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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.
NEW NEW
NEW
LCMS-8080
LCMS-8040
GCMS-TQ8030
LCMS-8030
LCMS-2020
LCMS-IT-TOF
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)
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
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
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
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
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
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
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
Diazinon
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.
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-2020
LCMS-IT-TOF
GCMSTQ8030
GCMS-QP2010 Ultra
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)
Qualification
LCMS-2020
LCMS-IT-TOF
Soil
Water
Fo od s
Ingredient analysis
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
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
(1) Capillary
(2) (1)
(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
(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.
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.
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.
10
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 -
Software - GCMS -
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
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.
12
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.
Laboratory
Internet Explorer
System
Office
Internet Explorer Internet Explorer Internet Explorer
Application
13
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.
14
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.
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.
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
15
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
16
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 -
Handbook
Result after filtering with the retention index (retention index allowance: 10)
Searching both the MS spectrum and retention index enhances reliability of identification.
System
NIST Library
This library contains 243,893 spectra for 212,961 general compounds.
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.
17
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.
18
Polymers
This software is used to analyze not only homopolymers, but also complicated copolymer compounds as well.
Software - LCMS -
%Int. 100 90 80 70 60 40
4365.97 5382.30 6255.85
7271.93
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
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).
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
19
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.
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.
20
Software - LCMS -
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.
Application
21
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)
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
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
0
208/146 (povitive)
0 250 500 750 Conc.
N H
DiOxIAA-Glu
(337>146, positive)
ICA-Glc
(322>89, negative)
OxIAA-Glc
(352>190, negative)
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
MS spectrum
Mass Chromatogram and MS and MS/MS Spectra for Components that Varied
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
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
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
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
400
m/z
Mass 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
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
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
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
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 -
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 -
(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
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
0.25
2.5
75000
10 ppb
S/N 38 1 ppb
S/N 82 1 ppb
S/N 73 1 ppb
S/N 73 1 ppb
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
1 ppb
0.5
4MRM
4MRM 5 ppb
0.9
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
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
min
26
GCMS
Software - LCMS -
Software - GCMS -
Rtx-5MS
(x10,000,000) 2.0 TIC
Rtx-OPPesticides2
(x10,000,000) TIC 2.5
1.5
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 -
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.
27
Geniposidic acid/3.451
2000
1750
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
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
1.5 1.0
15.6 mg
2.0
11.0 mg
Nicotinic acid
1.0
Nicotinamide
1500000
Pantothenic acid
Cyanocobalamin
1000000
Cyanocobalamin
Area (x100,000)
Riboflavin Biotin
Riboflavin
Area (x10,000)
Nicotinamide
Area (x100,000)
4.0
500000
2.0 1.5
43.4 mg
Folic acid
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 and Quantitation Results for Commercial Supplement Extract Solution
28
LC M S - 2 0 2 0
Software - LCMS -
Inten.(x100,000)
Positive
Negative
A
384.20
200
300
400
m/z
200
300
400
m/z
217.15
1.0 0.0
200
300
400
m/z
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
K
384.10 475.10
200
200
300
400
m/z
226.80
128.15
2.0
172.80 199.80 259.75 449.95
N
369.95
100
200
100
200
300
400
m/z
Software - AXIMA -
System Application
29
Chemical
LC M S - 8 0 3 0 Mass Chromatogram of Plastic Plate Extract by Synchronized Survey Scan
(100,000,000)
4.0
Tinuvin P
3.0
Irganox 245
2.0
1.0
Cyanox 425
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.
Product Ion Scan (-) Inten.(x100,000) Inten.(x100,000) 41.5 585.3 2.0 1.0 1.0 82.9 3.0
585.4
2.0
1.0
OH
149.3
233.3
367.0
0.0
m/z
m/z
250
500
m/z
HPLC/UV
(x1,000,000,000)
B
Mass chromatogram
A C D E
Peaks A, B, C, and E were detected using ESI+ ionization, whereas Peak D was detected using ESI-.
30
GCMS
Software - LCMS -
Software - GCMS -
Software - AXIMA -
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
4.0 3.0
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
0.0
396.10>213.10 () Bensulide
Calibration Curves for Representative Golf Course Pesticides MRM Chromatogram of Golf Course Pesticides
1.00
1 6 3 2 7 15 4 5
0.75
10 9 8 11 13 12 14 16 17 18 19 20
0.50
0.25
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
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
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
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