CN106057630B - A kind of ion sputtering film coating capillary pipe spray ionization device - Google Patents

Abstract

The invention discloses an ion sputtering coating capillary spray ionization device, which comprises an ion mobility spectrometer host (1), a coating borosilicate glass capillary (3), a bracket (4), a metal clip (5) and a power cord (6) ); the ion mobility spectrometer mainframe (1) includes an electrospray sample inlet and is provided with a lens, and the front end of the coated borosilicate glass capillary (3) is arranged near the lens, and the support (4 ) is provided with a fixed portion (2), the fixed portion (2) is connected to the coated borosilicate glass capillary (3), and the rear end of the coated borosilicate glass capillary (3) is connected to the coated borosilicate glass capillary (3) The metal clip (5) is connected, and the metal clip (5) is connected to the ion mobility spectrometer host (1) through the power line (6). The ion sputtering coating capillary spray ionization device of the invention greatly reduces the detection cost, improves the detection efficiency, and can be used for on-site rapid detection of samples.

Description

A capillary spray ionization device for ion sputtering coating

technical field

The invention relates to a detection device, in particular to an ion sputtering coating capillary spray ionization device.

Background technique

Alkylphenol polyoxyethylene ethers are widely used in textiles, plastics, rubber, daily chemicals, medicine, papermaking, electronics and other fields. They are mainly used as textile auxiliaries, detergents, emulsifiers, wetting agents, stabilizers, etc. Another large class of nonionic surfactants following fatty alcohol polyoxyethylene ethers. Among the alkylphenol polyoxyethylene ethers, nonylphenol polyoxyethylene ether is the most, accounting for 80-85%, and octylphenol polyoxyethylene ether accounts for about 15%. As an endocrine disruptor, the biodegradable metabolites of alkylphenol ethoxylates will accumulate in the organism and enter the human body through the food chain cycle, which will have a serious impact on the growth of human cancer cells and reproductive ability, and have a negative impact on the environment and human beings. It is potentially harmful to health, and there is a lack of detection devices that can quickly detect alkylphenol polyoxyethylene ethers in the prior art.

Contents of the invention

The technical problem to be solved by the present invention is to provide a method for ensuring the accuracy of detection data, greatly reducing detection cost, improving detection efficiency, and providing possible rapid detection of alkylphenol polyoxyethylene ether for real-time online detection. Ion sputter coating capillary spray ionization device.

The invention also provides a method for detecting nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether by using the ion sputtering coating capillary spray ionization device.

An ion sputtering coating capillary spray ionization device, comprising an ion mobility spectrometer host, a coated borosilicate glass capillary, a support, a metal clip and a power cord; the ion mobility spectrometer host includes an electrospray injection port, A lens is arranged at the spray sample inlet, the front end of the coated borosilicate glass capillary is arranged close to the lens, and the front end of the bracket is provided with a fixing part, and the fixing part is connected with the coated borosilicate glass capillary. The salt glass capillary is connected, the rear end of the coated borosilicate glass capillary is connected with the metal clip, and the metal clip is connected with the high-voltage output interface of the ion mobility spectrometer host through the power line; the coated boron The silicate glass capillary is composed of a borosilicate glass capillary and a film layer arranged on its outer wall, and the film layer is a metal material.

The ion sputtering coating capillary spray ionization device of the present invention, wherein, the metal material is high-purity gold, silver or platinum.

The ion sputtering coating capillary spray ionization device of the present invention, wherein, the preparation method of the coating borosilicate glass capillary (3) comprises the preparation and coating of the borosilicate glass capillary;

The coating comprises the following steps: placing the prepared borosilicate glass capillary horizontally on the sample seat of the ion sputtering instrument, the surface of the borosilicate glass capillary is 6 cm away from the sputtering head, and placed in the middle of the sample seat, In order to prevent the borosilicate glass capillary from rolling, fix it with carbon glue, cover the sample cover tightly, and evacuate; the sputtering gas is high-purity argon, with a purity greater than 99.9%, and a pressure of 0.1Mpa. Set the sputtering target , sputtering current, sputtering time; after the first sputtering is completed, the borosilicate glass capillary on the sputtered side is rotated, and the sputtering step is repeated until the entire outer wall of the borosilicate glass capillary is The sputtering process has been completed.

The ion sputtering coating capillary spray ionization device of the present invention, wherein, the metal material is high-purity gold, the thickness of the film layer is 30-40nm, the square resistance is 30 ohms per square, and gold sputtering is used in the sputtering process. The target, the sputtering current is 30mA, and the sputtering time is 180s.

The ion sputtering coating capillary spray ionization device of the present invention, wherein, the metal material is silver, the thickness of the film layer is 30-40nm, the square resistance is 30 ohms per square, and silver sputtering is used in the sputtering process. The target, the sputtering current is 35mA, and the sputtering time is 180s.

The ion sputtering coating capillary spray ionization device of the present invention, wherein, the metal material is platinum, the thickness of the film layer is 21-28nm, the square resistance is 32 ohms per square, and platinum sputtering is used in the sputtering process. The target, the sputtering current is 35mA, and the sputtering time is 180s.

The ion sputter coating capillary spray ionization device of the present invention, wherein the ion sputter coating capillary spray ionization device further includes a safety interlock device, the safety interlock device is arranged on the ion mobility spectrometer host, and close to the electrospray injection port;

The distance between the front end of the coated borosilicate glass capillary and the lens is 3 to 5 mm; the length of the coated borosilicate glass capillary is 5 cm, and the inner diameter of the front end, that is, the tip, is 5 to 15 μm. The rear end of the coated borosilicate glass capillary has an outer diameter of 1.5 mm and an inner diameter of 0.86 mm;

The preparation method of the borosilicate glass capillary includes the following steps: placing a standard-walled borosilicate glass blank in a microelectrode drawing apparatus, and setting various parameters of the microelectrode drawing apparatus: the heating temperature is 450° C. , the tension value is 0N, the rate is 5°C/s, the cycle time is 1s, and the air pressure is 600hpa, a borosilicate glass capillary is prepared.

The method for detecting nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether using the ion sputtering coating capillary spray ionization device of the present invention comprises the following steps:

Transfer the sample solution to be tested to the coated borosilicate glass capillary, place it at the front end of the electrospray inlet of the ion mobility spectrometer host, set the parameters of the ion mobility spectrometer host, the sample is ionized, and enters the transfer tube for separation After being detected by a Faraday cup detector, the corresponding spectrum is obtained, and the sample solution to be tested needs to be filled to the tip of the coated borosilicate glass capillary without generating air bubbles.

The method for detecting nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether of the present invention, wherein, the parameter setting of described ion mobility spectrometer host is:

Source voltage: 2500V, electrospray positive ion mode;

Migration tube voltage: 8000V;

Migration tube temperature: 180°C;

Gas preheating temperature: 180°C;

Spectrum width: 26ms;

Ion gate pulse width: 200μs;

Ion gate voltage: 40V;

Drift gas flow rate: 1.00L/min;

Exhaust pump flow rate: 0.60L/min.

The ion sputter coating capillary spray ionization device of the present invention differs from the prior art in that:

When the ion sputtering coating capillary spray ionization device of the present invention is used to detect the alkylphenol polyoxyethylene ether, the ionization of the sample is realized in an open atmosphere at atmospheric pressure, and the ion mobility spectrometry technology is used for rapid screening and detection at the microsecond time level; The detection by the device of the invention is accurate and reliable, and while ensuring the accuracy of detection data, the detection cost is greatly reduced and the detection efficiency is improved.

The capillary with ion sputtering coating can transmit current from the outer wall of the capillary through the metal coating, and it is used for spray ionization of the sample solution in the capillary. . This avoids the need to insert the metal microelectrode into the capillary. If a metal microelectrode is used, the sample solution in the capillary must continue to be in contact with the metal microelectrode. When the sample solution is consumed and separated from the front end of the metal microelectrode, it cannot continue to spray. ionization.

The ion sputter coating capillary spray ionization device of the present invention will be further described below in conjunction with the accompanying drawings.

Description of drawings

Fig. 1 is the overall structure schematic diagram of ion sputter coating capillary spray ionization device in the present invention;

Fig. 2 is the structural representation of the main part of ion sputter coating capillary spray ionization device in the present invention;

Fig. 3 is a partially enlarged view of the T area in Fig. 2;

Fig. 4 is the ion mobility spectrogram of the nonylphenol polyoxyethylene ether whose average degree of polymerization is 9 in the embodiment of the present invention;

Fig. 5 is the ion mobility spectrogram of the octylphenol polyoxyethylene ether whose average degree of polymerization is 10 in the embodiment of the present invention;

Fig. 6 is the magnified view of the optical microscope of the coated borosilicate glass capillary in the present invention (the inner diameter of the tip is 5-15 μm);

The Chinese comparison of English appearing in all accompanying drawings of the present invention is as follows:

Intensity: signal strength; Drift Time: migration time; ms: milliseconds.

detailed description

Example 1

As shown in Figures 1 to 3, an ion sputtering coating capillary spray ionization device includes an ion mobility spectrometer host 1 (the ion mobility spectrometer instrument includes an ion mobility spectrometer host 1 and an ion source, and the ion source is arranged on the ion mobility spectrometer host 1 At the electrospray injection port, the ion mobility spectrometer host 1 of the present invention is an ion mobility spectrometer instrument for removing the ion source), a coated borosilicate glass capillary 3, a support 4, a metal clip 5 and a power cord 6; the ion mobility spectrometer The main engine 1 includes an electrospray sample inlet, and a lens is arranged at the electrospray sample inlet, the front end of the coated borosilicate glass capillary 3 is arranged near the lens, and the front end of the bracket 4 is provided with a fixed part 2, and the fixed part 2 It is connected with the coated borosilicate glass capillary 3, the rear end of the coated borosilicate glass capillary 3 is connected with the metal clip 5, and the metal clip 5 is connected with the high voltage output interface of the ion mobility spectrometer host 1 through the power line 6; the coated borosilicate The salt glass capillary 3 is composed of a borosilicate glass capillary and a film layer arranged on its outer wall, and the film layer is made of metal material. The thickness of the film layer is 30-40nm, and the square resistance is 30 ohms per square. The fixed part 2 is a hollow cylinder or a semicircular structure with an upward opening, and the coated borosilicate glass capillary 3 is fixed at the center of the fixed part 2 .

The preparation method of the coated borosilicate glass capillary 3 comprises the preparation and coating of the borosilicate glass capillary;

The coating includes the following steps: Place the prepared borosilicate glass capillary horizontally on the sample holder of the ion sputtering instrument. The surface of the borosilicate glass capillary is 6 cm away from the sputtering head and placed in the middle of the sample holder to prevent borosilicate from Roll the salt glass capillary, fix it with carbon glue, cover the sample cover tightly, and vacuum; the sputtering gas is high-purity argon, the purity is greater than 99.9%, and the pressure is 0.1Mpa. Set the sputtering target, sputtering current, sputtering Sputtering time; after the first sputtering is completed, turn the borosilicate glass capillary on the side that has been sputtered, and repeat the sputtering step until the entire outer wall of the borosilicate glass capillary has completed the sputtering process.

The metal material is high-purity gold, silver or platinum, and the parameters in the sputtering method are set to one of the following three:

The metal material is high-purity gold, the thickness of the film layer is 30-40nm, the square resistance is 30 ohms per square, gold sputtering target is used in the sputtering process, the sputtering current is 30mA, and the sputtering time is 180s;

The metal material is silver, the thickness of the film layer is 30-40nm, the square resistance is 30 ohms per square, silver sputtering target is used in the sputtering process, the sputtering current is 35mA, and the sputtering time is 180s.

The metal material is platinum, the thickness of the film layer is 21-28nm, and the square resistance is 32 ohms per square. A platinum sputtering target is used in the sputtering process, the sputtering current is 35mA, and the sputtering time is 180s.

The high-voltage electricity sprays the solution therein through the metal coating of the coated borosilicate glass capillary 3 to form a charged spray, and the spray enters the desolution area at the front end of the transfer tube through the lens.

The ion sputtering coating capillary spray ionization device also includes a safety interlock device 7, the safety interlock device 7 is arranged on the ion mobility spectrometer host 1, and is close to the electrospray injection port; the front end of the coating borosilicate glass capillary 3 and the lens The distance between them is 3-5mm; the length of the coated borosilicate glass capillary 3 is 5cm, the inner diameter of the front end is 5-15μm, the outer diameter of the rear end of the coated borosilicate glass capillary 3 is 1.5mm, and the inner diameter is 0.86mm.

The preparation method of the borosilicate glass capillary includes the following steps: placing the standard wall borosilicate glass blank in the microelectrode drawing apparatus, setting various parameters of the microelectrode drawing apparatus: heating temperature 450°C, tension value 0N , a rate of 5° C./s, a cycle time of 1 s, and an air pressure of 600 hpa to prepare a borosilicate glass capillary.

Adopt the device of the present invention to detect the antibiotic in the cosmetic:

1. Instruments and devices

Ion mobility spectrometer host (USA EXCELLIMS company, model GA2100, use tryptophan and citric acid to calibrate the instrument in positive and negative ion modes before use), including ion gate controller, air filter device, high-resolution ion mobility analyzer , Faraday cup detector, instrument control and data processing system; standard wall borosilicate glass blank (outer diameter 1.5mm, inner diameter 0.86mm); microelectrode drawing instrument (SUTTER Company, USA, model P-1000); ion Sputtering instrument (British Cressington company, model is 108Auto type).

2. Reagents and materials

Methanol (U.S. Fisher Company) is chromatographically pure; tryptophan and citric acid (U.S. Sigma-Aldrich, made into 10 μg/mL with methanol for instrument calibration); nonylphenol polyoxyethylene ether (average degree of polymerization is 9) and Octylphenol polyoxyethylene ether (the average degree of polymerization is 10) was purchased from ChemService, USA) to prepare a 1 mg/mL standard stock solution with methanol as a solvent, and dilute it to 25 μg/mL with the same solvent for analysis and testing. The characteristic ion mobility spectra of nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether are shown in Figure 4 and Figure 5, respectively.

3. Experimental method:

Detection by ion mobility spectrometry: transfer the sample solution to be tested to the coated borosilicate glass capillary 3, place it on the front end of the electrospray injection port of the ion mobility spectrometer host 1, set the parameters of the ion mobility spectrometer host, and the sample passes through After ionization, enter the migration tube for separation, and then detect with the Faraday cup detector to obtain the corresponding spectrum. The sample solution to be tested needs to be filled to the tip of the coated borosilicate glass capillary 3 without generating air bubbles.

The parameters of the ion mobility spectrometer host are set as:

Source voltage: 2500V, electrospray positive ion mode;

Migration tube voltage: 8000V;

Migration tube temperature: 180°C;

Gas preheating temperature: 180°C;

Spectrum width: 26ms;

Ion gate pulse width: 200μs;

Ion gate voltage: 40V;

Drift gas flow rate: 1.00L/min;

Exhaust pump flow rate: 0.60L/min.

4. Results and Analysis

1. Preparation of borosilicate glass capillary

The key to the preparation of borosilicate glass capillary is the size of the inner diameter of the tip. If the inner diameter is too large, the sample spray effect will be poor and the ionization efficiency will be low, which will seriously affect the sensitivity of the target substance; Ejection also causes the sensitivity of the instrument to drop or even no signal. Therefore, the present invention draws a series of capillaries by optimizing the key parameters of the microelectrode drawing instrument, such as heating temperature and rate, calculates the inner diameter of the tip under an optical microscope, and selects a capillary with an inner diameter of 5-15 μm at the tip as the spray source , in order to achieve the best ionization effect. Fig. 6 is an enlarged view of an optical microscope of a coated borosilicate glass capillary in the present invention (the inner diameter of the tip is 5-15 μm).

2. Preparation of Coated Borosilicate Glass Capillary 3

The coated borosilicate glass capillary 3 is prepared by coating sputtering, which is a process in which gold to be sputtered is diffused and deposited on the surface of the capillary in an argon atmosphere. The amount of gold diffused from the target, the corrosion rate, is not dependent on the argon pressure or the distance from the sample, but on the sputtering current. It is worth noting that at a sputtering current of 40 mA and a sputtering time of 4500 s, the corrosion rate of gold can lead to target failure. During each sputtering, the amount of gold deposited on the capillary depends on two conditions, one is the pressure of argon, and the other is the distance from the target to the sample. Therefore, the sputtering conditions of gold coating should be optimized to achieve the shortest sputtering time to obtain the best coating effect. Finally, the sputtering argon pressure is set to 0.1Mpa, the distance between the capillary surface and the sputtering head is 6cm, the sputtering current is 30mA, and the sputtering time is 180s.

3. Optimization of migration tube and sample gas temperature

The influence of the temperature change of the transfer tube and the sample gas on the signal intensity of each substance is studied. Since the temperature settings of the sample gas and the transfer tube should be kept as consistent as possible to reduce the ion characteristic migration time caused by heat exchange or other factors Therefore, when optimizing the two parameters in this experiment, they are set to the same value for investigation. A series of temperatures (160°C, 170°C, 180°C, 190°C, 200°C) were set, and the signal intensity values of each ion were recorded. The experimental results show that increasing the temperature of the transfer tube and sample gas within a certain range can Reduce the influence of air humidity or temperature on the ion signal intensity in the atmospheric environment, reduce the half maximum width and position offset of the ion peak, thereby improving the resolution of the ion peak; when the temperature is set too high, the system will be unstable, and the temperature Ion diffusion and collision losses caused by too high are also more serious, resulting in weakened ion signals. The experimental results show that the signal is the strongest at 180°C, therefore, the method of the present invention sets the temperature of the transfer tube and the sample gas at 180°C during the analysis process.

4. Detection limit

Under the optimal conditions of the experiment, nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether were detected and analyzed, and the detection limit was calculated according to the signal-to-noise ratio of 3. Nonylphenol polyoxyethylene ether and octylphenol polyoxyethylene ether The detection limit of oxyethylene ether is 1 μg/mL.

The above embodiments are only descriptions of the preferred implementations of the present invention, and are not intended to limit the scope of the present invention. Without departing from the design spirit of the present invention, those skilled in the art may make various modifications and changes to the technical solutions of the present invention. Improvements should all fall within the scope of protection determined by the claims of the present invention.

Claims (6)

1. a kind of ion sputtering film coating capillary pipe spray ionization device, it is characterised in that：Including ion mobility spectrometry main frame (1), plating Film borosilicate glass capillary tube (3), support (4), metal clip (5) and power line (6)；Ion mobility spectrometry main frame (1) bag Electric spray sample introduction mouthful is included, lens are provided with the electric spray sample introduction mouth, the plated film borosilicate glass capillary tube (3) Front end is positioned close in place of the lens, and the front end of the support (4) is provided with fixed part (2), the fixed part (2) and institute State plated film borosilicate glass capillary tube (3) to be connected, rear end and the metal of the plated film borosilicate glass capillary tube (3) Press from both sides (5) to be connected, the metal clip (5) passes through the power line (6) and the High voltage output interface of the ion mobility spectrometry main frame (1) It is connected；Film layer of the plated film borosilicate glass capillary tube (3) by borosilicate glass capillary tube and setting on its external wall Constitute, the film layer is metal material；

The metal material is high-purity gold, silver or platinum；

The preparation method of the plated film borosilicate glass capillary tube (3) includes the preparation and plating of borosilicate glass capillary tube Film；

The plated film comprises the following steps：The borosilicate glass capillary tube prepared is lain in a horizontal plane in into ion sputtering instrument sample On seat, the borosilicate glass capillary tube surface distance sputter head 6cm is positioned over specimen holder centre position, described to prevent Borosilicate glass capillary tube is rolled, and is fixed with carbon paste, and covers tightly sample cover, is vacuumized；Sputter gas is high-purity argon gas, purity More than 99.9%, pressure is 0.1Mpa, sets sputtering target material, sputtering current, sputtering time；After sputtering is finished for the first time, by The borosilicate glass capillary tube for sputtering side is rotated, and repeats sputter step, until the whole borosilicate glass hair Tubule outer wall has completed sputter procedure.

2. ion sputtering film coating capillary pipe spray ionization device according to claim 1, it is characterised in that：The metal material Expect for High Purity Gold, the thickness of the film layer is 30~40nm, sheet resistance is using golden sputtering target in 30 ohms per squares, sputter procedure Material, sputtering current is 30mA, and sputtering time is 180s.

3. ion sputtering film coating capillary pipe spray ionization device according to claim 1, it is characterised in that：The metal material Expect for silver, the thickness of the film layer is 30~40nm, sheet resistance be in 30 ohms per squares, sputter procedure using silver-colored sputtering target material, Sputtering current is 35mA, and sputtering time is 180s.

4. ion sputtering film coating capillary pipe spray ionization device according to claim 1, it is characterised in that：The metal material Expect for platinum, the thickness of the film layer is 21~28nm, sheet resistance is to use platinum sputtering target material in 32 ohms per squares, sputter procedure, Sputtering current is 35mA, and sputtering time is 180s.

5. ion sputtering film coating capillary pipe spray ionization device according to claim 1, it is characterised in that：The ion splashes Penetrating plated film capillary pipe spray ionization device also includes safety interlock (7), the safety interlock (7) be arranged on it is described from On son migration spectrum main frame (1), and close to the electric spray sample introduction mouthful；

The distance between the front end of the plated film borosilicate glass capillary tube (3) and the lens are 3~5mm；The plated film The length of borosilicate glass capillary tube (3) is 5cm, and front end is that the internal diameter at tip is 5~15 μm, the plated film borosilicate glass The rear end external diameter of glass capillary (3) is 1.5mm, and internal diameter is 0.86mm；

The preparation method of the borosilicate glass capillary tube comprises the following steps：Standard wall borosilicate glass blank is placed in Microelectrode is drawn in instrument, sets the microelectrode to draw the parameters of instrument：450 DEG C of heating-up temperature, value of thrust 0N, 5 DEG C of speed/ S, circulation time 1s, air pressure 600hpa, prepare borosilicate glass capillary tube.

6. nonyl phenol is detected using ion sputtering film coating capillary pipe spray ionization device according to any one of claims 1 to 5 The method of APEO and OPEO, it is characterised in that：Comprise the following steps：

Testing sample solution is transferred to plated film borosilicate glass capillary tube (3), ion mobility spectrometry main frame (1) is placed on Electric spray sample introduction mouthful front end, ion mobility spectrometry main frame (1) parameter is set, sample is ionized, into migration tube separation Detected by Faraday cup detector, obtain corresponding collection of illustrative plates, the testing sample solution need to be filled to the plated film borosilicate The tip of capillary glass tube (3), and bubble can not be produced；

The parameter setting of the ion mobility spectrometry main frame (1) is：

Source voltage：2500V, electron spray positive ion mode；

Migrate tube voltage：8000V；

Migration tube temperature：180℃；

Gas preheater temperature：180℃；

Spectrum width：26ms；

Ion fence gate pulse width：200μs；

Ion fence gate voltage：40V；

Drift about gas velocity：1.00L/min；

It is vented flow rate pump：0.60L/min.