A kind of method of preparing molecule adduction isotope ion
Technical field
The present invention relates to field of analytic instrument, specifically refer to a kind of a kind of utilize taylor cone principle to prepare molecule adduction isotope ion method.
Background technology
Since the mid-80, since electric spray ion source is applied to large molecule mass spectral analysis by one of Nobel chemistry Prize winner in 2002 John B.Fenn, past more than 20 year, for electric spray ion source mechanism, still rest on two patterns: Ion Evaporation Model (IEM) ion evaporation, with the residual mechanism of Charged Residue Model (CRM) electric charge.The basic structure of electric spray ion source and the nineties there is no a difference in essence.
The basic structure of electric spray ion source is exactly in the middle of the metal of a hollow or capillary glass tube, to be full of liquid, facing to mass spectrometric ion entrance, on liquid, add plus or minus high voltage, in atmosphere, form negative ions, a part of ion is sucked mass spectrometric mass analyzer by mass spectrometric vacuum system.
For electric spray ion source, although ionization probability is very high, almost reach 100%, molecular ion is transferred to the effective ion of mass spectrum mass detector, only have total number of ions 0.01% to 0.1% between.
In order to address the above problem, a lot of inventors have invented the electric spray ion source of different institutions, and referenced patent number is: U.S. US 4861988, US 5412208, US 5432343, US 6992299, US 5504329.But all inventions are all that the transmitting needle point of electric spray ion source is among atmosphere, ion current and fluid flow are in close relations, cannot be in large range of flow 100 receive liter/min~100 microlitres/point obtain stable emission of ions, and ion transmission efficiency is not significantly improved.
For the formation of taylor cone, there is corresponding open explanation at " computer and applied chemistry " the 28th volume o. 11th, wherein by controlling voltage swing, make solution form drop all the time and not drip at the capillary mouth of pipe, at this moment, the drop of capillary lower end is the hemispherical of convex, and " solution is subject to the effect of surface tension and electric field force simultaneously at the capillary mouth of pipe, along with electric field strength increases, same sex electric charge in solution is gathered in drop surface, the electric field that surface charge produces causes that drop deformation is " in the time that voltage reaches a certain critical value Vc, the solution at mouth of pipe place gradually becomes taper by hemisphere, when balance, its angle, half top is approximately 493 ", this charged cone is called taylor cone (Tay lor Cone) by everybody ".
Electric spray ion source (ESI) is the most frequently used interface of current liquid chromatography-mass spectrography (LC-MS) coupling, belong to soft ionization mode, can be used for studying thermally labile and the larger compound of polarity. due to the molecular ion that can produce with multi-charge, the applicability of ESI at generation biomolecule ions that electric spray ion source also can be used for the first provings such as large biological molecule .Fenn such as Study on Protein, until the sixties in 20th century, Dole etc. [1] produce the mass spectrometer of First based on electron spray. afterwards, Fenn etc. [2] use ESI series connection level Four bar detector to detect molecular beam, recognize that Dole ion source exists defect, and result is made an explanation, revise the distance between ion source nozzle needle and end plate, thereby reducing the designed ion source of nozzle needle voltage .Fenn and developed into afterwards Fenn-Whitehouse design [3]. this design is used capillary glass tube that ion is delivered into the first vacuum chamber from atmospheric environment, can select according to demand different inner diameters capillary .1987, electrospray interface introduced by Aeroassisted sprayer by Bruins etc. [4]. and atomization gas contributes to stable electrical spraying, keep flow velocity to approach 0.2mL/min, be applicable to that liquid phase series connection ESI-MS. allows nozzle and to there being larger distance between electrode, reduce the generation of corona discharge. simultaneously, reduce the dependence of spray process to nozzle location, if place nozzle from axle, can obtain higher sensitivity. after this, electric spray ion source structural design has been passed through a series of improvement, its operation principle has also been had to more and more deep understanding.
At present, technical staff emphasizes at taylor cone generator (in this application always, the device that forms taylor cone phenomenon is referred to as to taylor cone generator) in liquid in capillary be produce ion basic, and always unknown for phenomenons the such as whether liquid at capillary outlet place can be ionized.In current demand, in order to obtain isotopic ionization, the effect forming by taylor cone of the prior art, causes in isotope ion process can the needs very high cost that has, so, be subject to suitable restriction for the application of isotope ion.
Summary of the invention
The present invention is directed to deficiency of the prior art, make full use of the support of technical know-how, break through tradition forms middle ionization liquid phenomenon analysis to taylor cone, show that ionization liquid not only has the part of liquid in capillary, all has ionization phenomena for atmosphere, the liquid vapour (gas) etc. at capillary outlet place.
The present invention is achieved by following technical proposals:
A method of preparing molecule adduction isotope ion, is characterized in that, a taylor cone generator is first set, and places isotope gas or liquid at the capillary outlet place of taylor cone generator; Polar liquid is passed through to taylor cone generator, form taylor cone at capillary outlet place, be ionized by isotope gas or liquid under electric field action, polar molecule in polar liquid is by electric field polarization, polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.In this application, taylor cone generator is that polar liquid is the material that must have in the application, if not polar liquid cannot realize for the application's goal of the invention according to the equipment of the designed preparation of mode of taylor cone formation; Because isotopic species is more, in this application, only have the isotope of gas, liquid just can be ionized, solid needs to be converted into afterwards liquid or is dissolved into after liquid, just can produce identical effect, otherwise can not tell in this application.
As preferably, taylor cone generator described in a kind of above-mentioned method of preparing molecule adduction isotope ion is one and comprises that there are a closed container and the electrode corresponding with capillary voltage in capillary, capillary outlet place, form a circuit loop, voltage capillaceous is 10V-100KV.Due to the structure diversity of taylor cone generator, in order better to realize the formation of taylor cone, and needed pressure reduction in this application, more be conducive to the factor such as economy that isotope utilizes, so adopted closed container, can make like this isotope material of small amount be used, and can in taylor cone generator, act on by the polar liquid that uses a large amount of cheapnesss, finally have the isotope ion bundle group of value to be brought into play value.Form in order to realize better taylor cone, taking the inwall of closed container as electrode, on the wall of closed container, have a passage collection hole.
As preferably, isotope gas, liquid or solution described in a kind of above-mentioned method of preparing molecule adduction isotope ion are: heavy water (D
2o), deuterated methanol, deuterochloroform, deuterated benzene, deuterated acetic acid, deuterated dimethyl sulfoxide, deuterated acetone, H
2o (O-18 represents that oxygen element is wherein to be made up of oxygen 18), acetaldehyde (O-18), acetic acid (O-18), adipic acid (O-18), ammonium nitrate (O-18), brium carbonate (O-18), benzoic acid (O-18) (O-18), benzophenone (O-18), cadmium oxide (O-18), calcium carbonate (O-18), carbon dioxide (O-18), carbon monoxide (O-18), carbonyl sulfide (O-18), ring penta (O-18), dimethyl formamide (O-18), ethanol (O-18), glycine (O-18), hydrogen peroxide (O-18), lead oxide (O-18), DL-leucine (O-18), manganese carbonate (O-18), mercury oxide (O-18), methyl alcohol (O-18), nitric acid (O-18), nitric oxide (O-18), nitrous oxide (O-18), nitrogen dioxide (O-18), oxygen (O-18), paraformaldehyde (O-18), phenol (O-18), phosgene (O-18), potash (O-18), potassium nitrate (O-18), potassium nitrite (O-18), silicon dioxide (O-18), sodium acetate (O-18), sodium carbonate (O-18), sodium nitrate (O-18), natrium nitrosum (O-18), sodium perchlorate (O-18), glauber salt (O-18), sulfur dioxide (O-18), sulfuric acid (O-18), urea (O-18), valine (O-18), " (O-18) " of above-mentioned each material all represents that the oxygen element in material is to be made up of isotope oxygen 18.
As preferably, when polar liquid described in a kind of above-mentioned method of preparing molecule adduction isotope ion is passed through taylor cone generator, be attended by assist gas capillary outlet place, assist gas is the mixing of several gases in nitrogen, oxygen, argon gas, hydrogen, air, helium or above-mentioned gas.
As preferably, described in a kind of above-mentioned method of preparing molecule adduction isotope ion, polar liquid is the mixture of water, ethanol, methyl alcohol, formaldehyde, acetonitrile or aforesaid liquid.
In the present invention, for isotope ion can be used widely, how realizing economic benefit becomes significant consideration, so it is of the prior art expensive to utilize cheap material to substitute, and reaches identical or better effect.
Beneficial effect: application of the present invention can make molecule adduction isotope ion more easily obtain, and economical and practical, can be widely used.
Brief description of the drawings
Fig. 1 apparatus structure schematic diagram of the present invention
Ion detection collection of illustrative plates in Fig. 2 embodiment of the present invention after ionization
Embodiment
Below enforcement of the present invention is illustrated:
Embodiment 1
According to the theory structure described in Fig. 1, a taylor cone generator is first set, place isotope material H at the capillary outlet place of taylor cone generator
2o (O-18); Polar liquid water by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 100V.Form taylor cone at capillary outlet place, be subject to the isotope H under electric field action
2o (O-18) is ionized, and the polar molecule in polar liquid water is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.
Embodiment 2
With step identical in embodiment, a taylor cone generator is first set, place isotope material D at the capillary outlet place of taylor cone generator
2o; Polar liquid water by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 1000V.Form taylor cone at capillary outlet place, be subject to the isotope D under electric field action
2o is ionized, and the polar molecule in polar liquid water is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer, after measured, can obtain characteristic value as shown in Figure 2.
Embodiment 3
With step identical in embodiment, a taylor cone generator is first set, place isotope material D at the capillary outlet place of taylor cone generator
2o; Polar liquid ethanol by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 1000V.Form taylor cone at capillary outlet place, be subject to the isotope D under electric field action
2o is ionized, and the polar molecule in polar liquid ethanol is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to nitrogen, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.
Embodiment 4
With step identical in embodiment, a taylor cone generator is first set, place isotope material D at the capillary outlet place of taylor cone generator
2o; Polar liquid ethanol by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 10KV.Form taylor cone at capillary outlet place, be subject to the isotope D under electric field action
2o is ionized, and the polar molecule in polar liquid ethanol is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to nitrogen, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.
Embodiment 5
With step identical in embodiment, a taylor cone generator is first set, place isotope material D at the capillary outlet place of taylor cone generator
2o; Using ethanol and formaldehyde in the mixed liquor of equal in quality ratio as polar liquid by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, form a circuit loop, by voltage for being adjusted to 10KV.Form taylor cone at capillary outlet place, be subject to the isotope D under electric field action
2o is ionized, and the polar molecule in polar liquid is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to helium, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.
Embodiment 6
With step identical in embodiment, a taylor cone generator is first set, place isotope material adipic acid (O-18) at the capillary outlet place of taylor cone generator; Polar liquid ethanol by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 10KV.Form taylor cone at capillary outlet place, be ionized by the isotope adipic acid (O-18) under electric field action, polar molecule in polar liquid ethanol is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to nitrogen, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.
Embodiment 7
With step identical in embodiment, a taylor cone generator is first set, place isotope material nitric oxide (O-18) at the capillary outlet place of taylor cone generator; Polar liquid ethanol by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 10KV.Form taylor cone at capillary outlet place, be ionized by the isotope nitric oxide (O-18) under electric field action, polar molecule in polar liquid ethanol is by electric field polarization, and polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to nitrogen, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.Through measuring with the equipment connection such as mass spectrometer, can obtain characteristic value as shown in Figure 2 and conform to.
Embodiment 8
With step identical in embodiment, a taylor cone generator is first set, place isotope material potassium nitrate (O-18) aqueous solution at the capillary outlet place of taylor cone generator; Polar liquid ethanol by taylor cone generator, because there is a closed container and corresponding with capillary outlet place voltage at capillary outlet place, is formed to a circuit loop, by voltage for being adjusted to 10KV.Form taylor cone at capillary outlet place, be ionized by the gas phase of isotope potassium nitrate (O-18) aqueous solution under electric field action, polar molecule in polar liquid ethanol is by electric field polarization, polar molecule absorption isotope or hydrogen ion after polarization, form molecule adduction isotope ion bundle group.On the wall of closed container, have a passage collection hole can with the equipment connections such as mass spectrometer.In order to obtain better effect, in the time that polar liquid is passed through taylor cone generator, be attended by assist gas at capillary outlet place, assist gas is nitrogen, nonpolar due to nitrogen, so can not cause polar liquid, isotopic impact, can make the direction directional trend of fluid simultaneously.