Chapter 7 - Mass spectrometry (part 2) Flashcards

1
Q

The construction of a typical QIT mass spectrometer consists of

A

a ring electrode with a hyperbolic inner surface and two electrically common hyperbolic end-cap electrodes.

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2
Q

The trajectory of ions inside the QIT resembles

A

a figure 8 with rotating and oscillating simultaneously.

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3
Q

As the ions repel each other in the QIT, their trajectories

A

expand as a function of time.

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4
Q

To avoid QIT expansion, the trap is maintained with a pressure of ________ gas around _______ Torr.

A

Helium

10-3

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5
Q

A single high-vacuum pump with a flow of about ________ is sufficient to maintain QIT vacuum compared with _______ for other mass spectrometers.

A

40 L/s

250 L/s

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6
Q

Ion motion in QIT can be analyzed by______ equations.

A

Mathieu

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7
Q

When solving equations of motion for ions withing QIT analyzer, three fundamental parameters of fundamental importance emerge

A

a, q, and beta

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8
Q

Most commercial QITs operate by applying a

A

fundamental RF voltage to the ring at constant frequency and varied amplitude.

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9
Q

The quadrupole ion trap will be operated along the ______ axis.

A

qu (x)

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10
Q

At a fixed value of the RF potential V applied to the ring electrode, heavier ions will have lower ______ values.

A

qz

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11
Q

If the value of V is equal to 0.908, betaz is equal to one, and the ion has reached its _________.

A

stability limit.

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12
Q

At the stability limit, a slight increase in V will cause

A

the ion to have an unstable trajectory and will be expelled from the trap in the z direction.

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13
Q

In QIT, only _____% of expelled ions will reach the detector.

A

50

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14
Q

The maximum internal mass can be increased by

A

increasing V at higher values without arcing, reducing the size of the trap, or using a lower RF frequency.

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15
Q

In an ideal QIT, the motions of the ions in the radial and axial directions are

A

mutually independent.

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16
Q

If a supplementary RF voltage to the end-cap electrodes is applied to the end caps,

A

resonant ejection of ions occurs at qz < 0.908

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17
Q

Principle of resonant ejection

A

Ions are stored in the 3D trap at a voltage VA of the fundamental RF.

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18
Q

MS scan based on resonant ejection may either be carried out in a

A

forward (low to high mass) or reverse manner.

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19
Q

Resonant ejection can serve for precursor ion selection in

A

tandem MS experiments.

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20
Q

_______ rather than _______ MS occurs in QIT.

A

Time-dependent, space-dependent

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21
Q

QIT can perform not only MS2, but also

A

MS3 and MSn

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22
Q

QIT instruments do not support what kind of scans?

A

constant neutral loss and precursor ion

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23
Q

General sequence for MS in QIT.

A
  1. Select ions of one m/z ratio
  2. Let those ions fragment
  3. Analyze the ions by one of the scanning methods
    1. Alternatively, select a fragment in the QIP, and let it fragment further
24
Q

To fragment ions by resonance excitation,

A

an RF voltage must be applied to adjust the qz value for the selected m/z ratio to the frequency of the RF generator used.

25
Q

In general, fragments with m/z values lower than about _____ of the precursor ions m/z will be lost in QIT.

A

20%

26
Q

Space charge effect

A

QIT has the capacity for a limited number of ions at any one time before repulsive charges cause the excess ions to be ejected.

27
Q

Concentrations of ions above the space charge limit lead to

A

poor performance with grossly deteriorated resolution and shifts in the mass axis calibration.

28
Q

The linear ion trap (LIT) adds sections

A

at each end of the quadrupole to create a potential well.

29
Q

Once in the LIT, ions are cooled by

A

collision with an inert gas.

30
Q

Placing electrodes of higher potential near the front and back ends of RF-only quadrupole creates

A

a trapping potential within the quadrupole.

31
Q

Two modes for the mass selective ejection of ions used in LIT

A
  1. ions are expelled axially using fringe field effects
    1. slots are hollowed out in two opposite rods and mass selective radial expulsion of ions is obtained
32
Q

One great advantage of LITs in comparison with QITs is a

A

more than 30-fold higher ion trapping capacity before space charge effects, and a more than 10 times higher trapping efficiency.

33
Q

LIT advantages increase

A

sensitivity and the dynamic range.

34
Q

The performance of LITs is highly dependent upon

A

mechanical construction.

35
Q

2D and 3D ion traps are commonly operated at _____ resolution with scan rates on the order of _____ m/z per second.

A

unit

11,000

36
Q

2D and 3D ion traps can trade spectral acquisition rate for

A

resolution.

37
Q

The orbitrap mass analyzer consists of

A

an outer barrel like external electrode and a central spindle like internal electrode along the axial axis.

38
Q

In orbitrap, both electrodes are connected to

A

independent voltage supplies.

39
Q

In orbitrap, the outer electrode is split into

A

an ion excitation part and an ion detection part.

40
Q

In orbitrap, the space between the internal and external electrodes forms

A

the measurement chamber under high vacuum conditions (~10-9).

41
Q

In orbitrap, ion introduction is achieved by using a

A

field compressor.

42
Q

Orbitrap uses a ___________ field, which is the sum of a quadrupole field of the ion trap and a logarithmic field of a cylindrical capacitor.

A

quadro-logarithmic

43
Q

Curved linear traps function in the same way as their linear counterparts with the added advantage that

A

ions can be focused in narrow areas to be ejected as compact bursts of ions.

44
Q

In curved linear traps, ions are focused by

A

altering the trapping fields of the electrodes at the front and rear of the instrument.

45
Q

The curved linear ion trap is one of the most _______ ways of injection ions to the orbitrap.

A

efficient

46
Q

Slow injection

A

When ions are injected equatorially.

47
Q

In order to eliminate gas carryover from the ion trap (linear or curved),

A

the ion beam is usually deflected by a set of transfer lenses.

48
Q

Fast injection

A

When ions are injected into the orbitrap at a position offset from its equator.

49
Q

The _______ mode allows for the highest mass resolution in orbitrap.

A

Fourier Transform

50
Q

Two modes of orbitrap mass detection

A
  1. Fourier Transform Mode
  2. Mass Selective Instability Mode
51
Q

MSI can be achieved by

A

resonance excitation.

52
Q

A convenient means of detection in MSI mode is

A

collision with a conversion dynode in the outer electrode.

53
Q

Instances in which MSI mode should be used:

A
  • Ions with certain m/z ratio can be stored for MS/MS analysis
    • High intensity signals from unwanted ions can be ejected to improve dynamic range
54
Q

The mass resolving power is half the

A

frequency resolving power.

55
Q

The orbitrap provides a resolving power up to 140000 at m/z

A

200