Inductively Coupled Plasma-Mass Spectrometry

ICP-MS

Stuart MorrowJune 12, 2015

Technique Overview

ICP-MS is a sensitive instrumental technique used for elemental analysis

Different than traditional MS No information on MW or structure

Data provides an accurate composition of inorganic elements in a sample (ppt % levels)

Technique OverviewPlasma Generation & Ionization

High Radio Frequency (27mHz) induces the formation of an argon plasma (6000 – 10000K)

Plasma has ionization potential (IP) of 15.76 electron volts – above 1st IP of most other elements in periodic table

Elements H

  He

Li ☐

Be ☐

B ☐

C N O F Ne

Na ☐

Mg ☐

Al ☐

Si ☐

P ☐

S ☐

Cl ☐

Ar

K ☐

Ca ☐

Sc ☐

Ti ☐

V ☐

Cr ☐

Mn ☐

Fe ☐

Co ☐

Ni ☐

Cu ☐

Zn ☐

Ga ☐

Ge ☐

As ☐

Se ☐

Br ☐

Kr

Rb ☐

Sr☐

Y ☐

Zr ☐

Nb ☐

Mo ☐

Tc ☐

Ru ☐

Rh ☐

Pd ☐

Ag ☐

Cd ☐

In ☐

Sn ☐

Sb ☐

Te ☐

I ☐

Xe

Cs ☐

Ba☐

LHf ☐

Ta ☐

W ☐

Re ☐

Os ☐

Ir ☐

Pt ☐

Au ☐

Hg ☐

Tl ☐

Pb ☐

Bi ☐

Po At Rn

Fr ☐

Ra ☐

A Rf Db Sg Bh Hs Mt Ds Rg  

 

  LLa ☐

Ce ☐

Pr ☐

Nd ☐

Pm ☐

Sm ☐

Eu ☐

Gd ☐

Tb ☐

Dy ☐

Ho ☐

Er ☐

Tm ☐

Yb ☐

Lu ☐

 

 A Ac

Th ☐

PaU ☐

NpPu ☐

Am Cm Bk Cf Es Fm Md No Lr  

  

  Unable to analyze on ICP-MS

  Quantitative Analysis Available  

Helium is used to eliminate polyatomic interferences Useful for trace analysis in high matrix samples

Interference RemovalCollision Cell Technology

Problem: Trace copper in seawater (High Matrix NaCl, H2O, N2)

Cu+ (m/z) = 63 or 65

a) Na+ (m/z) = 23

NaAr+ (m/z) = 63

b) Cl+ (m/z) = 35

NOCl+ (m/z) = 65

Solution:

a) NaAr+ + He Na+ + Ar + He dissociation

b) NOCl+ + He NO + Cl+ dissociation

c) Cu+ + He Cu+ + He no reaction

Effects of high pressure pasteurisation evaluated on freshly squeeze apple juice

Juice samples were subjected to various pressures while being cold pasteurised

Mineral content increased linearly with increasing pressure

Solution ICP-MSMinerals in Juice

2 3 Na [ He ]

2 4 Mg [ He ]

3 1 P [ He ] 3 4 S [ He ] 4 4 C a [ He ]

22

0.4

22

9.4

27

3.9

99

.4

12

7.8

23

5.5

24

5.0

29

0.0

10

8.4 13

4.7

24

9.4

25

8.4

30

5.7

11

6.7 14

3.1

26

2.6

27

3.1

32

5.4

12

4.6 15

1.0

Mineral Content of Juice

Baseline 400 500 600Element

Con

cen

trati

on

(p

pm

)

Novel ruthenium anti-cancer compounds were synthesised

Several were found to have the same IC50 value in HCT116 cells (human colon carcinoma)

Cell uptake studies are performed to determine how much compound is absorbed over time

Drug Screening

Cell Uptake data of Anti-Cancer Ruthenium compounds (Data courtesy of Mario Kubanik, Hartinger Group, SCS.)

Cell Uptake

072 075 122 144 146 1620

2

4

6

8

10

12

14

16

18

20

Ruthenium Compound Uptake

2h 4h 8h

Compound

Ru C

once

ntr

ati

on (

ppb)

N

ORu

Cl

I

Cl

MaKu 144

N

ORu

Cl

MaKu 146

Hyphenation

UV Spectra of Cisplatin and GMP (Data courtesy of Hannah Holtkamp, Hartinger Group, SCS.)

CE-ICP-MS

0 1 2 3 4 5 6 7 8 9 10 0

3000

6000

9000

12000

15000

18000

Time (min)

Ab

sorb

an

ce

(mA

U)

• Capillary Electrophoresis (CE) separates analytes under the influence of an electric field

PtCl NH3

NH3Cl

Hyphenation

CE-ICP-MS Time resolved analysis (chromatogram) of cisplatin and GMP (Data courtesy of Hannah Holtkamp, Hartinger Group, SCS.)

CE-ICP-MS

0 2 4 6 8 10 12 14

P31

Cis:GMP [1:5]

Time (min)

Inte

nsi

ty (

CP

S)

195Pt

31P

PtCl NH3

NH3Cl

Overlaying spectra allowed simultaneous determination of Pt and P, and thus the presence of a Cisplatin-GMP complex

Method can be applied to proteins

Other Analysis

• Environment• Mineral content of marine mussel shells

• Manufacturing • Composition of metallic alloys

• Health• Gold content in colloidal suspensions

Summary

Extremely sensitive (ppt - %)

Full spectrum of elements Except C, N, H, O, He, Ne, F, Ar

Fun & exciting tool for research!