A kind of plasma electrospray mass spectrometry ionization source
Technical field
The utility model relates to mass spectrum ionization source technical field, particularly relates to a kind of plasma electrospray mass spectrometry ionization source for analyzing liquid or gaseous sample.
Background technology
In existing plasma electrospray mass spectrometry ionization source, the development transformation of lower temperature plasma technology to high-tech expanding economy and traditional industry for many years has tremendous influence.Plasma technique is applied on the three-protection design of semi-conductor industry, thin polymer film, material antiseptic erosion, plasma electronics, plasma synthesis, plasma metallurgy, plasma Coal Chemical Industry, plasma.In recent years, along with the research of article on plasma body technique, this technology also starts the sample ionization field being applied to Mass Spectrometer Method gradually.Plasma can produce a lot of active component, and these active components comprise the neutral compound of UV, visible light photon, electronics, ion, free radical and high response, as active atomic, and excited atom, bioactive molecule fragment.These active components can directly and the gaseous sample molecule contacts gaseous sample made that reacts ionize, also can with solid sample or fluid sample generation desorption ionization.Plasma technique is applied to field of mass spectrometry, and obtain and develop widely, create multiple mass spectrum ionization source: directly on-line analysis, dielectric barrier discharge, atmospheric pressure flowing afterglow, low temperature plasma probe, microwave induced desorption ionization source etc.While the ion source development ionized based on plasma, based on spraying ionization ion source on the basis of electric spray ion source also in fast development, create electron spray desorption ionization source, electron spray extraction ion source etc.
In existing plasma electrospray mass spectrometry ionization source, low-temperature plasma jet device and mass spectrum mouth are in the same side and close together, there is the effect of rf electric field, under the sample molecule ionized needs the effect of repulsion electrode, just can enter mass spectrum mouth and be detected, and then add energy consumption.
Utility model content
The purpose of this utility model is to propose a kind of plasma electrospray mass spectrometry ionization source, and Ionization Efficiency is high, and can evade rf electric field effect, reduces energy consumption.
For reaching this object, the utility model by the following technical solutions:
A kind of plasma electrospray mass spectrometry ionization source, comprising:
Low-temperature plasma jet device, comprises insulation medium cavity, sparking electrode, wireway, discharge gas introducing device, reacting gas is stored in discharge gas introducing device, reacting gas enters in described insulation medium cavity by described wireway, low temperature plasma is produced under the discharge process of described sparking electrode, and sprayed by the gas exit of described insulation medium cavity, described insulation medium cavity is one end is gas exit, the other end is the cavity body structure sealed by sealing device, described gas exit inwardly shrinks opening, one end of described wireway is stretched in described sealing device, and be connected with one end of described insulation medium cavity, the other end stretches out described sealing device and is connected with discharge gas introducing device,
Sampling device, comprise sample feeding pipe, the tee pipe fitting be communicated with described sample feeding pipe and heater, described sample feeding pipe comprises gas sampling pipe and Liquid sample introduction pipe, described Liquid sample introduction pipe one end is stretched out the liquid leading-in end of described tee pipe fitting and is connected with liquid sampling device, the other end stretches out outside the nozzle of described tee pipe fitting, described gas sampling pipe one end is stretched in described tee pipe fitting, it is outer and be connected with gas sample injection device that the other end stretches out described tee pipe fitting, for gaseous sample leading-in end, described heater is coated on outside described tee pipe fitting, for the desolventizing of heating liquid sample, the nozzle of the metal nozzle of tee pipe fitting is liquid exit, be provided with the hatch frame inwardly shunk,
The gas exit of the insulation medium cavity of described low-temperature plasma jet device is mutually vertical near the metal nozzle of the tee pipe fitting of sampling device, under the indirectly-acting of plasma jet, the ionized sample molecule that the nozzle through the metal nozzle of tee pipe fitting sprays.
Preferably, described Liquid sample introduction pipe outer wall and tee pipe fitting inwall form sheath gas-bearing formation;
Described Liquid sample introduction pipe is external diameter is 0.19mm, and internal diameter is the vitreous silica capillary of 0.1mm;
Between the Liquid sample introduction pipe of the liquid leading-in end of described tee pipe fitting and tee pipe fitting liquid leading-in end, Liquid sample introduction seals is set;
Between the gas sampling pipe of the gas leading-in end of described tee pipe fitting and described tee pipe fitting gas leading-in end, gas sampling seal is set;
One end that described gas sampling pipe stretches in tee pipe fitting is connected with described sheath gas-bearing formation, and described gas sampling pipe is for passing into auxiliary carrier gas or the gaseous sample for analyzing, and described gas sampling pipe is the TeflonFEP pipe of 1/16;
During fluid sample sample introduction, fluid sample is introduced through Liquid sample introduction pipe, and now gas sampling pipe passes into high pure nitrogen as carrier gas, and when gas sampling, gaseous sample is introduced through gas sampling pipe.
Preferably, described Liquid sample introduction pipe stretches out the length range of the one end outside the nozzle of tee pipe fitting is 0-1mm.
Preferably, described sparking electrode comprises interior electrode and external electrode;
Described interior electrode is stick electrode or hollow tube cathode, it is located in described insulation medium cavity, described one end of interior electrode is connected with one end of power supply, and the other end of described interior electrode is positioned at described insulation medium cavity, and with the exit port of described insulation medium cavity at a distance of 3-10mm;
Described external electrode is arranged around described dielectric cavity outer wall, the periphery coated insulation medium of described external electrode, described external electrode is connected with the other end of described power supply, and close external electrode one end of described insulation medium cavity exit and the exit port of described insulation medium cavity are at a distance of 2-5mm.
Preferably, described interior electrode is tungsten bar, and diameter range is 1-2mm, and length is 120mm; Described dispatch from foreign news agency very thickness is 1-2mm, and length is the copper strips of 15-25mm.
Preferably, described power supply is high-voltage radio-frequency dielectric impedance power supply, and frequency is 0.5-500KHz, and crest voltage is 220-80000V, and operating power is 2-50W.
Preferably, described heater is heating wire, and outer layer covers has adiabatic cotton.
Preferably, described insulation medium cavity is near sample feeding pipe side, and the axial distance between gas exit and the nozzle of tee pipe fitting is 8mm, and radial distance is 15mm;
Distance between the gas exit of described insulation medium cavity and metal nozzle is 1-2mm;
Described insulation medium cavity is formed by quartz glass or ceramic making, and its internal diameter is 0-3mm, and length is 50-120mm.
Preferably, the discharge gas passed in described discharge gas introducing device is helium, and helium flow velocity is 300-450ml/min.
Preferably, the nozzle of indication tee pipe fitting is positioned at the dead ahead of mass spectrum mouth, and the spacing of its exit and mass spectrum mouth is 3-5mm.The beneficial effects of the utility model:
(1) the utility model provides a kind of plasma electrospray mass spectrometry ionization source, liquid or gaseous sample enter in threeway shower nozzle by the sample feeding pipe of sampling device, and the fluid sample after desolventizing is sprayed by the exit of threeway shower nozzle with carrier gas or gaseous sample, and reacting gas enters in insulation medium cavity by the wireway of dielectric barrier discharge device, under the discharge process of sparking electrode, produce low temperature plasma, and sprayed by the gas exit of insulation medium cavity, the gas exit of insulation medium cavity is vertical with the tee pipe fitting of sampling device to be arranged, when plasma jet contacts with tee pipe fitting, in plasma, the metal surface of the active component of high energy and the metal nozzle of tee pipe fitting interacts, the electron excitation of metal surface or surface plasma body resonant vibration form surface plasma excimer, due to the hatch frame that nozzle inwardly shrinks, make metal surface CHARGE DISTRIBUTION uneven, when fluid sample is through nozzle, generation Charger transfer or arc discharge make ionized sample molecule, effectively evade the effect of rf electric field, the sample molecule of ionization does not need in the effect of repulsion electrode, just can enter mass spectrum mouth to be detected, and then reduce energy consumption.Improve Ionization Efficiency and instrument detection sensitivity, providing possibility for expanding plasma technique further in the range of application of field of mass spectrometry.
(2) when fluid sample sample introduction, the solvent in fluid sample can effectively be removed by heater.
(3) insulation medium cavity is formed by quartz glass or ceramic making, not only has good heat-proof quality, also have good insulation property, and make handling ease, low price.
Accompanying drawing explanation
Fig. 1 is the structural representation of plasma electrospray mass spectrometry ionization source;
Fig. 2 is the structural representation of sampling device;
Fig. 3 is low-temperature plasma jet device.
In figure:
1, liquid sampling device; 2, Liquid sample introduction pipe; 3, Liquid sample introduction seals; 4, gas sample injection device; 5, gas sampling seal; 6, heater; 7, nozzle; 8, sample spraying; 9, tee pipe fitting; 10, sealing device; 11, discharge gas introducing device; 12, insulation medium cavity; 13, interior electrode; 14, external electrode; 15, low-temperature plasma jet; 16, power supply; 17, wireway; 18, gas exit; 19, mass spectrum mouth; 20, gas sampling pipe; 21, metal nozzle.
Embodiment
The technical solution of the utility model is further illustrated by embodiment below in conjunction with accompanying drawing.
Embodiment one:
Present embodiments provide a kind of plasma electrospray mass spectrometry ionization source, as shown in Figure 1-Figure 3, it comprises sampling device and low-temperature plasma jet device to the structure of this ionization source.
As shown in Figure 2, sampling device, comprises sample feeding pipe, the tee pipe fitting 9 be communicated with described sample feeding pipe and heater 6, described heater 6 is coated on outside described tee pipe fitting 9, for the desolventizing of heating liquid sample, concrete, described heater is heating wire, and outer layer covers has adiabatic cotton; The nozzle 7 of the metal nozzle 21 of tee pipe fitting 9 is positioned at the dead ahead of mass spectrum mouth 19, and two-port is at a distance of 5mm.
Wherein sample feeding pipe comprises Liquid sample introduction pipe 2, gas sampling pipe 20; The nozzle 7 of tee pipe fitting 9 is liquid exit, is provided with the hatch frame inwardly shunk; Liquid sample introduction pipe 2 outer wall and tee pipe fitting 9 inwall form sheath gas-bearing formation.
Fluid analysis sample is incorporated into Liquid sample introduction pipe 2 through liquid sampling device 1, and now gas sample injection device 4 is assist gas high-purity N
2, the sheath gas-bearing formation that assist gas is formed through Liquid sample introduction pipe 2 and tee pipe fitting 9, forms sample spraying 8 at nozzle 7 together with fluid sample.Heater 6 temperature-controllable, sets heating-up temperature by heater 6, removes solvent contained in sample, improves sample ionization efficiency.
Preferably, Liquid sample introduction pipe 2 one end is stretched out the liquid leading-in end of described tee pipe fitting 9 and is connected with liquid sampling device 1, the other end stretches out outside the nozzle 7 of described tee pipe fitting 9, the length range that Liquid sample introduction pipe 2 stretches out the one end outside the nozzle 7 of tee pipe fitting 9 is 0-1mm, described Liquid sample introduction pipe 2 is external diameters is 0.19mm, and internal diameter is the vitreous silica capillary of 0.1mm; Between the Liquid sample introduction pipe 2 of the liquid leading-in end of tee pipe fitting 9 and tee pipe fitting 9 liquid leading-in end, Liquid sample introduction seals 3 is set; Between the gas sampling pipe 20 of the gas leading-in end of tee pipe fitting 9 and described tee pipe fitting 9 gas leading-in end, gas sampling seal 4 is set.
Gas sampling pipe 20 one end is stretched in described tee pipe fitting 9, and be connected with described sheath gas-bearing formation, it is outer and be connected with gas sample injection device 4 that the other end stretches out described tee pipe fitting 9, for gaseous sample leading-in end, described gas sampling pipe 20 is for passing into auxiliary carrier gas or the gaseous sample for analyzing, and described gas sampling pipe 20 is the TeflonFEP pipe of 1/16.
During fluid sample sample introduction, fluid sample is introduced through Liquid sample introduction pipe 2, now gas sampling pipe 20 passes into high pure nitrogen as carrier gas, when gas sampling, gaseous sample is introduced through gas sampling pipe 20, Liquid sample introduction pipe 2 can introduce some function gases or liquid (H2, H2O), can also leave unused.
As shown in Figure 3, low-temperature plasma jet device comprises insulation medium cavity 12, sparking electrode, wireway 17, discharge gas introducing device 11 and power supply 16, and wherein sparking electrode comprises interior electrode 13 and external electrode 14.Insulation medium cavity 12 is quartz glass tube, the internal diameter 1.5mm of glass tube, length 100mm.Described insulation medium cavity 12 for one end be gas exit 18, the other end is the cavity body structure sealed by sealing device 10, described gas exit 18 inwardly shrinks opening, gas exit 18 inwardly shrinks opening, one end of wireway 17 is stretched in sealing device 10, and be connected with one end of insulation medium cavity 12, the other end stretches out sealing device 10 and is connected with discharge gas introducing device 11; The gas exit 18 of insulation medium cavity 12 is orthogonal with the tee pipe fitting 9 of sampling device, distance between the gas exit 18 of insulation medium cavity 12 and the metal nozzle 21 of the tee pipe fitting 9 of sampling device is 1-2mm and mutually vertical, described insulation medium cavity 12 is near the nozzle 7 axial distance 8mm of sample feeding pipe side and tee pipe fitting 9, radial distance 15mm.Interior electrode 13 is tungsten bar, and diameter is 1mm, and length is 120mm; Interior electrode 13 is positioned on the axis of insulation medium cavity 12, interior electrode 13 one end is connected with one end of power supply 16, the other end of interior electrode 13 is positioned at insulation medium cavity 12, and with the extraction port of insulation medium cavity 12 at a distance of 3-10mm, at a distance of 9mm in present embodiment.External electrode 14 is annular electrode, and material is copper strips, and its thickness is 1mm, and length is 15mm.External electrode 14 is coated on the outside of dielectric 12, and external electrode 14 is connected with the other end of power supply 16, with insulation medium cavity 12 exit at a distance of 5mm.
In the present embodiment, preferably, power supply 16 comprises interior electrode 13, external electrode 14, and power supply 16 is high-voltage radio-frequency dielectric impedance power supply, and frequency is 0.5-500KHz, and crest voltage is 220-80000V, and operating power is 2-50W.The discharge gas passed in discharge gas introducing device 11 is helium, helium flow velocity is 310ml/min, when helium through insulation medium cavity 12 from the process that the exit of insulation medium cavity 12 flows out, through the region of discharge that interior electrode 13 forms with external electrode 14, the discharge voltage that sparking electrode applies makes helium ionize, produce helium plasma, under the effect of air-flow, helium plasma flows out region of discharge with air-flow and forms plasma jet 15, and plasma jet 15 contacts with the tee pipe fitting 9 of sampling device.When plasma jet 15 contacts with tee pipe fitting 9, in plasma, the metal surface of the active component of high energy and the metal nozzle 21 of tee pipe fitting 9 interacts, the electron excitation of metal surface or surface plasma body resonant vibration form surface plasma excimer, like this, due to the hatch frame that nozzle 7 inwardly shrinks, make metal surface CHARGE DISTRIBUTION uneven, when fluid sample is through nozzle 7, generation Charger transfer or arc discharge make ionized sample molecule.
In the present embodiment, low-temperature plasma jet device and mass spectrum mouth 19 be not in the same side, and distant, then there is not the effect of rf electric field, and the sample molecule of ionization does not need in the effect of repulsion electrode, just can enter mass spectrum mouth and be detected, and then reduce energy consumption.
Embodiment two
Present embodiments provide a kind of plasma electrospray mass spectrometry ionization source, as shown in Figure 1-Figure 3, it comprises sampling device and low-temperature plasma jet device to the structure of this ionization source.
As shown in Figure 2, sampling device, comprises sample feeding pipe, the tee pipe fitting 9 be communicated with described sample feeding pipe and heater 6, concrete, and described heater 6 is heating wire, and outer layer covers has adiabatic cotton; Described heater 6 is coated on outside described tee pipe fitting 9, and for the desolventizing of heating liquid sample, the nozzle 7 of the metal nozzle 21 of tee pipe fitting 9 is positioned at the dead ahead of mass spectrum mouth 19, and two-port is at a distance of 3mm.
Wherein sample feeding pipe comprises 7 of the metal nozzle 21 of Liquid sample introduction Liquid sample introduction pipe 2, gas sampling pipe 4 and heater 6 tee pipe fitting 9 nozzle for exit, is provided with the hatch frame inwardly shunk; Liquid sample introduction pipe 2 outer wall and tee pipe fitting 9 inwall form sheath gas-bearing formation.
Preferably, Liquid sample introduction pipe 2 one end is stretched out the liquid leading-in end of described tee pipe fitting 9 and is connected with liquid sampling device 1, the other end stretches out outside the nozzle 7 of described tee pipe fitting 9, the length range that Liquid sample introduction pipe 2 stretches out the one end outside the nozzle 7 of tee pipe fitting 9 is 0-1mm, Liquid sample introduction pipe 2 is external diameters is 0.19mm, and internal diameter is the vitreous silica capillary of 0.1mm; Between the Liquid sample introduction pipe 2 of the liquid leading-in end of tee pipe fitting 9 and tee pipe fitting 9 liquid leading-in end, Liquid sample introduction seals 3 is set; Between the gas sampling pipe 20 of the gas leading-in end of tee pipe fitting 9 and described tee pipe fitting 9 gas leading-in end, gas sampling seal 4 is set.
Gas sampling pipe 20 one end is stretched in described tee pipe fitting 9, and be connected with described sheath gas-bearing formation, it is outer and be connected with gas sample injection device 4 that the other end stretches out described tee pipe fitting 9, for gaseous sample leading-in end, gas sampling pipe 20 is for passing into auxiliary carrier gas or the gaseous sample for analyzing, and described gas sampling pipe 20 is the TeflonFEP pipe of 1/16.
During gas sample introduction, now syringe 1 and Liquid sample introduction pipe 2 can leave unused, and can also pass into functional liquid or gas.Gaseous sample directly enters into by gas device 4 the sheath gas-bearing formation that Liquid sample introduction pipe 2 formed with tee pipe fitting 9, sprays at nozzle 7.
As shown in Figure 3, low-temperature plasma jet device comprises insulation medium cavity 12, sparking electrode, discharge gas introducing device 11 and power supply 16, and wherein sparking electrode comprises interior electrode 13 and external electrode 14.Insulation medium cavity 12 is earthenware, the internal diameter 2mm of earthenware, length 100mm.Described insulation medium cavity 12 for one end be gas exit 18, the other end is the cavity body structure sealed by sealing device 10, and gas exit 18 inwardly shrinks opening, and gas exit 18 is for inwardly to shrink hatch frame; One end of wireway 17 is stretched in sealing device 10, and is connected with one end of insulation medium cavity 12, and the other end stretches out sealing device 10 and is connected with discharge gas introducing device 11; The gas exit 18 of insulation medium cavity 12 and tee pipe fitting 9 perpendicular quadrature of sampling device, with the nozzle 7 axial distance 8mm of tee pipe fitting 9, radial distance 15mm.Sparking electrode comprises interior electrode 13 and external electrode 14, interior electrode 13 is tungsten bar, diameter 1.5mm, length 120mm, interior electrode 13 is positioned on the axis of insulation medium cavity 12,13 1 sections, interior electrode is connected with one end of power supply 16, and the other end of interior electrode 13 is positioned at insulation medium cavity 12, and with the extraction port of dielectric 12 at a distance of 9mm.External electrode 14 is annular electrode, and material is copper strips, thickness 2mm, length 25mm.External electrode 14 is coated on the outside of dielectric 12, and external electrode 14 is connected with the other end of power supply 16, with gas exit 18 2mm apart of insulation medium cavity 12.Power supply 16 is interior electrode 13, external electrode 14 is powered, and power supply 16 is high-voltage radio-frequency dielectric impedance power supply, and frequency is 0.5-500KHz, and crest voltage is 220-80000V, and operating power is 2-50W.The discharge gas passed in discharge gas introducing device 11 is helium, helium flow velocity 410ml/min, when helium through insulation medium cavity 12 from the process that the gas exit 18 of insulation medium cavity 12 flows out, through the region of discharge that interior electrode 13 forms with external electrode 14, the discharge voltage that sparking electrode applies makes helium ionize, produce helium plasma, under the effect of air-flow, helium plasma flows out region of discharge with air-flow and forms plasma jet 15, and plasma jet 15 contacts with the metal nozzle 21 of the tee pipe fitting 9 of sampling device.When plasma jet 15 contacts with metal nozzle 21, in plasma, the active component of high energy and the metal surface of tee pipe fitting 9 nozzle 7 end interact, the electron excitation of metal surface or surface plasma body resonant vibration form surface plasma excimer, like this, due to the hatch frame that nozzle 7 inwardly shrinks, its metal surface CHARGE DISTRIBUTION is uneven, and when gaseous sample is through nozzle 7, generation Charger transfer or arc discharge make ionized sample molecule.
In the present embodiment, low-temperature plasma jet device and mass spectrum mouth 19 be not in the same side, and distant, then there is not the effect of rf electric field, and the sample molecule of ionization does not need in the effect of repulsion electrode, just can enter mass spectrum mouth and be detected, and then reduce energy consumption.
Note, above display and describe general principle of the present utility model and principal character and advantage of the present utility model.The technical staff of the industry should understand; the utility model is not by the restriction of above-mentioned execution mode; what describe in above-mentioned execution mode and specification just illustrates principle of the present utility model; under the prerequisite not departing from the utility model spirit and scope; the utility model also has various changes and modifications; these changes and improvements all fall within the scope of claimed the utility model, and claimed scope of the present utility model is defined by appending claims and equivalent thereof.