CN102944629A - Eluting device for sampling program for detecting polychlorinated biphenyl of trace of water body by gas chromatography-mass spectrometry - Google Patents

Abstract

Translated fromChinese

本发明涉及一种气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，属于分析测试领域。现有的相关洗脱技术尚不能令人满意，本案针对该问题。本案在惯常的针筒加针筒过滤器的结构基础上，进一步在针筒上捆缚安装杆状或探针状超声波探头，并令该探头的工作端紧贴在针筒外壁表面上，该探头的工作端其安装位置邻近针筒底部。该装置其应用之中，是通过如下机制达成洗脱环节的强化：在针筒过滤器接通负压源之前施加高频频段的超声波，强力促成目标物的解吸、传质，而在针筒过滤器接通负压源进行抽滤的期间，高频频段的超声波仍然持续辐射，强力阻遏目标物在抽滤进程中的重新吸附。本案装置并且拆装两便，方便灵活组合应用。

The invention relates to an eluting device for a sample preparation program for detecting trace amounts of polychlorinated biphenyls in water by gas-mass spectrometry, belonging to the field of analysis and testing. The existing relevant elution technology is not satisfactory yet, and this case addresses this issue. In this case, on the basis of the conventional structure of a syringe plus a syringe filter, a rod-shaped or probe-shaped ultrasonic probe is further installed on the syringe, and the working end of the probe is closely attached to the surface of the outer wall of the syringe. The working end of the probe is mounted adjacent to the bottom of the barrel. In the application of this device, the strengthening of the elution link is achieved through the following mechanism: before the syringe filter is connected to the negative pressure source, ultrasonic waves in the high-frequency band are applied to strongly promote the desorption and mass transfer of the target, while the syringe filter When the filter is connected to the negative pressure source for suction filtration, the ultrasonic waves in the high-frequency band still radiate continuously, which strongly prevents the re-adsorption of the target object during the suction filtration process. The device of this case is easy to assemble and disassemble, which is convenient and flexible for combined application.

Description

Gas-matter coupling detects its standby sample program washing device of water body Trace Polychlorinated Biphenyls

Technical field

The present invention relates to a kind of gas-matter coupling and detect its standby sample program washing device of water body Trace Polychlorinated Biphenyls, belong to the analytical test field.

Background technology

About the origin of Trace Polychlorinated Biphenyls in the environment water and the general background of analyzing and testing thereof, can be referring to Chinese invention patent application case 201210099400.3.

In many detection methods of Trace Polychlorinated Biphenyls, comparatively speaking, comparatively accurate, reliable with the GC-MS method in for environment water.Described GC-MS analyzes, and refers to gas chromatography-mass spectrometry, the GC-MS character group its refer to and art-recognized meanings itself for the professional in analysis and testing technology field, be known.

As mentioned above, in environment water Trace Polychlorinated Biphenyls analyzing and testing, the GC-MS method is than the tool advantage, and this point is described in detail in above-mentioned Chinese invention patent application case 201210099400.3.

According to the detailed introduction of Chinese invention patent application case 201210099400.3, among the GC-MS analytical test program for Trace Polychlorinated Biphenyls in the water body, comprise important standby sample step, the namely step of adsorptive separation target substance from water body; Employing is adsorbed target substance through the good magnetic composite nano adsorbent of the hydrophilicity of modification from water body, and through magnetic separation, wash-out, evaporate, dry up, the step such as organic solvent constant volume, finish standby sample, be a more high efficiency sampling method.

Elution step wherein is the focus that this case is paid close attention to.

Analyze in the standby sample for water body Trace Polychlorinated Biphenyls GC-MS existing, its elution step, to be placed within the syringe through the magnetic composite nano adsorbent that from water body, has adsorbed target substance that magnetic separates, and the syringe filtrator in micron order aperture is installed at the syringe front end, with the described magnetic composite nano adsorbent of organic solvent drip washing, and in conjunction with the suction filtration means, reach the purpose of wash-out target substance.

In elution step, such as how the least possible wash-out organic solvent, reach one desirable as far as possible near 100% eluting rate, for saving analysis time, and, the reliability, the accuracy that improve analysis result are all significant, and about this point, any one professional who is engaged in the GC-MS analysis is clear.

In the prior art, comprise that GC-MS analyzes the standby sample program of multiple instrumental analysis of standby sample program, the absorb-elute step of its target substance, usually, all be to adopt simple, traditional syringe to add the apparatus structure of filtrator, and realize wash-out in the mode that the simple drip washing of organic solvent adds suction filtration; Because there is special affinity interaction power in the evaluating objects material usually and between the selected adsorbent, this is the basis that selected adsorbent has good trapping ability, yet, also just because the special affinity interaction power that exists between selected adsorbent and the evaluating objects material is difficult to reach a desirable eluting rate so that the simple drip washing of common organic solvents adds the mode of suction filtration; In other words, selected adsorbent its early stage is to the trapping ability of target substance, with the wash-out difficulty of evaluating objects material in the later stage elution step be the desorb difficulty, both are contradiction each other; Generally speaking, be to improve the eluting rate of evaluating objects material, must take sacrifice adsorbent early stage to the trapping ability of evaluating objects material as prerequisite, vice versa; More particularly, the Capture by Sorbents During ability is weak, comparatively speaking, and just easy wash-out, otherwise, if the Capture by Sorbents During ability is strong, just be not easy to reach desirable eluting rate.

As mentioned above, there is special affinity interaction power in the evaluating objects material usually and between the selected adsorbent, as the specialty chemical worker, this be extremely hold intelligible, as an example, can and evaluating objects thing polychlorinated biphenyl between form special π-π combination power, and has again special high-ratio surface, and carry out easily that magnetic separates, certainly the magnetic active carbon that first-selected is through hydrophilic modifying, this is the first-selected adsorbent that can reach optimum capture rate, but, just because of magnetic active carbon to polychlorinated biphenyl π-π combination power is strong, specific surface is large especially, capture Z-TEK not strong, so, the problem that causes is exactly that its eluting rate lowers greatly, usual wash-out means become fully unreliable at this, to such an extent as to can't consider to use among the actual analysis Test Application described magnetic active carbon to be used as trapping agent or to say adsorbent fully.Just because of this, adopt described magnetic active carbon through hydrophilic modifying to be used as the standby sample trapping agent of GC-MS and so on instrumental analysis or say adsorbent, in the prior art basic nobody mention, more report without pertinent literature.

Above-mentioned Chinese invention patent application case 201210099400.3, obviously be that the carbon nano-tube of magnetic coupling captures the polychlorinated biphenyl in the water body not as the trapping agent through the magnetic active carbon of hydrophilic modifying with a kind of trapping ability, the scheme of this application case is real to be a kind of power of capture and eluting rate two-phase balance unavoidable newly measures afterwards.

As seen, if rest on the existing elution technique level always, so, the situation that adsorbent selection face receives greatly to limit to will continue.

In brief, detect so specific field in water body Trace Polychlorinated Biphenyls gas-matter coupling, the wash-out means in the existing standby sample program usually can not be satisfactory; Therefore, how improving water body Trace Polychlorinated Biphenyls gas-matter coupling and detect it for the object elution technique in sample program, is a problem that merits attention.

Summary of the invention

Technical matters to be solved by this invention is, detects the unsafty present situation of elution technique in its standby sample program for water body Trace Polychlorinated Biphenyls gas-matter coupling, researches and develops a kind of new washing device of addressing this problem of helping.

The present invention is by the described technical matters of following solution, this scheme provides a kind of gas-matter coupling to detect its standby sample program washing device of water body Trace Polychlorinated Biphenyls, the structure of this device comprises syringe, and, syringe filter, a port of this syringe filter and the injection port of this syringe are socketed mutually, emphasis is, the structure of this device also comprises shaft-like or probe shape ultrasonic probe, described shaft-like or probe shape ultrasonic probe is tied with syringe and is installed in, this working end shaft-like or probe shape ultrasonic probe is close on the outer wall surface of syringe, be close to the contiguous syringe of its locations of structures of the described working end bottom on the syringe outer wall surface, be used for will be shaft-like or probe shape ultrasonic probe and syringe tie together to tie with member be the ribbon of flexibility, ropy, thread or ring, this shaft-like or its radiable ultrasonic frequency scope of probe shape ultrasonic probe is between 100KHz and 12MHz, and, higher-order of oscillation electric signal transmission cable, an end of this higher-order of oscillation electric signal transmission cable or probe shape ultrasonic probe shaft-like with this is connected.

Described shaft-like or probe shape ultrasonic probe, the market row is sold, and also can customize to ultrasound wave specialized factory.

The ultrasound wave of described frequency range between 100KHz and 12MHz is the ultrasound wave of the weak high-frequency band of ultrasonic cavitation effect, has many different from the ultrasound wave of the strong low frequency frequency range of ultrasonic cavitation effect; Its difference is known for the professional and technical personnel of art of ultrasound.

The structure of this device of this case can comprise higher-order of oscillation electric signal generator certainly, and the other end of described higher-order of oscillation electric signal transmission cable can be connected with this higher-order of oscillation electric signal generator.Described higher-order of oscillation electric signal transmission cable and higher-order of oscillation electric signal generator etc., market is on sale; Also can customize to ultrasound wave specialized factory.

This shaft-like or its radiable ultrasonic frequency of probe shape ultrasonic probe, further preferred scope is between 300KHz and 12MHz.

This syringe filter, the aperture of the filter bores of its filter membrane can be the arbitrarily selected apertures between from 0.01 micron to several microns, and still, the preferable range in its filter membrane aperture of this syringe filter is between 0.05 micron and 1.00 microns.Described syringe filter with and interior filter membrane market on sale, also can customize to specialized factory.

Described syringe, its pattern is analogous to usual medical syringe; Its material of described syringe can be plastics, glass, metal, pottery, etc.; Its preferred material of this syringe is quartz glass material or stainless steel.

Further preferred described to tie with member be stretch sticking cingulum, and this stretch sticking cingulum is the magic tape with telescopic resilience.Itself art-recognized meanings of this stretch sticking cingulum one word is known for the manufacturing technician of magic tape.Described stretch sticking cingulum market is on sale.

The structure of this device of this case can also comprise some annexes, and described annex for example; The fixed mount that is used for fixing described syringe; Described annex is also for example: the filtrate receiver that is used for receiving filtrate that is connected with syringe filter; Described annex is more for example: with the negative pressure source equipment of described filtrate receiver and syringe filter UNICOM, this negative pressure source refers to any equipment that can make vacuum condition, described negative pressure source specifically refers to the equipment of vacuum pump and so on, is known with regard to itself art-recognized meanings of vacuum pump one word in the vacuum technique field only; Etc..

Advantage of the present invention is, be that syringe adds on the basis of syringe filter with apparatus structure at usual standby sample, further tie in the syringe outer wall surface shaft-like or probe shape ultrasonic probe is installed, the working end of this shaft-like or probe shape ultrasonic probe and being close on the syringe outer wall surface, this is close to the contiguous syringe of its locations of structures of the described working end bottom on the syringe outer wall surface, so, when application this case device carries out the wash-out operation, can first the adsorbent that has captured object be moved in the syringe, and in the syringe filling of adsorbent region or spray wash-out organic solvent, simultaneously, open higher-order of oscillation electric signal generator, change via described form of energy shaft-like or probe shape ultrasonic probe, and see through the sound wave transmission of needle cylinder wall, to the syringe intracavity bottom adsorbent region sustained radiation ultrasonic cavitation effect ultrasound wave of weak high-frequency band, and during this period, connect off and on negative pressure source, off and on suction filtration; Among its application of this case device, it is the reinforcement of reaching the wash-out link by following mechanism: the ultrasound wave that before connecting negative pressure source, applies high-frequency band, brute force is facilitated desorb, the mass transfer of target substance, and during connection negative pressure source suction filtration, the ultrasound wave of high-frequency band still continues acting on simultaneously, and brute force checks the again absorption of target substance in the suction filtration process; Can so repeat to operate several times according to the needs of actual conditions, to reach desirable wash-out target.

In the situation that use stretch sticking cingulum to use member as described tying, each main member is easier to disassemble and the independent assortment use in this apparatus structure.

The application of this case device can be so that be similar to the trapping agent that its such inside of magnetic active carbon has the huge brute force of the specific surface in large and small duct of flood tide, and its object that captures no longer is difficult to wash-out; Based on the application of this case device, magnetic active carbon cheap and easy to get application in the standby sample program of instrumental analysis just becomes a kind of actual option that allows.

Description of drawings

Fig. 1 is the brief schematic diagram of this case apparatus structure.

Among the figure, the 1st, syringe, 2,3 is respectively two different the tying of locations of structures members, the 4th, syringe filter, the 5th, the working end of shaft-like or probe shape ultrasonic probe, the 6th, shaft-like or probe shape ultrasonic probe, the 7th, higher-order of oscillation electric signal transmission cable is not drawn described other annex among the figure.

Embodiment

In this case embodiment that Fig. 1 shows, the structure of this device comprises syringe 1, and, syringe filter 4, port of this syringe filter 4 and the injection port of this syringe 1 are socketed mutually, emphasis is, the structure of this device also comprises shaft-like or probe shape ultrasonic probe 6, described shaft-like or probe shape ultrasonic probe 6 is tied with syringe 1 and is installed in, this working end 5 shaft-like or probe shape ultrasonic probe 6 is close on the outer wall surface of syringe 1, be close to the contiguous syringe of 5 its locations of structures 1 bottom, described working end on syringe 1 outer wall surface, being used for will be shaft-like or tie together the usefulness member 2 of tying of probe shape ultrasonic probe 6 and syringe 1, the 3rd, flexible ribbon, ropy, thread or ring, these shaft-like or probe shape ultrasonic probe 6 its radiable ultrasonic frequency scopes are between 100KHz and 12MHz, and, higher-order of oscillation electric signal transmission cable 7, an end of this higher-order of oscillation electric signal transmission cable 7 or probe shape ultrasonic probe 6 shaft-like with this is connected.

The frequency values arbitrarily selected of this scope between 100KHz and 12MHz all is the preferred frequency enforcement value that this case allows.

The structure of this embodiment can comprise higher-order of oscillation electric signal generator certainly, and the other end of described higher-order of oscillation electric signal transmission cable 7 can be connected with this higher-order of oscillation electric signal generator.Described higher-order of oscillation electric signal transmission cable and higher-order of oscillation electric signal generator etc., market is on sale; Also can customize to ultrasound wave specialized factory.Do not draw described higher-order of oscillation electric signal generator in the accompanying drawing.

Among implementing, these shaft-like or probe shape ultrasonic probe 6 its radiable ultrasonic frequencies, further preferred practical range is between 300KHz and 12MHz; The ultrasonic frequency value of selecting arbitrarily between this 300KHz and 12MHz all is the described further preferred frequency values that this case allows enforcement.

Among implementing, this syringe filter 4, the aperture of the filter bores of its filter membrane can be the arbitrarily selected aperture between from 0.01 micron to several microns, and still, the preferred practical range in its filter membrane aperture of this syringe filter is between 0.05 micron and 1.00 microns; The filter membrane aperture value arbitrarily selected of scope between 0.05 micron and 1.00 microns all is the enforcement value in the described aperture of this case permission.Described syringe filter 4 with and interior filter membrane market all on sale, also can customize to relevant speciality producer.

Described syringe 1, its pattern is analogous to usual medical syringe; Described syringe 1 its enforcement material can be plastics, glass, metal, pottery, etc.; This syringe 1 its preferably to implement material be quartz glass material or stainless steel.

The structure of this device of this case can also comprise some annexes, described annex for example: the fixed mount that is used for fixing described syringe 1; Described annex is also for example: the filtrate receiver that is used for receiving filtrate that is connected with syringe filter 4; Described annex is more for example: with the negative pressure source equipment of described filtrate receiver and syringe filter 4 UNICOMs, this negative pressure source refers to any equipment that can make vacuum condition, described negative pressure source specifically refers to the equipment of vacuum pump and so on, is known with regard to itself art-recognized meanings of vacuum pump one word in the vacuum technique field only; Etc..Do not draw described annex in the accompanying drawing.

Among the implementation, tying in the apparatus structure do not limit with the quantity of member, and this quantity of tying with member for example can be one, two, three, four, etc.

Among the implementation, this is tied with member can be ribbon, ropy, thread or the ring of any flexibility of selecting.

Among the implementation, further preferred described to tie with member be stretch sticking cingulum; Described stretch sticking cingulum market is on sale.

Among the implementation, the quantity shaft-like or probe shape ultrasonic probe of tying together with syringe in the apparatus structure is not limit, with tie one of the minimum number of shaft-like or probe shape ultrasonic probe together of syringe, but, quantity also is the structure situation that this case allows in the structure situation more than.

Implement related syringe 1, its pattern is not limited to the pattern in the accompanying drawing; Described syringe 1 also can be the structure that its upper end open-mouth does not have the convex edge.

Implement related syringe 1, the pattern of its injection port is not limited to the pattern in the accompanying drawing.

Implement related syringe 1, make a general reference its similar function member.

Implement related syringe filter 4, be not limited to accompanying drawing legend structure, related syringe filter general reference similar function member.

Related syringe filter can certainly be by the multistage syringe filter of a plurality of syringe filter monomers through being in series.

The implementation of this case is not limited to this case accompanying drawing legend.

Claims (6)

Translated fromChinese

1.气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，该装置的结构包括针筒，以及，针筒过滤器，该针筒过滤器的一个端口与该针筒的注射口相互套接，其特征在于，该装置的结构还包括杆状或探针状超声波探头，所述杆状或探针状超声波探头与针筒捆缚装设在一起，该杆状或探针状超声波探头的工作端紧贴在针筒的外壁表面上，紧贴在针筒外壁表面上的所述工作端其结构位置邻近针筒底部，用于将该杆状或探针状超声波探头与针筒捆缚在一起的捆缚用构件是柔性的带状物、绳状物、线状物或环状物，该杆状或探针状超声波探头其所能辐射的超声波频率范围是介于100KHz与12MHz之间，以及，高频振荡电讯号传输电缆，该高频振荡电讯号传输电缆的一端与该杆状或探针状超声波探头连接。1. Gas-mass spectrometry detection of water body trace polychlorinated biphenyls and its sample preparation program use eluting device, the structure of this device includes a syringe, and, a syringe filter, a port of the syringe filter and the needle The injection ports of the cylinders are nested with each other. It is characterized in that the structure of the device also includes a rod-shaped or probe-shaped ultrasonic probe, and the rod-shaped or probe-shaped ultrasonic probe is bundled with the syringe. Or the working end of the probe-shaped ultrasonic probe is close to the outer wall surface of the syringe, and the structure position of the working end that is close to the outer wall surface of the syringe is adjacent to the bottom of the syringe, for the rod-shaped or probe-shaped The binding member that binds the ultrasonic probe and the syringe together is a flexible ribbon, rope, thread or ring. The ultrasonic frequency range that the rod-shaped or probe-shaped ultrasonic probe can radiate is It is between 100KHz and 12MHz, and a high-frequency oscillating electrical signal transmission cable, one end of the high-frequency oscillating electrical signal transmission cable is connected to the rod-shaped or probe-shaped ultrasonic probe.2.根据权利要求1所述的气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，其特征在于，该装置的结构包括高频振荡电讯号发生器，所述高频振荡电讯号传输电缆的另一端与该高频振荡电讯号发生器连接。2. gas-mass spectrometry according to claim 1 detects trace polychlorinated biphenyls in water body and its sample preparation program uses eluting device, it is characterized in that, the structure of this device comprises high-frequency oscillating electrical signal generator, described The other end of the high-frequency oscillating electrical signal transmission cable is connected with the high-frequency oscillating electrical signal generator.3.根据权利要求1所述的气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，其特征在于，该杆状或探针状超声波探头其所能辐射的超声波频率范围是介于300KHz与12MHz之间。3. gas-mass spectrometry according to claim 1 detects trace polychlorinated biphenyls in water body and its sample preparation program uses eluting device, it is characterized in that, the ultrasonic wave that it can radiate of this rod shape or probe shape ultrasonic probe The frequency range is between 300KHz and 12MHz.4.根据权利要求1所述的气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，其特征在于，该针筒过滤器其滤膜的孔径介于0.05微米与1.00微米之间。4. gas-mass spectrometry according to claim 1 detects trace polychlorinated biphenyls in water body and its sample preparation program uses eluting device, it is characterized in that, the aperture of its filter membrane of this syringe filter is between 0.05 micron and between 1.00 microns.5.根据权利要求1所述的气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，其特征在于，该针筒其材质是石英玻璃材质或不锈钢材质。5. The gas-mass spectrometry detection water body trace polychlorinated biphenyls according to claim 1 and its sample preparation program eluting device, is characterized in that, its material of this syringe is quartz glass material or stainless steel material.6.根据权利要求1所述的气-质联用检测水体痕量多氯联苯其备样程序用洗脱装置，其特征在于，所述捆缚用构件是松紧粘扣带，该松紧粘扣带是具有伸缩弹性的粘扣带。6. Gas-mass spectrometry according to claim 1 detects water body trace polychlorinated biphenyls and its sample preparation program uses eluting device, it is characterized in that, described binding member is elastic hook and loop, and this elastic stick The buckle is a hook and loop with stretch elasticity.