shuang wang weimin wang keyong hou haiyang li* presentations/li h.pdf · tatp hmtd easy to...

Shuang Wang Weimin Wang Keyong Hou Haiyang Li*

Key Laboratory of Separation for Analytical Chemistry

Dalian Institute of Chemical Physics(DICP)

Chinese Academy of Sciences(CAS)

Oxnard , September 18-21, 2017

Make Monitoring Easy

Why to couple ion mobility and ion trap mass spectrometer

Hardware development of a hybrid IMS and MS

VUV lamp based ionization source

Sampling inlets

Hardware developments

Preliminary application

Detection of TATP and HMTD in complex matrix

On-site analysis of seized illicit drugs

On-line detection accident leak of harmful solvents

Summary and outlook


15 September 2017

London Underground explosion at Green tube station


TATP HMTD

Easy to synthesis from readily starting materials

Sensitive to heat, shock and friction

7 July 2005 London bombings

2015·11·13 Paris Terrorist Attack

2016 Brussels bombings

2017 Catalonia attacks

On-site screening explosives is highly demanded


China

High humidity in a very dirty

environment

High speed screening of

drugs for suspect materials.


Rapid

High sensitivity (especially after event analysis)

Identification of molecular species

Quantitative measurement

Portable

Low power

Easy and simple to use

etc.,

Field deployable

Mass spectrometer & ion mobility spectrometer


Vd = K E

HV

1/2

0

3 2 (1 )( )

16D

KN k

ze

T

tdrift =L

KE


Isomer ions may have different K0 due to the

differences of collision cross section ΩD

Compare to m/z, K0 is not a constant actually, which

is depend on temperature(T), pressure(P) and the

electric field strength (E), more importantly, K0 may

vary with the humidity of the drift gas.

( )( ) ( ) (( )

)1 1

2

e eff

2

ff D

ze3 2π +M 1+m

N

αK =

ΩMT T16 k m


Fast, up to 100 spectra/s

High sampling volume of gas (3-6 mL/s),

very sensitive for vapor sample

High usage and high transmission of ions

Working at ambient pressure

Cheap to manufacture

Easy to integrate

Light weight, less than 1 Kg


Peak Capacity of IMS is limited, and it is difficult to

change the composition of drift and carrier gas to

increase the peak capacity on-site.

The resolving power of IMS is not very high.

R = t/dt = 80 ~100

The reduced mobility K0 is weakly dependent on the

mass/charge of ions, and the differences of reactant ion

and product are small, 2- 0.5 cm-2 Vs -1

K0 ≈ a(m/z)-1/3+b


Dopant-assisted APPI

Mass range: 50~450 Da

Sensitivity: 500 pg for

Methylamphetamine

Resolution: 1.3 Da (at m/z=370)

Dynamic range: 103

Analysis time : < 10 s

Weight : 16 Kg


进样出气口

离子门

尾吹气

微电流引出

VUV-灯VUV-lamp

IMS ITMS

K0 m/z

Concentration profilesat sub-second resolution

MS/MS


Actone

Analyte

VUV Lamb

PTFE Swab

Heating plate

Dry air + actone (g) + sample molecules (g)

Dry air

DA

PI

A/D

IMS

ITMS

Vacuum pump

Drift gas (Dry air)

Off-gases

electron

multiplier

Dry air + actone (g)Dry air

Ion mobility spectrum, K0

Mass spectrum and MS/MS spectrum

high resolution temporal concentration profile


Analyte

VUV Lamb

PTFE Swab

Heating plate


Dry air

DA

PI

Off-gases

Ion gate

air + analytes (g)

Pump

Electrode slice

Direct gas sample inlet by internal pump

Thermal desorption inlet for solid and liquid samples

Thermal desorption


进样出气口

离子门

尾吹气

微电流引出

VUV-灯VUV-lamp


VUV Kr Lamp


3

2

2

2

2 2

3 3

2 2 2 2

3 2 3 2

2 2 3 3 2 1 2 2

hv e

et al

hv

e

e

2 m

2 2

2 n 2

-

- -

- -

- -n

- -n

-

-3

-n n-

3 2 2

Dopant

O O O

O O O

O M O M M N , O , H O, .)

O M O M

O nH O M O H O M

O nH O M O H O M

O H O O O H O O H O

O (H O) CO H O OCO (H O)

(

( )

( )

( ) ( )

(n m)


Change the gas flow direction

Adding O3 by another VUV lamp


IMS

DAPI

ITMS


DAPI

RF Amplitude

AC Amplitude

Detector

Sampling Cooling Scan Zero

Next cycle

20ms

200ms

180ms

20ms

One cycle

One cycle

20ms

Ion gate

Next n cycle

on

off

4000V

0V

0V

10V

on

off

on

off


0 10 20 30 40 50 600

500

1000

1500

2000

Mass spectrometry injecion

Inte

rsit

y o

f R

IP

Time/s


0 5 10 15 20

0

100

200

300

400

500

5.88

6.40

Inte

nsit

y

Drift time / ms

50 100 150 200 2500

300

600

900

1200

1500

95

175

147

73

Inte

nsit

y

m/z

Methyl tert-butyl ether


MS/MS of MTBE

50 100 150 200 2500

200

400

600

800Inte

nsit

y

m/z

50 100 150 200 2500

150

300

450

600

89

175

175175

50 100 150 200 2500

100

200

300

400

7759

9189

115

Inte

nsit

ym/z

50 100 150 200 2500

150

300

450

600

147

147147

73：[MTBE-CH3]+；

89：[MTBE+H]+；147：[2(MTBE-CH3)+H]+

175：[2MTBE-H]+

115：[2MTBE-CH3-CH3OH]+；58：[MTBE-OCH3+H]+；


100 150 200 250 300 350 400 450

0

200

400

600

800

1000

1200

342

Inte

nsit

y

M/Z

JWH-018

Acetyl codeine

0 5 10 15 200

20

40

60

80

1005.24

7.92

8.72Inte

nsit

y

Drift time / ms

JWH-018

Acetyl codeine

9.20

JWH-018 C24H23NO 341.45

Acetyl

codeineC24H23NO 341.40

10


340 360 380 400

0.0

0.2

0.4

0.6

0.8

1.0 Heroin

Gauss fitting

rela

tive in

ten

sit

y

m/z

370

FWHM=1.4

Ionization source: SPI, positive

and negative Dopant-APPI

Sample inlets: direct vapor inlet,

thermal-desorption for liquid and

solid

IMS:

Resolving power 20-30

Sensitivity: 0.2ppb/mV

Drift tube temp. 100 0C

ITMS:

Mass range: 50~450 Da

Resolution: 1.4 Da at m/z=370

Dynamic range: 103

0 5 10 15 20

0

200

400

600

800

1000

Inte

nsit

y

Drift time / ms

5.24


0 200 400 600 800 1000 1200

0

200

400

600

800

1000

1200

Inte

nsit

y

Time / s

134 136 138 140 142

0

200

400

600

800

1000

1200

Inte

nsit

y

Time / s

5-10Hz real time concentration

data for continuous

measurements mounted on a

high-speed vehicle


Dopant Toluene Acetone 2-Butanone 2-Pentanone

K0 RIP 2.07 1.84 1.66 1.50

K0 TATP 2.15 2.05 2.05 2.05

K0 HMTD 1.55 1.53 1.53 1.53

ΔK0TATP-RIP 0.08 0.21 0.39 0.55

ΔK0RIP- HMTD 0.52 0.31 0.13 0.03


CH3COCH3 + hν → CH3COCH3 + + e

CH3COCH3 + + CH3COCH3 → CH3COCH3 H

+ + CH3COCH3 •

CH3COCH3 H+ + CH3COCH3 → (CH3COCH3)2H

+

H3C

H3CO

O

O

H3C CH3

OO H

O CH3

CH3

m/z 91+

CH3COCH3m/z 149

Reaction Mechanism: reactant ion

(CH3COCH3)2H+ + TATP → [TATP+H]+ + 2CH3COCH3

(CH3COCH3)2H+ + HMTD → [HMTD+H]+ + 2CH3COCH3

Proton Transfer Reaction：

HMTD[TATP+H]+


100 200 300 400 5000

200

400

600

800

340286

312 370

Inte

nsit

y

m/z

414

0 2 4 6 8 10 12 14

0

80

160

240

320

400

9.408.16

6.566.08

Inte

nsit

y

Drift time / ms

5.12

Morphine m/z 286, paramorphine m/z 312, papaverine m/z 340,

heroin m/z 370, narcotine m/z 414


9

Hybrid improves quantitative measurements

0 5 10 15 20 25 30 35

0

20

40

60

80

100

Inte

nsit

y

Thermal desorption time / s

Narcotine

0 5 10 15 20 25 30 350

80

160

240

320

400

Inte

nsit

y

Thermal desorption time / s

Ketamine

Thermal desorption profiles of narcotine and ketamine

stand-alone Hybrid0

500

1000

1500

2000

Inte

ns

ity

of

mo

lec

ula

r io

n

Narcotine

RSD=16%

RSD=23%

stand-alone Hybrid0

500

1000

1500

2000

2500

RSD=13%

RSD=30%

Inte

ns

ity

of

mo

lec

ula

r io

n

Ketamine


VUV Lamb


DA

PI

A/D

IMS

ITMS

Vacuum pump

Drift gas (Dry air)

Off-gases

electron

multiplier

air + analytes (g)


0 5 10 15 20

0

100

200

300

400

500

8.64

6.84

6.24

4.32 e

d

c

b

Inte

nsit

y

Drift time / ms

a

5.24

50 100 150 200 2500

150

300

450

600

750

900

73

175

147

105

Inte

nsit

ym/z

117

Ion mobility speak m/z

4.32, 5.246.24;6.84, 8.64

73,105,117147,175


T1 T2 T3

cd

ba

e

0 50 100 150 200 250 300

0

200

400

600

800

1000

Drift time / ms

Inte

nsit

y

mixturesIMSpeak

m/z

?4.325.246.246.848.64

73105117147175

Acetone + Styrene + MTBE

The differences in

temporal profiles tell

there are three

compound exist.

IMS peak m/z

acetone 5.24 117

styrene 6.92, 8.56 105

MTBE 5.88, 6.40 73,147,175


The hybrid of ion mobility spectrometer and rectangle linear ion trap mass

spectrometer could obtain reduced mobility and mass spectrum of compounds

simultaneously, which help rapid identification of unknown compounds on-site.

The high resolution temporal concentration profiles obtained by IMS could

give useful information for compound identification, and could be fast trigger of

mass spectrometer for long-term continuous monitoring.

Low-power VUV lamp based negative and positive ionization sources fit the

hybrid IMS/MS spectrometer.

Next:

IMS(R>100)+ MS(ΔM<.5 Da)

working in Parallel or Tandem modes


Thanks for Your Attention!

Welcome to visit us in DICP


Length drift tube: 5-10 cm

Diameter of drift tube: 2-3 cm

Sample rate: 3-6 mL/s

Sensitivity: 5 mV/ppb

Velocity of ions: 8-15 m/s

Flow speed: 0.5-1 m/s

Analysis speed: sub-second

进样出气口

离子门

尾吹气

微电流引出

VUV-灯VUV-lamp


0 5 10 15 20

0

200

400

600

800

1000

Inte

nsit

y

Drift time / ms

5.24

50 100 150 200 250

0

300

600

900

1200

1500

Inte

nsit

y

m/z

117

[2M+H]+


0 5 10 15 20

0

100

200

300

400

500

8.56

Inte

nsit

y

Drift time / ms

6.92

50 100 150 200 2500

100

200

300

400

500

Inte

nsit

y

m/z

105[M+H]

+

shuang wang weimin wang keyong hou haiyang li* presentations/li h.pdf · tatp hmtd easy to...

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