CN105527381A - Ammonia catcher, ammonia detection device and method for detecting ammonia - Google Patents
Ammonia catcher, ammonia detection device and method for detecting ammonia Download PDFInfo
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- CN105527381A CN105527381A CN201610006288.2A CN201610006288A CN105527381A CN 105527381 A CN105527381 A CN 105527381A CN 201610006288 A CN201610006288 A CN 201610006288A CN 105527381 A CN105527381 A CN 105527381A
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- ammonia
- grabber
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- acid
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—Specially adapted to detect a particular component
- G01N33/0054—Specially adapted to detect a particular component for ammonia
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/02—Devices for withdrawing samples
- G01N1/22—Devices for withdrawing samples in the gaseous state
- G01N1/2247—Sampling from a flowing stream of gas
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4044—Concentrating samples by chemical techniques; Digestion; Chemical decomposition
Abstract
The invention discloses an ammonia catcher, an ammonia detection device and a method for detecting ammonia. An ammonia catcher main body consists of a collecting base body and an ammonia collector formed by acid loaded on the collecting base body; the ammonia detection device comprises the ammonia catcher and a sensor; through the ammonia catcher and the ammonia detection device, the catching and fixing of gaseous ammonia can be effectively realized, the accurate detection on the ammonia can be realized, and the ammonia catcher, the ammonia detection device and the method for detecting the ammonia can be widely applied to the disease detection of human bodies and various animals.
Description
Technical field
The ammonia pick-up unit that the present invention relates to a kind of ammonia grabber and set up based on ammonia grabber, and with the catching and detecting of method, particularly gaseous ammonia of ammonia pick-up unit detection ammonia, belong to ammonia detection technique field.
Background technology
Ammonia is present in a gaseous form in the breathing thing of human body, but it can be used to refer to disease and have the potentiality being used as screening disease on a large scale.These comprise kidney trouble, cirrhosis, or infect, such as helicobacter pylori or candida albicans microorganism.Meanwhile, the increase of ammonia in human body respiration body, also can show human body stress increases.Due to these reasons, provide measure this compound one simply and fast method seem particularly important.
In a healthy individuality, the typical content of ammonia in tidal air is the magnitude at 1,000,000,000/800-900, in unsound human body, then and can up to 1,000,000/1-15 (volume ratio).Because the difference of the reduced levels in this scope between healthy individuals and unhealthy individuality is little, therefore, need to provide a kind of method of accurate detection ammonia very important.
The induction of gaseous ammonia sample presents many potential problems, be included in the content of ammonia in tidal air relatively low, difference is very little sometimes for a level that is healthy and ammonia between unsound individuality, the method for sampling (sampling of such as mouth or nose all needs to select suitable detection solution and catching method).
In patent GB1315803.5 (September 5 2013 applying date), report the method that can detect ammonia in tidal air delicately of an innovation, ammonia can be detected on the level of significance of diagnosis.The method selectivity is strong, highly sensitive, is a kind of indirect detection ammonia electrochemical method relating to the front ammonia chemical conversion of detection.
Breathing sampling is an extremely important aspect, often out in the cold, needs efficient seizure to analyze thing (as ammonia), to be detected.Such as, the analytical approach of much ammonia requires ammonia solution, but solvent water, organic solvent, gel or ionic liquid.The problem that needs will overcome how to present breathing (or other gas) sample best to enter to make ammonia the solution be connected with sensor.
If breath sample is logical directly pass into solvent (or using controlled method injection), the solution of catching gas needs large volume and causes the concentration of ammonia to be diluted.Under low ammonia density condition, dilution brings problem and final concentration may be caused too low and exceed and cannot effectively detect.In order to overcome this problem in liquid device (water system or non-water system), the solution of very small size can be used.But the gas sample volume that typical single is breathed out is about 500mL.The solvent that the tidal air of large volume passes into small size can cause solute to volatilize instead of the dissolving of ammonia.Even if this can not occur, this method of catching sample of breath is also be difficult to obtain repeatably result.Gel/ionic liquid/other conducting mediums are used to be more complicated, because the oneself viscosity of solution is less than aqueous solution.In addition, ammonia solubleness in the solution is also a limiting factor.Therefore, seemingly the simple ammonia sample obtaining analysis in an appropriate manner from tidal air is also a challenge outwardly.
Once in the solution, ammonia produces a kind of derivant with some performance by chemical reaction, causes the stronger detection signal of generation feasibility (such as, by generating the stronger material of a kind of photolytic activity with a kind of chemical reagent reaction).But before ammonia dissolves, such chemical reagent can not occur in a solvent, because they will reduce the solubleness of ammonia, and reduces signal intensity.Therefore, they will add after ammonia dissolves, and this step makes whole complicate, adds manufacturing cost, reduces the reliability of analysis in some cases.And other compositions in tidal air also may occur in the solution, may disturb the detection of ammonia.So need to develop a kind of device only having the ammonia in tidal air to be captured, when analyzing, in tidal air, other gas componant is excluded.
Summary of the invention
For the defect existed in prior art, first object of the present invention be to provide a kind of can efficient capture gaseous ammonia, gaseous state is changed into the ammonia grabber of stable ammonium salts, this ammonia grabber be conducive to ammonia effective, accurately detect.
Second object of the present invention is that providing a kind of effectively catches gaseous ammonia and fix, and the pick-up unit that realization accurately detects the ammonia of catching.
3rd object of the present invention be to provide a kind of based on described ammonia grabber fast, the method for Accurate Determining gaseous ammonia.
4th object of the present invention be to provide a kind of based on described ammonia pick-up unit fast, the method for Accurate Determining gaseous ammonia.
In order to realize above-mentioned technical purpose, first aspect of the present invention provides a kind of ammonia grabber, and its main part forms by collecting matrix and being fixed on the acid of collecting on matrix.This grabber can obtain a proton by ammonia and be converted into ammonium ion from acid, and realizes gaseous ammonia to be fixed on matrix.Consistent with well-known reaction equation below:
Equally, after contact ammonia, ammonia grabber comprises to be collected matrix, the ammonium ion that collection matrix is caught and is fixed on the excessive acid of the relative ammonia collected on matrix.
Ammonia is generally gaseous state, the straightforward procedure of collection ammonia described herein, is catch ammonia from air-flow, and converts it into ammonium salt and fix.Allow other all gas to drain as waste gas, this is very simple and effective.Gaseous ammonia, once after captured, can pass through release, detect, or is directly detected on collection matrix, and this accurate method depends on the type of the sensor detected.But, can find out no matter be detect again or in situ detection after ammonia is released, use ammonia grabber of the present invention can obtain high concentration, high-purity sample.This makes to be easier to analyze ammonia.Have been found that this grabber is effective to gaseous ammonia height, accurately, extract the extraction ratio that ammonia has 100% from tidal air.
The term " ammonia " used is intended to comprise protonated ammonium ion.Significantly, for the reader of this area, refer to the detection of ammonia in some cases, specifically this is also that ammonium ion detects, and is also like this when referring to detection method.Especially like this when detecting in aqueous, in this case, depend in pH, can ammonium ion be formed.
Gaseous ammonia is generally in the tidal air from human or animal.Term used herein " expiratory air " refers to the potpourri of the some or all compositions of being discharged by lung.This may comprise one or two and be breathed, generally containing gaseous composition by respiratory nasal or mouth.Such as, air, air is here generally depleted oxygen, is rich in carbon dioxide.And steam, liquid parts also may exist, such as water vapor or water.Steam, liquid composition may comprise the material of dissolving.Similarly, grabber of the present invention is intended to catch the ammonia in breathing.Grabber of the present invention may be caught gaseous ammonia or catch ammonia from breathing condensation product, and breathing condensation product here refers to the steam component of liquid composition in breathing or condensation.
Under normal circumstances, acid is strong acid, because can guarantee that ammonia can change rapidly when ammonia and collection substrate contact like this.Acid is mineral acid mainly, such as H
3pO
4, H
2sO
4, HCl, HNO
3and the combination of these acid and weak acid.Have been found that independent organic acid is strong not, effectively can not catch the ammonia of 100%, in some cases can Interference Detection.Common hydrochloric acid, nitric acid be gaseous acid in aqueous.When using this aqueous acid, hydrochloric acid and nitric acid have the risk of volatilization and stop providing the proton of catching ammonia.Have been found that sulfuric acid has too strong corrosion to many devices, often can corrode collection matrix.But when using acid proof collection matrix, sulfuric acid may be able to use.Have been found that phosphoric acid has enough intensity and catches whole ammonia in air-flow, be particularly easy to when phosphoric acid is dried to oily be fixed on and collect on matrix.So the present invention most preferably adopts phosphoric acid.
Term used herein " strong acid " refers to and can dissociate completely when it is water-soluble." weak acid " then in contrast, namely can not dissociate completely.The Typical pKa values of strong acid is between-10 to-2, and the pKa value of weak acid is then between-2 to 12.
Usually, collecting matrix is porous structure.The collection matrix often selecting those to have abundant hole air-flow can be made to pass through, thus guarantee that all ammonia is all captured, and collection matrix should have enough intensity and can not be destroyed by air-flow, also very thin so that it is extremely minimum to the resistance drop of air-flow, make the air-flow body of breathing out be easy to enter grabber.Porous structure or directly can use porosint to obtain by the non-porous base material (as plastic material) of perforation.Usual matrix uses fibrous material, and under many circumstances, these fibrous materials are from paper or textile material.Matrix is also often porous paper, such as, consider the reason such as price and actual availability, can select filter paper.
Usually this grabber comprises the outer cover that is collected matrix, and matrix is just placed in this outer cover or is suspended from wherein.Usual collection matrix can be full of this outer cover, across the xsect of outer cover, and the necessary and matrix phase interaction by any gas of outer cover.In many cases, enclosure configurations is allow gas inlet and outlet grabber.General outer cover is equipped with an entrance and enters grabber to allow gas, and an outlet discharges grabber to allow gas.Meanwhile, may also be and only have a hole, both can be used as entrance and also can be used as outlet.Usual entrance and exit is that following form is placed, and gas enters from entrance, flows through collection matrix, to exporting discharge.Preferred scheme is that outer cover cover body is provided with gas access and gas vent.Outer cover cover body center of inside arranges Ammonia collector, and cover body two ends are respectively equipped with gas access and gas vent, to ensure that gas enters from gas access, flows through Ammonia collector, discharges, ammonia all in air-flow can be made all to be extracted to gas vent.It is that sample of breath spreads/flow through filter paper that this structure has added advantage, does not have obvious harm to user.Such as, the detection method of known use liquid device has the risk sucking liquid.Owing to not having liquid in grabber described here, thus such situation can not occur.The accurate structure of outer cover can improve to be adapted to provide an economically viable product further.
Outer cover may by plastics, metal, glass or other materials (such as paper).But regulation shell is atresia, and outer cover is made up of hard material under normal circumstances, these materials are inertia, do not react in other words with the component in air-flow.
Chemical Trapping allows to use the solution (comprising reagent) of minimum volume to carry out measuring/detecting.
Second aspect of the present invention provides a kind of ammonia pick-up unit, and it comprises the ammonia grabber described in first aspect, and an ammoniacal sensor.Any type of ammoniacal sensor all may use, although the sensor often used selects from electroanalysis sensor, biology sensor, optical sensor, fluorescent optical sensor, pot, the chromatography of ions or their combination.In many cases, sensor makes electrical energy consumption analysis sensor, at this moment can use the Indirect Detecting Method described in patented claim (GB1315803.5).
Especially, the detection method in GB1315803.5 comprises the electroactive ammonia derivant of indirect detection tool.Except under high voltage, ammonia itself is not electroactive.A kind of method addressed this problem uses mercaptoacetic acid (thioglycolate salt) and o-pthalaldehyde (phthalic aldehyde) ammonia to be changed into alpha mercaptoacetic acid indoles salt (thioisoindole).This combination is what to find in known OPA derivative reagent.In the reaction, mercaptoacetic acid and phthalic aldehyde define mercaptal compound.Then with ammonia generation annulation, alpha mercaptoacetic acid indoles salt (thioisoindole) is formed.Forming process is as shown in reaction equation 1.
Alpha mercaptoacetic acid indoles salt (thioisoindole) can be used for directly measuring the ammonia in air-flow (normally tidal air), because form alpha mercaptoacetic acid indoles salt (thioisoindole) molecule to need an amino molecule.Guarantee the concentration of Accurate Measurement ammonia.And use OPA reagent, well-known reaction is extremely reliable, guarantees that all ammonia of catching can be detected.Reaction 2 shows the electrochemical reaction that alpha mercaptoacetic acid indoles salt (thioisoindole) occurs.
As mentioned above, reacted by ammonia and phthalic aldehyde, mercaptoacetic acid and produce mercaptal intermediate, and then generate alpha mercaptoacetic acid indoles salt (thioisoindole), use this electroactive material existence and the concentration thereof of ammonia indirectly can be detected.Which provides the method for ammonia density in a kind of reliable detection tidal air.
Being beneficial to the generation of alpha mercaptoacetic acid indoles salt (thioisoindole) under alkali condition, by promoting the formation of mercaptal, impelling reaction to complete quickly.
The reaction conditions of OPA reagent classics is phthalic aldehydes: mercaptoacetic acid is about 2:1 to guarantee only to form single mercaptal, does not form bisacetal, because bisacetal can hinder the annulation with ammonia.Therefore, the phthalic aldehyde of use: the ratio of mercaptoacetic acid is in 0.5:1 to 5:1 scope.But find to make reaction rate at high proportion faster, usually this ratio being set in 3.5:1to4.5:1, is often 4:1.
Interelectrode electrochemical potential scope is-2.0 ~ 2.0V, normally-1.0 ~ 1.0V.The exemplary currents scope that the present invention can detect is-5.0 × 10
-9~ 1.0 × 10
-4a. the current potential of these parameters is used to be conducive to the oxidation of alpha mercaptoacetic acid indoles salt (thioisoindole).This transformation can cause the electric current that can measure in scope above-mentioned.
Usually this ammonia pick-up unit device also comprises solvent cell, and described solvent cell closes on ammonia grabber and arranges, the medium of the in-built dissolving ammonium salt of described solvent cell.Medium comprises simple solvent, damping fluid or contains the solution that can promote the reagent that ammonia salt discharges from collection matrix.Solvent cell has solvent and damping fluid usually.Detect and relate to the derivant comprising OPA, solvent cell contains damping fluid.
Usually this ammonia pick-up unit can be equipped with lateral flow devices, and the thing at this moment in solvent cell discharges and enters solution arrival sensor from the ammonia salt collecting matrix.Before testing, also need ammonia salt to react further, first ammonia salt enter reaction chamber, and then to sensor.
Usually this ammonia pick-up unit is disposable.By this ammonia pick-up unit (or grabber) is designed to disposable apparatus, guarantee each sample by the pollution of sample before, remove and in use clean and the requirement of device of resetting.These steps may introduce user error (such as, cleaning sensor is abundant not), increase the possibility of read untrue.If grabber is disposable, these will be excluded.Lose after whole ammonia pick-up unit can be finished.If possible, this ammonia pick-up unit will be classified by size, hand-held to make it be easier to, desirable pocket-sized, so that operator can once carry several table apparatus.Which provides the possibility of onsite application, and be not only simple clinical manifestation.The onsite application of this device is an importance of the present invention, because this device low cost of manufacture, dependable performance, simple to operate.These three features become ideal when making it use at the scene, because do not need when using this device to test tightly to control environment.
When air-flow is tidal air, if it is useful that ammonia pick-up unit contains receiver, receiver is arranged on one end, gas access of ammonia grabber, for the reception of exhaling.Receiver can be exhale in oral cavity, also can be an accessory receiving nose expiratory air.The existence of such receiver makes it possible to direct sample from tidal air, does not need to be stored or transfer sample by pipeline or other parts.Receiver can use the material manufacture of wide range, such as plastics, metal, glass or paper products.When receiver is multifunction component, it is made up of metal, glass or plastics usually, more usually plastics, because plastics are easy to manufacture and cost is low, can provide economic, safe product.Such as, the receiver with level and smooth profile is favourable, because it can meet mouth or nose well, can not damage because of sharp-pointed edge to user.Alternatively, when receiver is the disposable unit of this device, no matter only receiver is as the disposable unit of device, or catches as disposable unit together with device with flutterring with sensor, and receiver is normally manufactured by paper product, such as cardboard.
Reader normally connects together with sensor display analysis result.When device is limited or disposable use unit, reader may be dismountable.In this case, device reversibly connects together with display.And disposable apparatus can be connected with display, to such an extent as to be not substituted once remove the combination of any special disposable unit, the unit that preventing pollution reuses.Single use unit can comprise fuse component, and in the controlled path situation of electric charge, its destruction electrical contact of can degenerating, prevents reusing of disposable unit.
Reader can be connected the technology using any one traditional with sensor.Connection reversibly processes limited or disposable use unit.Comprising reversible editing technology for connecting limited or disposable use unit and reader method of attachment, being such as clasped, boning, frictional fit, threaded engagement, hook-loop coordinate, screw thread or tack coordinate or their combination.Because reader is high cost, reader connect reversibility the reader when device is dropped can be remained, be beneficial to so repeatedly use and can be equally not contaminated with device.
The product that reader is normally common, usual reader is that a kind of electronic product uses running software, and it the electric signal produced in sensor can be transformed into can be exported by the result of operator or user's understanding, thus for diagnosis.In addition, this reading device comprises the software that some can carry out diagnosing explanation.Such as, reader can work out a program for providing the possibility containing candida albicans, or provide " with/without " simply indicate.When use cyclic voltammetry, this software can set the size of current range, when current value exceedes certain confinement of setting, shows to contain some biological label things.Chronoamperometry is a kind of time dependent method of record current, and at some time, it detects than cyclic voltammetry and more allows reliably effectively.
In a third aspect of the present invention, disclose a kind of device detecting ammonia, comprise catching and and sensor of the ammonia in first aspect present invention.This device also comprises previously described solvent cell.This device can be the breath test of specialty also can be general testing tool; Can be disposable also can be nonexpondable; Sensor and grabber can be comprised, receiver, solvent cell, usually also be connected use containing sensor with display reader, optionally can connect reader and use.Also containing operation instructions in device.Operation instructions can be simple assembling instructions, may comprise measurement of concetration, may comprise that patient feels under the weather concentration level or these combination.Such device provides light, quick, the simple instrument using point, ammonia density in the parameter area inner evaluation tidal air of expection can to user and operator.
In in 4th of the present invention, disclose a kind of method detecting ammonia, comprise the following steps:
(1) gaseous ammonia is sent into the grabber of first aspect of the present invention;
(2) ammonia and acid reaction form ammonium ion;
(3) ammonium ion is detected.
This method may be used for detecting various diseases, comprises ephrosis, cirrhosis, anxiety, Mycophyta infectious disease (as candida albicans) or bacterium class infectious disease (as helicobacter pylori).Ammonia may in the tidal air of people or mammal, and device of the present invention is intended to use in the mankind.
Usually, gaseous ammonia being sent into this step of grabber is repeatedly, and this can increase the concentration of entrapping ammine, guarantees that ammonia has enough concentration and can be detected.During use, number of times is repeatedly generally guarantee the repeatability of result and the consistance of diagnosis according to the agreement of definition.
The ammonia of catching is sent in the sensor selected.If sensor needs solution, solution is sent into and catches on ammonia to guarantee the carrying out of measuring.Or by from discharging ammonia with buffer solution when collecting matrix and being fed in the sensor of other points in device.This method may comprise the step discharging ammonia/ammonium ion before detection from grabber, discharges this step and comprises wash-out ammonia/ammonium ion from collection matrix.Wash-out is the most frequently used method for releasing because like this can the soonest, the simplest from matrix release ammonia.
The step of usual detection ammonia/ammonium ion comprises the chemical conversion of the ammonium ion before analysis, and this has the advantage of the analysis thing of the detection signal that can provide stronger, can provide more stable analysis thing simply in addition under testing conditions.As previously mentioned, detection method normally electroanalysis, optics, fluorescence, pot, biology or their combination.
The invention discloses a kind of ammonia grabber, comprising: collect matrix, the porous matrix be made up of the fibrous material from paper and textile material can be selected; Fix on the acid of collecting on matrix, can strong acid be selected, as H
3pO
4, H
2sO
4, HCl, HNO
3and the potpourri of they and weak acid; Optional collection matrix outer cover, optionally, outer cover has entrance and exit to make gas energy inlet and outlet grabber, and the position of entrance and exit can be selected to determine like this: gas enters through gatherer from entrance and discharges to outlet.
The invention discloses a kind of ammonia pick-up unit, comprising: grabber as described; Ammoniacal sensor, this sensor can from electroanalysis sensor, biology sensor, optical sensor, fluorescent optical sensor, pot, chromatography of ions or their combination.
Ammonia pick-up unit also comprises solvent cell, for being discharged from the ammonia that matrix is caught by buffer solvent; Optional reader; Wherein, this device is partly or entirely selectively disposable product.
The invention discloses a kind of method that ammonia detects, comprise following steps:
Grabber described in being sent into by gaseous ammonia (can select the tidal air from human or animal), can select repeatedly to carry out several times;
(1) ammonia and acid reaction form ammonium salt;
(2) before detection ammonium salt, can select to discharge ammonium ion from grabber, wash-out from collection matrix can be selected;
(3) detect ammonium ion, can select the ammonium ion detecting chemical transformation before analysis, detection method can select electroanalysis, optics, fluorescence, pot, biology, chromatography of ions or their combination.
Unless otherwise mentioned, described each integral part can combine with other described any one integral parts, understood by those skilled in the art.And, although all aspects of the present invention contain described relative feature better.Imagine them and meet or substantially meet those features pointed out in claim.In addition, all terms, unless specifically defined at this, are intended to be given its implication usually understood in the art.
In addition, in discussion of the present invention, except as otherwise noted in contrast, the upper limit of disclosed parameter or the substitution value of lower limit, think each intermediate value of implicit described parameter, between less and larger substitution value, itself is also as the probable value of parameter.
In addition, unless otherwise mentioned, occur that all numerical value are in this application modified by " about ".
Hinge structure, the Advantageous Effects that technical scheme of the present invention is brought:
(1) the ammonia collecting device energy Efficient Collection gaseous ammonia of the present invention's proposition, can realize the fixing of gaseous ammonia, be conducive to the indirect determination to gaseous ammonia.
(2) ammonia pick-up unit of the present invention effectively can realize gaseous ammonia collecting, fixing and Accurate Measurement.
(2) ammonia test method of the present invention, realizes based on ammonia collecting device or pick-up unit, simple to operate, quick, and the detection of energy effective implemention gaseous ammonia, can be widely used in human body or animal various diseases.
Accompanying drawing explanation
[Fig. 1] a is acquisition equipment sketch of the present invention, and b is the sketch of single grabber in grabber of the present invention.
[Fig. 2] a, b, c is the schematic diagram of ammonia pick-up unit of the present invention: a is outside schematic diagram, and Fig. 2 b, c are schematic internal view.
[Fig. 3] shows the ammonia density (ammonium ion) recorded by the mercaptoacetic acid chromatography of ions of variable concentrations, error bar N=3; Ammonia theoretical value (if all ammonia is all captured) is 5ppm.
[Fig. 4] shows and propagates by solution the amount of gaseous ammonia to catch the amount of ammonia impact on acid solution.Diamond spot represents the theoretical value that ammonia is caught by 100%, and square dot represents the ammonia density recorded by the chromatography of ions.
[Fig. 5] shows the percent loss of gaseous ammonia and the relation (gas velocity 336mL/min) of the amount of the gaseous ammonia propagated by mercaptoacetic acid solution.
[Fig. 6] shows linear sweep voltammetry response (sweep speed 100mV/s) of (in solution) on graphite screen printing electrode in the gaseous ammonia of the variable concentrations that gas generator produces.
[Fig. 7] is the calibration curve of the gaseous ammonia (in solution) that gas generator produces, error bar (N=3).
[Fig. 8] shows the chromatography of ions testing result of gaseous ammonia in the tidal air being collected in and catching in balloon, by the mercaptoacetic acid solution of 1mL120mM.
[Fig. 9] shows the electrochemical method testing result of gaseous ammonia in the tidal air being collected in and catching in balloon, by the mercaptoacetic acid solution of 1mL120mM.
Embodiment
Below in conjunction with accompanying drawing and concrete example, the present invention is further described in detail, be easier to make the present invention understand.
Fig. 1 a shows grabber of the present invention (5), containing H
3pO
4matrix (10) collected by the Whatman filter paper of dipping.Dried H
3pO
4it is visible oily sheet (15).Grabber (5) comprises to be supported and packs the plastic housing (20) collecting matrix (10).Shown in figure, entrance (25) and outlet (30), grabber (5) runs like this, is sent to by the tidal air of people collects matrix (10) place by entrance (25).The xsect of the oily sheet size (15) on matrix (10) and entrance (25) and outlet (30) is suitable, and they are each has identical size.In outlet 30, place utilizes air extractor to be extracted out by tidal air, and because tidal air needs by collecting matrix (10) in the process be drawn out of, ammonia is wherein captured, extraction be not containing other compositions of ammonia.Grabber of the present invention (5) can carry out catching of multiple tidal air sample simultaneously, and Fig. 1 b shows single acquisition equipment.
Once tidal air is sent to grabber (5), take off from grabber and collect matrix (10), be put on a Screen-printed electrochemical biosensor (not showing in FIG).Add sensing solution to detect ammonia density.
This grabber (5) allows to use the solution (comprising reagent) of minimum volume to analyze.Grabber (5) is highly effective to ammonia, have been found that can 100% from tidal air, extract ammonia.
Fig. 2 show sensing ammonia a kind of alternative scheme, ammonia pick-up unit (50) comprises grabber (5), no longer need as shown in Figure 1 remove grabber (5) before analysis.Lateral flow devices in Fig. 2 comprises receiver, and (55, Fig. 2 a), user to be placed on mouth and to exhale.Receiver (55) guides tidal air to enter grabber (5) (Fig. 2 b, c).What close on grabber is a solvent cell (60) containing damping fluid, after expiration, uses release-push (65) to be discharged from pond (60) by buffering agent.Buffer wash is by grabber (5), ammonium ion wash-out from collection matrix (10) out, is flow on the porous paper reaction film (70) containing OPA reagent along lateral flow devices (50) by capillarity.Along with ammonia is through reaction film (70), alpha mercaptoacetic acid indoles salt (thioisoindole) (85) generate, and are sent to electrochemical sensor (75) and detect.
Sensor (75) is inserted on reader (80), and the electric signal of sensor (75) is converted to concentration value in the future.
Disclose a kind of breath detector (50) of reliable, disposable detection ammonia.In order to read the content of ammonia in breathing subsequently, device (50) couples together with reader (80) simply, and this process can be carried out repeatedly.
Chemical process does not become, if needed, can use the identical device (50) being equipped with optics or other sensors (75).
Embodiment 1
The gaseous ammonia from gas generator and tidal air is detected by OPA method:
All chemicalss are all from SigmaAldrich company.Employ OPA (titanium dialdehyde cas.No.643-79-8M.W.134.13), mercaptoacetic acid (Cas.No.68-11-1) and NaOH.Resistivity is that the deionized water of 18.2M Ω cm is for the preparation of all aqueous solution.Ammonia is produced by OwlstoneOVG-4 correcting gas generator.Chromatography of ions detects ammonium ion to carry out on Dionex ion chromatograph (ICS-2000).The pH value of catching solution (mercaptoacetic acid, 115-120mM) is 2.5, and the pH value of the final solution of all detections was for 12.75 (after adding OPA/NaOH solution), and pH value is recorded by MettlerToledoSevenCompact acidometer.Unless otherwise mentioned, the test of all voltammetries is all use potentiostat (μ AUTOLABTypeIII, MetrohmAutolabB.V.) to carry out after two minutes adding all reagent.
Serigraphy three-electrode structure has the geometry graphite working electrode that a diameter is 3mm, and Ag/AgCl contrast electrode and graphite are to electrode.Use the test of serigraphy three-electrode structure.The inner stencil design of serigraphy carbon-based electrode (representing with SPEs) uses silk screen microDEK1760RS printing machine (DEK, Weymouth, UK).
Gaseous state generator comprises ammonia osmos tube, and seepage velocity is 200ng/min, and running temperature is 30 DEG C, and gas velocity is 336mL/min.Unless otherwise mentioned, the concentration in all ammonia solutions is μ g/mL (ppm), and in liquid solution, the concentration relationship of ammonia and the middle ammonia of gas solution (such as tidal air) can be represented by the formula:
X is the concentration (ppm=μ L/L) of gaseous ammonia in gas solution (such as tidal air)
Y is the concentration (ppm=μ g/mL) analyzing thing (such as ammonia) in aqueous solution
Vaqueous is the volume (mL) of the aqueous solution of catching ammonia
24.5 is 1mol ideal gases at the volume (L/mol) of room temperature (25 DEG C) and normal pressure (1atm)
M.W. be the molecular weight (such as ammonia is 17.03g/mol) analyzing thing
Vgas is volume (such as tidal air) (mL) of gas solution
Such as, if ammonia is from 336mL tidal air, caught by 0.5mL aqueous solution (containing mercaptoacetic acid), then the ammonia of 1ppm (μ g/mL) is introduced into aqueous solution, and the concentration of gaseous ammonia in gaseous sample is then 2.141ppm (μ L/L).Aqueous solution volume is reduced to 0.2mL, and concentration is then 0.856ppm (μ L/L).
The analytic process detecting ammonia in gas solution can be divided into two steps:
1, in mercaptoacetic acid aqueous solution, gaseous ammonia (tidal air or other source) is caught by ammonia being converted to ammonium ion;
2, electroanalysis ammonia, is dissolved in sodium hydroxide solution by OPA, and NaOH changes ammonium ion into ammonia, and ammonia and OPA are reacted.
Unless otherwise mentioned, for catching the mercaptoacetic acid that the solution of ammonia is about 0.5mL (being 0.471mL in these embodiments) 115mM.Air-flow is blown into solution by glass pipette.For second step, use the OPA solution of the 69mg/mL being dissolved in 6M sodium hydroxide solution.This solution of 0.029mL is joined in the mercaptoacetic acid solution of the first step to obtain the final solution of 0.5mL.After reagent being mixed 2.0 minutes, the final solution of 0.200mL is used for SPE surface and linear sweep voltammetry is tested, 100mV/s sweep speed under, test from (-0.6V) ~ (1.2V).
Chromatography of ions is used to assess this catching method.Fig. 3 shows change mercaptoacetic acid concentration and does not change the amount of catching ammonia significantly.Mercaptoacetic acid concentration higher than 120mM, otherwise should not can increase the capacitance current of second step (sensor).
Fig. 4 shows and propagates by solution the amount of gaseous ammonia to catch the amount of ammonia impact on acid solution.The percent loss that Fig. 5 shows gaseous ammonia is about 20%.Gaseous ammonia percent loss seems the impact of the gaseous ammonia do not propagated significantly, and this comes from stable gas velocity.In all experiments, gas velocity is identical, and variable is the duration that air-flow passes through to catch solution.
Finally, have studied the impact of the holding time of the mercaptoacetic acid solution capturing ammonia in refrigerator on ammonia reserved in solution.At least after catching one week, solution was stable.
The detection of gaseous ammonia (from gas generator):
Use the gaseous ammonia that 11 kinds of different Bottle detection that the 120mM mercaptoacetic acid of 471 μ L is housed are produced by gas generator.Be blown into by ammonia in vial, the time is respectively 15 seconds, 1 minute 15 seconds, 1 minute 52 seconds, 2 minutes 30 seconds, 5 minutes, 7 minutes 30 seconds, 10 minutes, 12 minutes 30 seconds, 15 minutes, 20 minutes, 25 minutes.It is 200ng/min that gas generator produces gas velocity, final concentration (add the 30mMOPA of 29 μ l in 6M sodium hydroxide solution after, liquor capacity is 500uL) is respectively 0.1,0.5,0.75,1,2,3,4,5,6,8,10ppm.Fig. 6 shows linear sweep voltammetry figure, and Fig. 7 is calibration curve.
Gaseous ammonia in sulfate by ion chromatography tidal air:
A complete expiration is collected in balloon, and the tidal air collected by the method imports the 120mM mercaptoacetic acid solution of 1mL into by glass pipette.Then, to import the 120mM mercaptoacetic acid of another 1mL into molten for the gas of two balloons (twice complete breathing).Identical process is used for 3 and 4 balloons.By the ammonia that this four solution of sulfate by ion chromatography are caught, testing result as shown in Figure 8.
Chromatography of ions and electrochemical method detect the correlativity of gaseous ammonia in tidal air:
The result detecting the result of draft and the ion chromatographic method standard detecting method of ammonia (in the tidal air) is associated.A complete expiration is collected in balloon, and the tidal air collected by the method imports the 120mM mercaptoacetic acid solution of 1mL into by glass pipette.Then, to import the 120mM mercaptoacetic acid of another 1mL into molten for the gas of two balloons (twice complete breathing).Identical process is used for 3 and 4 balloons.Detect by electro-chemical test method the ammonia that this four solution catch, testing result as shown in Figure 9.
Between two kinds of methods, there is good correlativity, confirm electrochemical techniques as the method detecting ammonia in tidal air.The same with chromatography of ions, electrochemical techniques are at least sensitive, effective, and can tackle the change of ammonia density, (in this case, concentration shows non-linear increase, Fig. 8 and Fig. 9)
The process that the present invention relates to and device can be implemented with various methodologies, before only set forth wherein some.
Claims (17)
1. an ammonia grabber, is characterized in that: comprise the Ammonia collector be made up of in the acid of collecting on matrix collection matrix and load.
2. ammonia grabber according to claim 1, is characterized in that: described acid is H
3pO
4, H
2sO
4, HCl, HNO
3, at least one in mercaptoacetic acid, or be H
3pO
4, H
2sO
4, HCl, HNO
3, at least one in mercaptoacetic acid and weak acid combination.
3. ammonia grabber according to claim 1, is characterized in that: described collection matrix has porous structure.
4. ammonia grabber according to claim 3, is characterized in that: described collection matrix is paper or textile material.
5. ammonia grabber according to claim 1, is characterized in that: also comprise the outer cover being arranged on Ammonia collector outside.
6. ammonia grabber according to claim 5, is characterized in that: described outer cover cover body is provided with gas access and gas vent.
7. ammonia grabber according to claim 6, it is characterized in that: described outer cover cover body center of inside arranges Ammonia collector, and cover body two ends are respectively equipped with gas access and gas vent, to ensure that gas enters from gas access, flow through Ammonia collector, discharge to gas vent.
8. an ammonia pick-up unit, is characterized in that: comprise the ammonia grabber described in any one of claim 1 ~ 6 and sensor.
9. ammonia pick-up unit according to claim 8, is characterized in that: described sensor is one or several combination in electroanalysis sensor, biology sensor, optical sensor, fluorescent optical sensor, pot, chromatography of ions.
10. ammonia pick-up unit according to claim 8, is characterized in that: also comprise solvent cell, and described solvent cell closes on ammonia grabber and arranges, the medium of the in-built dissolving ammonium salt of described solvent cell.
11. ammonia pick-up units according to claim 10, is characterized in that: described medium is solvent, damping fluid or containing promoting that ammonium salt is from the solution of reagent collected matrix and discharge.
12. ammonia pick-up units according to claim 10, is characterized in that: described solvent cell is provided with release-push, for the release of solvent cell medium.
13. ammonia pick-up units according to claim 8, is characterized in that: one end, gas access of described ammonia grabber is provided with receiver, for the reception of exhaling.
14. ammonia pick-up units according to claim 8, is characterized in that: be provided with the porous paper reaction film containing OPA reagent between described ammonia grabber and sensor.
15. ammonia pick-up units according to claim 8, is characterized in that: described sensor is provided with corresponding reader.
The detection method of 16. ammonia, is characterized in that: first utilize the ammonia grabber collecting gaseous ammonia described in any one of claim 1 ~ 7 to obtain ammonium salt, detect ammonium ion by sensor.
17. detect the method for ammonia based on the ammonia pick-up unit described in any one of claim 8 ~ 15, it is characterized in that: comprise the following steps:
(1) gaseous ammonia is sent in ammonia grabber carry out collecting, obtain ammonium salt;
(2) medium in release solvent pond carries out wash-out to the ammonium salt collected in Ammonia collector, and ammonium salt reacts with the porous paper reaction film containing OPA reagent, ammonium salt is changed into alpha mercaptoacetic acid indoles salt;
(3) alpha mercaptoacetic acid indoles salt is detected by sensor.
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| CN109187451A (en) * | 2018-08-02 | 2019-01-11 | 北京华泰诺安技术有限公司 | It is a kind of for detecting the fluorescent optical sensor of chemical vapor |
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| CN103033600A (en) * | 2012-12-12 | 2013-04-10 | 武汉钢铁(集团)公司 | Determination method and determination device for ammonia escape |
| CN104820035A (en) * | 2015-05-12 | 2015-08-05 | 川渝中烟工业有限责任公司 | Method for determining ammonia content in cigarette main stream smoke by ion chromatography |
| WO2015166246A1 (en) * | 2014-04-30 | 2015-11-05 | Kanichi Research Services Ltd | Ammonia Trap |
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2016
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103033600A (en) * | 2012-12-12 | 2013-04-10 | 武汉钢铁(集团)公司 | Determination method and determination device for ammonia escape |
| WO2015166246A1 (en) * | 2014-04-30 | 2015-11-05 | Kanichi Research Services Ltd | Ammonia Trap |
| CN104820035A (en) * | 2015-05-12 | 2015-08-05 | 川渝中烟工业有限责任公司 | Method for determining ammonia content in cigarette main stream smoke by ion chromatography |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109187451A (en) * | 2018-08-02 | 2019-01-11 | 北京华泰诺安技术有限公司 | It is a kind of for detecting the fluorescent optical sensor of chemical vapor |
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