. The display of usage count for consumables allows viewing estimated maintenance periods at a glance.

F l exi bl e R e p o r t C r e a t i o n Fu n ctio n
Report formats can be edited easily by put a given size of desired report elements at a target location and within a blank report window. A variety of elements are available for including in reports, such as chromatograms, spectral search results, and quantitation results.

Preview

Print

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GC/MS Method Package Ver. 2 for Compound Composer Database Residual Pesticides in Foods Software for Simultaneous Analysis
This package contains method files for quantitative analysis of 542 pesticides. These methods include analytical parameters optimized for residual pesticides in food. It also attach a glass insert suited to pesticide analysis and specifies which columns to use, which eliminates any doubt about setting analytical conditions or selecting parts. This database includes information registered for 942 environmental pollutant compounds. This enables identifying and estimating the concentration of environmental pollutants, residual pesticides, and other substances without using standard samples.
Masses, calibration curves, Database spectra Retention times (target compounds n-alkane) n-alkane analysis data Compound Composer

Software - LCMS -

Masses, calibration curves, spectra Predicted retention times (target compounds) GCMSsolution method

Software - GCMS -

Flavor & Fragrance Natural & Synthetic GC/MS Metabolite Component Database Compounds GCMS library Ver. 2 (FFNSC 2) (amino acids, fatty acids, and organic acids)
MS spectra, retention indexes, CAS number, compound name, molecular formula of 3,000 flavor and fragrance compounds are included. By utilizing both MS spectrum and retention index, high accurate identification results can be provided.
The measured spectrum (retention index 1090) and the spectra of compounds with a high score running a library search
Measured mass spectrum

This database includes retention indices and mass spectra for 311 metabolites (amino acids, fatty acids, and organic acids). It also includes method files with optimized sample and data analysis settings, reducing the effort required for determining analytical conditions and postrun analyses.
Index
Compound

Software - AXIMA -

Simple library search results

Handbook

Candidate 1 (Similarity : 95)

Candidate 2 (Similarity : 95)

Result after filtering with the retention index (retention index allowance: 10)

Searching both the MS spectrum and retention index enhances reliability of identification.

System

GC/MS Forensic Toxicological Database


This database includes 1,011 mass spectra for 502 components including their free bases and TMS and TFA derivatives, that are necessary for forensic analysis, such as drugs of abuse, psychotropic drugs, general drugs, and pesticides. For components often linked to poisoning, quantitative values can be estimated without using standard samples.

Oth e r Lib ra rie s


Pesticide Library Ver. 3 for Foods
Mass spectra for 578 pesticides measured using electron ionization (EI) and 383 pesticides measured using negative chemical ionization (NCI).

NIST Library
This library contains 243,893 spectra for 212,961 general compounds.

Wiley Library (9th edition)

Application

This library contains about 662,000 spectra for about 592,000 general compounds.

Drug Library
This library contains spectra for 7,840 compounds including drugs, toxins, pesticides, and environmental pollutants. It includes information on.

VOC Analysis Software


This software includes a library for 74 volatile organic compounds.

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Software AXIMA

LAUNCHPAD TM
LAUNCHPADTM is workstation software for controlling and processing data from MALDI-TOF MS (AXIMA series) systems.

Dat a Ac qu i s i t i o n
This software is intuitive and easy to understand, with features such as a CCD window for monitoring the laser light irradiation status and a window that indicates the instrument status. This makes the MALDI-TOF MS system easy to use, even for firsttime users. An Autoquality function enables automatically optimizing parameters during measurements to keep the quality of mass spectra data acquired by automatic measurements.

Dat a Anal y s i s
The peak processing function can select the several type of settings window from a drop-down list, ranging from a simple settings window to a detailed settings window, based on the user experience level. Seamless integration with many optional software programs ensures smooth data analysis. Measurement data can be exported in a variety of formats to allow further analysis using third-party software. Batch processing is also possible. Protein identification optional software can perform from MALDIMS to MS/MS analysis, Mascot search, automatically.

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Polymers
This software is used to analyze not only homopolymers, but also complicated copolymer compounds as well.

Software for Microorganism Identification System


This software identifies microorganisms based by peak pattern matching.

Software - LCMS -

%Int. 100 90 80 70 60 40
4365.97 5382.30 6255.85

7271.93

Escherichia coli NBRC 3972

7333.07 7707.16

8325.38

50 30 20 10 0

9064.89

11183.73

13001.25

9738.82

10298.41

10692.83

4000

6000
6601.17

8000

10000

Bacillus subtilis NBRC 3134


13670.54

12000

14000

%Int. 100 90 80 60 50
4522.16

5819.04

70

5257.39

10007.47

10379.52

7994.51

20 10 0

m/z

12907.95

30

5464.66

11636.03

13878.63

7429.52

40

9210.48

11144.40

13803.27

Software - GCMS -

L C-M AL DI
This software uses automatically analyze sample fractions spots on a MALDI sample plate, which are separated by HPLC and loaded by spotting system (AccuSpot).

S o ftwa re fo r Accu ra te Gly ca n An a ly ze r 2


This software is used to identify the structure of glycans. Used in combination with an AXIMA Resonance system, it allows identifying glycan structures with high precision.

Software - AXIMA System

M AL DI M S I m a g i n g S o f t wa re
This software is used for MS imaging. It is especially useful for measuring the distribution of new drugs and metabolite products on tissue specimens.

Application
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Systems
GCMS H e a d s p a c e A n a ly sis S y stem
Headspace analysis systems are used for qualitative and quantitative analysis of substances such as flavorings in foods, odors in chemical products, volatile organic compounds (VOCs) in public drinking water, environmental water, or waste water, and residual solvents in pharmaceuticals.

Purge & Trap Analys is Sys tem


Purge and trap analysis systems are used to perform highly sensitive measurements of VOCs or moldy odor-causing substances in public drinking water, rivers, groundwater, and so on.

P y ro l y s i s S y stem
This system thermally decomposes polymer materials, such as plastics, rubbers and resins, over 500 C and analyzes the resulting pyrolysates with GC/MS. It is used for structural analysis of polymer compounds, such as plastics and rubbers.

Thermal Des orption Sys tem


This system prepares samples for introduction into a GS-MS system by using thermal desorption to decompose volatile organic compounds collected in a tube filled with adsorbent material. Samples can also be placed directly in the tube and heated to analyze the evolved gases.

LCMS L C M S - 2 0 2 0 P rep ara tiv e S y stem


This high-throughput preparative purification system is made possible by combining LCMSsolution with an instrument control solution capable of controlling the Gilson 215 Liquid Handler and IFC PAL liquid handler from CTC Analytics.

2-Dimensional LC/LCMS-IT-TOF System


Co-Sense impurities LCMS-IT-TOF is an LC-MS system with column-switching technology that is designed specifically for analyzing impurities. Existing HPLC methods, such as those using phosphate buffer solutions or ion pair reagents, are used for the fist dimension to identify peaks required for structural analysis. A mobile phase suited to LC-MS is used to separate components in the second dimension before introduction to the LC-MS system.

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Software - LCMS -

Solid Phase Microextraction (SPME) System


Solid phase microextraction (SPME) enables the analysis of organic substances with high sensitivity by first concentrating organic substances in a water or gas phase onto SPME fibers, then desorbing the substances in the GC injection unit. Using an AOC-5000 Plus autosampler enables automating the entire process and ensuring good reproducibility.

GC GC- M S Sys tem


This system separates components using two columns with different polarity. Unlike multi-dimensional analysis, this system provides comprehensive 2-dimensional separation across the entire chromatogram by repeatedly injecting samples into the second column in an extremely short time.

Software - GCMS -

D i re c t S a mp le In jectio n Sy stem
Direct sample injection is a method of bypassing the gas chromatograph (GC) and injecting samples directly into the ion source. This is especially suited to analyzing non-volatile compounds or thermally unstable compounds, which are difficult to analyze in a GC unit.

Multifunctional Sample Injection System


The OPTIC-4 is a GC injection port that enables using various GC/MS sample injection modes, such as high volume injection, injection port derivativization, thermal desorption, or DMI (difficult matrix introduction). Used in combination with an AOC-5000 Plus autosampler, inserts can be replaced automatically to increase productivity during multianalyte analysis.

Software - AXIMA System

AXIMA S E C - M A L D I (LC -MA LD I) Sy stem


The SEC-MALDI system first separates samples into their components by size exclusion chromatography (SEC), then measures the components using MALDI-TOF MS. This is especially useful for analyzing mixtures containing multiple components, such as synthetic polymers.

CHIP-1000/MALDI Imaging System


The CHIP-1000/MALDI imaging system is new technology that uses MALDI-TOF mass spectrometry to directly measure biological molecules and metabolites on tissue specimens, without sample extraction or labeling. The system displays the 2-dimensional distribution of the targeted biological molecules, based on their positional information and the signal intensities of detected ions.

Application
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Applications
LC M S - 8 0 4 0/80 3 0 Qu a n ti ta tiv e a n d Qu alita tiv e Analys is of Plant Hormone M etabolit es
LC/MS/MS systems are an essential tool for quantitative and qualitative analysis of bioactive substances, which only exist in small amounts in organisms. An example of using LC/MS/MS to analyze metabolites of the plant hormone indole-3-acetic acid (IAA) is shown. All 7 types of IAA metabolites can be detected by MRM measurement from 1 nM, which allowed creating a calibration curve from 1 to 1000 nM. In addition, all seven metabolite types were detected in a measurement of a rice root sample doped 10 M IAA.
H N O N H COOH COOH N H O N H O N H O HO COOH COOH O HO H N COOH COOH

Area (10,000,000)

4.0

3.0

1:IAA-Asp 2:OxlAA (x60) 3:DiOxlAA (x35) 4:DiOxIAA-Asp (x4) 5:DiOxIAA-Glu (x30) 6:ICA-Glc (x130) 7:OxlAA-Glc (x3600)

Compound IAA-Asp OxIAA DiOxIAA

Conc. (nmol/L) 781 5.31 17.1 156 11.9 16.4 1.60

2.0

DiOxIAA-Asp DiOxIAA-Glu

1.0

ICA-Glc OxIAA-Glc
2.0 3.0 4.0 5.0 6.0 7.0 8.0 min

0 1.0

MRM Chromatogram of Metabolites in Rice Root Sample Doped 10 M IAA


Area(100,000)

Concentration of Metabolites in Rice Root Sample Doped 10 M IAA

322/89 (Negative)

1.0

IAA-Asp
(291>130, positive)

OxIAA
(192>146, positive)

DiOxIAA
(208>146, positive)

DiOxIAA-Asp
(323>146, positive)

0.5

MRM Chromatogram of ICA-Glc


HO O O COOH N H H N COOH O O OH HO O HO OH N H O HO O O HO O HO OH OH

0
208/146 (povitive)
0 250 500 750 Conc.

N H

Calibration Curve of ICA-Glc

DiOxIAA-Glu
(337>146, positive)

ICA-Glc
(322>89, negative)

OxIAA-Glc
(352>190, negative)

MRM Chromatogram of DiOxIAA

Structural Formula of 7 Types of IAA Metabolites

LC M S - I T- T OF B i o m a rk e r D isco v e ry U sin g LCM S- IT- TOF


Low-molecular-weight compounds in biological organisms, such as endogenous metabolites in blood and tissue, are remarkable as biomarker candidates. An example of using LCMS-IT-TOF to discover biomarkers in blood plasma from a type II diabetes model rat (Zucker rat) is shown below. After pretreatment, samples were analyzed u s i n g L C M S - I T- T O F. T h e n t h e d i ff e re n c e s between the groups of normal and type II diabetes model rats were detected by primary component analysis using multivariate analysis software.

Ty p e I I d i a b e t e s m o d e l r a t

Normal rat

Metabolite Array
Mass chromatogram

Primary Component Analysis Results

(Type II diabetes model rat)

MS spectrum

MS2 spectrum Precursor ion

Mass Chromatogram and MS and MS/MS Spectra for Components that Varied

Formula Prediction Example

22

GCMS Analysis of Amino, Organic, and Fatty Acids Using GC/MS Metabolite Component Database
GC-MS systems are often used in metabolomic and biochemical diagnostic research fields to measure amino acids, organic acids, or fatty acids in urine or blood. Shimadzu worked jointly with the Shimane University Faculty of Medicine to develop a GC/MS Metabolite Component Database, containing information on over 300 types of metabolites and other substances (amino acids, organic acids, and fatty acids). The figures below show results from using this database to analyze fats and fatty acids in human blood serum and show results from simultaneous analysis of organic acid, amino acid, saccharide, and other metabolites in canine cerebral fluid, conducted jointly with Osaka Prefecture University Graduate School of Life and Environmental Sciences associate professor Shigeo Takenaka.
(x1,000,000) TIC 5.0 12 4.5 4.0 39 3.5 3.0 2930 31 2.5 22 9 8 14 2.0 1.5 1.0 1011 6 0.5 1 2 3 4 15.0 20.0 5 16 3.0 2.5 2.0 3637 1 1.5 1.0 7 1 7 9 0.5 45.0 12 45 94 1 8 0 1 8 1 1 8 3

Software - LCMS -

13

17 19

21

34

1 4 3 1 8 4 1 8 5 1 8 6 1 8 7 47

40

4.0 3.5

1 8 8

(x10,000,000) TIC 4

21

31

Software - GCMS -

26 29

38

23 24 26 2725 28

33

44

1 4 7

20

38 40 50 56 58 60 59 63 70 68 76 80 86 87

1 1 4 6 1 1 81 2 2

1 8 2

15

1 6 4

1 0 9

20

25.0

30.0

35.0

40.0

10.0

15

15.0

20.0

25.0

30.0

1 3 5 1 3 8

32

35

35.0

40.0

Total Ion Current Chromatogram (TIC) of Methyl Fatty Acids in Blood Serum

Total Ion Current Chromatogram (TIC) of TMSs in Canine Cerebral Fluid

1 7 5 45.0

18

Software - AXIMA -

Component numbers correspond to serial numbers in the GC/MS Metabolite Component Database.

A XI M A Identification of Glycan Structures Using the Accurate Glycan Analyzer and AXIMA Resonance
Since many proteins are modified by glycans, the glycans to which they are bonded can have a significant influence on protein function. The structure of multiple branched molecules, such as glycans, cannot be determined from simple mass spectra, but using MSn analysis allows identifying different structures of even glycans with identical masses. In this case, by following software instructions up to MS3 analysis, the system was able to distinguish between the structures of two types of pyridylamino derivatives of N-glycans with identical masses (m/z 1725) that differed only in the position of glucose bonds on non-reducing terminals.
MS/MS
1707.62 1280.45

System

%Int.

Fraction 2)
%Int. 100 80 1725.63

100

915.30 712.22 0 1077.32 1342.49

1570.91 1725.71

60 40 20 0

300

500

700

900 m/z

1100

1300

1500

1700

%Int. 100

MS3

915.31

712.19

1077.36 1280.45

1690

1700

1710

1720

1730 m/z

1740

1750

1760

1770

1780
0 300

388.10 509.12 500 700 m/z 900 1100

1300

%Int.

MS/MS
1707.62 1280.42

Fraction 4)
%Int. 100 80 1725.63

100

915.29

Application

712.20 0

1077.33 1725.64

60 40 20 0

200

400

600

800 m/z

1000

1200

1400

1600

%Int. 100

MS3
712.21

915.30

1077.34

1690

1700

1710

1720

1730 m/z

1740

1750

1760

1770

1780
0 200

388.08

550.14 128042 600 800 1000 1200

400

m/z

Mass Spectra

MS/MS and MS3 Spectra

Search Results Based on MS3 Spectra

23

Application
LCMS-8080 LCMS-8080 CYP cocktail assay: Reagents
This assay is standard method for checking toxicity and safety of drug candidates. P450 enzymes metabolizes toxin. The inhibition of drug candidates is investigated by mixing substrates, P450 and drug and react enzyme. The mixture of 5 substrates were metabolized in human liver microsome (=P450 enzyme) and then metabolites were quantified by LCMS-8080. All five metabolites were successfully quantified even though their actual concentration ranging from 0.9 to 900nM. The results with polarity switching experiment did not pale against the results with dedicated polarity. The 20 msec polarity switching capability helps researchers need to grab the ultra high sensitivity and data quality.
Substrates Resorun ethyl ether Bufuralol hydrochloride (S)-Mephenytoin Nifedipine Tolbutamide
Resorufin (+) 214.0>186.0 1-Hydroxy bufuralol (+) 278.2>186.0

Metabolites/Products Resorun 1 -Hydroxy bufuralol (+/-)-4 -Hydroxy mephenytoin Oxidized nifedipine Hydroxy tolbutamide

P450 Enzyme CYP 1A2 CYP 2D6 CYP 2C19 CYP 3A4 CYP 2C9

LOD / nM 0.01 0.21 0.37 0.002 0.003

LOQ / nM 0.6 0.6 0.6 0.6 0.6


Hydroxy tolbutamide (-) 285.0>186.0

(+/-)-4-Hydorxy mephenytoin (+) 235.0>150.2

Oxidized nifedipine (+) 345.0>284.0

L C M S - I T- T O F 2-Dimensional LC/LCMS-IT-TOF System Capable of Using Mobile Phase Conditions Not Suited to MS analysis
Two-dimensional LC/LCMS-IT-TOF systems can use unmodified HPLC purity test conditions. The first dimension separates impurities into fractions in the fraction loop, then the fractioned impurities are injected into the second dimension LCMS system. The UV chromatogram in Fig. 1 was created by using a 2-dimensional LC/LCMS-IT-TOF system to measure atorvastatin hydrates, which were added to the Japanese Pharmacopoeia 16th revision. Nineteen impurity peaks were detected in measurements, with 10 impurities having an area that is 0.1 % or more of primary components.
mAU (x10) 254nm,4nm (1.00) 1.5 1.0 0.5 0.0 0 10 20 30 40 50 60 70 min

Conc. 0.013%

Impurity 2

Impurity 2

Fig. 1 First Dimension HPLC UV Chromatogram (254 nm)

uV (x100) 6.0 5.0 4.0 3.0

Sample

Of the 19 impurities, impurity 2 has the smallest area value. This area was only 0.013 % the area of primary components. A UV chromatogram, mass chromatogram, and mass spectra of impurity 2 measured using a 2-dimensional LC/LCMS-IT-TOF system is shown to the left.
min

Fig. 2 shows an overlay of UV chromatograms from the 2-dimensional LC/LCMS-IT-TOF system. The impurities can be identified by comparing peaks to blank sample results. The mass spectra in Fig. 3 Fig. 2 Second Dimension HPLC UV Chromatogram (254 nm) were integrated for the elution range for impurity 2.
Blank
4.25 4.50 4.75 5.00 5.25 5.50

Inten. (x1,000,000)

Inten. (x1,000,000)

557.2470
2.0

573.2400

MS1 spectrum negative

2.0

597.2381
1.0

MS spectrum positive

1.0

613.2161
0.0 500 550 600 650 m/z 0.0 500 550 600 650 m/z

Fig. 3 Mass Spectra of Impurity 2

A molecular mass of 573 is observed in the ESI- spectrum. This presumably corresponds to impurity 2, which has a molecular weight of 574. The 597 value in the ESI+ spectrum is a Na adduct ion. Even though the impurity concentration was a trace 0.013 %, a mass spectrum with good sensitivity was obtained.

24

GCMS
Software - LCMS -

Analysis of Potential Genotoxic Impurities in Active Pharmaceutical Ingredients Using GCMS


During the process of synthesizing active pharmaceutical ingredients, methanesulfonic acid (mesylate), benzenesufonic acid (besylate), and p -toluenesulfonic acid (tosylate) can generate sulfonic acid esters as a reaction by-product. These compounds are known to be potential genotoxic impurities (PGIs), which is a major concern to pharmaceutical manufacturers. Results from analyzing sulfonic acid ester PGIs are shown below.

(x1,000,000) TIC 4.0 5 3.0 2.0 1.0 2 6 7 8 9

10 11

12

Software - GCMS -

4
3

Ester methanesulfonate

2.5

5.0

7.5

10.0

12.5

ID 1 2 3 4 5 6

Compound name Retention time 3.047 Methyl methanesulfonate 3.864 Ethyl methanesulfonate Isopropyl methanesulfonate 4.268 n-propyl methanesulfonate 4.985 8.677 Methyl benzenesulfonate Ethyl benzenesulfonate 9.278

ID 7 8 9 10 11 12

Compound name Retention time 9.801 Methyl p-toluensulfonate 10.345 Ethyl p-toluensulfonate Isopropyl p-toluensulfonate 10.536 10.885 Butyl benzenesulfonate n-propyl p-toluensulfonate 11.071 11.828 Butyl p-toluensulfonate

R: alkane

Ester benzenesulfonate

Ester p -toluensulfonate

Software - AXIMA -

Total Ion Current Chromatogram Structural Formula of Sulfonic Acid Esters

M A L D I - T O F MS Pharmacokinetic Applications (mass imaging of brain tissue sections)


MALDI-TOF MS imaging is a revolutionary new technology that provides images showing the distribution of molecules in biological tissue, based on the signal intensities and masses of ions detected with a mass spectrometer. Therefore, it is possible to investigate the presence and localization of drugs administered to animals, or their metabolic products, in tissue sections. It is expected to apply drug delivery and pharmacokinetics research. An ion at m/z 327, which corresponds to the mass of clozapine, is detected of mass spectra on brain tissue section. The ion was confirmed to be clozapine from MS/MS analysis results. A mass image of the detected clozapine (figure (c) on the left) shows that clozapine is detected in a variety of locations throughout the brain tissue section, but it is strongly detected especially in the cerebral cortex. In contrast, the distribution of demethylated clozapine differs from clozapine (figure (d) on the left).
Ion intensity scale:

(a) Diagram of Dissected Rat Brain Tissue 1 2 9 8 12 3 4 5 10 6 7

(b) Rat Brain Tissue Section (optical microscope image with H&E staining)

System

11
1 2 3 4 5 6

Cerebral cortex 7 Olfactory bulb Cerebellum 8 Pons Midbrain 9 Medulla oblongata Fornix 10 Hypothalamus Thalamus 11 Spinal cord Septum 12 Pituitary gland

(c) Mass Image of Clozapine (m/z 327)

(d) Mass Image of Demethylated Clozapine (m/z 313)

Application
25

Food Safety
L C M S - 8 0 4 0 / G C MS-TQ8 0 3 0 Multi-class pesticides analysis in vegetable using ultra fast LC/MS/MS and GC/MS/MS
Many regulatory authorities have established multi-class residual pesticides methods for the analysis of vegetables, fruits and other food stus. There is, however no global agreement on the provision of a target list of pesticides and this presents a risk with products moving between dierent regulatory requirements. In order to eliminate this risk, food safety laboratories need to ideally screen as many compounds as possible in a single run which may reach maximum residual limits (MRL); typically 10 ppb in food matrices. In this study, we report the application of ultra-fast 5 msec MRM with 15 msec polarity switching for the analysis of 138 pesticides in vegetable matrices (72 and 66 compounds measured by LC-QqQ and GC-QqQ in the European Union Reference Laboratory (EURL) method). Approximately 90% of pesticides represented good recoveries in the range of 70-120% in all studied matrices.
Compounds for LC-QqQ
Azoxystrobin Areax10,000,000 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 0 2.00 1.75 1.50 1.25 1.00 0.75 0.50 0.25 0.00 6.0 7.0 0.0 5.0 6.0 500 x100,000 Conc. 2.5 5.0 0.50 7.5 0.75 5.0 Carbofuran Areax10,000,000 1.00 Ethion Areax100,000,000

Compounds for GC-QqQ


Methidathion Areax10,000,000 7.5

5 ppb standards spiked Matrix blank


150000 20000 17500 125000 15000 100000 60000 200000 50000 40000 30000 20000 50000 2500 0 10000 0 3.5 4.0 4.5 0 150000 100000 80000 70000 300000 250000

1-1000 ppb r2=0.9999


0.0

1-1000 ppb r2=0.9992


0 500 x100,000 2.0 Conc.

0.25

2.5

12500 10000 7500

1-1000 ppb r2=0.9999


0.00 0 2.00 500 Conc. x100,000 0.0 0 500 x100,000

1-1000 ppb r2=0.9996


Conc.

75000

50000 5000 25000

10 ppb

S/N 38 1 ppb

S/N 82 1 ppb

1.75 1.50 1.25

S/N 73 1 ppb

1.75 1.50 1.25 1.00 0.75 0.50 0.25 0.00

S/N 73 1 ppb

0 6.0 6.5 7.0

1.5

3.5

4.0

4.5

6.5

7.0

7.5

5 ppb
1.0

Azoxystrobin

Imidacloprid

Clothianidin

Fludioxonil

1.00 0.75

Azoxystrobin 5 ppb standards spiked Matrix blank MRL Japan


6.0 7.0

Imidacloprid 8.99 ppb 3.19 ppb 3 ppm

Clothianidin 25.78 ppb 21.39 ppb 15 ppm

Fludioxonil 556.58 ppb 550.92 ppb 10 ppm

1 ppb

0.5

0.50 0.25 0.00 9.0 10.0

8.19 ppb 3.77 ppb 5 ppm

4MRM

4MRM 5 ppb

LC M S - 8 0 3 0 A n a l y s i s of Vete rin ary D ru g s Us ing M ethod Pac kages


As concern grows for food safety and the ecology, the number of substances regulated to protect our lifestyles continues to increase. Consequently, there is now an increased needs for an easier inspection method and faster multiple components simultaneous analysis. Therefore, more LC/MS/MS systems are being utilized in recent years, due to sample pretreatment requirements that can be made shorter than using GC/MS systems. Using an LC/MS/MS Method Package allows starting quantitative analysis quickly by simply confirming separation parameters, without having to optimize MS parameters for each compound required before starting LC/MS/MS analysis. Each type of method package includes simultaneous analysis method files, a list of MRM transitions, and report templates. Measurement methods can be completed by simply selecting text files for necessary components from the list of MRM transitions and correcting retention times by analyzing a standard sample.
1.0 (1,000,000)
HPLC

0.9

Column Mobile Phase A

Shim-pack HR-ODS (3.0 mmI.D. x 150 mmL., 3 m) 0.1% Formic acid - water Acetonitrile 1 %B (0 min) - 100 %B (35-40 min) - 1 %B (40.01 - 50 min) 0.4 mL / min 40C

0.8

Mobile Phase B Gradient Program

0.7

Flow Rate Column Temperature

0.6

0.5

0.4

Method Package (LC Parameters) for Veterinary Drugs

0.3

0.2

0.1

0.0

Method Package (MS Parameters) for Veterinary Drugs

5.0

10.0

15.0

20.0

25.0

30.0

35.0

min

MRM Chromatograms of Veterinary Drugs

26

GCMS
Software - LCMS -

Analysis of Residual Pesticides in Food Using Twin Line-GC/MS


By using a twin line system, two columns can be installed in a GC-MS. Switching between the columns is accomplished simply by changing settings. To analyze pesticides in foods, two columns with different types of solid phases were installed using the twin lines. By comparing the results obtained from each column, reliability can be increased for both quantitative and qualitative analysis. In particular, if a pesticide overlaps with an impurity, in some cases the second column enables separation with a different type of solid phase. Therefore, comparing data from two columns makes data analysis easier and improves reliability.

Software - GCMS -

Rtx-5MS
(x10,000,000) 2.0 TIC

Rtx-OPPesticides2
(x10,000,000) TIC 2.5

1.5

2.0 1.5 1.0

1.0

0.5 0.5

5.0

7.5

10.0

12.5

15.0

17.5

20.0

22.5

25.0

27.5

5.0

7.5

10.0

12.5

15.0

17.5

20.0

22.5

25.0

27.5

Total Ion Chromatograms Using Columns with Different Types of Solid Phase (1 g/mL of 97 types of pesticides)

Software - AXIMA -

A XI M A The fastest and easiest microorganism identification by MALDI-TOFMS


When MALDI-MS spectra are measured directly on microorganism like bacteria, mainly several dozens of ribosome proteins are detected. MS spectrum pattern is dependent on microorganism species, because the amino acid sequence of ribosome protein is different each species. By storing those MS spectra in database just for MALDI-TOFMS and identification, three steps microorganism ID are enabled without complicated sample preparation. High throughput analysis, a thousand sample run per day, is capable1). By compiling many data, which are acquired with varying strains and culture conditions, as a mass spectrum of a species in database, incorrect rate can be reduced and microorganism ID can be stable. Figure 2 shows identification results of Trichophyton rubrum isolates.
1) Time for measurement and identification is dependent on measurement parameters and sample condition.

System Application

1.Sample preparation
Bacterial cells spotted on MALDI sample plate and mixed with matrix reagent

2.Mass analysis
MS fingerprints of bacterial samples are automatically acquired using MALDI-TOF MS

3.Matching fingerprint
Matching fingerprints of the samples to database Upper: MS spectrum of Trychophyton rubrum in Database Middle and Lower: Mass spectrum of two clinical isolates . Both isolates were identified as Trichophyton rubrum.

Schematic Overview of Identification of Microorganisms Using MALDI-TOF MS

Identification of unknown samples: matching mass fingerprints to database

27

Food ingredients alalysis


L C M S - 8 0 4 0 / LC MS -80 3 0 A n a l y s i s of G en ip o sid ic A cid and Chlorogenic Ac id in Toc hu Tea
Tochu tea, made from the leaves of tochu (Eucommia ulmoides), is one of the five most popular Chinese herbal medicines. Tochu tea is rich in the iridoids geniposidic acid and chlorogenic acid (3-caffeoylquinic acid), and the antihypertensive effects of geniposidic acid is well known. LC/MS has been employed in recent years to analyze the polyphenols in these plant extracts. MRM chromatograms of geniposidic acid and chlorogenic acid in the 1,000 to 1 diluted tochu tea is shown (Fig. 1). Analysis was accomplished without significant interference from impurity components. The 1,000 to 1 dilution of tochu tea contained approximately 600 to 700 ppb geniposidic acid and chlorogenic acid.

Geniposidic acid/3.451

2000

1750

27500 25000 22500 20000 17500

1500

1250

1000

15000 12500

750 10000 500 7500 5000 250 2500 0 2.0 3.0 4.0 min 0 6.0 7.0 8.0 9.0 min

MRM Chromatograms of Geniposidic Acid (A) and Chlorogenic Acid (B) in Tochu Tea

LC M S - 8 0 4 0 / LC MS-80 3 0 A n a l y s i s of Wate r S o lu b le V itamins


On August 24, 2007, the U.S. Food and Drug Administration (FDA) published cGMP (Current Good Manufacturing Practice) in Manufacturing, Packaging, Labeling, or Holding Operations for Dietary Supplements, 21 CFR (Code of Federal Regulations) Part 111. This regulation mandates testing the ingredients in supplements. The following shows an example of using LC/MS/MS to quantitatively analyze water soluble vitamins in a commercial dietary supplement. Nine water soluble vitamins were measured with good separation and sensitivity. In addition, each ingredient was successfully quantitated in a supplement extract solution without being affected by contaminant components. Quantitation results are shown below.
Thiamin
1:265.10>122.10(+)(0.80) 2:170.10>152.20(+)(0.50) 3:124.20>80.0(+)(5.00) 4:123.10>80.0(+)(0.60) 5:220.10>90.00(+)(1.60) 6:678.55>146.80(+)(9.00) 7:377.20>242.80(+)(10.00) 8:245.10>227.10(+)(0.80) 9:440.20>295.10(+)(10.00)

Chlorogenic acid/7.622

373.00>123.30(-)

30000

353.00>191.20(-)

Thiamin
Area (x100,000)

Pyridoxine
Area (x1,000,000)

Thiamin
Area (x100,000)

Pyridoxine
Area (x100,000)

Pyridoxine
2000000

7.5 5.0

0.5500 ng/mL R 2 = 0.9999

1.00 0.75 0.50

1500 ng/mL R 2 = 0.9993

1.5 1.0

15.6 mg

2.0

11.0 mg

Nicotinic acid

1.0
Nicotinamide
1500000

2.5 0.25 0.0 0.00 0 250 Conc. 0 250 Conc.

0.5 0 1.50 2.00 2.50 min 0 2.50 3.00 3.50 min

Pantothenic acid

Cyanocobalamin
1000000

Cyanocobalamin
Area (x100,000)
Riboflavin Biotin

Riboflavin
Area (x10,000)

Nicotinamide
Area (x100,000)

4.0
500000

5010,000 ng/mL R 2 = 0.9992

2.0 1.5

101,000 ng/mL R 2 = 0.9999

4.0 3.0 2.0

43.4 mg

Folic acid

3.0 2.0 1.0

1.0 0.5 0.0 0 5000 Conc. 0 500 Conc.


1.0 0

0.0
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 min

Compound Quantitation Results (for about 10 tablets) Thiamin 15.6 mg Pyridoxine 11.0 mg Nicotinic acid 0 mg Nicotinamide 43.4 mg Pantothenic acid 20.6 mg Cyanocobalamin 23.3 g Riboflavin 6 mg Biotin 35.6 g Folic acid 218.4 g
min

4.00

5.00

MRM Chromatograms of Water Soluble Vitamins

Calibration Curves of Water Soluble Vitamins

MRM Chromatograms and Quantitation Results for Commercial Supplement Extract Solution

28

LC M S - 2 0 2 0
Software - LCMS -

C o mp o n e n tial A n a ly sis U sin g DART- M S of Ultra- Fas t Polarity Switc h in g


DART (Direct Analysis in Real Time) is the atmospheric pressure ionization method, which is easy and useful for analyzing the molecules in food without pretreatment. DART ionizes multicomponent in a moment and LCMS-2020/8030/8040 ultrafast polarity switching and ultra fast scanning function allows multicomponent direct analysis in food. This data is the analysis results of soy-source and fish source in different producing district and raw material, and this shows the difference of spectra pattern owing to amino acid balance in each raw material.
Inten.(x100,000) 2.0 115.75 1.0
69.85 230.80 146.75 198.75

Inten.(x100,000)

Positive

3.0 2.0 1.0 0.0

217.10 187.10 128.15 189.10 51.25 238.10 289.10 164.05 117.15

Negative
A
384.20

0.0 100 Inten.(x100,000) 1.0 0.5


69.75 115.75 226.80 146.80 196.80

200

300

400

m/z

100 Inten.(x100,000) 2.0

200

300

400

m/z

217.15

1.0 0.0

128.15 51.55 146.15 117.10

202.15 236.10 384.20

0.0 100 Inten.(x100,000) 1.0


111.75 88.80 226.80 196.85 240.85

200

300

400

m/z

100 Inten.(x100,000) 3.0 2.0 1.0 0.0


51.95128.15

200

300

400

m/z

217.10

0.5 71.85 0.0 100 Inten.(x100,000) 3.0 115.75 2.0 1.0 0.0
69.80 137.80

C
202.20 480.15 418.10

Software - GCMS -

200

300

400

m/z

100 Inten.(x100,000)

200

300

400

m/z

187.10

2.5
228.80 252.80

0.0 300 400 m/z

217.10 128.10 189.10 117.10164.10 51.30 238.15 89.15

K
384.10 475.10

100 Inten.(x100,000) 1.5 1.0 0.5 0.0


83.80 113.75 59.85

200

100 Inten.(x100,000) 3.0

200

300

400

m/z

226.80

128.15

2.0
172.80 199.80 259.75 449.95

1.0 0.0 m/z 300 400

164.10 117.15 51.40 166.10 89.15 209.10 257.15

N
369.95

100

200

100

200

300

400

m/z

Analysis results of several kinds of soy-source and fish source by DART-MS

Software - AXIMA -

DART-SVP ion source and LCMS-2020

DART is a product of IonSense Inc. (http://www.ionsense.com/).

GCMS A n a l y s i s of D ie sel Fu e l U sin g GCGC- M S


GCGC is state-of-the-art chromatography technology that involves directly connecting two different columns together to achieve high separation levels. GC Image was used to create two-dimensional results from analyzing diesel fuel using a GCGC-MS system, as shown to the left. A column with high polarity was used for the second column, which enabled separating aromatic hydrocarbons, which tend to overlap with paraffins. These can be detected as a blob distribution pattern that reflects the compound structure.

System Application

2-Dimensional Image of GCGC-MS Analysis Results for Diesel Fuel

29

Chemical
LC M S - 8 0 3 0 Mass Chromatogram of Plastic Plate Extract by Synchronized Survey Scan
(100,000,000)

4.0

Q3 Scan TIC(+) Q3 Scan TIC(-)

Tinuvin P

3.0

Irganox 245

2.0

1.0

Cyanox 425

0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 min

Analyzing the additives in polymer materials is extremely important for investigating the performance of different polymer materials and for making product improvements. An example of measuring a plastic plate extract using the ultrafast polarity switching, ultrafast scanning performance, and Synchronized Survey Scan function offered on the LCMS-8030 is shown. Based on the detected masses and MS/MS spectra, it was determined that the plastic plate contains Irganox 245, Tinuvin P, and Cyanox 425. These results also suggest it contains other additives as well.

Mass Chromatogram of Plastic Plate Extract by Synchronized Survey Scan


Q3 Scan (-) Inten.(x1,000,000)
O O HO O O O O

Product Ion Scan (-) Inten.(x100,000) Inten.(x100,000) 41.5 585.3 2.0 1.0 1.0 82.9 3.0

Product Ion Scan (-)

585.4

2.0

1.0

Irganox 245 MW 586.7 250

OH

0.5 234.6 367.0 0.0 250 500

149.3

233.3

367.0

717.3 0.0 500

0.0

m/z

m/z

250

500

m/z

Mass Spectra of Peaks at an Elution Time of 2.82 Minutes

L C M S - I T- T O F Analysis of Additives in Polymer Extract Solution Using LCMS-IT-TOF


It is known that the additives added to polymer materials can vary even for identical types of products, depending on the grade or manufacturer. Therefore, identifying the additives in polymer materials provides important information for investigating the performance of competitor products or improving one's own products. Based on the formula (C28H52N2O4) predicted for peak A using Formula Predictor and accurate masses obtained from MS, MS/MS, and MS/MS/MS analysis, peak A presumably corresponds to decanedoic acid bis (2,2,6,6-tetramethyl-4-piperidyl) ester.
Detector A

HPLC/UV

(x1,000,000,000)
B

Mass chromatogram

A C D E

UV Chromatogram and Mass Chromatogram

Peaks A, B, C, and E were detected using ESI+ ionization, whereas Peak D was detected using ESI-.

30

GCMS
Software - LCMS -

A n a l y s i s of D iesel Fu e l U sin g GCGC- M S


GCGC is state-of-the-art chromatography technology that involves directly connecting two different types of columns together to achieve high separation levels. GC Image was used to create two-dimensional results from analyzing diesel fuel using a GCGC-MS system, as shown to the left. A high polarity capillary column was used for the second column separated aromatic hydrocarbons, which tend to overlap with paraffins. These can be detected as a blob distribution pattern that reflects the compound structure.

Software - GCMS -

2-Dimensional Image of GCGC-MS Analysis Results for Diesel Fuel

Software - AXIMA -

A XI M A Analysis of Polyethylene Terephthalate (PET) Oligomer Using SEC-MALDI


Recycled PET (cleaning utensil)

Elution Time

Legend : -(m/n)-; linear oligomers (m/n); cyclic oligomers m; Number of terephthalic acid (TA) units n; Number of ethylene glycol (EG) units

Soxhlet extraction or precipitation methods are used to pretreat samples for oligomer analysis, and HPLC, NMR, or MALDI-TOF MS (particularly more recently) systems are used for detection. However, polymer materials are, by definition, a mixture of multiple components, which means small amounts of components cannot be detected by simply analyzing the extract with mass spectrometry. Using this system, which combines size exclusion chromatography (SEC) with MALDI-TOF MS, enables detailed oligomer analysis. An example of using this system to analyze a recycled PET product is shown. Compared to oligomers in standard PET polymers, a relatively broader distribution of molecular weights was obtained and more linear type oligomers were detected from the recycled item.

System Application
31

Environmental
L C M S - I T- T O F Screening Analysis of Golf Course Pesticides
(1,000,000) 17.0 16.0 15.0 14.0 13.0 12.0 11.0
292.00>211.10 (+) Thiamethoxam

The LCMS-8030 was used to simultaneously analyze 21 of the pesticide components subject to evaluation by LC/MS, as specified in the Provisional Guidance Indicators for the Prevention of Water Pollution from Pesticides Used in Golf Courses, published by Japan's Ministry of the Environment on September 29, 2010. Good linearity was obtained for all the components in the range of 0.5 to 100 g/L.

10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0

223.05>126.05 (+) Acetamiprid 435.05>182.00 (+) Harosulfuron-methyl 399.10>261.00 (+) Ethoxysulfuron 202.10>124.15 (+) Simazine 422.05>261.05 (+) Cyclosulfamuron 280.00>220.15 (+) Metalaxyl 404.10>372.05 (+) Azoxystrobin 270.05>119.10 (+) Mepronil 303.05>185.15 (+) Cumyluron 308.10>70.05 (+) 342.00>69.10 (+) Tebuconazole Propiconazole

Area (x1,000,000)
Acetamiprid

Area (x1,000,000)

3.0

0.5-100 g/L R2=0.9998

4.0 3.0

Isoxathion 0.5-100 g/L R2=0.9998

305.05>169.15 (+) Diazinon 333.05>180.15 (+) Butamifos 314.00>105.05 (+) Isoxathion 329.05>125.10 (+) Pencycuron 346.05>278.15 (+) Triflumizole 376.05>190.20 (+) Oxaziclomefone 331.05>181.15 (+) Pyributicarb 254.10>228.05 () Propyzamide
0.0 2.5 5.0 7.5 10.0 12.5 15.0 min

2.0 2.0 1.0 1.0 0.0 0 50 Conc. 0 50 Conc.

0.0

396.10>213.10 () Bensulide

Calibration Curves for Representative Golf Course Pesticides MRM Chromatogram of Golf Course Pesticides

LC M S - 8 0 3 0 Analysis of Carbamate Pesticides Using Prominence UFLC and LCMS-2020


If multiple components need to be analyzed simultaneously, it may be difficult to achieve full separation using HPLC alone. The high selectivity offered by mass spectrometers is especially useful in such cases. The figure below shows an example of results from analyzing carbamate pesticides. Even at low 500 ppb concentrations, the mass spectrometer provided more than adequate detection sensitivity. Furthermore, high throughput can be achieved for processing multiple analytes by combining it with a UFLC system.
(x10,000,000) TIC

1.00

207.00(60.47) 240.00(8.47) 237.00(14.56) 163.00(16.38)

1 6 3 2 7 15 4 5

0.75

242.00(8.49) 220.00(50.06) 239.00(1.20) 258.00(67.41)

10 9 8 11 13 12 14 16 17 18 19 20

0.50

222.00(3.94) 224.00(9.71) 208.00(6.66) 226.00(7.43)

0.25

202.00(27.56) 355.00(5.65) 180.00(9.38) 194.00(5.73)

0.00

411.00

1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 min

1: Aldicarb sulfoxide 2: Aldicarb sulfone 3: Oxamyl 4: Methomyl 5: Methiocarb sulfoxide 6: 3-OH Carbofuran 7: Methiocarb sulfone 8: Aldicarb 9: Bendiocarb 10: Carbofuran 11: Carbaryl 12: Thiodicarb 13: Ethiofencarb 14: XMC 15: Pirimicarb 16: Isoprocarb 17: Trimethacarb 18: Fenobcarb 19: Methiocarb 20: Benfuracarb

32

GCMS-TQ8030
Software - LCMS -

The Screening Analysis of PCBs in transformer oil by Using Neutral Loss Scan of GC/MS/MS
Neutral loss scan selectively detects precursor ions with a specific neutral loss and used for the screening analysis compound family, which includes common partial molecular structure or residues. For example, neutral loss scans at m/z 35 and 37 are representative of compounds containing chlorine. PCBs were spiked to transformer oil and PCBs screening analysis were performed by neutral loss scans of chlorine.

Software - GCMS -

Measured spectrum

Library spectrum

Chromatogram of Transformer Oil Spiked with PCBs


Black: Scan mode Red: Neutral loss scan mode

Scan measurement and similarity search of peaks detected by neutral loss scan

Software - AXIMA -

ASMS Measurement of Contaminants in River Water Using Compound Composer Database Software for Simultaneous Analysis
Environmental analysis involves monitoring target compounds, but it is also important to verify the presence and approximate concentration of non-target hazardous substances. Therefore, it is important to perform a simple and rapid screening process to analyze as many applicable chemical substances as possible. Compound Composer Database Software for Simultaneous Analysis provides an easy way to screen for hazardous chemicals without the use of standard samples. Measuring contaminants in river water, it enabled detecting low concentrations of pharmaceuticals and personal care products (PPCPs), such as crotamiton and L-menthol, which have gained attention in recent years, bisphenol A, nicotine, and caffeine.
Quantitation graph ID#:2 m/z:213.00 Type: Target Compound name: 2;3;0;Bisphenol A Retention time:26.332 Area:7943 Similarity:84 Concentration:0.0723ug Spectral graph #2 Retention time: 26.3 (Scan #: 4667) Number of peaks:265 Spectrum average:26.3-26.3(4666-4668) Background: Group 1 - Event 1 calculated from peaks

System

Spectrum of unknown components

Application

Registered spectrum

Results from River Water Analysis Bisphenol A was detected automatically and a semi-quantitative result was obtained without using a standard sample.

33

Mass Spectrometer General Product Catalog

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