DE2020947A1 - A method and apparatus for ionizing a material and introducing the ionized material into a mass spectrometer and using a mass spectrometer as a detector for a liquid chromatograph - Google Patents

Description

ASSOCIATED ELECTRICAL INDUSTRIES LTD., London, England

Method and device for ionizing a material and Entering the ionized material into a mass spectrometer and using a mass spectrometer as a detector for a liquid chromatograph

The invention is in the field of mass spectrometry and particularly relates to ion sources for mass spectrometers.

So far it is not possible to use certain materials because they are non-volatile or non-evaporable, a To create a mass spectrogram. These materials can can be divided into three broad groups:

1. Compounds with a very high molecular weight,

like proteins and polymers. . f

2. Highly polar, lower molecular weight compounds.

3. Unstable lower molecular weight compounds.

The invention is based on the object of a method for determining the mass spectra of these types of materials and to specify an ionizing device that, together with a Mass spectrometer can be operated and allows the ionization of these materials, so that their mass

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spectra can thereby be determined.

In accordance with the invention there is a method of ionizing a material and introducing the ionized material into a mass spectrometer, which preferably has a magnetic analyzer, through which ions are passed before they reach one collector, and one the magnetic field of the magnetic analyzer through a field strength range through such changing device contains that the respective point in time in which ions the collector during such a change (which can also be referred to as the temporal deflection of the magnetic field), A measure of the respective mass of the ions is that the material is dissolved in a solvent is, the dissolved material together with the solvent through an area of such high electrical stress is directed that the material is ionized, that the solvent evaporates and thereby the ionized Material is largely separated from the solvent and that the ionized material then enters the mass spectrometer is directed. A further development of this method consists in that the ionized material along a path which leads into the mass spectrometer, and the ionized material is focused into a beam. The beam of the ionized material is preferably deflected in this case. Another further training is characterized by it from that the ionized material is further ionized in the mass spectrometer.

Another feature of the invention is the use of a mass spectrometer as a sensor or detector for a liquid chromatograph, which is characterized in that the outflow of the liquid chromatograph is passed through an area of so high electrical stress that the effluent is ionized, and that the

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ionized AusfTuB is then passed into the mass spectrometer. A development of that Anwendungsver-, proceedings there; in that the ionized effluent is additionally accelerated along a path leading in the direction of the mass spectrometer and the ionized effluent is focused into a beam. With this method, too, the beam of the ionized discharge can be deflected. In addition, this method also preferably ensures that the ionized effluent is further ionized in the mass spectrometer.

The ionizer according to the invention for a mass spectrometer | meter, which is preferably a magnetic analyzer, through which ions are passed before they reach a collector reach, and one the magnetic field of the magnetic analyzer contains devices that change through a field strength range in such a way that the respective point in time at which ions leave the collector during such a. . ■ Change (which can also be referred to as the temporal deflection of the magnetic field), a measure of the The respective mass of the ions is characterized by the fact that the device has a hollow needle, at least one. the Tip of the Hadel an area so high electrical stress training device that in solvent. ■ ' dissolved material is ionized, the solution ■

medium evaporating device, one that in the solvent Dissolved material through the needle-conducting device and a device that attracts the ions of the material formed in the process and to a beam focusing device contains' and that the ionizing device is designed and arranged in such a way that it enters the ion beam into the mass spectrometer directs. . ·.

The drops of material dissolved in solvent, that through the handle into the area of high electrical

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shear stress, get a high charge, which causes expansion forces in the droplets, which are greater than their surface tension, so that the drops expand and their surface area increases. These The increased surface area supports the evaporation of the solvent, but hinders the cooling during the evaporation the loss of solvent. Therefore, the evaporation is increased by heating the droplets.

According to the invention, the heat can be supplied to the drops in that the drops are passed through a gas that is not ionizable to such an extent that adequate ionization of the droplets is prevented. Suitable Gases are air and nitrogen. Preferably, the gas is constantly or periodically renewed to prevent that the gas cools down too much and an explosive gas / solvent mixture forms ο

Another method for heating the drops is according to the invention that the drops in vacuum with an ultraviolet or infrared radiation. Suitable radiation sources include a Nernst filament and laser.

Material ions formed on this V / eise are largely free of solvent and so strongly charged that one Agglomeration of high molecular weight ions is prevented.

■ After the ions are formed, the ions are replaced by a with an aperture provided plate focused, which is at a high potential, for example in the order of magnitude of 2 kV can be lower than that of the needle.

When the ionon is formed in the manner mentioned in a gas the ion beam is passed through a nozzle

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system directed j in which the ions at a high speed, preferably of the order of. Mach 7, are accelerated and a flow wave is formed, which causes a deflection of the relatively light molecules and ions of the solvent and gas, but does not deflect relatively heavy molecules of the ion beam and thereby allows them to pass through the nozzle system. One or more vacuum pumps can be connected to the nozzle system, so that the ion beam is optionally passed through a vacuum. This leads to ύ

It is expedient to separate the probe and the surrounding gas, which can have normal pressure, from the mass spectrometer, the interior of which is evacuated during operation . '■ ^: ' ■ "'■■" - ■ ....-....

The nozzle system is not required if the ionization takes place almost in a vacuum. ·

Correct guidance of the ion beam into the mass spectrometer can be achieved by electrostatic deflection of the beam reach.

The ionizer is preferably equipped with devices equipped, with the help of which the ion beam in the mass spectrometer can be further focused.

An additional device is preferably also provided , which is the device causing the further focusing with appropriate adaptation can and which is designed such that it can Ion beam, for example by electrostatic forces so accelerated that very high speeds in front of it Analysis to be changed »

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If a stronger ionization of the ion beam is desired, e.g. to break further bonds or a To achieve stronger splitting, an ionization beam source, for example electrons or photons emits, be arranged so that it hits the ion beam at some point prior to its entry into the analyzer of the mass spectrometer acts.

The solvent and material dissolved in the solvent can be the effluent from a liquid chromatograph.

At present, the use of liquid chromatography is largely overshadowed by gas chromatography because of the lack of a sensitive detector or sensor, or a sensitive detection device. However, gas chromatography is limited to compounds that volatilize or evaporate without decomposition can be, so that. the creation of a sensitive detector for a liquid chromatograph than greater Progress is to be seen. The ionizer according to the invention enables the direct connection of a Liquid chromatograph on a mass spectrometer, which has a much higher sensitivity than previously known Having liquid chromatography detectors.

The invention and its developments are described in more detail below with reference to schematic drawings of preferred exemplary embodiments.

Pig. 1 is a partially sectioned view of a first embodiment.

FIG. 2 is an enlarged cross-sectional view of a portion of the embodiment of FIG. 1.

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Pig. 3 is a partially sectioned view of a second exemplary embodiment. ·

Pig. Fig. 4 is an enlarged sectional view of a part of the Pig embodiment. 3 dar and

Pig. 5 shows a schematic block diagram of a third embodiment. '■

The ionizer according to the Pig. 1 and 2 contains a hollow one Needle 10 attached to inlet tube 12 ". The j Point 14 of needle 10 is close to a focusing plate 16, which contains an opening 18. A converging nozzle 20 is aligned with opening 18 and opening 26 a divergent nozzle 24. Both orifices 22 and 26 may be as close as 0.102 mm (0.004 inches) in diameter.

A grounded plate 28 having an opening 30, which can have a diameter of 0.051 mm (0.02 inches), arranged next to ^v and coaxial with the nozzle 24th

The device includes two baffles 32 and 34 relatively close to the grounded plate 28 and further away a Pokussierlinsensystem with three perforated plates 36, 38 and 40. '·. |

The mentioned components can be replaced by any suitable Device are kept in their correct relative position. This device can also be used for a mutual Insulate these components as far as they are at different potentials.

The space between the nozzles 20 and 24 can be via a pipe 23 be connected to a backing pump (rough pump), not shown, and the space between the nozzle 24 and the grounded plate 28 can via a tube 27 with a not diffusion pump shown ve - "" - be unden.

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A gas-tight housing 42 surrounds the needle 10 and the various Plates and nozzles that make up the device. The inlet tube 12 is adjustable in a wall 44 of the housing 42 held.

The entire device can be connected to a mass spectrometer ", and according to. Pig. 1 it is on an end flange 46 of the unit containing the ion source not shown mass spectrometer of known design connected. A suitable mass spectrometer is that double focusing IVL.S.9, provided by the Associated Electrical Industries Ltd. will be produced. Instead, however, a familiar simple focusing Mass spectrometer can be used.

■ The material to be analyzed is dissolved in a suitable solvent, e.g. a mixture of benzene and acetone, dissolved and passed into the inlet pipe 12.

(Other suitable solvents include acetone, ethyl ether, methanol, a mixture of 75 % methanol and 25 % water, butyl alcohol and η-hexane.)

The solvent and the dissolved material, are through passed the hollow needle 10 and enter the tip 14 the end. Here they get into an area of high electrical field strength, which is generated in example by the fact that the needle 10 with respect to earth at a very high potential (e.g. 6kV) with a polarity that corresponds to the polarity of the ions that is to be generated is held.

Drops emerging from the needle tip 14 are therefore retained a very high charge that causes expansion forces in the drops that are greater than the surface tension of the Drops are and thereby expand so that their.

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Enlarged surface. The enlarged surface supports the evaporation of the solvent, but hinders it the cooling that occurs during evaporation, the emergence or loss of the solvent from the droplets. The droplets are therefore heated by a gas that is located in the housing 42. This gas shouldn't be that strong be ionizable that it is the electric field strength in the Reduced area of the needle tip 14. Suitable gases are nitrogen and air. The gas should be changed periodically or constantly to prevent the To prevent gas, which could lead to un- * v / becomes effective, and / or to prevent the formation of an explosive gas / solvent vapor mixture in the housing 42. . ■ -...- '

The material ions formed are largely free of Solvent and sufficiently charged to cause agglomeration of high molecular weight ions impede.

After their formation, the ions are passed through the plate 16, which is at a lower potential with respect to earth than the needle tip H is attracted to the opening 22 and | focused on this. This lower potential can be, for example, 3.5 kV and has the same polarity like the potential of the needle 10. During their passage s through the opening 22 the ions are at a high level Speed accelerates on the order of Mach 7 lies.

The system of nozzles 20 and 24 creates a round shock wave around the opening 26, which strives to be above the opening 22 from 'the chamber 42 coming gas to the upstream deflect lying surface of the nozzle 24 around. This deflected gas is via the pipe 23 from the space between

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the nozzles 20 and 24 sucked by the backing pump, not shown, so that the space between the nozzles largely evacuated "remains. The ions of the relatively heavy material are not deflected by the shock wave and fly through opening 26 towards grounded plate 28.

The space between the plate 28 and the nozzle 24 is through the diffusion pump (not shown) kept at almost absolute vacuum.

The stream of ionized material then goes through the opening JO, after which it becomes electrostatic in the required manner can be deflected by the orthogonally arranged pairs of plates 32 and 34 to get it on properly to bring the path leading into the mass spectrometer.

This further focusing of the beam or bundle of rays, if necessary, this can be achieved by placing plates 36, 38 and 40 at appropriate relative potentials will. The ion beam is preferably accelerated even further to a very high speed. This can be achieve that, for example, the plates 36, 38 and 40 at suitable potentials, for example in of the order of a few kilovolts, with respect to the preceding parts of the ionizing device. The material can then be analyzed in the usual manner in the mass spectrometer.

If the beam is judged to be insufficiently ionized, it can be stopped by any suitable means (not shown) direction can be further ionized in the mass spectrometer, e.g. by a cross beam of electrons or photons. The needle 10 can be a hypodermic needle such as that used for intravenous injections, so that the .Spitze H bevelled or pointed sharply

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tzw. is flattened. However, the tip is preferred 14 to form that the needle 10 approximately in the right .Angle cut off to its longitudinal axis and at least the outer edge of the tip 14 is rounded, whereby an undesired field ionization largely avoided will, ■.

The inlet tube 12 of the ionizer described can be connected to a liquid chromatograph, so that it picks up its outflow and the mass spectro - · - meter as a sensitive sensor or detector for the chro- '1 matographen works.

The second embodiment of an ionizer according to the invention, shown in FIGS. 3 and 4, contains (like the first embodiment) the hollow needle 10 attached to the inlet tube 12. The tip T4 of the needle. * 10 is located in the immediate vicinity of an opening 118 in a spherical cap-shaped focusing plate 116. Two divergent nozzles 120 and 124 are aligned with the needle 10 and ertthal-: each ten openings 122 and 126 whose diameter is preferably in the order of 0.102 mm (0, , .Q04 inches). A thin electrostatic lens «11: 7 with a g

protruding opening 119 is coaxial with and near ": the opening 122 of the nozzle 120 is arranged. The plate 116 is largely focused on the opening 122.

A plate 128 with variable potential and an opening 130, which can be 0.051 mm (0.02 inches) in diameter, is positioned near and coaxial with nozzle 124. '' ..: ■ - ■;

The second embodiment also includes the two pairs of baffles 32 and 34 relatively close to plate 128 and a little further away the focus lens system with the three pierced plates 36, 38th and 40th.

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The mentioned components can be held in their correct relative position by any suitable device which at the same time ensures that these components are mutually isolated during operation of the ionizing device must be at different potentials, as will be described in more detail.

The space between the nozzles 120 and 124 can be about a
Pipe 23 connected to a known powerful (not shown) steam booster or diffusion pump

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to create a vacuum of about 10 to 10 torr. The space between the nozzle 124 and the plate can via the pipe 27 to a (not shown) known Be connected to the diffusion pump.

A gas-tight housing 42 surrounds the needle 10 and the various plates and nozzles that make up the device. That
Inlet tube 12 is adjustably supported in a wall 44 of housing 42.

-The entire device can be connected to a mass spectrometer, and according to Pig. 1, it is connected to an end flange 46 of the unit containing the ion source of a known type of mass spectrometer (not shown). A suitable mass spectrometer is the dual focusing MS9 available from the Associated
.Electrical Industries ltd. Is manufactured. Instead, however, you can also use a familiar simple focusing
Mass spectrometer can be used.

The material to be analyzed is in a suitable
Solvent, for example a mixture of benzene and acetone, dissolved and passed into the inlet pipe 12 '.

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(Other suitable solvents include acetone, 'ethyl ether', methanol, a mixture 'of 75 ° i of methanol and 25' fo water, butyl alcohol and n-hexaene.) "

The solvent and the dissolved material will '" passed through the hollow needle 10 and step at "the tip 14 off. Here 'they get into an area of high electric field strength, which is generated, for example is that the needle 10 opposite the first nozzle "120 at a very high potential (e.g. 6 kV) with a Polarity, which, corresponds to the polarity of the ions, which are to be generated, is held. '' .. '"*'" "'

Drops emerging from the needle tip 14 therefore receive a very high charge, which cause expansion forces in the droplets that are greater than the surface tension of the droplets and thereby cause the droplets to be divided into a number of smaller droplets and thus the individual molecules Isolate the dissolved substance in separate solvent / solvent systems and also enlarge their surface area. The enlarged surface supports the evaporation of the solvent, do.ch prevents the cooling that occurs during evaporation from escaping or the loss of the solvent from aen. Drops. The droplets are therefore ery / ärmt by a gas that is located in the housing 42. This gas should not be so strongly ... ionizable that it reduces the electrical "field strength - in the area of the needle tip .14. Suitable gases are nitrogen and air. The gas should be changed periodically or constantly to make it too strong to prevent cooling of the gas, could lead .which to ■ -that. e.s_ is ineffective. ', and / or to prevent the Ausbiid.ung an explosive gas / Lösuri _i gsmitte.l-vapor mixture in the housing 42.

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The material ions formed are largely free of solvent and sufficiently charged to cause an agglomeration of ions of high molecular weight to prevent. ■ ■. .

The plate 116, which is kept at approximately the same electrical potential as the needle tip 14, reduces the fixed exit angle of the sprayed from the needle tip 14. By means of and due to its curvature around the opening 122, a sharp focus takes place in the direction of the opening 122. The lens 117 is at a potential of approximately 40 ^r / o to 60 ^α / of that lying between the needle and the nozzle .120 Voltage held so that the electric field in the area of the opening 122 is very large. Has gradients. . ·. -. \ - ..-..- ·. ·,

Instead of the spherical cap-shaped plate. 116 can also-; a largely flat plate can be used, - _:

If the solvent used is insufficient Has volatility, or the volatility of the. should be increased by means of, the solvent evaporation area can be irradiated by .Infrared light,; ; generated e.g. by a Nernst filament 130 »,, ..

The nozzles 120 and 124 are axially relative to one another , depending on the type of material to be sprayed:,. D'movable .: In some .cases it can be advantageous to "generate" a shock wave in front of the opening 126, which - causes - that the 'jet' emerging from the nozzle 120 at the speed of bursting reverberation . Untersehallges'chwiridigkeit ■ off 'brakes, increased in temperature and' light ^gases: · "(gases iriit low Molokularg ^ weight) the major-ch-'the ^ ^~:>: - opening 122 -from 'the Chamber 42-want to exit ^ 'um-ä

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upstream surface of the nozzle 124 can be deflected * ■

For example, a shock wave can be generated of the opening 126 may be undesirable when deflecting or scanning unstable materials, so that the device in the Molecular beam operation must be operated. This is accomplished by either having the nozzle 124 axially in Shifts in the direction of the nozzle 122 or increases the pumping capacity of the pump of the first stage or a combination of both methods ... ·

In both cases, the materials to be examined pass through the opening 126 in the direction of the plate 128, whose potential is changeable. >

The space between the plate 128 and the nozzle 124 is \ kept at an almost absolute vacuum by the diffusion pump, not shown.

The stream of ionized material then passes through port 130, after which it is electrostatic as required by the orthogonally arranged pairs of plat- ■ | th 32 and 34 can be deflected to properly bring it onto the path leading into the mass spectrometer.

This further focusing of the beam or bundle of rays, if necessary, can be achieved by placing the plates 36, 38 and 40 at suitable relative potentials will. The ion beam is preferably increased even further accelerates a very high speed. This can be achieve that, for example, the plates 36 * 38 and 40 at suitable potentials, for example on the order of a few. Kilovolts, with respect to the previous parts of the ionizer are held.

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After that, the material can be used in the mass spectrometer in the usual way Way to be analyzed.

Ions that are generated at atmospheric pressure and are exposed to a gradient of an electric field for acceleration, collide with the molecules of the surrounding gas at a speed of 10 per centimeter of ion movement. Prevent these collisions that the ions are accelerated transversely to the potential gradient, so that they are more or less constant Assume speed and prevent proper ion focusing in the normal ion-optical sense. The described Focusing device maximizes the number of ions that are actually passed through nozzles 120 and 124 be, so that there is an ionizer that has advantages over the first embodiment of the Has ionizer.

If the beam is considered insufficiently ionized, it can be done by any suitable device (not shown) be further ionized in the mass spectrometer, e.g. by a transverse beam of electrons or photons. The needle 10 can be a hypodermic needle such as that used for intravenous injections, so that the tip 14 is sharply chamfered or pointed or flattened. However, Ss is preferred to be the top To form H in that the needle 10 is cut approximately at right angles to its longitudinal axis and at least the outer edge of the tip 14 is rounded, as a result of which undesired field ionization is largely avoided.

Fig. 5 is a schematic representation of a third embodiment the invention. The needle tip 14 is arranged so that it brings the dissolved material into an eva-

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Cuated chamber 24-2 sprays. Since the drops of the solution _: ni-fuel and. Dissolved material are to be heated, -as it has already been mentioned, must be because of the in-.the chamber. 242 missing gas another heat supply means may be provided. In this exemplary embodiment, the required low-energy source is generated by an optical source, preferably an infrared source, which can be a Ernst lamp or an ITernst filament .250 The radiation emitted by the filament 230 penetrates through a collimation slit diaphragm 250 and an optical lens system 252 into the chamber 242, in which the radiation supports the evaporation of the solvent. Material ions leave the chamber 242 . through the opening 222 of a nozzle 220, and then enter the (not shown) mass spectrometer the chamber ^242;. is kept evacuated by unillustrated means' ■.

At any time ^"DER.: ■ infrared absorption in the chamber 242 display, including a hinreic-rising radiation for a angemessene- solution ■ with-telverdampfung to ensure and to" easily the Äugenbliekswert -safe - zu'gehen, ■ that 'the Temperatur'-y not so / eit increases that either' · -to the material under test or das'Losungsmittel dissociated (as the Dissöziationsprodufete cause incorrect results may ä) -ist- the lens system 252, a photo cell 254-- the --'- ■■ kind arranged opposite ^ that they all unabsorbed radiation on g ti- "'■,. · ■ -

In many cases it is useful to 'remove the filament. To control "automatically 230 emitted radiation or regulate Therefore, kähn be 'for' ensured that the radiation of the heating -. Yarn 230 by means of further Kollimationsspaltblende 260 that the 'Bl end e similar 250 is I' and e in further lens system 26Ό, because it is similar to lens system 252,

is directed, and zv / är so 'that' they "on another photo

cell 264, which is similar to photocell 254,

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The output signals of the photocells 254 and 264 are fed to a differential amplifier 270, the output signal of which proportional to the difference "on the respective photocells falling radiation and thus the radiation absorbed in the chamber 242 and an actuator 272 so controls that it changes the temperature of the filament 230 and / or the aperture of the aperture 250 so that the in radiation absorbed by chamber 242 maintains an optimal level.

Instead of the Nernst filament, other radiation sources can also be used and instead of the sailing device described, other control devices can also be used. An advantageous one An alternative to the radiation source would be a laser.

The main advantage of this third embodiment of the invention, which is sprayed in a vacuum, in relation to the The first two exemplary embodiments, in which a gas which is at atmospheric pressure is sprayed into, consists in the increased sensitivity. In the second exemplary embodiment, an ion current of about 100 nano-amps leaves the needle 10 while it is expected that only one ion of 10,000 ions reached the first nozzle 120. Spraying in a vacuum increases the proportion of ions that reach nozzle 220, to at least 1 in 100.

The inlet pipe 12 can in each of the described embodiments be connected to a liquid chromatograph so that it picks up its effluent so that the mass spectrometer acts as a sensitive probe or detector for the chromatograph.

The invention therefore consists in a method and apparatus for spectrometric analyzes of materials that have hitherto

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were not suitable for such analyzes, and also represents an advantageous extension of the field of application of liquid chromatographs.

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Claims (22)

Claims 1. / Method of ionizing a material and entering it of the ionized material in a mass spectrometer, characterized in that the material V / ird dissolved in a solvent, the dissolved material together with the solvent by a Area with such high electrical stress is conducted, that the material is ionized, that the solvent evaporates and the ionized material from the solvent is largely separated and that the ionized material is then passed into the mass spectrometer. 2. The method according to claim 1, characterized in that that the ionized material is accelerated along a path which leads into the mass spectrometer, and focusing the ionized material into a beam. 3. The method according to claim 1 or 2, characterized in that that the beam of ionized material is deflected. 4. The method according to claim 1 or 2 or 3, characterized in that the ionized material is further ionized in the mass spectrometer. 5. Using a mass spectrometer as a probe for one '' Liquid chromatographs, characterized in that that the outflow of the liquid chromatograph is passed through an area of so high electrical stress that the effluent ionizes and that the ionized effluent is then passed into the mass spectrometer. 009845/1677 BATH ORIGINAL 20 209Λ7 6. The method according to claim 5> d a d u r c h g e k e η η ζ eic h net that the ionized discharge is additional along a leading in the direction of the mass spectrometer Orbit is accelerated and the ionized effluent is focused into a beam. ■. 7. The method according to claim 5 or 6, since you r e h g e ken η ζ ei c ή e t that the beam of the ionized discharge is deflected « 8. The method according to claim 5 or 6 or 7, characterized in that " g e k e η η ζ e i c h η e t that the ionized effluent is further ionized in the Hem mass spectrometer. 9. Device for ionizing a material and entering the ^; ionized material in a mass spectrometer, characterized in that the device has a hollow needle (10), one at least at the tip (14) of the needle (10) an area of such high electrical stress; A device that forms the material dissolved in the solvent is ionized, a device that evaporates the solvent, a device that conducts the material dissolved in the solvent through the needle (10) and a device (16 or 116) which attracts the ions of the material thereby formed and focuses them into a beam, and in that the ionizing device is constructed and arranged in such a way that it directs the ion beam into the mass spectrometer. 10. Ionizer according to claim 9V dad ure hg e k e ri η show that it contains a means -that drops of heat emerging from the needle tip (H) * leads. . ■ - ■. ■■ ■ - ■ - ■ ·. ■ ■ · ■; .-, ·.-.... · ■ 009845/1677 ' BATH ORIGINAL 202Ü947 11. Ionizer, according to. Claim 10, characterized in that that the means for supplying heat to the droplets comprises a gas through which the droplets are passed and that this gas is not ionic It is possible that there is sufficient ionization of the droplets prevented. - 12. Ionizer according to claim 11, characterized ze ichnet that there is a constant or gas contains periodically renewing device to prevent the gas from cooling too much and an explosive ™ Forms a gas / solvent mixture. · 13. Ionizing device according to claim 10, characterized in that the drop Y / poor feeding Means a source of ultraviolet or infrared radiation (130 or 230). 14. Ionizer according to one of claims 9 - ^, characterized characterized in that it removes the solvent from the ions prior to the entry of the ion beam in the mass spectrometer separating device (20, 24; 120, 124; 220). 15. ionizing device according to claim 14, cL a. & U r c h characterized in that the solvent of the ion separating device comprises a nozzle system (20, 24; 120, 124; 220), in which the ions are accelerated and a shock wave is generated which causes the relatively light molecules and ions of the solvent deflected and the relatively heavy molecules of the ion beam are not deflected, but by the Nozzle system. 16. Ionizing device according to claim 15 »d a d u r c h g e indicates, that there is one or more vacuum 009845/1677 ^: contains pumps that are connected to the nozzle system (20, 24-; Τ2Ό, 124-; 220) are connected to the separated solvent to eliminate. 17. Ionizer according to claim 15 or 16, since d u r c h g e k e η η ζ e i c h η e t that it contains a charged plate (16 or 116) provided with an opening which with the opening (18 or 118) near the tip (14) the needle (10) is arranged so that the ions on the The nozzle system can be focused and accelerated. 18. Ionizer according to claim 15 or 16 or 17, since -_ ^ d u rc h g e k e η η ζ ei oh η c t that the Lüs system contains two nozzles (20 and 24 or T20 and 124), which are displaceable relative to one another in the axial direction so that the formation of the shock wave can be modified '" 19. Ionizer according to claim 13, dad u rc h g e ken η indicates that there is an absorption of the Contains radiation from the drop monitoring device (254). 20. Ionizer according to claim 19, because, durchge - ke nn ζ eic hn et _t that there is a radiation emitted by the radiation source (230); Control pre-like device (264) and an adjustable diaphragm of the radiation source (230) 'emitted radiation and / or (250) as a function of the difference between the output signals of the two monitoring devices (254 »264) so controlling device (270, 272) that the. The intensity or the amount of radiation reaching the drops is changed. 21. The method according to any one of claims 1-8, d a d u r ch g e know that the mass spectrometer a magnetic analyzer through which ions passed '. ' 009845/1677 20209A7 before they reach a collector, and one the magnetic field of the magnetic analyzer through one Field strength range through such changing device contains that the respective point in time at which the ions Collector during such a change (which is also referred to as the temporal deflection of the magnetic field can), is a measure of the respective mass of the ions. 22. Analyzer according to one of claims 9-20, d. a -. α by .gekisiert that the mass spectrometer a magnetic analyzer through which ions are passed before they reach a collector, and a device which changes the magnetic field of the magnetic analyzer in this way through a field strength range contains that the respective point in time, in which ions the Collector during such a change (which is also referred to as the temporal deflection of the magnetic field can), is a measure of the respective mass of the ions. 9845/1677 BAD ORiGINAL