最新高分辨质谱技术及全二维色谱技术应用—李莉

Ultra-High Resolution
Mirr ors Lens es Mirr ors
High Resolution
Nominal
Focusing
More Focusing Still More Focusing
A D
R=100,000 40 meters
A D
R=50,000 m/z = 50 – 2500 20 meters
1.0e4
1.5e4
2.0e4
2.5e4
3.0e4
3.5e4
1.0e4
1.5e4
2.0e4
2.0e4
3.0e4
4.0e4
5.0e4
5.0e3 Caliper - sample "3001KS2011w40-012 Sample 3 B9", 0 s to 150 s
Caliper - sample "3001KS2011w40-011 Sample 2 B8", 0 s to 150 s 1.0e4
A D
R=2,500 m/z = 50-2500
Folded Flight Path of up to 40 m yields ultra-high resolution Vernchikov et.al. US Patent 7385187‫‏‬
Conventional short flight path LC-HRT Folded Filght Path 60000 50000 40000
32SH4
0.50
0.25 m/ z 0.00
248.1500 248.1520 248.1540
248.1380 248.1400 248.1420 248.1440 248.1460 248.1480
Sample dilution: 1 mg/mL in 66% Toluene, 33% MeOH, 1% (10 M NH3 in H2O) Infusion device: Advion Triversa Nanomate Negative ion nano ESI-MS Caliper - sample "3001KS2011w40-011 Sample 2 B8", 0 s to 150 s (Glass well plates)
Data Acquisition 200 sps Speed Ionization EI, CI
16
Analysis of Crude Oil Samples
• Introduction
Crude Oil Classification
• Experimental
Instrumentation Samples
325.18373 327.17100 328.18358 329.21600
325.18359 327.17135
326.16772 327.17119 328.18386 328.20729 329.21548
330
331.26440 333.27986
330
330
330.10570
331.26452 333.21016 333.93769 333.21056
CITIUS HRT
LECO Citius LC-HRT
12
Intensity(counts)
Intensity(counts)
Intensity(counts)
5.0e3
311.17045 311.94442 313.15622 314.16840 314.16820 313.15635 310.12054 311.17048 311.94446 313.15616
335
335
335.13975 336.12124
335.13958 336.12115
334.25357 335.13978 336.15230 337.31115
339.20050 340.18341 341.18692 342.19914 343.23115 344.09011
339.20039
1.‹#›
A revolution in TOF-MS
Mass Resolving Power
LECO Pegasus HRT
The Next Generation of TOF MS
Courtesy of Tony Bristow
8
8
Citius 分辨率性能
55000
High Resolution
2
OR The Next Step in the Evolution of TOF MS
??
Linear
Oa-TOF Reflectron
3
如何提高TOFMS的分辨率？
◎ 分辨率增加
×
仪器所占空间增大
MS
飞行管增长
4
LECO HRT Using FFP™
Folded Flight Path™ (FFP™) Technology in three modes of operation.
340 350 360
357.24686
340 345
340
340.18461 341.18693 342.19949 344.09004
341.18717
345
345.27959 347.29530 349.15534 350.13732
345.21016 346.25955 347.22589 349.15536
338.2800 338.2820 338.2840 338.2860 338.2880 338.2900
C19H30ON33.0 ppm
316.24259 C H ON S16 34 3
-0.7 ppm
1.00 13C3 0.75
32SH4
0.50
0.25
CITIUS HRT
0.00
2.0e2 0.0e0 M/Z
358.10572
358.10587360
Байду номын сангаас
13
Light Crude Analysis by Direct infusion
1.25
C18H18NC15H22NS-
Expected Profile at R = 82141.73889
Scaled 1st Derivative
1.00 13C3 0.75
Data Acquisition 200 sps Speed Ionization EI, CI
11
应用直接灌输nanoESI-MS负离子模式 分析轻质原油
Sample dilution:1 mg/mL in 66% Toluene, 33% MeOH, 1% (10 M NH3 in H2O)
Infusion device: Advion Triversa Nanomate Pressure: ESI potential: MS: 0.15 PSI -1.25 kV
15
LECO HRT Performance
Property Mass Accuracy Mass Range Resolving Power Detection Limit Linear Dynamic Range Target Pegasus GC-HRT Performance <1ppm 10-1500 m/z up to 50,000 1 pg OFN >4 orders Target Citius LC-HRT Performance <1ppm 50-2400 m/z up to 100,000 1 pg Reserpine >4 orders 200 sps ESI, APCI, nESI, DESI
最新高分辨质谱技术 及全二维色谱技术应用
李 莉
美资力可仪器（上海）有限公司
1
Brief History of LECO in TOFMS
Pegasus 4D GC-TOFMS
TruTOF HT GC-TOFMS
2001
PEGASUS® GC-HRT
2007
CITIUS® LC-HRT
2011
超高分辨率 超高分辨率
RFWHM
Allows ultra-fast capture of high resolution spectra
30000 20000
10000
0
0 500 1000 1500
m/ z
2000
2500
3000
5
LECO HRT的性能
高采集速率
超高分辨率
各项指标均衡，无妥协
性能稳定
谱图解卷积
6
9/7/2016
Ultra-High Resolution
110000
50000
105000
100000
R>95,000 at m/z = 500
Resolution (FWHM)
Resolution (FWHM)
45000
95000 90000 85000 80000
40000
Asymptotic Resolution of 45000 – 51000 (3 weeks)
0.0e0 M/ Z 4.0e4
0.0e0 M/ Z 2.5e4
311.17027
314.19151
317.17944
319.26413
320
321.12387 322.10533 323.29507
320 325
320 325
320.23807 321.27962 322.13642 323.29493
-0.25
316.235
316.24 316.243
316.248 316.25 316.253
14
Characterizing crude by heteroatom classes
O2 class 1.00
N orma lized Area
N class
0.80 0.60
0.40 0.20 0.00 1 2 Sample Number 3
R > 100000
> 70% Signal Recovery in HR vs UHR
CITIUS HRT
10
LECO HRT Performance
Property Mass Accuracy Mass Range Resolving Power Detection Limit Linear Dynamic Range Target Pegasus GC-HRT Performance <1ppm 10-1500 m/z up to 50,000 1 pg OFN >4 orders Target Citius LC-HRT Performance <1ppm 50-2400 m/z up to 100,000 1 pg Reserpine >4 orders 200 sps ESI, APCI, nESI, DESI
345.21031 347.22599 349.15567
350
350
350.13726
351.32732 353.20044 353.18710 354.19980 353.20035
355
355
355.20291
355.20265 356.21495 357.12396
355.20304
358.10570 359.29536 359.10918 359.29564
• • Results/Discussion Conclusion
7.0e6 6.0e6 5.0e6
4.0e6
3.0e6
2.0e6
1.0e6
0.0e0 T ime (s)
1000
1200
1400 T IC
1600
1800
17
Challenges of Petroleum Analysis
35000
30000 75000 25000 0 500 m/z 1000 1500 70000 150 250 350 m/z 450 550 650
CITIUS
9
Signal Retention in HR and UHR
Sulfadimethoxime @ 30 ng/ml (2.5 mcl inj) R > 45000
Caliper - sample "3001KS2011w40-009 Sample 1 B6", 0 s to 150 s
Negative ion ESI spectra of three crude samples
0.0e0 M/ Z 315 315
315.19999 316.08973 317.22555 319.24083 321.12373 322.13602 323.29481 317.24886 319.26405 315.19938 318.22253
316.24038
-0.25
1.2e3
Expected Profile at R = 85335.19536
Scaled 1st Derivative
Intensity(counts)
1.25
C24H36NC21H40NS1.0e3 8.0e2 6.0e2 4.0e2
m/ z
338.2920 338.2940